A double glass white adhesive film and a preparation method thereof

Abstract

The present application relates to the technical field of photovoltaic adhesive film, especially to a double-glass white adhesive film and a preparation method thereof, comprising an anti-overflow white layer, a white anti-polarization layer and a high adhesion layer which are sequentially stacked from top to bottom, wherein the anti-overflow white layer is a reticular structure film, and its composition comprises: 50-75 parts by weight of inorganic fiber, 20-50 parts by weight of organic fiber and 0.2-3 parts by weight of silane coupling agent; the anti-overflow white layer in the present application ensures the appearance yield of the module, and optimizes the adhesive film production process; the reliability is higher than that of the conventional white pretreatment type adhesive film, and there is no problem of long-term storage peel strength and no problem of delamination after aging; the anti-overflow white layer is covered by inorganic fiber monofilament and organic fiber monofilament, which can increase the strength of the anti-overflow white layer, avoid the fracture of the anti-overflow white layer and thus cause the lamination overflow of the module and the appearance defect.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of photovoltaic adhesive film, in particular to a double-glass white adhesive film and a preparation method thereof. BACKGROUND

[0002] With the increasing demand for some double-glass components for roof buildings and the like that do not generate electricity on the back, component manufacturers choose white films with higher gain and more mature technology to replace glazed glass and transparent adhesive films to improve the power of the components.

[0003] Currently, white films on the market are mostly used for single-glass component packaging, and white films for double-glass component packaging have new requirements due to changes in their collocation methods. Single-glass white films mostly use high-energy electron beam irradiation pre-crosslinking schemes to form a low-flow crosslinking layer on the surface of the film, preventing the white adhesive film from flowing to the upper transparent adhesive film, thereby solving the problem of white overflow. However, after high-energy electron beam bombardment, the free radicals will accelerate the failure of the silane coupling agent in the system, resulting in a significant decrease in the peel strength of the adhesive film after aging, and even delamination. In addition, the residual free radicals will further consume the silane coupling agent in the system, resulting in a significant decrease in the long-term peel strength of the white film and glass, which seriously affects the shelf life of the adhesive film. Single-glass white films do not have this problem because they are in contact with the backsheet, but if they are used for double-glass packaging, they will directly affect the service life and reliability of the components.

[0004] On the other hand, due to the use of double-glass packaging, white films with EVA as the base resin have a lower high-temperature bulk resistance, resulting in a smaller voltage division in the glass→adhesive film→cell→adhesive film→glass circuit system, which cannot meet the anti-polarization requirement, and the PID resistance is poor. After being used outdoors for a period of time, the power will decrease significantly, affecting the power generation of photovoltaic components. If a white film with POE as the base resin is used, the additive absorption is poor and the crosslinking is more difficult than that of the EVA base resin, so the irradiation dose needs to be increased to meet the appearance requirements. However, increasing the irradiation dose will affect the peel strength and long-term peel of the adhesive film, and the equipment will be damaged, so there is an urgent need for a white film that can be used for double-glass component packaging to ensure the appearance, reliability, and service life of the components. SUMMARY

[0005] The purpose of the present application is to provide a double-glass white adhesive film that can solve at least one of the above technical problems by using inorganic fiber filaments and organic fiber filaments to increase the strength of the anti-overflow layer and prevent the anti-overflow layer from breaking, thereby preventing the overflow of the laminated components and causing poor appearance.

[0006] To achieve the above-mentioned purposes, the technical solutions adopted in the present application are as follows:

[0007] A double glass white adhesive film, comprising an anti-overflow white layer, a white polarization-resistant layer and a high-adhesion layer which are sequentially stacked from top to bottom,

[0008] The anti-overflow white layer is a reticular structure film, and its composition comprises: 50-75 parts by weight of inorganic fibers, 20-50 parts by weight of organic fibers, and 0.2-3 parts by weight of silane coupling agent.

[0009] Further, the inorganic fibers are laid flat in the warp and weft directions of the anti-overflow white layer without interweaving, and the organic fibers and the inorganic fibers are interwoven in the warp and weft directions.

