Adhesive film and application thereof

Abstract

The invention provides an adhesive film and application thereof, the adhesive film comprises an adhesive film matrix layer and micron-sized glass sheets, and the micron-sized glass sheets are distributed in and / or on the surface of the adhesive film matrix layer. The micron-sized glass sheets are distributed in the adhesive film, when the adhesive film is subjected to external impact, energy dissipation can be accelerated, the impact resistance is improved, meanwhile, sound can be reflected by the micron-sized glass sheets, sound loss is increased, and the sound insulation effect is improved, so that the adhesive film has low water absorption rate and proper adhesive force, and the adhesive film is suitable for being used as a sound insulation material. The adhesive film has excellent sound insulation effect and good stability, and laminated glass prepared from the adhesive film has excellent impact resistance.

Description

Technical Field

[0001] The present invention relates to the technical field of functional materials, and in particular to an adhesive film and applications thereof. Background Art

[0002] Adhesive films, such as PVB (polyvinyl butyral), EVA (ethylene vinyl acetate), and POE (ethylene-alpha-olefin copolymer), are widely used in the automotive and architectural industries due to their excellent impact resistance and optical properties. However, when used with unmodified adhesive films in the "sandwich" structure of laminated glass, the adhesion is too strong, weakening the impact resistance of the laminated glass and making it susceptible to penetration during falling ball impacts. To address this issue, inorganic salts, such as water-soluble calcium, magnesium, or potassium salts, are used in actual production to adjust the adhesive film's adhesion. Inorganic salts absorb water, forming a nano-layer of water on the film's surface. Hydroxyl groups on the film occupy hydrogen bonds, reducing the interaction between the film and the glass surface. However, the addition of inorganic salts can affect the film's water absorption, resulting in higher water absorption and increased debonding between the film and the glass. Therefore, ensuring appropriate adhesive strength while simultaneously improving the impact resistance of laminated glass is crucial.

[0003] For example, the glass transition temperature of PVB film is adjusted by the plasticizer content, thereby achieving excellent sound insulation. Commercial sound insulation PVB film has a three-layer structure, which achieves excellent sound insulation by combining different PVB resins with different plasticizer content ratios. For example, CN106543612B discloses a three-layer sound insulation PVB film, in which the side layers are made of low melt index material as a mechanical performance support layer, and the middle layer is made of high melt index material as a sound insulation damping reinforcement layer. Its main focus is on product processing and giving the PVB film excellent sound insulation performance. However, the three-layer structure has high requirements for processing equipment, and the product is subject to the risk of reduced mechanical properties, reduced aging performance, and plasticizer precipitation.

[0004] Therefore, the existing adhesive film needs to be improved. Summary of the Invention

[0005] The present invention aims to solve one of the technical problems in the prior art at least to a certain extent. To this end, one object of the present invention is to provide an adhesive film and its application.

[0006] The first aspect of the present invention provides a film. According to an embodiment of the present invention, reference Figure 1 The adhesive film includes an adhesive film base layer 100 and micron-sized glass flakes 200 , wherein the micron-sized glass flakes 200 are distributed in and / or on the surface of the adhesive film base layer 100 .

[0007] According to the adhesive film of the above-described embodiment of the present invention, by distributing micron-sized glass flakes 200 within and / or on the surface of the adhesive film base layer 100, when the laminated glass is subjected to external impact, the interface between the micron-sized glass flakes 200 and the adhesive film base layer 100 is first destroyed, and then the crack propagates to the laminated glass interface, rapidly dissipating energy, thereby enabling the laminated glass to exhibit excellent impact resistance. Furthermore, the micron-sized glass flakes 200 have low water absorption and water vapor transmission rates, blocking the water vapor pathway and reducing the water absorption of the adhesive film base layer 100, thereby maintaining appropriate adhesion and avoiding the debonding problem caused by conventional inorganic salts. Furthermore, when sound passes through the adhesive film, it is reflected by the glass when encountering the micron-sized glass flakes 200. Consequently, the sound is repeatedly reflected by several micron-sized glass flakes 200, increasing sound loss, thereby achieving excellent sound insulation. Furthermore, the micron-sized glass flakes 200 are stable, thus providing the adhesive film with excellent stability. Therefore, the adhesive film has low water absorption, suitable adhesion, excellent sound insulation effect and good stability, and the laminated glass prepared using the adhesive film has excellent impact resistance.

[0008] In some embodiments of the present invention, the mass ratio of the adhesive film substrate layer to the micron-sized glass flakes is 100:(1-15), preferably 100:(3-12), such as 100:1, 100:2, 100:3, 100:5, 100:7, 100:7, 100:11, 100:13, 100:15, or any range between any two of the aforementioned values. Controlling the mass ratio of the adhesive film substrate layer to the micron-sized glass flakes within this range can reduce the water absorption of the adhesive film, ensure appropriate adhesion, and enhance impact resistance.

