Composition of adhesive film, adhesive film, preparation method of adhesive film and laminated glass

Abstract

The invention provides a composition of an adhesive film, the adhesive film, a preparation method of the adhesive film and laminated glass. The composition comprises an ethylene-vinyl acetate copolymer and an acrylate polymer, wherein the mass of the ethylene-vinyl acetate copolymer accounts for 80-90% of the total mass of the ethylene-vinyl acetate copolymer and the acrylate polymer, and the mass ratio of the acrylate polymer in the composition is 12-20%; the number-average molecular weight of the acrylate polymer is not more than 5000 g / mol; a double bond is carried in a side chain of the acrylate polymer. A double bond is carried in a side chain of the acrylate polymer, a cross-linking reaction can be further carried out due to the existence of the double bond, an interpenetrating structure is formed in a molecular chain of the ethylene-vinyl acetate copolymer, and the sound insulation effect and the thermal stability of the adhesive film can be further improved. Therefore, the adhesive film formed by the composition of the adhesive film has excellent sound insulation effect, visible light transmittance and thermal stability.

Description

Technical Field

[0001] The present invention relates to the technical field of laminated glass, and in particular, to a composition of a glue film, the glue film, a preparation method thereof, and laminated glass. Background Art

[0002] Noise pollution caused by mechanical vibration can be seen everywhere, and efficient sound insulation and noise reduction have always been a popular research field. Due to the unique viscoelasticity of polymer materials under the action of alternating stress, the change in deformation lags behind the change in stress, resulting in a hysteresis phenomenon. A part of the work (mechanical energy) is consumed in the form of heat or other forms, thereby generating mechanical loss and playing a damping role, and having excellent sound insulation effect. Many EVA damping materials are modified by blending, grafting polymers or adding nano-fillers, or by introducing a hollow structure to improve sound absorption performance. Many products only consider the sound insulation performance and do not balance other properties. Therefore, there are few sound-insulating laminated products. Because most nano-fillers are opaque, the light transmittance will be affected after addition. For polymer blending, the material compatibility is poor and the haze of the glue film will be relatively high. Interpenetrating polymer networks, interface interpenetration can achieve a double-phase continuous phase state, and incompatible components can also achieve forced compatibility through kinetic control. By preparing an EVA interpenetrating polymer network, a high light transmittance and sound-insulating EVA glue film can be obtained.

[0003] A Chinese patent with the patent authorization announcement number CN105835497B discloses a sound insulation structure. The processing method of this sound insulation structure is complex. The laminated material is PVB material, and there are holes left in the middle. Under the conditions of high temperature and high pressure during the glass laminating process, the sound insulation structure is prone to collapse and the performance will be reduced. At the same time, the reserved air channels in the three-layer PVB structure will reduce the overall optical performance of the glue film and will also become a water vapor channel. After long-term aging, interlayer foaming is likely to occur, and the glue film will be debonded when the moisture content is too high. Summary of the Invention

[0004] The main purpose of the present invention is to provide a composition of a glue film, the glue film, a preparation method thereof, and laminated glass, so as to solve the problem in the prior art that it is difficult for the glue film to have both good sound insulation effect and visible light transmittance.

[0005] To achieve the above object, according to one aspect of the present invention, there is provided a composition of a glue film, the composition comprising: ethylene-vinyl acetate copolymer and acrylate polymer; wherein, the mass of the ethylene-vinyl acetate copolymer accounts for 80-90% of the total mass of the ethylene-vinyl acetate copolymer and the acrylate polymer, and the mass ratio of the acrylate polymer in the composition is 12-20%; the number average molecular weight of the acrylate polymer does not exceed 5000 g / mol; and the side chain of the acrylate polymer carries a double bond.

[0006] Further, the number average molecular weight of the above acrylate polymer is 3000 to 5000 g / mol; and / or; the number of double bond-containing side chains in the acrylate polymer accounts for 4% to 8% of the total number of side chains.

[0007] Further, the total number of carbon atoms in the carbon chain of the side chain of the above acrylate polymer is less than 5.

[0008] Further, the above acrylate polymer is prepared by copolymerizing an acrylate monomer with a double bond in the side chain and an acrylate monomer without a double bond in the side chain; preferably, the acrylate monomer with a double bond in the side chain is selected from any one or more of allyl methacrylate, allyl acrylate, vinyl methacrylate, and vinyl acrylate; and / or, the acrylate monomer without a double bond in the side chain is selected from any one or more of propyl methacrylate, methoxyethyl methacrylate, methyl methacrylate, ethyl methacrylate, and 2-hydroxyethyl methacrylate.

[0009] Further, in the monomers for synthesizing ethylene-vinyl acetate copolymer, the mass content of vinyl acetate monomer is 28 to 33%; and / or, the melt index of ethylene-vinyl acetate copolymer at 190 °C and 2.16 kg / cm 3 is 9 to 15 g / 10 min.

