Ultrahigh-strength waterproof safe laminated glass intermediate film and preparation method thereof

Abstract

The invention relates to the field of laminated glass intermediate films, in particular to an ultrahigh-strength waterproof safe laminated glass intermediate film and a preparation method thereof. The intermediate membrane comprises the following components: an ethylene-vinyl acetate copolymer, a coupling agent, an initiator, an assistant crosslinking agent, a crosslinking monomer, a chain extender and a molecular weight regulator. The preparation method comprises the following steps: mixing an ethylene-vinyl acetate copolymer, an initiator A and a crosslinking monomer A in a low-speed mixer to obtain a first mixture; mixing the first mixture, a coupling agent, a molecular weight regulator, an initiator B and a crosslinking monomer B in a high-speed stirrer to obtain a second mixture; and inputting the second mixture into a screw extruder, and extruding the second mixture into an intermediate film, wherein the screw extruder is provided with nine temperature intervals. The middle film provided by the invention takes EVA as a main component, has very high tensile strength, and can be applied to laminated glass requiring certain strength, such as automobile front glass.

Description

Technical Field

[0001] The invention relates to the field of laminated glass intermediate films, and in particular to an ultra-high strength waterproof safety laminated glass intermediate film and a preparation method thereof. Background Art

[0002] Laminated glass is made of two or more pieces of glass bonded together. The bonding layer in the middle of the laminated glass is the interlayer film of the laminated glass. The good toughness and bonding ability of the interlayer film can improve the safety performance of glass breakage and fall, making the laminated glass have strong impact resistance. Laminated glass can be used in automobiles, buildings and public facilities. At present, there are roughly three types of interlayer films for laminated glass: EVA film, PVB film and SGP film. Among them, EVA film is slightly softer and has a smaller tensile strength of about 12MPa, which is generally used for decorative glass; PVB film is relatively soft, with a tensile strength of about 30MPa, and can be used for automobile front glass; and SGP film has a high hardness and a tensile strength of about 40MPa, which can be used for facilities with high safety requirements such as glass planks. The main material of SGP film is sarling resin, which is expensive; PVB film is easy to turn yellow and has poor water resistance; EVA film has low strength and can only be used for decorative materials.

[0003] In the prior art, there are improvements to EVA films, but the effect of enhancing tensile strength is general. For example, CN109796907A discloses an EVA intermediate film for high light transmittance and aging-resistant laminated glass and its preparation method, which improves the performance by adding ethylene ethyl acrylate copolymer-ethylene propylene rubber compound, and increases the tensile strength of the EVA film to 23MPa. Another example is CN114940878A discloses an intermediate film for high-strength fireproof laminated glass and its preparation method, which uses polyethylene, polypropylene, polybutene, ethylene propylene rubber or butyl rubber as reinforcing resin to improve the tensile strength of the EVA film, and the tensile strength of the obtained EVA intermediate film is ≥25MPa. The above-mentioned improvement method for EVA film can only increase the tensile strength to about 25MPa, and the haze is high and the tear strength is low, which is still difficult to meet the application in laminated glass requiring a certain strength such as automobile front glass, building curtain wall, door and window guardrail. Summary of the invention

[0004] In order to overcome the shortcomings of the prior art, the purpose of the present invention is to provide an ultra-high strength waterproof safety laminated glass interlayer film, which has EVA as the main component and has high tensile strength, and can be applied to laminated glass requiring a certain strength, such as automobile front glass, building curtain walls, door and window guardrails;

[0005] Another object of the present invention is to provide a method for preparing an ultra-high strength waterproof safety laminated glass intermediate film, and to improve product performance by limiting the mixing sequence and process temperature.

[0006] The technical solution adopted by the present invention is:

[0007] An ultra-high strength waterproof safety interlayer glass film, whose components include ethylene-vinyl acetate copolymer, coupling agent, initiator, co-crosslinking agent, crosslinking monomer, chain extender and molecular weight regulator.

[0008] Further, the components of the ultra-high strength waterproof safety interlayer glass film include, by weight, 100 parts of ethylene-vinyl acetate copolymer, 0.3 - 0.8 parts of coupling agent, 0.5 - 1.8 parts of initiator, 0.3 - 1.2 parts of co-crosslinking agent, 0.5 - 5 parts of crosslinking monomer, 0.3 - 1.8 parts of chain extender and 0.3 - 2 parts of molecular weight regulator.

[0009] Further, the components of the ultra-high strength waterproof safety interlayer glass film include, by weight, 100 parts of ethylene-vinyl acetate copolymer, 0.3 - 0.8 parts of coupling agent, 0.5 - 1.8 parts of initiator, 0.8 - 1 part of co-crosslinking agent, 1.2 - 2 parts of crosslinking monomer, 0.5 - 0.8 parts of chain extender and 0.5 - 1 part of molecular weight regulator.

[0010] Further, the VA content of the ethylene-vinyl acetate copolymer is 26 - 33%, and the MI index is 3 - 15%.

[0011] Further, the crosslinking monomer is selected from one or more of hydroxypropyl methacrylate, 1,6-hexanediol diacrylate and triethylene glycol dimethacrylate.

[0012] Further, the molecular weight regulator is selected from one or two of AMSD, tert-dodecyl mercaptan and 2,4-diphenyl-4-methyl-1-pentene.