[0009] In some embodiments of the present invention, the micron-sized glass flakes include modified micron-sized glass flakes.

[0010] Preferably, the modified micron-sized glass sheet is connected to at least one side of the micron-sized glass sheet with a silane coupling agent. Modification with a silane coupling agent can also increase the compatibility of the micron-sized glass sheet, thereby improving the mechanical properties and damping absorption effect of the adhesive film.

[0011] More preferably, the silane coupling agent is grafted with an ester compound containing double bonds. The inventors have discovered that because the modified micron-sized glass flakes 200 are grafted with polymer molecular chains, the glass transition temperature of the polymer molecular chains ranges from 20-40°C, resulting in a film with excellent damping and absorption properties, further enhancing the film's sound insulation. The modified glass flakes also exhibit improved dispersibility, greater compatibility with the substrate material, and superior mechanical properties, further enhancing the film's effectiveness and impact resistance. Furthermore, the grafting of polymer molecular chains can reduce the film's light transmittance loss.

[0012] In some embodiments of the present invention, the silane coupling agent includes 3-(trimethoxysilyl)propyl methacrylate, 、 、 、 , at least one of methacryloxypropyltriethoxysilane and vinyltris(2-methoxyethoxy)silane.

[0013] In some embodiments of the present invention, the ester compound containing a double bond includes at least one of a vinyl ester compound and a propenyl ester compound.

[0014] Preferably, the ester compound containing a double bond includes at least one of methyl acrylate, ethyl acrylate, butyl acrylate, vinyl acetate, vinyl propionate, and vinyl butyrate.

[0015] In some embodiments of the present invention, the method for preparing the modified micron-sized glass sheet includes: treating the micron-sized glass sheet in a solution containing a silane coupling agent and then drying the micron-sized glass sheet. The micron-sized glass sheet is treated with the solution containing the silane coupling agent, thereby bonding the silane coupling agent to the micron-sized glass sheet.

[0016] In some embodiments of the present invention, the micron-sized glass flakes are treated in the solution containing the silane coupling agent at a temperature of 20-30°C for a time of 6-10 hours. By controlling the treatment temperature and time within these ranges, the glass surface can be successfully modified with the silane coupling agent.

[0017] In some embodiments of the present invention, the solvent of the solution containing the silane coupling agent includes one or more of toluene, methylbenzene, xylene, petroleum ether, and cyclohexane.

[0018] In some embodiments of the present invention, the volume proportion of the silane coupling agent in the solution containing the silane coupling agent is 20% to 30%. By controlling the content of the silane coupling agent in the solution, the modification efficiency of the silane coupling agent on the glass surface is improved.

[0019] In some embodiments of the present invention, the method for preparing the modified micron-sized glass flake further includes: treating and drying the micron-sized glass flake in a solution containing the silane coupling agent, and then placing the resulting micron-sized glass flake in a solution containing the double-bond ester compound to undergo a grafting reaction. After the surface of the micron-sized glass flake has been modified with the silane coupling agent, the ester compound containing double bonds and the silane coupling agent undergo a grafting reaction in a solution containing the double-bond ester compound under the action of an initiator, thereby forming polymer molecular chains on the surface of the micron-sized glass flake, thereby obtaining the modified micron-sized glass flake.

[0020] In some embodiments of the present invention, the grafting reaction temperature is 70° C. to 75° C., and the time is 1.5 hours to 3 hours. By controlling the grafting reaction temperature and time within the above ranges, the ester compound can be grafted onto the silane coupling agent, thereby increasing the grafting rate.

[0021] In some embodiments of the present invention, the solvent of the solution containing the ester compound containing a double bond includes one or more of toluene, ethyl acetate, propyl acetate, and benzene.

[0022] In some embodiments of the present invention, the initiator used in the grafting reaction includes but is not limited to peroxides, azo compounds, nitrogen oxides, etc. In some embodiments of the present invention, the surface-modified micron-sized glass flakes have a median particle size D50 of 10 μm to 25 μm. For example, the median particle size D50 of the micron-sized glass flakes is 10 μm, 13 μm, 15 μm, 17 μm, 20 μm, 25 μm, or a range between any two of the aforementioned values.

[0023] In some embodiments of the present invention, the length-to-width ratio of the micron-sized glass flakes is (20-30):1. For example, the width-to-length ratio is 1:20, 1:22, 1:24, 1:26, 1:28, 1:30, etc., or a range between any two of the above values.