[0010] Further, the above composition further comprises any one or more of a crosslinking agent, a co-crosslinking agent, a silane coupling agent, and an anti-ultraviolet agent; preferably, the mass ratio of the crosslinking agent to the total mass of the ethylene-vinyl acetate copolymer and the acrylate polymer is 0.8-1.2:100; and / or, the mass ratio of the co-crosslinking agent to the total mass of the ethylene-vinyl acetate copolymer and the acrylate polymer is 1.2-1.5:100; and / or, the mass ratio of the silane coupling agent to the total mass of the ethylene-vinyl acetate copolymer and the acrylate polymer is 0.6-0.9:100; and / or, the mass ratio of the anti-ultraviolet agent to the total mass of the ethylene-vinyl acetate copolymer and the acrylate polymer is 0.1-0.25:100; preferably, the crosslinking agent is selected from any one or more of 2-ethylhexyl peroxydicarbonate, 2,5-di-tert-butylperoxy-2,5-dimethylhexane, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyisopropyl carbonate, dilauroyl peroxide, isopropyl tert-butyl percarbonate, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 2-ethylhexyl peroxydicarbonate, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-amylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-amylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,2-bis(tert-butylperoxy)butane, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, tert-amyl peroxycarbonate, and tert-butyl peroxy-3,3,5-trimethylhexanoate; and / or, the co-crosslinking agent is selected from any one or more of triallyl isocyanurate, 2,4,6-triallyloxy-1,3,5-triazine, diallyl isocyanurate, triallyl cyanurate, and trimethallyl isocyanate; and / or, the silane coupling agent is selected from any one or more of 3-(methacryloyloxy)propyltrimethoxysilane, (3-methacryloyloxypropyl)triacetoxysilane, 3-(trimethoxysilyl)propyl 2-[(2-propen-1-yloxy)methyl]-2-acrylate, γ-aminopropyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-(2,3-epoxypropoxy)propyltrimethoxysilane, vinyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, and vinyltriethoxysilane; and / or, the ultraviolet absorber is selected from any one or more of 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, tris(1,2,2,6,6-pentamethylpiperidinol) phosphite, 2,2'-methylenebis(4-tert-octyl-6-benzotriazolylphenol), 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, and 2-hydroxy-5-chlorobenzophenone..

[0011] According to another aspect of the present invention, there is provided a method for preparing a film, using the foregoing composition to prepare the film, and the preparation method includes: mixing, granulating, and casting and molding ethylene-vinyl acetate copolymer and acrylate polymer in sequence to obtain the film.

[0012] Further, the temperature of the granulation is 100 - 120°C; and / or, the preparation method further includes: mixing the granulated product with any one or more of a crosslinking agent, a co-crosslinking agent, a silane coupling agent, and an ultraviolet absorber, and then performing casting molding; preferably, the casting molding includes a feeding section, a compression section, and a homogenization section; preferably, the temperature of the feeding section is 60 - 70°C; and / or, the temperature of the compression section is 75 - 85°C; and / or, the temperature of the homogenization section is 85 - 120°C.

[0013] According to another aspect of the present invention, there is provided a film, which is prepared by the aforementioned preparation method.

[0014] According to another aspect of the present invention, there is provided a laminated glass, including a film and glass, and the film is the aforementioned film.

[0015] Applying the technical solution of the present invention, both the ethylene-vinyl acetate copolymer and the acrylate polymer contain ester groups and have high compatibility, which helps to form an interpenetrating network structure. If the addition amount of the acrylate polymer is too low, the interpenetrating network structure is incomplete, which is not conducive to improving the sound insulation effect of the film. If the addition amount of the acrylate polymer is too high, the acrylate polymer is prone to agglomeration and phase separation occurs locally, which is not conducive to improving the visible light transmittance of the film. Preferably, controlling the mass ratio of the ethylene-vinyl acetate copolymer and the acrylate polymer within the above range helps to form a film with a higher visible light transmittance and a better sound insulation effect. If the molecular weight of the acrylate polymer is too high, the fluidity of the acrylate polymer is poor, which is not conducive to the uniform dispersion of the acrylate polymer in the ethylene-vinyl acetate copolymer. The acrylate polymer with a lower molecular weight is easy to flow and disperse during the processing, which helps to form an interpenetrating network structure, thereby helping to improve the sound insulation effect and visible light transmittance of the film. The side chain of the acrylate polymer carries double bonds, and the presence of the double bonds can further undergo a crosslinking reaction to form an interpenetrating structure in the molecular chain of the ethylene-vinyl acetate copolymer, which helps to further improve the sound insulation effect and thermal stability of the film. Therefore, the film formed by the composition of the film of the present application has excellent sound insulation effect, visible light transmittance, and thermal stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] The specification drawings forming a part of the present application are used to provide a further understanding of the present invention. The schematic embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation to the present invention. In the drawings:

[0017] Figure 1 The schematic diagram of the interpenetrating network structure of the ethylene-vinyl acetate copolymer molecular chain and the acrylate polymer molecular chain of the present application is shown.

[0018] Wherein, the above-mentioned drawings include the following reference numerals:

[0019] 1. Ethylene-vinyl acetate copolymer molecular chain; 2. Acrylate polymer molecular chain. Specific embodiments

[0020] It should be noted that, without conflict, the embodiments in this application and the features in the embodiments can be combined with each other. The present invention will be described in detail below with reference to the drawings and in conjunction with the embodiments.