[0013] Further, the co-crosslinking agent is selected from one or two of triallyl isocyanurate and trimethylolpropane trimethacrylate.

[0014] Further, the components of the ultra-high strength waterproof safety interlayer glass film also include, by weight, 0.1 - 0.8 parts of ultraviolet absorber, 0.1 - 0.8 parts of light stabilizer and 0.5 - 5 parts of antioxidant.

[0015] Correspondingly, the present invention also provides a preparation method of an ultra-high strength waterproof safety interlayer glass film, including the following steps:

[0016] (1) Mix ethylene-vinyl acetate copolymer, initiator A and crosslinking monomer A in a low-speed mixer at a mixing temperature of 65 - 85°C to obtain a first mixture;

[0017] (2) At room temperature, mix the first mixture, coupling agent, molecular weight regulator, initiator B, and crosslinking monomer B in a high-speed mixer to obtain a second mixture; wherein, initiator A and initiator B are the same substance or different substances, and crosslinking monomer A and crosslinking monomer B are the same substance or different substances;

[0018] (3) Input the second mixture into a screw extruder and extrude to obtain the above-mentioned ultra-high-strength waterproof safety interlayer glass interlayer film; wherein, the temperature of the screw extruder is set as follows: the first section is 58 - 62 °C, the second section is 68 - 72 °C, the third section is 78 - 82 °C, the fourth section is 83 - 84 °C, the fifth section is 85 °C, the sixth section is 85 °C, the seventh section is 85 °C, the eighth section is 78 - 82 °C, the ninth section is 78 - 82 °C, and the die head temperature is 68 - 72 °C.

[0019] Furthermore, in the step (1), an antioxidant is also added to the low-speed mixer; in the step (2), an ultraviolet absorber and a light stabilizer are also added to the high-speed mixer.

[0020] The beneficial effects of the present invention are as follows:

[0021] 1. The crosslinking monomers in the formulation system participate in the crosslinking reaction, and the network structure formed by ethylene-vinyl acetate copolymer (EVA), co-crosslinking agent, and crosslinking monomer is denser. The chain extender connects the EVA molecules, expands the chain length of the main chain, achieves the effect of increasing the molecular weight, and improves the tear strength. The molecular weight regulator is used to adjust the crosslinking state, prevent the molecular weight from being too large or too small, ensure that the interlayer film has a very high tensile strength, make the tensile strength of the interlayer film reach more than 30 MPa, meet the application in high-strength safety interlayer glass, and synergize with the water resistance and yellowing resistance advantages of EVA itself. The safety interlayer glass interlayer film of the present invention has the characteristics of ultra-high strength and waterproofness.

[0022] 2. The preparation method of the present invention achieves the effects of sufficient mixing and sufficient reaction by limiting the mixing order and process temperature to obtain an ultra-high-strength and waterproof safety interlayer glass interlayer film. Specific Embodiments

[0023] The technical solutions in the embodiments of the present invention will be described clearly and completely below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0024] The present invention provides a technical solution: an ultra-high-strength waterproof safety interlayer glass interlayer film, the components of which include ethylene-vinyl acetate copolymer, coupling agent, initiator, co-crosslinking agent, crosslinking monomer, chain extender, and molecular weight regulator.

[0025] In this technical solution, the crosslinking monomers in the formulation system participate in the crosslinking reaction, and the network structure formed by ethylene-vinyl acetate copolymer (EVA), co-crosslinking agent and crosslinking monomers is denser. The chain extender connects between EVA molecules, expands the chain length of the main chain, achieves the effect of increasing the molecular weight, and improves the tear strength. The molecular weight regulator is used to adjust the crosslinking state, prevent the molecular weight from being too large or too small, and ensure that the interlayer film has a very high tensile strength. The tensile strength of the interlayer film of laminated glass obtained with the formulation system of this solution reaches more than 30 MPa, and can reach up to 39 MPa at most, meeting the application in high-strength safety laminated glass. Combining with the advantages of water resistance and yellowing resistance of EVA itself, the safety interlayer film of laminated glass of the present invention has the characteristics of ultra-high strength and waterproofness.

[0026] In one embodiment of the present invention, the components of the ultra-high strength waterproof safety interlayer film of laminated glass include 100 parts by weight of ethylene-vinyl acetate copolymer, 0.3 - 0.8 parts of coupling agent, 0.5 - 1.8 parts of initiator, 0.3 - 1.2 parts of co-crosslinking agent, 0.5 - 5 parts of crosslinking monomer, 0.3 - 1.8 parts of chain extender and 0.3 - 2 parts of molecular weight regulator. By limiting the dosage of each component, and thus limiting the raw material ratio, while ensuring the ultra-high tensile strength of the interlayer film, the haze is reduced. If the dosages of the crosslinking monomer, chain extender and molecular weight regulator are too high, the haze of the product is high; if the dosages are too low, it is difficult for the product to have ultra-high strength.

[0027] Preferably, the components of the ultra-high strength waterproof safety interlayer film of laminated glass include 100 parts by weight of ethylene-vinyl acetate copolymer, 0.3 - 0.8 parts of coupling agent, 0.5 - 1.8 parts of initiator, 0.8 - 1 part of co-crosslinking agent, 1.2 - 2 parts of crosslinking monomer, 0.5 - 0.8 parts of chain extender and 0.5 - 1 part of molecular weight regulator. By further limiting the dosage of each component in the formulation, the safety interlayer film of laminated glass has higher tensile strength and lower haze.