[0024] In some embodiments of the present invention, the thickness of the micron-sized glass sheet is 0.9 μm to 1.3 μm, for example, 0.9 μm, 1.0 μm, 1.1 μm, 1.2 μm, 1.3 μm, etc., or a range between any two of the above values.

[0025] The inventors have discovered that controlling the average size, length-to-width ratio, and thickness of surface-modified micron-sized glass sheets within the above-mentioned ranges can better conduct impact force. When the length-to-width ratio is too large, the micron-sized glass is easily broken when subjected to force impact. When the length-to-width ratio is too small, it is difficult to disperse in the matrix material.

[0026] In some embodiments of the present invention, the refractive index of the micron-sized glass flakes is 1.51 to 1.54. For example, the refractive index is 1.51, 1.52, 1.53, 1.54, or any range between any two of these values. By controlling the refractive index of the micron-sized glass flakes within this range, a refractive index close to that of the film resin can be ensured, thereby improving the optical performance of the film.

[0027] In some embodiments of the present invention, the adhesive film base layer includes a PVB adhesive film base layer, a POE adhesive film base layer or an EVA adhesive film base layer.

[0028] In some embodiments of the present invention, the PVB film substrate layer includes a PVB resin and a plasticizer, wherein the mass ratio of the PVB resin to the plasticizer is (70-75):(25-30). Controlling the mass ratio of the PVB resin to the plasticizer within this range can reduce plasticizer precipitation and improve the film's stability and sound insulation.

[0029] In some embodiments of the present invention, the plasticizer includes one or more of triethylene glycol diisooctanoate, diethyl phthalate, tetraethylene glycol diisooctanoate, and dibutyl dioctanoate.

[0030] In some embodiments of the present invention, the PVB film base layer further includes at least one of an antioxidant and an anti-ultraviolet agent. Based on the total mass of the PVB film base layer, the mass proportion of the antioxidant is 0.2%~0.3%, and the mass proportion of the anti-ultraviolet agent is 0.2%~0.3%.

[0031] In some embodiments of the present invention, the antioxidant includes but is not limited to antioxidant 1010, antioxidant TPP, antioxidant 264, antioxidant DLTP, and the like.

[0032] In some embodiments of the present invention, the anti-ultraviolet agent includes but is not limited to UV326, UV329, UV360, UV980, etc.

[0033] In some embodiments of the present invention, the acetal value of the PVB resin is 80% to 83%.

[0034] In some embodiments of the present invention, the refractive index of the PVB resin is not less than 1.51. By controlling the refractive index of the PVB resin to be not less than 1.51, the refractive index of the PVB resin is close to that of the micron-sized glass sheet, thereby improving the optical performance of the film.

[0035] In some embodiments of the present invention, the POE film base layer includes POE resin, peroxide, and a cross-linking agent.

[0036] Preferably, the POE film base layer further includes a silane coupling agent and a light stabilizer.

[0037] It should be noted that peroxides, co-crosslinking agents, silane coupling agents and light stabilizers are conventional reagents in the field, and those skilled in the art can select them according to actual conditions. For example, peroxides include tert-butyl peroxycarbonate-2-ethylhexyl ester, 2,5-di-tert-butyl peroxy-2,5-dimethylhexane, tert-butyl peroxy-2-ethylhexanoate, isopropyl tert-butyl peroxide and dilauroyl peroxide, isopropyl tert-butyl peroxycarbonate, 1-bis(tert-butyl peroxide)-3,3,5-trimethylcyclohexane, tert-butyl peroxide 2-ethylhexyl carbonate, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane; auxiliary crosslinking agents include triallyl isocyanurate, 2,4,6-triallyloxy-1,3,5-triazine, diallyl isocyanurate, triallyl cyanurate and trimethylallyl isocyanate; silane coupling agents include 3-(methacryloyloxy)propyltrimethoxysilane, (3-methacryloyloxypropyl)triacetoxysilane, 2-[(2-propylene-1-oxy)methyl]-2-propenoic acid 3-(trimethoxysilyl)propyl ester, γ-aminopropyl triethoxysilane, γ-methacryloyloxypropyl trimethoxysilane, γ-(2,3-epoxypropoxy)propyl trimethoxysilane, vinyl trimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl trimethoxysilane; light stabilizers include bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, poly[1-(2'-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidinyl succinate], poly[[6-[(1, 1,3,3-tetramethylbutyl)amino]-S-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl-[(2,2,6,6-tetramethyl-4-piperidinyl)imino], 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-benzotriazolephenol).