[0010] Further, the fiber monofilament diameter is 1-30 microns, the inorganic fibers are modified by the silane coupling agent, the fibers are high-transmittance fibers with a light transmittance of greater than or equal to 92% in the 380-1100 nm wavelength band, and the anti-overflow white layer has a mesh number of 200-1000.

[0011] Further, the inorganic fibers are one or more of high-purity silica fibers, quartz fibers, glass fibers and alumina fibers, and the organic fibers are one or more of polypropylene fibers, polyacrylonitrile fibers, polyamide fibers and polyester fibers.

[0012] Further, the thickness of the anti-overflow white layer is 50-120 microns, the thickness of the white polarization-resistant layer is 150-300 microns, and the thickness of the high-adhesion layer is 100-150 microns.

[0013] Further, the composition of the white polarization-resistant layer comprises: 80-95 parts by weight of polyolefin elastomer resin, 5-15 parts by weight of white filler, 0.1-1.5 parts by weight of peroxide initiator, 0.3-1.5 parts by weight of crosslinking agent, 0.05-0.5 parts by weight of silane coupling agent, 0.05-0.5 parts by weight of polarization-resistant additive, 0.01-0.2 parts by weight of light stabilizer, and 0.01-0.15 parts by weight of antioxidant.

[0014] The composition of the high-adhesion layer comprises: 80-95 parts by weight of base resin, 5-20 parts by weight of tackifying resin, 0.1-1.5 parts by weight of peroxide initiator, and 0.5-1.0 parts by weight of silane coupling agent.

[0015] Further, the polyolefin elastomer resin is selected from one or more of ethylene-octene copolymer, ethylene-hexene copolymer, ethylene-butene copolymer and metallocene-catalyzed polyethylene, the polyolefin elastomer resin has a melt index of 1-10 g / 10 min, a melting point of 55-105°C, and a volume resistivity of greater than or equal to 1*10^15 Ω*cm.

[0016] Further, the white filler is selected from one or more of titanium dioxide, barium sulfate, calcium carbonate and zinc white.

[0017] The peroxide initiator consists of one or more of the group consisting of t-butyl peroxy-2-ethylhexyl carbonate, t-amyl peroxy-2-ethylhexyl carbonate, 1,1-bis(t-butyl)peroxy cyclohexane, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, t-butyl peroxy maleate, t-butyl peroxy 3,5,5-trimethyl hexanoate, t-butyl peroxy acetate, benzoyl peroxide;

[0018] The crosslinking agent is selected from one or more of the group consisting of triallyl isocyanurate, triallyl cyanurate, trimethallyl isocyanurate, tripropylene glycol diacrylate, 1,6-hexanediol diacrylate, dipropylene glycol diacrylate, neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, polyethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated glyceryl triacrylate, bis-trimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, pentaerythritol triacrylate, trivinyltrimethylcyclotrisiloxane, tetra-vinyltetramethylcyclotetrasiloxane, penta-vinylpenta-methylcyclopentasiloxane;

[0019] The silane coupling agent is selected from one or more of the group consisting of 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltris(trimethoxysiloxy)silane, vinylmethyldiethoxysilane, vinylmethyldimethoxysilane, vinyltriacetoxysilane, vinyltriisopropenoxysilane, vinyltris(2-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, further, the silane coupling agent is one or more of the group consisting of vinylmethyldiethoxysilane, vinylmethyldimethoxysilane, vinyltriacetoxysilane, vinyltriisopropenoxysilane, vinyltris(2-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane;

[0020] The anti-polarization aid is selected from one or more of the group consisting of ion-capturing agents, metal salts of stearic acid, alkali metal salts of alkyl sulfonic acid, phosphoric acid or dithiocarbamic acid, polyacrylamides, xanthate and dithiocarbamate derivatives;