[0028] In the present invention, the VA content of the ethylene-vinyl acetate copolymer is 26 - 33%, and the MI index is 3 - 15%. The lower the VA content, the closer the properties of EVA are to low-density high-pressure polyethylene (LDPE), and the higher the VA content, the closer the properties of EVA are to rubber. The VA content in the present invention is 26 - 33%, enabling the interlayer film to have a lower haze and appropriate hardness. The MI index, namely the melt index, represents the fluidity of EVA, and the impact resistance of EVA can be limited through the MI index. Preferably, the VA content is 26 - 28%, and the MI index is 8 - 10%.

[0029] Further, the crosslinking monomer is selected from one or more of hydroxypropyl methacrylate, 1,6 - hexanediol diacrylate, and triethylene glycol dimethacrylate. The crosslinking monomer is used to connect multiple EVA molecules, cooperate with the co - crosslinking agent to form a denser network structure, and improve the tensile strength of the intermediate film. Among them, hydroxypropyl methacrylate and 1,6 - hexanediol diacrylate can also improve the adhesion of the intermediate film, and triethylene glycol dimethacrylate can improve the tensile strength of the intermediate film to a greater extent. In addition, based on the denser crosslinking effect, the crosslinking monomer can improve the hardness of the intermediate film. Specifically, hydroxyethyl methacrylate (HEMA), 1,6 - hexanediol diacrylate (HDDA), and triethylene glycol dimethacrylate (TEGDMA) have good compatibility with other components of the formulation system, can fully participate in the crosslinking reaction and improve the crosslinking efficiency.

[0030] Further, the molecular weight regulator is selected from one or two of AMSD, tert - dodecyl mercaptan, and 2,4 - diphenyl - 4 - methyl - 1 - pentene. AMSD is α - methylstyrene dimer, and in the present invention, AMSD - GRS or AMSD - GRH is specifically selected. The above several molecular weight regulators play a role in controlling the molecular weight and molecular weight distribution in the formulation system, and improve the product performance.

[0031] Further, the co - crosslinking agent is selected from one or two of triallyl isocyanurate and trimethylolpropane trimethacrylate. The branched chain groups of the co - crosslinking agent connect at least three EVA molecules, improving the crosslinking speed. In the present invention, triallyl isocyanurate and / or trimethylolpropane trimethacrylate is used as the co - crosslinking agent, which has good compatibility with other components in the formulation system, ensuring the performance of the intermediate film.

[0032] Specifically, the chain extender is used to increase the chain length, increase the molecular weight of the polymer, and enhance the toughness of the intermediate film. Existing chain extenders can be selected as the chain extender. Preferably, in an embodiment of the present invention, the chain extender is selected from one or two of 1,4 - butanediol and 1,6 - ethylene glycol. 1,4 - butanediol and 1,6 - ethylene glycol have a high participation degree in the system reaction, and the performance improvement of the intermediate film is obvious.

[0033] The coupling agent of the present invention is selected from silane coupling agents. Preferably, it is selected from one or two of γ-methacryloxypropyltrimethoxysilane and γ-(2,3-epoxypropoxy)propyltrimethoxysilane, so that the interlayer film has excellent adhesion performance. The initiator of the present invention is selected from peroxide initiators. Preferably, the initiator is selected from one or more of tert-butyl 2-ethylhexyl carbonate peroxide (TBEC), tert-amyl peroxy-2-ethylhexanoate (TAPEH), and 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxide). During the cross-linking reaction process, the peroxy group of the initiator breaks to generate free radicals, which initiate the polymerization of monomers. The above initiators have good reaction activity and promote the cross-linking reaction.

[0034] It can be understood that the safety laminated glass is often used outdoors and needs to have a certain weather resistance. Therefore, the interlayer film of the present invention further includes 0.1-0.8 parts by weight of an ultraviolet absorber, 0.1-0.8 parts by weight of a light stabilizer, and 0.5-5 parts by weight of an antioxidant, so that the interlayer film has the properties of ultraviolet resistance and oxidation resistance and prolongs the service life. Specifically, the ultraviolet absorber is selected from one or two of 2-hydroxy-4-n-octyloxybenzophenone and 2-(2'-hydroxy-3',5'-di-tert-phenyl)-5-chlorobenzotriazole, which has the effects of reducing yellowing, protecting the appearance and anti-aging of the interlayer film; the light stabilizer is selected from one or two of the polymer of succinic acid and (4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol), poly[[6-[(1,1,3,3-tetramethylbutyl)amine]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imine]-1,6-dihexanediyl[(2,2,6,6-tetramethyl-1-piperidyl)imine]]], which is used to protect the ultraviolet absorber and the body, and has a good synergistic effect with the antioxidant and the ultraviolet absorber, further improving the heat resistance and light aging resistance of the interlayer film. The antioxidant is selected from one or more of pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], n-octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and tris(2,4-di-tert-butylphenyl) phosphite.