[0038] In some embodiments of the present invention, the mass ratio of the POE resin, the peroxide, the auxiliary cross-linking agent, the silane coupling agent and the light stabilizer is (90~95): (1~2): (2~3): (1~2): (0.3~1).

[0039] In some embodiments of the present invention, under the test conditions of 190° C. and 2.16 kg, the melt index of the POE resin is no more than 5 g / 10 min.

[0040] In some embodiments of the present invention, the EVA film base layer includes EVA resin, peroxide, and a cross-linking agent.

[0041] Preferably, the EVA film base layer further includes a silane coupling agent and a light stabilizer.

[0042] It should be noted that peroxide, co-crosslinking agent, silane coupling agent and light stabilizer are conventional reagents in the field, and those skilled in the art can select them according to actual conditions. The specific types of the above additive system can be the same as those of the POE film base layer.

[0043] In some embodiments of the present invention, the mass ratio of the EVA resin, the peroxide, the auxiliary cross-linking agent, the silane coupling agent, and the light stabilizer is (92~96): (1~2): (2~3): (1~2): (0.3~1).

[0044] In some embodiments of the present invention, the VA content of the EVA resin is 28% to 33%.

[0045] In some embodiments of the present invention, under the test conditions of 190° C. and 2.16 kg, the melt index of the EVA resin is no more than 5 g / 10 min.

[0046] In some embodiments of the present invention, a method for preparing the aforementioned PVB film is provided, wherein the method comprises: extruding a mixture comprising micron-sized glass sheets and film base layer ingredients into a film.

[0047] In some embodiments of the present invention, the extrusion temperature is 145-150°C.

[0048] In a second aspect, the present invention provides laminated glass. According to an embodiment of the present invention, the laminated glass includes the aforementioned adhesive film. As a result, the laminated glass exhibits good water resistance, excellent impact resistance, sound insulation, and optical properties, as well as a long service life.

[0049] In a third aspect, the present invention provides a photovoltaic module. According to an embodiment of the present invention, the photovoltaic module includes the above-mentioned adhesive film. As a result, the photovoltaic module has excellent impact resistance.

[0050] The present invention has at least the following technical effects: (1) When laminated glass is subjected to external impact, the presence of micron-sized glass flakes can quickly dissipate energy, making the laminated glass exhibit excellent impact resistance; micron-sized glass flakes have low water absorption and water vapor permeability, which reduces the water absorption of the film and enables the film to maintain appropriate adhesion; when sound passes through the film, it will be reflected by the glass when it encounters micron-sized glass flakes, increasing the sound loss, so that the film exhibits excellent sound insulation effect.

[0051] (2) The surface-modified micron-sized glass sheets improve the damping and absorption effect of the film and have a strong sound reflection ability, thereby significantly improving the sound insulation effect of the film.

[0052] (3) The laminated glass of the present application has good water resistance, excellent impact resistance, sound insulation and optical properties, and a long service life. BRIEF DESCRIPTION OF THE DRAWINGS

[0053] In order to more clearly illustrate the technical solutions in the present invention or the prior art, a brief introduction is given below to the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0054] Figure 1 Schematic diagram of the structure of the adhesive film according to an embodiment of the present invention; Figure 2 Schematic diagram of the structure of the modified micron-sized glass sheet according to an embodiment of the present invention. DETAILED DESCRIPTION

[0055] Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without creative work shall fall within the scope of protection of the present invention. The present invention will be described below with reference to specific embodiments. It should be noted that these embodiments are merely illustrative and do not limit the present invention in any way.

[0056] Example 1 This embodiment provides an adhesive film, the raw materials for its preparation include: micron-sized glass sheets and adhesive film base layer ingredients; The median particle size D50 of the micron-sized glass flakes is 15 μm, the width-to-length ratio is 1:25, the thickness is 1 μm, and the refractive index is 1.52; The ingredients of the film base layer include 72 parts by weight of PVB resin powder (the acetal value of the PVB resin is 81%, and the refractive index of the PVB resin is 1.52), 27.6 parts by weight of a plasticizer (triethylene glycol diethyl octanoate), 0.2 parts by weight of an antioxidant (antioxidant 1010) and 0.2 parts by weight of an anti-ultraviolet agent (UV326).

[0057] The mass ratio of the micron-sized glass sheet to the film substrate layer is 10:100.

[0058] This embodiment provides a film, and its preparation process is as follows: The micron-sized glass sheet and the film base layer ingredients were mixed evenly and then extruded into a film at 147° C. using a screw machine.