[0021] As analyzed in the background art of this application, in the prior art, there is a problem that it is difficult for the adhesive film to have both good sound insulation effect and visible light transmittance. To solve the above problems, this application provides a composition of an adhesive film, an adhesive film, a preparation method thereof, and laminated glass.

[0022] In a typical embodiment of this application, a composition of an adhesive film is provided. The composition includes: ethylene-vinyl acetate copolymer and acrylate polymer; wherein, the mass of the ethylene-vinyl acetate copolymer accounts for 80-90% of the total mass of the ethylene-vinyl acetate copolymer and the acrylate polymer, and the mass fraction of the acrylate polymer in the composition is 12-20%; the number average molecular weight of the acrylate polymer does not exceed 5000 g / mol; the side chain of the acrylate polymer carries a double bond, preferably a carbon-carbon double bond.

[0023] As Figure 1 shown, both the ethylene-vinyl acetate copolymer and the acrylate polymer contain ester groups, and have high compatibility, which helps to form an interpenetrating network structure of the ethylene-vinyl acetate copolymer molecular chain 1 and the acrylate polymer molecular chain 2. If the addition amount of the acrylate polymer is too low, the interpenetrating network structure is incomplete, which is not conducive to improving the sound insulation effect of the adhesive film. If the addition amount of the acrylate polymer is too high, the acrylate polymer is prone to agglomeration and phase separation occurs locally, which is not conducive to improving the visible light transmittance of the adhesive film. Preferably, controlling the mass ratio of the ethylene-vinyl acetate copolymer and the acrylate polymer within the above range helps to form an adhesive film with a higher visible light transmittance and a better sound insulation effect. If the molecular weight of the acrylate polymer is too high, the fluidity of the acrylate polymer is poor, which is not conducive to the uniform dispersion of the acrylate polymer in the ethylene-vinyl acetate copolymer. The acrylate polymer with a lower molecular weight is easy to flow and disperse during the processing, which helps to form an interpenetrating network structure, thereby helping to improve the sound insulation effect and visible light transmittance of the adhesive film. The side chain of the acrylate polymer carries a double bond, and the presence of the double bond can further undergo a cross-linking reaction to form an interpenetrating structure in the molecular chain of the ethylene-vinyl acetate copolymer, which helps to further improve the sound insulation effect and thermal stability of the adhesive film. Therefore, the adhesive film formed from the composition of the adhesive film of this application has excellent sound insulation effect, visible light transmittance and thermal stability.

[0024] In an embodiment of the present application, the number-average molecular weight of the above acrylate polymer is 3,000 to 5,000 g / mol, specifically, it can be 3,000 g / mol, 3,500 g / mol, 4,000 g / mol, 4,500 g / mol, 5,000 g / mol, and the range values between any two of these values; and / or; the number of side chains containing double bonds in the acrylate polymer accounts for 4% to 8% of the total number of side chains, specifically, it can be 4%, 5%, 6%, 7%, 8%, and the range values between any two of these values.

[0025] If the molecular weight of the acrylate polymer is too low, the polymer chain segments are too short, which is not conducive to the formation of an interpenetrating network structure; if the molecular weight of the acrylate polymer is too high, the fluidity of the acrylate polymer is poor, which is not conducive to the full mixing and mutual penetration of the molecular chains of ethylene-vinyl acetate copolymer, and affects the formation efficiency and structural integrity of the interpenetrating network structure. Preferably, controlling the molecular weight of the acrylate polymer within the above range helps the acrylate polymer to form a more stable interpenetrating network structure in the ethylene-vinyl acetate copolymer, thereby helping to improve the transparency and sound insulation effect of the adhesive film. Controlling the value of the number of side chains containing double bonds in the acrylate polymer accounting for the total number of side chains within the above range helps to control the degree of crosslinking and improve the stability of the interpenetrating network structure, thereby helping to improve the sound insulation effect, visible light transmittance and thermal stability of the adhesive film.

[0026] In an embodiment of the present application, the total number of carbon atoms in the carbon chain of the side chain of the above acrylate polymer is less than 5, preferably 3 to 4.

[0027] Controlling the total number of carbon atoms in the carbon chain of the side chain of the acrylate polymer within the above range helps to form a more stable interpenetrating network structure, and at the same time helps to increase the glass transition temperature of the acrylate polymer, thereby helping to improve the sound insulation effect and transparency of the adhesive film.

[0028] In order to further improve the stability of the interpenetrating network structure, thereby improving the sound insulation effect and visible light transmittance of the adhesive film, in an embodiment of the present application, it is preferred that the above acrylate polymer is prepared by copolymerization of acrylate monomers with double bonds in the side chain and acrylate monomers without double bonds in the side chain; preferably, the acrylate monomers with double bonds in the side chain are selected from any one or more of allyl methacrylate, acrylate acrylate, vinyl methacrylate and vinyl acrylate; and / or, the acrylate monomers without double bonds in the side chain are selected from any one or more of propyl methacrylate, methoxyethyl methacrylate, methyl methacrylate, ethyl methacrylate and hydroxyethyl methacrylate.