[0035] Correspondingly, the present invention also provides a method for preparing an interlayer film for ultra-high strength waterproof safety laminated glass, including the following steps:

[0036] (1) Mix ethylene-vinyl acetate copolymer, initiator A and cross-linking monomer A in a low-speed mixer at a mixing temperature of 65-85 °C to obtain a first mixture;

[0037] (2) At room temperature, mix the first mixture, coupling agent, molecular weight regulator, initiator B, and crosslinking monomer B in a high-speed mixer to obtain the second mixture; wherein, initiator A and initiator B are the same substance or different substances, and crosslinking monomer A and crosslinking monomer B are the same substance or different substances;

[0038] (3) Input the second mixture into a screw extruder and extrude to obtain the above-mentioned ultra-high-strength waterproof safety interlayer glass interlayer; wherein, the temperature of the screw extruder is set as follows: the first section is 58 - 62 °C, the second section is 68 - 72 °C, the third section is 78 - 82 °C, the fourth section is 83 - 84 °C, the fifth section is 85 °C, the sixth section is 85 °C, the seventh section is 85 °C, the eighth section is 78 - 82 °C, the ninth section is 78 - 82 °C, and the die head temperature is 68 - 72 °C.

[0039] The preparation method of the present invention achieves the effects of sufficient mixing and sufficient reaction by limiting the mixing sequence and process temperature to obtain an ultra-high-strength and waterproof safety interlayer glass interlayer. Specifically, in step (1), EVA, initiator A, and crosslinking monomer A are mixed at 65 - 85 °C for a pre-reaction to ensure deep crosslinking between the crosslinking monomer and EVA; in step (2), the remaining components are mixed at room temperature, and this mixing process is a physical mixing to achieve the effect of uniform mixing, and the second mixture maintains a good feeding effect and can be smoothly input into the screw extruder. The screw extruder is designed with nine temperature sections and uses the specified temperature, which not only ensures the full completion of the crosslinking reaction but also ensures good fluidity of the material in the screw extruder. It should be noted that, according to the formula amount, the initiator is divided into initiator A and initiator B, and the initiator is divided into initiator A and initiator B, and the mixing is carried out in steps. Preferably, the weight ratio of initiator A to initiator B is (3 - 4):(6 - 7), and the weight ratio of crosslinking monomer A to crosslinking monomer B is (6 - 7):(3 - 4).

[0040] Further, in step (1), an antioxidant is also added to the low-speed mixer; in step (2), an ultraviolet absorber and a light stabilizer are also added to the high-speed mixer. Adding the antioxidant during the first mixing plays an antioxidant role in the pre-reaction process and protects the reaction process.

[0041] The present invention will be further elaborated below through examples and comparative examples.

[0042] Example 1

[0043] The intermediate film component of the ultra-high strength waterproof safety laminated glass in this embodiment includes 100 parts by weight of ethylene-vinyl acetate copolymer, 0.3 parts of γ-methacryloxypropyltrimethoxysilane, 0.5 parts of TBEC, 0.3 parts of triallyl isocyanurate, 0.5 parts of hydroxypropyl methacrylate, 0.3 parts of 1,4-butanediol, and 0.3 parts of AMSD-GRH. Among them, the VA content of EVA is 26-28%, and the MI index is 8-10%.

[0044] The intermediate film of this embodiment is prepared through the following steps:

[0045] (1) According to the formula amount, mix ethylene-vinyl acetate copolymer, initiator A, and crosslinking monomer A in a low-speed mixer at a mixing temperature of 85-90 °C to obtain the first mixture;

[0046] (2) At room temperature, mix the first mixture, coupling agent, molecular weight regulator, initiator B, and crosslinking monomer B in a high-speed mixer according to the formula amount to obtain the second mixture; among them, both initiator A and initiator B are TBEC, and the weight ratio of the two is 4:6, and the crosslinking monomer A and crosslinking monomer B are hydroxypropyl methacrylate, and the weight ratio of the two is 6:4;

[0047] (3) Input the second mixture into a screw extruder and extrude to obtain the above-mentioned ultra-high strength waterproof safety laminated glass intermediate film; among them, the temperature of the screw extruder is set as follows: the first section is 58 °C, the second section is 68 °C, the third section is 78 °C, the fourth section is 83 °C, the fifth section is 85 °C, the sixth section is 85 °C, the seventh section is 85 °C, the eighth section is 78 °C, the ninth section is 78 °C, and the die head temperature is 68 °C.

[0048] Example 2

[0049] The intermediate film component of the ultra-high strength waterproof safety laminated glass in this embodiment includes 100 parts by weight of ethylene-vinyl acetate copolymer, 0.8 parts of γ-methacryloxypropyltrimethoxysilane, 1.8 parts of TBEC, 1.2 parts of triallyl isocyanurate, 5 parts of hydroxypropyl methacrylate, 1.8 parts of 1,4-butanediol, and 2 parts of AMSD-GRH. Among them, the VA content of EVA is 26-28%, and the MI index is 8-10%.

[0050] The intermediate film of this embodiment is prepared through the following steps:

[0051] (1) According to the formula amount, mix ethylene-vinyl acetate copolymer, initiator A, and crosslinking monomer A in a low-speed mixer at a mixing temperature of 85-90 °C to obtain the first mixture;

[0052] (2) At room temperature, mix the first mixture, coupling agent, molecular weight regulator, initiator B, and crosslinking monomer B in a high-speed mixer according to the formulation amounts to obtain a second mixture; wherein, both initiator A and initiator B are TBEC, and the weight ratio of the two is 4:6, and crosslinking monomer A and crosslinking monomer B are hydroxypropyl methacrylate, and the weight ratio of the two is 6:4;

[0053] (3) Input the second mixture into a screw extruder and extrude to obtain the above-mentioned ultra-high strength waterproof safety laminated glass interlayer film; wherein, the temperature of the screw extruder is set as follows: the first section is 58 °C, the second section is 68 °C, the third section is 78 °C, the fourth section is 83 °C, the fifth section is 85 °C, the sixth section is 85 °C, the seventh section is 85 °C, the eighth section is 78 °C, the ninth section is 78 °C, and the die head temperature is 68 °C.