[0059] Example 2 The difference between Example 2 and Example 1 is: The ingredients of the film base layer include 95 parts by weight of EVA resin with a VA content of 28-33wt% (the melt index of the EVA resin is 4.5g / 10min), 1.5 parts by weight of peroxide (tert-butyl peroxide 3,3,5-trimethylhexanoate), 2 parts by weight of a cross-linking agent (triallyl cyanurate), 1 part by weight of a silane coupling agent (3-(methacryloyloxy)propyltrimethoxysilane), and 0.5 parts by weight of a light stabilizer (2,2'-methylenebis(4-tert-octyl-6-benzotriazolephenol)).

[0060] Example 3 The difference between Example 3 and Example 1 is: The ingredients of the film base layer include 93.7 parts by weight of POE resin (the melt index of POE resin is 4.5g / 10min), 2 parts by weight of peroxide (tert-amyl peroxycarbonate), 2.3 parts by weight of a cross-linking agent (trimethylallyl isocyanate), 1.5 parts by weight of a silane coupling agent (γ-(2,3-epoxypropoxy)propyltrimethoxysilane), and 0.5 parts by weight of a light stabilizer (bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate).

[0061] Example 4 The difference between Example 4 and Example 1 is: Example 4 uses modified micron-sized glass sheets, and its specific preparation process is as follows: Glass slides were cleaned with a piranha solution (3 parts concentrated sulfuric acid, 1 part water, and 1 part 30% hydrogen peroxide solution). The dried micron-sized glass slides were placed in a treatment solution consisting of a 3:1 volume ratio of toluene and a silane coupling agent (3-(trimethoxysilyl)propyl methacrylate). After treatment at room temperature for 8 hours, the slides were dried and then added to a mixture of toluene and a double-bond ester compound (methyl acrylate) (2.5:1 volume ratio of toluene to methyl acrylate). Benzoyl peroxide was then added to initiate the grafting reaction. The reaction temperature was 73°C for 2 hours, resulting in surface-modified micron-sized glass slides. The slides had a median particle size (D50) of 15 μm, a width-to-length ratio of 1:25, a thickness of 1 μm, and a refractive index of 1.52.

[0062] Example 5 The difference between Example 5 and Example 4 is: Example 5 uses modified micron-sized glass sheets, and its specific preparation process is as follows: A glass slide was cleaned with a piranha solution (3 parts concentrated sulfuric acid, 1 part water, and 1 part 30% hydrogen peroxide solution). The dried micron-sized glass slide was then placed in a treatment solution consisting of a 3:1 volume ratio of toluene and a silane coupling agent (3-(trimethoxysilyl)propyl methacrylate). The treatment was performed at room temperature for 8 hours and then dried to obtain a surface-modified micron-sized glass slide. The micron-sized glass slide had a median particle size (D50) of 15 μm, a width-to-length ratio of 1:25, a thickness of 1 μm, and a refractive index of 1.52.

[0063] Example 6 The difference between Example 6 and Example 4 is that the mass ratio of the modified micron-sized glass sheet to the adhesive film base layer ingredients is 1:100.

[0064] Example 7 The difference between Example 1 and Example 4 is that the mass ratio of the modified micron-sized glass sheet to the adhesive film base layer ingredients is 3:100.

[0065] Example 8 The difference between Example 8 and Example 4 is that the mass ratio of the modified micron-sized glass sheet to the adhesive film base layer ingredients is 5:100.

[0066] Example 9 The difference between Example 9 and Example 4 is that the mass ratio of the modified micron-sized glass sheet to the adhesive film base layer ingredients is 12:100.

[0067] Example 10 The difference between Example 10 and Example 4 is that the mass ratio of the modified micron-sized glass sheet to the adhesive film base layer ingredients is 15:100.

[0068] Example 11 The difference between Example 11 and Example 4 is that the mass ratio of the modified micron-sized glass sheet to the adhesive film base layer ingredients is 20:100.

[0069] Example 12 The difference between Example 12 and Example 4 is: Glass slides were cleaned with piranha solution (3 parts concentrated sulfuric acid, 1 part water, and 1 part 30% hydrogen peroxide solution). The dried micron-sized glass slides were placed in a treatment solution consisting of toluene and a solution containing a silane coupling agent (2-[(2-propylene-1-oxy)methyl]-2-acrylate, 3-(trimethoxysilyl)propyl ester) (3:1 by volume). After treatment at room temperature for 8 hours, the slides were dried and then added to a mixture of toluene and a double-bond ester compound (butyl acrylate) (toluene:butyl acrylate, volume ratio: 2.5:1). A peroxide (lauroyl peroxide) was then added to initiate the grafting reaction. The reaction temperature was 73°C for 2 hours, resulting in surface-modified micron-sized glass slides. The slides had a median particle size (D50) of 15 μm, a width-to-length ratio of 1:25, a thickness of 1 μm, and a refractive index of 1.52.