[0029] In an embodiment of the present application, among the monomers for synthesizing ethylene-vinyl acetate copolymer, the mass content of vinyl acetate monomer is 28-33%; and / or, the melt index of ethylene-vinyl acetate copolymer at 190 °C and 2.16 kg / cm 3 is 9-15 g / 10 min.

[0030] Preferably controlling the mass content of vinyl acetate monomer in the monomers for synthesizing ethylene-vinyl acetate copolymer within the above range helps to improve the polarity of ethylene-vinyl acetate copolymer, thereby helping to improve the compatibility between ethylene-vinyl acetate copolymer and acrylate polymer. At the same time, the crystallinity inside the ethylene-vinyl acetate copolymer is relatively low, making the ethylene-vinyl acetate copolymer have a high light transmittance and a low haze, thus helping to improve the visible light transmittance of the adhesive film. Preferably controlling the melt index of ethylene-vinyl acetate copolymer at 190 °C and 2.16 kg / cm 3 within the above range helps to make the ethylene-vinyl acetate copolymer have good fluidity, thereby helping to form an interpenetrating network structure.

[0031] In one embodiment of the present application, the above composition further comprises any one or more of a crosslinking agent, a co-crosslinking agent, a silane coupling agent, and an anti-ultraviolet agent; preferably, the mass ratio of the crosslinking agent to the total mass of the ethylene-vinyl acetate copolymer and the acrylate polymer is 0.8-1.2:100; and / or, the mass ratio of the co-crosslinking agent to the total mass of the ethylene-vinyl acetate copolymer and the acrylate polymer is 1.2-1.5:100; and / or, the mass ratio of the silane coupling agent to the total mass of the ethylene-vinyl acetate copolymer and the acrylate polymer is 0.6-0.9:100; and / or, the mass ratio of the anti-ultraviolet agent to the total mass of the ethylene-vinyl acetate copolymer and the acrylate polymer is 0.1-0.25:100; preferably, the crosslinking agent is selected from any one or more of bis(2-ethylhexyl) peroxydicarbonate, 2,5-di-tert-butylperoxy-2,5-dimethylhexane, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyisopropyl carbonate, dilauroyl peroxide, isopropyl peroxycarbonate, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, bis(2-ethylhexyl) peroxydicarbonate, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-amylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-amylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,2-bis(tert-butylperoxy)butane, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, tert-amyl peroxycarbonate, and tert-butyl peroxy-3,3,5-trimethylhexanoate; and / or, the co-crosslinking agent is selected from any one or more of triallyl isocyanurate, 2,4,6-triallyloxy-1,3,5-triazine, diallyl isocyanurate, triallyl cyanurate, and trimethallyl isocyanate; and / or, the silane coupling agent is selected from any one or more of 3-(methacryloyloxy)propyltrimethoxysilane, (3-methacryloyloxypropyl)triacetoxysilane, 3-(trimethoxysilyl)propyl 2-[(2-propenyloxy)methyl]-2-propenoate, γ-aminopropyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-(2,3-epoxypropoxy)propyltrimethoxysilane, vinyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, and vinyltriethoxysilane; and / or, the ultraviolet absorber is selected from any one or more of 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, tris(1,2,2,6,6-pentamethylpiperidinol) phosphite, 2,2'-methylenebis(4-tert-octyl-6-benzotriazolylphenol), 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, and 2-hydroxy-5-chlorobenzophenone.

[0032] The crosslinking agent initiates the crosslinking reaction of double bonds, thus helping to form a more stable interpenetrating network structure. Preferably, controlling the ratio of the mass of the crosslinking agent to the total mass of the ethylene-vinyl acetate copolymer and the acrylate polymer within the above range helps to further improve the stability of the interpenetrating network structure, thereby contributing to the improvement of the sound insulation effect and transparency of the film. Preferably, controlling the type of the crosslinking agent within the above range helps to further improve the efficiency of the crosslinking reaction. The addition of the co-crosslinking agent helps to improve the efficiency of the crosslinking reaction. Preferably, controlling the ratio of the mass of the co-crosslinking agent to the total mass of the ethylene-vinyl acetate copolymer and the acrylate polymer within the above range helps to further improve the efficiency of the crosslinking reaction. The co-crosslinking agent preferably does not use trimethylolpropane trimethacrylate, and using the co-crosslinking agent of the above type helps to avoid the competition of double bonds with similar molecular structures for active sites, resulting in a decrease in the crosslinking degree. The addition of the silane coupling agent helps to improve the bonding force at the interface between the components, thereby contributing to the improvement of the thermal stability of the film. Preferably, controlling the ratio of the mass of the silane coupling agent to the total mass of the ethylene-vinyl acetate copolymer and the acrylate polymer and the type of the silane coupling agent within the above range helps to further improve the thermal stability of the film. The addition of the ultraviolet absorber helps to reduce the aging of the film caused by ultraviolet light. Preferably, controlling the ratio of the mass of the ultraviolet absorber to the total mass of the ethylene-vinyl acetate copolymer and the acrylate polymer and the type of the ultraviolet absorber within the above range helps to further improve the ultraviolet light aging resistance of the film.