[0021] The light stabilizer is selected from one or more of 2,2,6,6-tetramethylpiperidin-4-one, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-decyloxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-hydroxy-4-methoxybenzophenone, phenyl salicylate, 2-cyano-3,3'-diphenyl acrylate isooctyl ester, decanedioic acid bis-2,2,6,6-tetramethylpiperidinol ester, and poly(4-hydroxyethyl-2,2,6,6-tetramethyl-1-piperidinethanol) succinate;

[0022] The antioxidant is selected from one or more of 2,6-di-tert-butyl-4-methylphenol, butylated hydroxyltoluene, n-octadecyl beta-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentaerythritol tetrakis[beta-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], triethylene glycol-bis-3-(2-tert-butyl-4-hydroxy-5-methyl-phenyl)propionate, 1,6-hexanediol-3-(3,5-di-tert-butyl-4-hydroxy-phenyl)propionate, dilauryl thiodipropionate, didodecyl thiodipropionate, triphenyl phosphite, tris(nonylphenyl) phosphite, diphenyl-octyl phosphite, and dioctadecyl pentaerythritol phosphite;

[0023] The base resin is selected from one or more of a copolymer of ethylene and vinyl acetate, an ethylene octene copolymer, and an ethylene butene copolymer, with a melt index of 5-30 g / 10 min and a melting point of 55-80℃;

[0024] The tackifying resin is selected from one or more of an ethylene and acrylic acid EAA copolymer, a terpene resin, and a rosin resin.

[0025] Another object of the present application is to provide a preparation method of a double-glass white adhesive film, which solves at least one of the above technical problems, and the preparation of the anti-overflow white layer in the white adhesive film does not require irradiation treatment, thereby solving the problems of overflow white in the appearance of a laminated component and low peel strength after long-term storage.

[0026] To achieve the above object, the technical solution adopted in the present application is as follows:

[0027] A preparation method of a double-glass white adhesive film, the preparation method comprising the following steps:

[0028] S1. Preparing an anti-overflow white layer: preparing an acidic aqueous solution with a pH value of 4-5, slowly adding a silane coupling agent into the acidic aqueous solution and stirring until transparent, filtering with gauze to obtain a cooling liquid; melting and blowing inorganic materials into fibers, drying after passing through the cooling liquid to prepare inorganic fibers, and obtaining the anti-overflow white layer through braiding technology of the inorganic fibers and organic fibers;

[0029] S2. Preparing a white polarization-resistant layer and a high-adhesion layer;

[0030] S3 coextruding the prepared anti-overflow white layer, white anti-polarization layer and high adhesion layer to form an anti-overflow white layer / white anti-polarization layer / high adhesion layer three-layer structure, and obtaining the double-glass white adhesive film after shaping.

[0031] Further, the preparation of the white anti-polarization layer and the high adhesion layer in the step S2 specifically comprises the following steps:

[0032] 1) preparing white polyolefin masterbatch: adding white filler and polyolefin resin into a high-speed mixer to mix uniformly, and then adding into a double-screw extruder to prepare white polyolefin masterbatch;

[0033] 2) preparing raw materials for the white anti-polarization layer and the high adhesion layer:

[0034] adding polyolefin resin, white polyolefin masterbatch, peroxide initiator, crosslinking agent, silane coupling agent, light stabilizer, antioxidant and anti-polarization additive into a mixer 1 for dispersion mixing; and adding EVA resin, tackifying resin, peroxide initiator and silane coupling agent into a mixer 2 for dispersion mixing;

[0035] 3) preparing the white anti-polarization layer and the high adhesion layer: opening a co-extrusion machine, setting the extrusion temperature of the main machine at 65-90℃, setting the die temperature at 80-90℃, and respectively adding the materials in the mixer 1 and the mixer 2 in the step 3) into the silos 1 and 2, and making the white anti-polarization layer extrude on the rubber roller side and the high adhesion layer extrude on the steel roller side through a distributor to respectively obtain the white anti-polarization layer and the high adhesion layer for standby.