[0070] Example 13 The difference between Example 13 and Example 4 is: Glass slides were cleaned with a piranha solution (3 parts concentrated sulfuric acid, 1 part water, and 1 part 30% hydrogen peroxide solution). The dried micron-sized glass slides were placed in a treatment solution consisting of toluene and a silane coupling agent (γ-aminopropyltriethoxysilane) (2.5:1 volume ratio) at room temperature for 2 hours. The slides were then dried and placed in a mixture of toluene and an ester compound (vinyl butyrate) (3:1 volume ratio). A peroxide (tert-butyl peroxypivalate) was then added to initiate the grafting reaction. The reaction temperature was 85°C for 4 hours, resulting in surface-modified micron-sized glass slides with a median particle size (D50) of 15 μm, a width-to-length ratio of 1:25, a thickness of 1 μm, and a refractive index of 1.52.

[0071] Example 14 The difference between Example 14 and Example 4 is: Glass slides were cleaned with piranha solution (3 parts concentrated sulfuric acid, 1 part water, and 1 part 30% hydrogen peroxide solution). The dried micron-sized glass slides were placed in a treatment solution consisting of toluene and a silane coupling agent (methacryloxypropyltriethoxysilane) (3:1 by volume) at room temperature for 2 hours. After drying, the slides were then added to a mixture of toluene and a double-bond ester compound (vinyl acetate) (toluene:vinyl acetate volume ratio of 2.8:1). Peroxide (didecanoyl peroxide) was then added to initiate the grafting reaction. The reaction temperature was 75°C for 4 hours, resulting in surface-modified micron-sized glass slides. The slides had a median particle size (D50) of 15 μm, a width-to-length ratio of 1:25, a thickness of 1 μm, and a refractive index of 1.52.

[0072] Example 15 The difference between Example 15 and Example 4 is: The median particle size D50 of the micron-sized glass flakes is 8 μm, the width to length ratio is 1:25, the thickness is 1 μm, and the refractive index is 1.52.

[0073] Example 16 The difference between Example 16 and Example 4 is: The median particle size D50 of the micron-sized glass flakes is 10 μm, the width to length ratio is 1:25, the thickness is 1 μm, and the refractive index is 1.52.

[0074] Example 17 The difference between Example 17 and Example 4 is: The median particle size D50 of the micron-sized glass flakes is 25 μm, the width to length ratio is 1:25, the thickness is 1 μm, and the refractive index is 1.52.

[0075] Example 18 The difference between Example 18 and Example 4 is: The median particle size D50 of the micron-sized glass flakes is 30 μm, the width to length ratio is 1:25, the thickness is 1 μm, and the refractive index is 1.52.

[0076] Example 19 The difference between Example 19 and Example 4 is: The median particle size D50 of the micron-sized glass flakes is 15 μm, the width to length ratio is 1:18, the thickness is 1 μm, and the refractive index is 1.52.

[0077] Example 20 The difference between Example 20 and Example 4 is: The median particle size D50 of the micron-sized glass flakes is 15 μm, the width to length ratio is 1:20, the thickness is 1 μm, and the refractive index is 1.52.

[0078] Example 21 The difference between Example 21 and Example 4 is: The median particle size D50 of the micron-sized glass flakes is 15 μm, the width to length ratio is 1:30, the thickness is 1 μm, and the refractive index is 1.52.

[0079] Example 22 The difference between Example 22 and Example 4 is: The median particle size D50 of the micron-sized glass flakes is 15 μm, the width to length ratio is 1:32, the thickness is 1 μm, and the refractive index is 1.52.

[0080] Example 23 The difference between Example 23 and Example 4 is: The median particle size D50 of the micron-sized glass flakes is 15 μm, the width to length ratio is 1:25, the thickness is 0.7 μm, and the refractive index is 1.52.

[0081] Example 24 The difference between Example 24 and Example 4 is: The median particle size D50 of the micron-sized glass flakes is 15 μm, the width to length ratio is 1:25, the thickness is 0.9 μm, and the refractive index is 1.52.

[0082] Example 25 The difference between Example 25 and Example 4 is: The median particle size D50 of the micron-sized glass flakes is 15 μm, the width to length ratio is 1:25, the thickness is 1.1 μm, and the refractive index is 1.52.

[0083] Example 26 The difference between Example 26 and Example 4 is: The median particle size D50 of the micron-sized glass flakes is 15 μm, the width to length ratio is 1:25, the thickness is 1.3 μm, and the refractive index is 1.52.