[0033] In another typical embodiment of the present application, a method for preparing a film is provided. The film is prepared using the aforementioned composition. The preparation method includes: mixing, granulating, and casting and molding the ethylene-vinyl acetate copolymer and the acrylate polymer in sequence to obtain the film.

[0034] Mixing the ethylene-vinyl acetate copolymer and the acrylate polymer helps to form an interpenetrating network structure of the ethylene-vinyl acetate copolymer and the acrylate polymer. Preferably, the granulation is carried out in a twin-screw granulator with a length-to-diameter ratio of 30:1 to 44:1, which helps to reduce the degradation of the acrylate polymer molecular chain caused by frictional heat generation. Preferably, the homogenization section of the granulation is carried out under vacuum and negative pressure conditions, which helps to reduce the oxidation of the polymer. Preferably, single-screw extrusion casting and molding is used.

[0035] In one embodiment of the present application, the temperature of the above granulation is 100 to 120 °C; and / or, the preparation method further includes: mixing the granulated product with any one or more of a crosslinking agent, a co-crosslinking agent, a silane coupling agent, and an ultraviolet absorber and then carrying out casting and molding; preferably, the casting and molding includes a feeding section, a compression section, and a homogenization section; preferably, the temperature of the feeding section is 60 to 70 °C; and / or, the temperature of the compression section is 75 to 85 °C; and / or, the temperature of the homogenization section is 85 to 120 °C.

[0036] Preferably, controlling the granulation temperature within the above range helps the granulation to be carried out in a twin-screw granulator with an aspect ratio of 30:1 to 44:1, thereby helping to reduce the degradation of acrylate polymer molecular chains caused by frictional heat generation and helping to form an interpenetrating network structure. Preferably, controlling the temperature of the feeding section, the compression section, and the homogenization section within the above range helps to improve the uniformity of dispersion between the components, thereby helping to improve the stability of the formed adhesive film.

[0037] In another typical embodiment of the present application, an adhesive film is provided, which is prepared by the foregoing preparation method; preferably, the visible light transmittance of the adhesive film is not less than 90%; and / or, the temperature range of the adhesive film with tanδ>0.2 is -20°C to 45°C; and / or, the haze of the adhesive film is 0.5 to 0.9%; and / or, the peel strength between the adhesive film and the glass is 95 to 147 N / cm; and / or, the yellow index of the dry heat aging of the adhesive film is 1.0 to 3.1.

[0038] The above-mentioned adhesive film has a high visible light transmittance and sound insulation effect, and is more suitable for use in laminated glass.

[0039] In another typical embodiment of the present application, a laminated glass is provided, which includes an adhesive film and glass, and the adhesive film is the foregoing adhesive film.

[0040] The above-mentioned laminated glass has a high visible light transmittance and sound insulation effect, and can better meet the market demand.

[0041] The beneficial effects of the present application will be further described below in conjunction with examples.

[0042] Example 1

[0043] By mass percentage, 85% of ethylene-vinyl acetate copolymer (EVA) and 15% of allyl methacrylate (ALMA)-2-hydroxyethyl methacrylate (HEMA) copolymer are mixed and then granulated using a twin-screw granulator with an aspect ratio of 44:1. Under vacuum and negative pressure conditions, the granulation temperature is 120°C to obtain resin pellets. Among them, the mass fraction of VA in the EVA resin is 30%, and the melt index of the EVA resin at 190°C and 2.16 kg / cm 3 is 11 g / 10 min. The number average molecular weight of the allyl methacrylate (ALMA)-2-hydroxyethyl methacrylate (HEMA) copolymer is 3500 g / mol. The number of side chains containing double bonds in the allyl methacrylate (ALMA)-2-hydroxyethyl methacrylate (HEMA) copolymer accounts for 5% of the total number of side chains, and the total number of carbon atoms in the carbon chain of the side chain of the allyl methacrylate (ALMA)-2-hydroxyethyl methacrylate (HEMA) copolymer is 4.

[0044] Mix the resin particles with tert-butyl peroxy-2-ethylhexyl carbonate (TBEC), triallyl isocyanurate (TAIC), 3-(methacryloyloxy)propyltrimethoxysilane, and 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol in a mixing kettle. Then, extrude and cast the mixed particles using a single-screw extruder. Among them, the temperature of the feeding section is 60°C, the temperature of the compression section is 75°C, and the temperature of the homogenization section is 85°C. The mass ratio of tert-butyl peroxy-2-ethylhexyl carbonate (TBEC) to the resin particles is 1.15:100, the mass ratio of triallyl isocyanurate (TAIC) to the resin particles is 1.4:100; the mass ratio of 3-(methacryloyloxy)propyltrimethoxysilane to the resin particles is 0.8:100; the mass ratio of 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol to the resin particles is 0.2:100, and a film is obtained.