[0054] Example 3

[0055] The components of the ultra-high strength waterproof safety laminated glass interlayer film in this example include 100 parts by weight of ethylene-vinyl acetate copolymer, 0.6 part of γ-methacryloxypropyltrimethoxysilane, 1.2 parts of TBEC, 1 part of triallyl isocyanurate, 1.2 parts of hydroxypropyl methacrylate, 0.5 part of 1,4-butanediol, and 0.5 part of AMSD-GRH. Among them, the VA content of EVA is 26-28%, and the MI index is 8-10%.

[0056] The interlayer film of this example is prepared through the following steps:

[0057] (1) According to the formulation amounts, mix the ethylene-vinyl acetate copolymer, initiator A, and crosslinking monomer A in a low-speed mixer at a mixing temperature of 85-90 °C to obtain a first mixture;

[0058] (2) At room temperature, mix the first mixture, coupling agent, molecular weight regulator, initiator B, and crosslinking monomer B in a high-speed mixer according to the formulation amounts to obtain a second mixture; wherein, both initiator A and initiator B are TBEC, and the weight ratio of the two is 4:6, and crosslinking monomer A and crosslinking monomer B are hydroxypropyl methacrylate, and the weight ratio of the two is 6:4;

[0059] (3) Input the second mixture into a screw extruder and extrude to obtain the above-mentioned ultra-high strength waterproof safety laminated glass interlayer film; wherein, the temperature of the screw extruder is set as follows: the first section is 60 °C, the second section is 70 °C, the third section is 80 °C, the fourth section is 84 °C, the fifth section is 85 °C, the sixth section is 85 °C, the seventh section is 85 °C, the eighth section is 80 °C, the ninth section is 80 °C, and the die head temperature is 70 °C.

[0060] Example 4

[0061] The intermediate film component of the ultra-high strength waterproof safety laminated glass in this embodiment comprises 100 parts by weight of ethylene-vinyl acetate copolymer, 0.6 part of γ-methacryloxypropyltrimethoxysilane, 1.2 parts of TBEC, 1 part of triallyl isocyanurate, 2 parts of hydroxypropyl methacrylate, 0.8 part of 1,4-butanediol, and 1 part of AMSD-GRH.

[0062] The intermediate film of this embodiment is prepared through the following steps:

[0063] (1) According to the formula amount, mix the ethylene-vinyl acetate copolymer, initiator A, and crosslinking monomer A in a low-speed mixer at a mixing temperature of 85-90°C to obtain a first mixture.

[0064] (2) At room temperature, mix the first mixture, coupling agent, molecular weight regulator, initiator B, and crosslinking monomer B in a high-speed mixer according to the formula amount to obtain a second mixture; wherein, both initiator A and initiator B are TBEC, and the weight ratio of the two is 4:6, and the crosslinking monomer A and crosslinking monomer B are hydroxypropyl methacrylate, and the weight ratio of the two is 6:4.

[0065] (3) Input the second mixture into a screw extruder and extrude to obtain the above-mentioned ultra-high strength waterproof safety laminated glass intermediate film; wherein, the temperature of the screw extruder is set as follows: the first section is 60°C, the second section is 70°C, the third section is 80°C, the fourth section is 84°C, the fifth section is 85°C, the sixth section is 85°C, the seventh section is 85°C, the eighth section is 80°C, the ninth section is 80°C, and the die head temperature is 70°C.

[0066] Example 5

[0067] The intermediate film component of the ultra-high strength waterproof safety laminated glass in this embodiment comprises 100 parts by weight of ethylene-vinyl acetate copolymer, 0.6 part of γ-methacryloxypropyltrimethoxysilane, 1.2 parts of TBEC, 1 part of triallyl isocyanurate, 1.5 parts of hydroxypropyl methacrylate, 0.6 part of 1,4-butanediol, and 0.6 part of AMSD-GRH. Among them, the VA content of EVA is 26-28%, and the MI index is 8-10%.

[0068] The intermediate film of this embodiment is prepared through the following steps:

[0069] (1) According to the formula amount, mix the ethylene-vinyl acetate copolymer, initiator A, and crosslinking monomer A in a low-speed mixer at a mixing temperature of 85-90°C to obtain a first mixture.

[0070] (2) At room temperature, mix the first mixture, coupling agent, molecular weight regulator, initiator B, and crosslinking monomer B in a high-speed mixer according to the formulation amounts to obtain a second mixture; wherein, both initiator A and initiator B are TBEC, and the weight ratio of the two is 4:6, and crosslinking monomer A and crosslinking monomer B are hydroxypropyl methacrylate, and the weight ratio of the two is 6:4;

[0071] (3) Input the second mixture into a screw extruder and extrude to obtain the above-mentioned ultra-high-strength waterproof safety interlayer glass interlayer; wherein, the temperature of the screw extruder is set as follows: the first section is 60 °C, the second section is 70 °C, the third section is 80 °C, the fourth section is 84 °C, the fifth section is 85 °C, the sixth section is 85 °C, the seventh section is 85 °C, the eighth section is 80 °C, the ninth section is 80 °C, and the die head temperature is 70 °C.