[0084] Example 27 The difference between Example 27 and Example 4 is: The median particle size D50 of the micron-sized glass flakes is 15 μm, the width to length ratio is 1:25, the thickness is 1.5 μm, and the refractive index is 1.52.

[0085] Example 28 The difference between Example 28 and Example 4 is: The median particle size D50 of the micron-sized glass flakes is 15 μm, the width to length ratio is 1:25, the thickness is 1 μm, and the refractive index is 1.48.

[0086] Example 29 The difference between Example 29 and Example 4 is: The median particle size D50 of the micron-sized glass flakes is 15 μm, the width to length ratio is 1:25, the thickness is 1 μm, and the refractive index is 1.51.

[0087] Example 30 The difference between Example 30 and Example 4 is: The median particle size D50 of the micron-sized glass flakes is 15 μm, the width to length ratio is 1:25, the thickness is 1 μm, and the refractive index is 1.54.

[0088] Example 31 The difference between Example 31 and Example 4 is: The micron-sized glass flakes have a median particle size D50 of 15 μm, a width-to-length ratio of 1:25, a thickness of 1 μm, and a refractive index of 1.60.

[0089] Comparative Example 1 This comparative example provides a PVB film, the preparation raw materials of which include: 72 parts by weight of PVB resin powder (the acetal value of the PVB resin is 81%, and the refractive index of the PVB resin is 1.52), 27.6 parts by weight of a plasticizer (triethylene glycol diethyl octanoate), 0.2 parts by weight of an antioxidant (antioxidant 1010) and 0.2 parts by weight of an anti-ultraviolet agent (UV326).

[0090] This comparative example provides a PVB film, and its preparation process is as follows: The above-prepared raw materials were mixed uniformly and extruded into a film at 147° C. using a screw machine.

[0091] Comparative Example 2 This comparative example provides an EVA film, the raw materials for its preparation include: 95 parts by weight of an EVA resin with a VA content of 28-33wt% (the melt index of the EVA resin is 4.5g / 10min), 1.5 parts by weight of a peroxide (1-bis(tert-butylperoxide)-3,3,5-trimethylcyclohexane), 2 parts by weight of a co-crosslinking agent (triallyl isocyanurate), 1 part by weight of a silane coupling agent (3-(methacryloyloxy)propyltrimethoxysilane), and 0.5 parts by weight of a light stabilizer (poly[1-(2'-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine succinate]).

[0092] This comparative example provides an EVA film, and its preparation process is as follows: The above-prepared raw materials were mixed uniformly and extruded into a film at 147° C. using a screw machine.

[0093] Comparative Example 3 This comparative example provides a POE film, the raw materials for its preparation include: 93.7 parts by weight of POE resin (the melt index of POE resin is 4.5 g / 10 min), 2 parts by weight of peroxide (1-bis(tert-butylperoxide)-3,3,5-trimethylcyclohexane), 2.3 parts by weight of a cross-linking agent (triallyl isocyanurate), 1.5 parts by weight of a silane coupling agent (2-[(2-propylene-1-oxy)methyl]-2-acrylate 3-(trimethoxysilyl)propyl ester), and 0.5 parts by weight of a light stabilizer (poly[1-(2'-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine succinate]).

[0094] This comparative example provides a POE film, and its preparation process is as follows: The above-prepared raw materials were mixed uniformly and extruded into a film at 147° C. using a screw machine.

[0095] The performance of the films of the embodiments and comparative examples was tested, and the specific methods are as follows: Penetration resistance: According to the test requirements of GB 9656-2021, penetration is recorded as unqualified, and non-penetration is recorded as qualified; Adhesion: According to the test requirements of GB / T 29848-2018; Sound insulation: According to the test requirements of GB / T 8485-2008; Water-blocking effect: Ordinary float glass with a size of 300*300*2cm was used, and laminated with a glass + film + glass structure. The laminated glass was edge-chamfered and aged at 85°C, 85% RH for 1500h. The bubbling and fogging at the edges were recorded. No fogging and bubbling were recorded as A, fogging and bubbling less than 2cm from the edge were recorded as B, and fogging and bubbling more than 2cm from the edge were recorded as C.

[0096] Haze: Tested according to the method for determining the haze of transparent plastics in GB / T2410-2008.

[0097] The test results of the film properties of the embodiments and comparative examples are shown in Table 1.

[0098] Table 1 The test results for the adhesive films of the Examples and Comparative Examples in Table 1 show that, compared to the conventional adhesive films of Comparative Examples 1-3, the adhesive films of the present invention, due to the inclusion of micron-sized glass flakes, exhibit significantly improved impact resistance, sound insulation, and water barrier properties. Comparing Example 1 with Examples 4-5, the use of modified micron-sized glass flakes resulted in more suitable adhesive viscosity, and significantly improved water barrier and sound insulation properties. In summary, the addition of micron-sized glass flakes to the adhesive films of the present invention effectively addresses the issues of poor impact resistance and weak water barrier properties of existing adhesive films, resulting in superior sound insulation and stability.