[0045] Example 2

[0046] The difference from Example 1 is that the number-average molecular weight of the allyl methacrylate (ALMA)-2-hydroxyethyl methacrylate (HEMA) copolymer is 3000 g / mol, and a film is finally obtained.

[0047] Example 3

[0048] The difference from Example 1 is that the number-average molecular weight of the allyl methacrylate (ALMA)-2-hydroxyethyl methacrylate (HEMA) copolymer is 5000 g / mol, and a film is finally obtained.

[0049] Example 4

[0050] The difference from Example 1 is that the molecular weight of the allyl methacrylate (ALMA)-2-hydroxyethyl methacrylate (HEMA) copolymer is 2500 g / mol in terms of number-average, and a film is finally obtained.

[0051] Example 5

[0052] The difference from Example 1 is that the number of side chains containing double bonds in the allyl methacrylate (ALMA)-2-hydroxyethyl methacrylate (HEMA) copolymer accounts for 4% of the total number of side chains, and a film is finally obtained.

[0053] Example 6

[0054] The difference from Example 1 is that the number of side chains containing double bonds in the allyl methacrylate (ALMA)-2-hydroxyethyl methacrylate (HEMA) copolymer accounts for 8% of the total number of side chains, and a film is finally obtained.

[0055] Example 7

[0056] The difference from Example 1 is that the number of double-bond-containing side chains in the allyl methacrylate (ALMA)-2-hydroxyethyl methacrylate (HEMA) copolymer accounts for 9% of the total number of side chains, and a film is finally obtained.

[0057] Example 8

[0058] The difference from Example 1 is that the mass ratio of VA in the EVA resin is 28%, and the melt index of the EVA resin at 190 °C and 2.16 kg / cm 3 is 9 g / 10 min, and a film is finally obtained.

[0059] Example 9

[0060] The difference from Example 1 is that the mass ratio of VA in the EVA resin is 33%, and the melt index of the EVA resin at 190 °C and 2.16 kg / cm 3 is 15 g / 10 min, and a film is finally obtained.

[0061] Example 10

[0062] The difference from Example 1 is that the mass ratio of VA in the EVA resin is 35%, and the melt index of the EVA resin at 190 °C and 2.16 kg / cm 3 is 20 g / 10 min, and a film is finally obtained.

[0063] Example 11

[0064] The difference from Example 1 is that the mass ratio of tert-butyl peroxy-2-ethylhexyl carbonate (TBEC) to resin pellets is 0.8:100, the mass ratio of triallyl isocyanurate (TAIC) to resin pellets is 1.2:100; the mass ratio of 3-(methacryloyloxy)propyltrimethoxysilane to resin pellets is 0.6:100; the mass ratio of the ultraviolet absorber to resin pellets is 0.1:100, and a film is finally obtained.

[0065] Example 12

[0066] The difference from Example 1 is that the mass ratio of tert-butyl peroxy-2-ethylhexyl carbonate (TBEC) to resin pellets is 1.2:100, the mass ratio of triallyl isocyanurate (TAIC) to resin pellets is 1.5:100; the mass ratio of 3-(methacryloyloxy)propyltrimethoxysilane to resin pellets is 0.9:100; the mass ratio of 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol to resin pellets is 0.25:100, and a film is finally obtained.

[0067] Example 13

[0068] The difference from Example 1 is that the mass ratio of tert-butyl peroxy-2-ethylhexyl carbonate (TBEC) to resin particles is 1.5:100, the mass ratio of triallyl isocyanurate (TAIC) to resin particles is 2:100; the mass ratio of 3-(methacryloyloxy)propyltrimethoxysilane to resin particles is 1:100; the mass ratio of 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol to resin particles is 0.3:100, and finally a film is obtained.

[0069] Example 14

[0070] The difference from Example 1 is that trimethylolpropane trimethacrylate is used to replace triallyl isocyanurate, and finally a film is obtained.

[0071] Example 15

[0072] The difference from Example 1 is that the granulation temperature is 100 °C, and finally a film is obtained.

[0073] Example 16

[0074] The difference from Example 1 is that the granulation temperature is 130 °C, and finally a film is obtained.

[0075] Example 17

[0076] The difference from Example 1 is that the acrylate polymer is an acryloyl acrylate-methyl methacrylate copolymer with a number average molecular weight of 3500 g / mol. The number of side chains containing double bonds in the acryloyl acrylate-methyl methacrylate copolymer accounts for 5% of the total number of side chains, and the total number of carbon atoms in the carbon chain of the side chains of the acryloyl acrylate-methyl methacrylate copolymer is 4, and finally a film is obtained.

[0077] Example 18

[0078] The difference from Example 1 is that the acrylate polymer is a vinyl methacrylate-propyl methacrylate copolymer with a number average molecular weight of 3500 g / mol. The number of side chains containing double bonds in the vinyl methacrylate-propyl methacrylate copolymer accounts for 5% of the total number of side chains, and the total number of carbon atoms in the carbon chain of the side chains of the vinyl methacrylate-propyl methacrylate copolymer is 4, and finally a film is obtained.