[0072] Example 6

[0073] The components of the ultra-high-strength waterproof safety interlayer glass interlayer in this example include 100 parts by weight of ethylene-vinyl acetate copolymer, 0.6 part of γ-methacryloxypropyltrimethoxysilane, 1.2 parts of TBEC, 1 part of triallyl isocyanurate, 1.5 parts of hydroxypropyl methacrylate, 0.6 part of 1,4-butanediol, 0.6 part of AMSD-GRH, 0.1 part of 2-hydroxy-4-n-octyloxybenzophenone, 0.8 part of the polymer of succinic acid and (4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol), and 5 parts of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]. Among them, the VA content of EVA is 26-28%, and the MI index is 8-10%.

[0074] The interlayer in this example is prepared through the following steps:

[0075] (1) According to the formulation amounts, mix ethylene-vinyl acetate copolymer, initiator A, crosslinking monomer A, and pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] in a low-speed mixer at a mixing temperature of 85-90 °C to obtain a first mixture;

[0076] (2) At room temperature, mix the first mixture, coupling agent, molecular weight regulator, initiator B, crosslinking monomer B, 2-hydroxy-4-n-octyloxybenzophenone, and the polymer of succinic acid and (4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol) in a high-speed mixer according to the formulation amounts to obtain a second mixture; wherein, both initiator A and initiator B are TBEC, and the weight ratio of the two is 4:6, and crosslinking monomer A and crosslinking monomer B are hydroxypropyl methacrylate, and the weight ratio of the two is 6:4;

[0077] (3) Feed the second mixture into a screw extruder and extrude to obtain the above-mentioned ultra-high strength waterproof safety interlayer glass interlayer film; wherein, the temperature of the screw extruder is set as follows: the first section is 60 °C, the second section is 70 °C, the third section is 80 °C, the fourth section is 84 °C, the fifth section is 85 °C, the sixth section is 85 °C, the seventh section is 85 °C, the eighth section is 80 °C, the ninth section is 80 °C, and the die head temperature is 70 °C.

[0078] Example 7

[0079] The components of the ultra-high strength waterproof safety interlayer glass interlayer film in this example include 100 parts by weight of ethylene-vinyl acetate copolymer, 0.6 parts of γ-methacryloyloxypropyltrimethoxysilane, 1.2 parts of TBEC, 1 part of triallyl isocyanurate, 1.5 parts of hydroxypropyl methacrylate, 0.6 parts of 1,4-butanediol, 0.6 parts of AMSD-GRH, 0.8 parts of 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 0.1 part of poly[[6-[(1,1,3,3-tetramethylbutyl)amine]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imine]-1,6-dihexanediyl[(2,2,6,6-tetramethyl-1-piperidinyl)imine]]], and 0.5 part of n-octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate.

[0080] The interlayer film of this example is prepared through the following steps:

[0081] (1) According to the formula amount, mix ethylene-vinyl acetate copolymer, initiator A, crosslinking monomer A, and n-octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate in a low-speed mixer at a mixing temperature of 85-90 °C to obtain the first mixture.

[0082] (2) At room temperature, mix the first mixture, coupling agent, molecular weight regulator, initiator B, crosslinking monomer B, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, and poly[[6-[(1,1,3,3-tetramethylbutyl)amine]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imine]-1,6-dihexanediyl[(2,2,6,6-tetramethyl-1-piperidinyl)imine]]] in a high-speed mixer according to the formula amount to obtain the second mixture; wherein, both initiator A and initiator B are TBEC, and the weight ratio of the two is 4:6, and both crosslinking monomer A and crosslinking monomer B are hydroxypropyl methacrylate, and the weight ratio of the two is 6:4.

[0083] (3) Input the second mixture into a screw extruder and extrude to obtain the above-mentioned ultra-high-strength waterproof safety interlayer glass interlayer film; wherein, the temperature of the screw extruder is set as follows: the first section is 62°C, the second section is 72°C, the third section is 82°C, the fourth section is 84°C, the fifth section is 85°C, the sixth section is 85°C, the seventh section is 85°C, the eighth section is 82°C, the ninth section is 82°C, and the die head temperature is 72°C.

[0084] Comparative Example 1

[0085] The components of the ultra-high-strength waterproof safety interlayer glass interlayer film in this comparative example include 100 parts by weight of ethylene-vinyl acetate copolymer, 0.6 parts of γ-methacryloxypropyltrimethoxysilane, 1.2 parts of TBEC, and 1 part of triallyl isocyanurate. Among them, the VA content of EVA is 26-28%, and the MI index is 8-10%. The preparation steps and process parameters of this comparative example are the same as those in Example 5.

[0086] Comparative Example 2

[0087] The components of the ultra-high-strength waterproof safety interlayer glass interlayer film in this example include 100 parts by weight of ethylene-vinyl acetate copolymer, 0.6 parts of γ-methacryloxypropyltrimethoxysilane, 1.2 parts of TBEC, 1 part of triallyl isocyanurate, 1.5 parts of hydroxypropyl methacrylate, and 0.6 parts of AMSD-GRH. Among them, the VA content of EVA is 26-28%, and the MI index is 8-10%. The preparation steps and process parameters of this comparative example are the same as those in Example 5.