[0099] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. A film, characterized in that: It comprises an adhesive film base layer and micron-sized glass flakes, wherein the micron-sized glass flakes are distributed in and / or on the surface of the adhesive film base layer.

2. The adhesive film according to claim 1, characterized in that: The mass ratio of the adhesive film base layer to the micron-sized glass sheet is 100:(1-15), preferably 100:(3-12).

3. The adhesive film according to claim 1, characterized in that: The micron-sized glass flakes include modified micron-sized glass flakes; Preferably, the modified micron-sized glass sheet is a micron-sized glass sheet having at least one side connected to a silane coupling agent; More preferably, the silane coupling agent is grafted onto an ester compound containing a double bond.

4. The adhesive film according to claim 3, characterized in that: The silane coupling agent includes 3-(trimethoxysilyl)propyl methacrylate, 、 、 、 , at least one of methacryloxypropyltriethoxysilane and vinyltris(2-methoxyethoxy)silane; And / or, the ester compound containing a double bond includes at least one of a vinyl ester compound and a propenyl ester compound, preferably the ester compound containing a double bond includes at least one of methyl acrylate, ethyl acrylate, butyl acrylate, vinyl acetate, vinyl propionate, and vinyl butyrate.

5. The adhesive film according to claim 3, characterized in that: The preparation method of the modified micron-sized glass sheet comprises: The micron-sized glass sheet is treated in a solution containing the silane coupling agent and then dried; preferably, the micron-sized glass sheet is treated in the solution containing the silane coupling agent at a temperature of 20 to 30° C. for a time of 6 to 10 hours; More preferably, after the micron-sized glass sheet is treated and dried in a solution containing the silane coupling agent, the obtained micron-sized glass sheet is placed in a solution containing the ester compound containing double bonds to undergo a grafting reaction; preferably, the grafting reaction temperature is 70° C. to 75° C., and the time is 1.5 h to 3 h.

6. The adhesive film according to any one of claims 1 to 5, characterized in that: The median particle size D50 of the micron-sized glass flakes is 10 μm to 25 μm, and / or the length to width ratio of the micron-sized glass flakes is (20 to 30):1, and / or the thickness of the micron-sized glass flakes is 0.9 μm to 1.3 μm; And / or, the refractive index of the micron-sized glass sheet is 1.51-1.

54.

7. The adhesive film according to any one of claims 1 to 5, characterized in that: The adhesive film base layer includes a PVB adhesive film base layer, a POE adhesive film base layer or an EVA adhesive film base layer.

8. The adhesive film according to claim 7, characterized in that: The PVB film base layer includes a PVB resin and a plasticizer, and the mass ratio of the PVB resin to the plasticizer is (70-75): (25-30). Preferably, the PVB film base layer further includes at least one of an antioxidant and an anti-ultraviolet agent. Based on the total mass of the PVB film base layer, the mass proportion of the antioxidant is 0.2%-0.3%, and the mass proportion of the anti-ultraviolet agent is 0.2%-0.3%. More preferably, the acetal value of the PVB resin is 80%-83%, and the refractive index of the PVB resin is not less than 1.

51. The POE film matrix layer includes a POE resin, a cross-linking agent, and a co-cross-linking agent. Preferably, the POE film matrix layer also includes a silane coupling agent and a light stabilizer. More preferably, the mass ratio of the POE resin, the cross-linking agent, the co-cross-linking agent, the silane coupling agent, and the light stabilizer is (90-95): (1-2): (2-3): (1-2): (0.3-1). More preferably, the melt index of the POE resin is not greater than 5 g / 10 min. The EVA film matrix layer includes EVA resin, a cross-linking agent, and a co-cross-linking agent. Preferably, the EVA film matrix layer also includes a silane coupling agent and a light stabilizer. More preferably, the mass ratio of the EVA resin, the peroxide, the co-cross-linking agent, the silane coupling agent, and the light stabilizer is (92~96): (1~2): (2~3): (1~2): (0.3~1). More preferably, the VA content of the EVA resin is 28%~33%, and the melt index of the EVA resin is not greater than 5g / 10min.

9. A laminated glass, characterized in that: The invention comprises the adhesive film according to any one of claims 1 to 8.

10. A photovoltaic module, characterized in that: The invention comprises the adhesive film according to any one of claims 1 to 8.

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