[0079] Example 19

[0080] The difference from Example 1 is that the acrylate polymer is an allyl methacrylate - 2 - methoxyethyl methacrylate copolymer, with a number - average molecular weight of 3500 g / mol. The number of side chains containing double bonds in the allyl methacrylate - 2 - methoxyethyl methacrylate copolymer accounts for 5% of the total number of side chains, and the total number of carbon atoms in the carbon chain of the side chains of the allyl methacrylate - 2 - methoxyethyl methacrylate copolymer is 4, and finally a film is obtained.

[0081] Example 20

[0082] The difference from Example 1 is that the acrylate polymer is a vinyl acrylate - 2 - hydroxyethyl methacrylate copolymer, with a number - average molecular weight of 3500 g / mol. The number of side chains containing double bonds in the vinyl acrylate - 2 - hydroxyethyl methacrylate copolymer accounts for 5% of the total number of side chains, and the total number of carbon atoms in the carbon chain of the side chains of the vinyl acrylate - 2 - hydroxyethyl methacrylate copolymer is 3, and finally a film is obtained.

[0083] Comparative Example 1

[0084] The difference from Example 1 is that the mass fraction of EVA resin is 70%, and the mass fraction of allyl methacrylate (ALMA) - 2 - hydroxyethyl methacrylate (HEMA) copolymer is 30%, and finally a film is obtained.

[0085] Comparative Example 2

[0086] The difference from Example 1 is that the number - average molecular weight of the allyl methacrylate (ALMA) - 2 - hydroxyethyl methacrylate (HEMA) copolymer is 10000 g / mol, and finally a film is obtained.

[0087] Comparative Example 3

[0088] The difference from Example 1 is that the allyl methacrylate (ALMA) - 2 - hydroxyethyl methacrylate (HEMA) copolymer is replaced with a propyl methacrylate - 2 - hydroxyethyl methacrylate copolymer, and finally a film is obtained.

[0089] Comparative Example 4

[0090] The difference from Example 1 is that the allyl methacrylate (ALMA) - 2 - hydroxyethyl methacrylate (HEMA) copolymer is replaced with nano - silica aerogel, and finally a film is obtained.

[0091] Performance test: The thickness of the sample is 0.76 mm;

[0092] The transmittance and haze are tested according to the method for determining the transmittance and haze of transparent plastics in GB / T 2410 - 2008 standard.

[0093] Loss factor tanδ: Select the TAQ800 instrument, select the tensile mode, test at a frequency of 1 Hz, a heating rate of 3 °C / min, and a test temperature range of -100 °C to 100 °C.

[0094] Peeling strength: Conduct in accordance with the test requirements of GB / T29848-2018.

[0095] Dry heat aging: Conduct in accordance with the test requirements of GB / T29848-2018.

[0096] Test the visible light transmittance, haze, loss factor tanδ, peeling strength, and dry heat aging of the adhesive films prepared in the examples and comparative examples. The test results are shown in Table 1.

[0097] Table 1

[0098]

[0099]

[0100] From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:

[0101] Both ethylene-vinyl acetate copolymer and acrylate polymer contain ester groups and have high compatibility, which helps to form an interpenetrating network structure. If the addition amount of acrylate polymer is too low, the interpenetrating network structure is incomplete, which is not conducive to improving the sound insulation effect of the adhesive film. If the addition amount of acrylate polymer is too high, the acrylate polymer is prone to agglomeration and phase separation occurs locally, which is not conducive to improving the visible light transmittance of the adhesive film. Preferably controlling the mass ratio of ethylene-vinyl acetate copolymer and acrylate polymer within the above range helps to form an adhesive film with a relatively high visible light transmittance and a good sound insulation effect. If the molecular weight of the acrylate polymer is too high, the fluidity of the acrylate polymer is poor, which is not conducive to the uniform dispersion of the acrylate polymer in the ethylene-vinyl acetate copolymer. The acrylate polymer with a lower molecular weight is easy to flow and disperse during the processing, which helps to form an interpenetrating network structure, thereby helping to improve the sound insulation effect and visible light transmittance of the adhesive film. The side chain of the acrylate polymer carries double bonds, and the presence of double bonds can further undergo a cross-linking reaction to form an interpenetrating structure in the molecular chain of the ethylene-vinyl acetate copolymer, which helps to further improve the sound insulation effect and thermal stability of the adhesive film. Therefore, the adhesive film formed by the composition of the adhesive film of the present application has excellent sound insulation effect, visible light transmittance, and thermal stability.

[0102] The above are only embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention can have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A composition of an adhesive film, characterized in that: The composition comprises: ethylene-vinyl acetate copolymer and acrylic ester polymer; wherein the mass of the ethylene-vinyl acetate copolymer accounts for 80-90% of the total mass of the ethylene-vinyl acetate copolymer and the acrylic ester polymer, and the mass of the acrylic ester polymer in the composition accounts for 12-20%; The number average molecular weight of the acrylic ester polymer is no more than 5000 g / mol; and the side chain of the acrylic ester polymer carries a double bond.