[0088] Comparative Example 3

[0089] The interlayer film components in this comparative example are the same as those in Example 5. The interlayer film in this comparative example is prepared through the following steps:

[0090] (1) At room temperature, mix the ethylene-vinyl acetate copolymer, coupling agent, molecular weight regulator, initiator, and crosslinking monomer in a high-speed mixer according to the formula amounts to obtain a mixture.

[0091] (2) Input the mixture into a screw extruder and extrude to obtain the above-mentioned ultra-high-strength waterproof safety interlayer glass interlayer film; wherein, the temperature of the screw extruder is set as follows: the first section is 60°C, the second section is 70°C, the third section is 80°C, the fourth section is 84°C, the fifth section is 85°C, the sixth section is 85°C, the seventh section is 85°C, the eighth section is 80°C, the ninth section is 80°C, and the die head temperature is 70°C.

[0092] Comparative Example 4

[0093] The interlayer film components in this comparative example are the same as those in Example 5. The interlayer film in this comparative example is prepared through the following steps:

[0094] (1) According to the formulation amounts, mix ethylene-vinyl acetate copolymer, initiator A, and crosslinking monomer A in a low-speed mixer at a mixing temperature of 85-90 °C to obtain a first mixture.

[0095] (2) At room temperature, mix the first mixture, coupling agent, molecular weight regulator, initiator B, and crosslinking monomer B in a high-speed mixer according to the formulation amounts to obtain a second mixture; wherein, both initiator A and initiator B are TBEC, and the weight ratio of the two is 4:6, and crosslinking monomer A and crosslinking monomer B are hydroxypropyl methacrylate, and the weight ratio of the two is 6:4.

[0096] (3) Input the second mixture into a screw extruder and extrude to obtain the above-mentioned ultra-high-strength waterproof safety interlayer glass interlayer film; wherein, the temperature settings of the screw extruder are: the first section is 65 °C, the second section is 75 °C, the third section is 85 °C, the fourth section is 84 °C, the fifth section is 85 °C, and the die head temperature is 70 °C.

[0097] Test the properties of the interlayer films obtained in Examples 1-7 and Comparative Examples 1-4. Conduct tensile strength test, tear strength test on the interlayer film sheet with a thickness of 0.76 mm and calculate the elongation at break; clamp the 0.76 mm thick interlayer film sheet between two 5 mm thick glasses to prepare a laminated glass specimen, and conduct haze test and glass adhesion peel strength test. The test results are shown in the following table.

[0098]

[0099] As can be seen from the above table, the tensile strength of the interlayer films in Examples 1-7 of the present invention reaches more than 30 MPa, and the highest can reach 38 MPa. At the same time, the haze is small and it has a large tear strength and glass adhesion peel strength. The addition of ultraviolet absorber, light stabilizer, and antioxidant has almost no effect on the strength performance of the interlayer film. The chain extender and molecular weight regulator have obvious effects on the strength of the interlayer film, and the pre-reaction step and basic temperature setting in the process have obvious effects on the interlayer film performance.

[0100] The present invention will be further described below through example groups.

[0101] Example Group A

[0102] The formulation of the interlayer film in this example group is: 100 parts by weight of ethylene-vinyl acetate copolymer, 0.6 part of γ-methacryloxypropyltrimethoxysilane, 1.2 parts of TBEC, 1 part of triallyl isocyanurate, 1.5 parts of crosslinking monomer, 0.6 part of 1,4-butanediol, and 0.6 part of AMSD-GRH. Among them, the VA content of EVA is 26-28%, and the MI index is 8-10%.

[0103] The specific components selected for the crosslinking monomer in this example group are shown in the following table.

[0104]

[0105] Tensile strength test, tear strength test and glass adhesion peel strength test were carried out on the interlayer film of this example group, and the results are shown in the following table.

[0106]

[0107]

[0108] Hydroxypropyl methacrylate and 1,6 - hexanediol diacrylate can improve the adhesion of the interlayer film, and triethylene glycol dimethacrylate can improve the tensile strength of the interlayer film. When either hydroxypropyl methacrylate or 1,6 - hexanediol diacrylate synergizes with triethylene glycol dimethacrylate, the interlayer film has better performance.

[0109] Example Group B

[0110] The formula of the interlayer film in this example group is: 100 parts of ethylene - vinyl acetate copolymer, 0.6 part of γ - methacryloxypropyltrimethoxysilane, 1.2 parts of TBEC, 1 part of triallyl isocyanurate, 1.5 parts of hydroxypropyl methacrylate, 0.6 part of chain extender and 0.6 part of AMSD - GRH by weight. Among them, the VA content of EVA is 26 - 28%, and the MI index is 8 - 10%.

[0111] The specific components selected for the chain extender in this example group are shown in the following table.

[0112] Example Specific components Example B1 1,6-Ethylene glycol Example B2 Glycerol Example B3 Ethylenediamine

[0113] Tensile strength test, tear strength test and glass adhesion peel strength test were carried out on the interlayer film of this example group, and the results are shown in the following table.