2. The composition according to claim 1, characterized in that The number average molecular weight of the acrylic ester polymer is 3000-5000 g / mol; and / or; the number of the side chains containing double bonds in the acrylic ester polymer accounts for 4%-8% of the total number of side chains.

3. The composition according to claim 1 or 2, characterized in that The total number of carbon atoms in the side chain of the acrylic ester polymer is less than 5.

4. The composition according to any one of claims 1 to 3, characterized in that The acrylic ester polymer is prepared by copolymerizing an acrylic ester monomer having a double bond in the side chain and an acrylic ester monomer having no double bond in the side chain; Preferably, the acrylic acid ester monomer containing a double bond in the side chain is selected from any one or more of propylene methacrylate, propylene acrylate, vinyl methacrylate and vinyl acrylate; And / or, the acrylic acid ester monomer having no double bond in the side chain is selected from any one or more of propyl methacrylate, methoxyethyl methacrylate, methyl methacrylate, ethyl methacrylate and hydroxyethyl methacrylate.

5. The composition according to any one of claims 1 to 4, characterized in that The weight content of vinyl acetate monomer in the monomers used to synthesize the ethylene-vinyl acetate copolymer is 28-33%; and / or the ethylene-vinyl acetate copolymer is heated to 190°C and 2.16 kg / cm 3 The melt index is 9 to 15 g / 10 min.

6. The composition according to any one of claims 1 to 5, characterized in that The composition further comprises: any one or more of a cross-linking agent, a co-cross-linking agent, a silane coupling agent and an anti-ultraviolet agent; Preferably, the ratio of the mass of the cross-linking agent to the total mass of the ethylene-vinyl acetate copolymer and the acrylic ester polymer is 0.8 to 1.2:100; and / or, the ratio of the mass of the auxiliary cross-linking agent to the total mass of the ethylene-vinyl acetate copolymer and the acrylic ester polymer is 1.2 to 1.5:100; and / or, the ratio of the mass of the silane coupling agent to the total mass of the ethylene-vinyl acetate copolymer and the acrylic ester polymer is 0.6-0.9:100; And / or, the ratio of the mass of the anti-ultraviolet agent to the total mass of the ethylene-vinyl acetate copolymer and the acrylic ester polymer is 0.1-0.25:100; Preferably, the crosslinking agent is selected from tert-butyl peroxycarbonate-2-ethylhexyl ester, 2,5-di-tert-butyl peroxy-2,5-dimethylhexane, tert-butyl peroxy-2-ethylhexanoate, isopropyl tert-butyl peroxide, dilauroyl peroxide, isopropyl tert-butyl peroxycarbonate, 1-bis(tert-butyl peroxide)-3,3,5-trimethylcyclohexane, tert-butyl peroxycarbonate-2-ethylhexyl ester, 1,1-bis(tert-butyl peroxy) -3,3,5-trimethylcyclohexane, 1,1-bis(tert-amylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-amylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,2-bis(tert-butylperoxy)butane, 2,5-dimethyl-2,5-bis(benzoylperoxy)-hexane, tert-amyl peroxycarbonate and tert-butyl peroxy-3,3,5-trimethylhexanoate; and / or, the auxiliary cross-linking agent is selected from any one or more of triallyl isocyanurate, 2,4,6-triallyloxy-1,3,5-triazine, diallyl isocyanurate, triallyl cyanurate and trimethallyl isocyanate; And / or, the silane coupling agent is selected from any one or more of 3-(methacryloyloxy)propyltrimethoxysilane, (3-methacryloyloxypropyl)triacetoxysilane, 2-[(2-propylene-1-oxy)methyl]-2-acrylate 3-(trimethoxysilyl)propyl ester, γ-aminopropyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-(2,3-epoxypropyloxy)propyltrimethoxysilane, vinyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane and vinyltriethoxysilane; And / or, the anti-ultraviolet agent is selected from any one or more of 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, tris(1,2,2,6,6-pentamethylpiperidinol)phosphite, 2,2'-methylenebis(4-tert-octyl-6-benzotriazolephenol), 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone and 2-hydroxy-5-chlorobenzophenone.

7. A method for preparing an adhesive film, characterized in that: The adhesive film is prepared using the composition according to any one of claims 1 to 6, and the preparation method comprises: The ethylene-vinyl acetate copolymer and the acrylic ester polymer are sequentially mixed, granulated and cast to obtain the adhesive film.

8. The preparation method according to claim 7, characterized in that: The granulation temperature is 100-120°C; and / or, the preparation method further comprises: mixing the granulated product with any one or more of a cross-linking agent, a co-cross-linking agent, a silane coupling agent and an anti-ultraviolet agent, and then performing the tape casting; preferably, the tape casting comprises a feeding section, a compression section and a homogenizing section; preferably, the temperature of the feeding section is 60-70°C; and / or, the temperature of the compression section is 75-85°C; and / or, the temperature of the homogenizing section is 85-120°C.

9. An adhesive film, characterized in that: The adhesive film is prepared by the preparation method described in claim 7 or 8.

10. A laminated glass, comprising a film and glass, characterized in that: The adhesive film is the adhesive film according to claim 9.

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