[0114]

[0115] It can be seen that in the solution of the present invention, using 1,4 - butanediol or 1,6 - ethylene glycol as the chain extender is more conducive to improving the strength of the interlayer film.

[0116] Example Group C

[0117] The intermediate film formulation of this example group is as follows: 100 parts of ethylene-vinyl acetate copolymer, 0.6 parts of γ-methacryloyloxypropyltrimethoxysilane, 1.2 parts of TBEC, 1 part of triallyl isocyanurate, 1.5 parts of hydroxypropyl methacrylate, 0.6 parts of 1,4-butanediol, and 0.6 parts of molecular weight regulator, all by weight. Among them, the VA content of EVA is 26-28%, and the MI index is 8-10%.

[0118] The specific components selected for the molecular weight regulator in this example group are shown in the following table.

[0119] Example Specific components Weight ratio Example C1 AMSD-GRS / Example C2 tert-Dodecyl mercaptan / Example C3 2,4-Diphenyl-4-methyl-1-pentene / Example C4 AMSD, tert-Dodecyl mercaptan 1:1

[0120] Tensile strength test, tear strength test, haze test, and glass adhesion peel strength test were carried out on the intermediate film of this example group. The properties of the intermediate films obtained in Examples C1-C4 were basically the same, and all could reach a tensile strength of 38 MPa. It can be seen that the above-mentioned molecular weight regulators can all play a good role in regulating the molecular weight in the formulation of the present invention.

[0121] Finally, it should be noted that the above are only preferred examples of the present invention and are not used to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements on some of the technical features. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. An ultra-high strength waterproof safety laminated glass interlayer film, characterized in that: The components include ethylene-vinyl acetate copolymer, coupling agent, initiator, auxiliary cross-linking agent, cross-linking monomer, chain extender and molecular weight regulator.

2. The ultra-high strength waterproof safety laminated glass interlayer film according to claim 1, characterized in that: The components include, by weight, 100 parts of ethylene-vinyl acetate copolymer, 0.3-0.8 parts of coupling agent, 0.5-1.8 parts of initiator, 0.3-1.2 parts of auxiliary crosslinking agent, 0.5-5 parts of crosslinking monomer, 0.3-1.8 parts of chain extender and 0.3-2 parts of molecular weight regulator.

3. The ultra-high strength waterproof safety laminated glass interlayer film according to claim 2, characterized in that: The components include, by weight, 100 parts of ethylene-vinyl acetate copolymer, 0.3-0.8 parts of coupling agent, 0.5-1.8 parts of initiator, 0.8-1 parts of auxiliary crosslinking agent, 1.2-2 parts of crosslinking monomer, 0.5-0.8 parts of chain extender and 0.5-1 parts of molecular weight regulator.

4. The ultra-high strength waterproof safety laminated glass interlayer film according to claim 1, 2 or 3, characterized in that: The VA content of the ethylene-vinyl acetate copolymer is 26-33%, and the MI index is 3-15%.

5. The ultra-high strength waterproof safety laminated glass interlayer film according to claim 1, 2 or 3, characterized in that: The cross-linking monomer is selected from one or more of hydroxypropyl methacrylate, 1,6-hexanediol diacrylate and triethylene glycol dimethacrylate.

6. The ultra-high strength waterproof safety laminated glass interlayer film according to claim 1, 2 or 3, characterized in that: The molecular weight regulator is selected from one or two of AMSD, tert-dodecyl mercaptan and 2,4-diphenyl-4-methyl-1-pentene.

7. The ultra-high strength waterproof safety laminated glass interlayer film according to claim 1, 2 or 3, characterized in that: The auxiliary cross-linking agent is selected from one or both of triallyl isocyanurate and trimethylolpropane trimethacrylate.

8. The ultra-high strength waterproof safety laminated glass interlayer film according to claim 2 or 3, characterized in that: The components thereof further include 0.1 to 0.8 parts of ultraviolet absorber, 0.1 to 0.8 parts of light stabilizer and 0.5 to 5 parts of antioxidant by weight.

9. A method for preparing an ultra-high strength waterproof safety laminated glass intermediate film, characterized in that: The following steps are involved: (1) mixing ethylene-vinyl acetate copolymer, initiator A and crosslinking monomer A in a low-speed mixer at a mixing temperature of 65 to 85° C. to obtain a first mixture; (2) mixing the first mixed material, coupling agent, molecular weight regulator, initiator B and crosslinking monomer B in a high-speed mixer at room temperature to obtain a second mixed material; wherein the initiator A and the initiator B are the same substance or different substances, and the crosslinking monomer A and the crosslinking monomer B are the same substance or different substances; (3) The second mixed material is input into a screw extruder and extruded to obtain the ultra-high strength waterproof safety laminated glass intermediate film according to any one of claims 1 to 7; wherein the temperature of the screw extruder is set to: 58-62°C in the first section, 68-72°C in the second section, 78-82°C in the third section, 83-84°C in the fourth section, 85°C in the fifth section, 85°C in the sixth section, 85°C in the seventh section, 78-82°C in the eighth section, 78-82°C in the ninth section, and the die head temperature is 68-72°C.

10. The method for preparing the ultra-high strength waterproof safety laminated glass intermediate film according to claim 9, characterized in that: In the step (1), an antioxidant is also added to the low-speed mixer; in the step (2), an ultraviolet absorber and a light stabilizer are also added to the high-speed stirrer.

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