[0036] The technical scheme of the present application has the following beneficial effects:

[0037] 1) The anti-overflow white layer in the present application ensures the appearance yield of the module, optimizes the adhesive film production process, has higher reliability than the conventional white pretreatment type adhesive film, has no problem of peeling strength after long storage, and has no problem of delamination after aging.

[0038] 2) The anti-overflow white layer in the present application is covered with inorganic fiber filaments and organic fiber filaments, which can increase the strength of the anti-overflow white layer and avoid the fracture of the anti-overflow white layer, thereby avoiding the lamination overflow of the white layer of the module and causing appearance defects.

[0039] 3) The addition of the polyolefin matrix resin and the anti-polarization additive in the present application improves the PID resistance of the module during outdoor work, and has no problem of significant power attenuation.

[0040] 4) The addition of the tackifying resin in the present application can further improve the adhesive force of the adhesive film and increase the reliability of the photovoltaic module. BRIEF DESCRIPTION OF DRAWINGS

[0041] Figure 1 It is a structural schematic diagram of the double-glass white adhesive film in the present application.

[0042] Figure 2 The schematic diagram of the stack of inorganic fibers and organic fibers in the anti-overflow white layer.

[0043] In the figure: 1 anti-overflow white layer, 2 white polarization-resistant layer, 3 high-adhesion layer. DETAILED DESCRIPTION

[0044] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0045] As Figure 1 described, the double-glass white adhesive film in the present application comprises, from top to bottom, an anti-overflow white layer, a white polarization-resistant layer and a high-adhesion layer which are sequentially stacked, the thickness of the anti-overflow white layer is 50-120 μm, the thickness of the white polarization-resistant layer is 150-300 μm, and the thickness of the high-adhesion layer is 100-150 μm.

[0046] As Figure 2 shown, the inorganic fibers in the anti-overflow white layer in the present application are laid flat in the warp and weft directions of the anti-overflow white layer and are not interwoven, and the organic fibers and the inorganic fibers are interwoven in the warp and weft directions.

[0047] The fiber monofilament diameter is 1-30 microns, the inorganic fibers are modified by a silane coupling agent, the fibers are high-transmittance fibers with a light transmittance ≥ 92% in the 380-1100 nm wavelength band, and the anti-overflow white layer has a mesh number of 200-1000 meshes.

[0048] Example Formula 1

[0049] 1. Anti-overflow white layer formula design:

[0050] Inorganic fibers: 55 wt% quartz fibers

[0051] Organic fibers: 44.5 wt% polypropylene fibers

[0052] Silane coupling agent: 0.5 wt% vinyltriethoxysilane

[0053] 2. Polarization-resistant layer formula design:

[0054] Polyolefin elastomer: 87.73 wt% ethylene-octene copolymer (melting point: 85°C, melt index: 5 g / 10 min, volume resistivity 2.5*10^15 Ω*cm)

[0055] White filler: 10 wt% titanium white

[0056] Peroxide initiator: 1.2 wt% t-amyl peroxy 2-ethylhexyl carbonate

[0057] Crosslinking agent: 0.7 wt% triallyl cyanurate

[0058] Silane coupling agent: 0.15 wt% vinyl triethoxysilane

[0059] Antipolarization aid: 0.08 wt% magnesium stearate

[0060] Light stabilizer: 0.03 wt% 2-hydroxy-4-methoxy benzophenone, 0.05 wt% polybutanedioic acid (4-hydroxyethyl-2,2,6,6-tetramethyl-l-piperidinoethanol) ester

[0061] Antioxidant: 0.01 wt% 2,6-di-tert-butyl-4-methyl phenol, 0.05 wt% dilauryl thiodipropionate

[0062] 3. High adhesion layer formulation design:

[0063] Matrix resin: 80 wt% ethylene vinyl acetate copolymer (melting point: 75°C, melt index: 25 g / 10 min, VA: 28%)

[0064] Tackifying resin: 19.3 wt% ethylene and acrylic acid (EAA) copolymer

[0065] Peroxide initiator: 0.2 wt% t-amyl peroxy 2-ethylhexyl carbonate

[0066] Silane coupling agent: 0.5 wt% vinyl triethoxysilane

[0067] Example formulation 2:

[0068] 1. Spill-proof white layer formulation design:

[0069] Inorganic fiber: 75 wt% quartz fiber

[0070] Organic fiber: 24 wt% polyester fiber

[0071] Silane coupling agent: 1 wt% vinyl triethoxysilane

[0072] 2. Antipolarization layer formulation design:

[0073] Polyolefin elastomer: 87.69 wt% ethylene octene copolymer (melting point: 85°C, melt index: 5 g / 10 min, volume resistivity 2.5*10^15 ohm*cm)

[0074] White filler: 8 wt% titanium dioxide, 2 wt% calcium carbonate

[0075] Peroxide initiator: 0.2 wt% t-amyl peroxy 2-ethylhexyl carbonate

[0076] Crosslinker: 0.9 wt% triallyl cyanurate

[0077] Silane coupling agent: 0.25 wt% vinyl triethoxysilane

[0078] Antipolarization aid: 0.1 wt% sodium dodecylsulfonate

[0079] Light stabilizer: 0.05 wt% 2-hydroxy-4-methoxy benzophenone

[0080] Antioxidant: 0.01 wt% 2,6-di-tert-butyl-4-methyl phenol

[0081] 3. High adhesion layer formulation design:

[0082] Matrix resin: 80 wt% ethylene octene copolymer (melt point: 65°C, melt index: 14 g / 10 min)

[0083] Tackifying resin: 19.3 wt% ethylene and acrylic acid (EAA) copolymer

[0084] Peroxide initiator: 0.2 wt% t-amyl peroxy 2-ethylhexyl carbonate

[0085] Silane coupling agent: 0.5 wt% vinyl triethoxysilane

[0086] Example formulation 3:

[0087] 1. Spill-proof white layer formulation design:

[0088] Inorganic fiber: 60 wt% high purity silica fiber

[0089] Organic fiber: 39.2 wt% polypropylene fiber

[0090] Silane coupling agent: 0.8 wt% vinyl triethoxysilane

[0091] 2. Antipolarization layer formulation design:

[0092] Polyolefin elastomer: 89.29 wt% ethylene butene copolymer (melt point: 78°C, melt index: 8 g / 10 min, volume resistivity 3.0*10^15 ohm*cm)

[0093] White filler: 8 wt% titanium dioxide

[0094] Peroxide initiator: 0.9 wt% 2,5-dimethyl-2,5-bis(tert-butylperoxy) hexane

[0095] Crosslinker: 1.0 wt% tripropylene glycol diacrylate

[0096] Silane Coupling Agent: 0.65 wt% Vinyltriethoxysilane

[0097] Antipolarization Aid: 0.10 wt% Sodium Stearate

[0098] Light Stabilizer: 0.05 wt% 2-Hydroxy-4-methoxybenzophenone

[0099] Antioxidant: 0.01 wt% 2,6-Di-tert-butyl-4-methylphenol

[0100] 3. High Adhesion Layer Formulation Design:

[0101] Base Resin: 89.4 wt% Ethylene butene copolymer (Melting Point: 75°C, Melt Index: 25 g / 10 min)

[0102] Tackifying Resin: 9.3 wt% Rosin Resin

[0103] Peroxide Initiator: 0.5 wt% Tert-amyl peroxy-2-ethylhexyl carbonate

[0104] Silane Coupling Agent: 0.8 wt% Vinyltrimethoxysilane

[0105] Example Formulation 4:

[0106] 1. Spill-Proof White Layer Formulation Design:

[0107] Inorganic Fiber: 80 wt% Glass Fiber

[0108] Organic Fiber: 18 wt% Polypropylene Fiber

[0109] Silane Coupling Agent: 2 wt% 3-Methacryloyloxypropyltrimethoxysilane

[0110] 2. Antipolarization Layer Formulation Design:

[0111] Polyolefin Elastomer: 43.09 wt% Ethylene octene copolymer (Melting Point: 85°C, Melt Index: 5 g / 10 min, Volume Resistivity 2.5*10^15 ohm*cm) 40 wt% Ethylene butene copolymer (Melting Point: 78°C, Melt Index: 8 g / 10 min, Volume Resistivity 3.0*10^15 ohm*cm)

[0112] White Filler: 15 wt% Zinc Sulfate

[0113] Peroxide Initiator: 0.55 wt% Benzoyl peroxide

[0114] Crosslinking Agent: 0.3 wt% Triallyl cyanurate, 0.6 wt% Tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester

[0115] Silane Coupling Agent: 0.15 wt% 3-methacryloxypropyltrimethoxysilane

[0116] Antipolarization Aid: 0.25 wt% polyacrylamide

[0117] Light Stabilizer: 0.05 wt% 2-hydroxy-4-methoxybenzophenone

[0118] Antioxidant: 0.01 wt% 2,6-di-tert-butyl-4-methylphenol

[0119] 3. High Adhesion Layer Formulation Design:

[0120] Matrix Resin: 40 wt% EVA (Melting Point: 75°C, Melt Index: 25 g / 10 min, VA: 28%) 40 wt% ethylene butene copolymer (Melting Point: 75°C, Melt Index: 25 g / 10 min, VA: 28%)

[0121] Tackifying Resin: 18.7 wt% ethylene and acrylic acid (EAA) copolymer

[0122] Peroxide Initiator: 0.5 wt% benzoyl peroxide

[0123] Silane Coupling Agent: 0.8 wt% vinyltrimethoxysilane

[0124] Example Formulation 5:

[0125] 1. Spill-Proof White Layer Formulation Design:

[0126] Inorganic Fiber: 35 wt% high purity silica fiber, 35 wt% glass fiber

[0127] Organic Fiber: 27 wt% polypropylene fiber

[0128] Silane Coupling Agent: 3 wt% vinylmethyldimethoxysilane

[0129] 2. Antipolarization Layer Formulation Design:

[0130] Polyolefin Elastomer: 82.33 wt% metallocene-catalyzed polyethylene (Melting Point: 100°C, Melt Index: 1 g / 10 min, Volume Resistivity 1.0*10^16 Ω*cm)

[0131] White Filler: 15 wt% calcium carbonate

[0132] Peroxide Initiator: 0.6 wt% t-amyl peroxy-2-ethylhexyl carbonate, 0.2 wt% benzoyl peroxide

[0133] Crosslinking Agent: 0.7 wt% triallyl cyanurate, 0.2 wt% tetra-vinyl tetramethyl cyclotetrasiloxane

[0134] Silane Coupling Agent: 0.5 wt% vinyl tri(2-methoxyethoxy) silane

[0135] Antipolarization Aid: 0.3 wt% sodium phosphate

[0136] Light Stabilizer: 0.08 wt% 2,2,6,6-tetramethylpiperidine-4-one

[0137] Antioxidant: 0.08 wt% trisnonylphenyl phosphite, 0.01 wt% 2,6-di-tert-butyl-4- methylphenol

[0138] 3. High Adhesion Layer Formulation Design:

[0139] Base Resin: 85 wt% EVA (melting point: 75°C, melt index: 25 g / 10 min, VA: 28%)

[0140] Tackifying Resin: 14.1 wt% terpene resin

[0141] Peroxide Initiator: 0.2 wt% t-amyl peroxy-2-ethylhexyl carbonate

[0142] Silane Coupling Agent: 0.7 wt% vinyl tri(2-methoxyethoxy) silane

[0143] Example Formulation 6:

[0144] 1. Spill-Proof White Layer Formulation Design:

[0145] Inorganic Fiber: 25 wt% alumina fiber, 30 wt% high purity silica fiber

[0146] Organic Fiber: 42 wt% polypropylene fiber

[0147] Silane Coupling Agent: 3 wt% vinyl triethoxysilane

[0148] 2. Antipolarization Layer Formulation Design:

[0149] Polyolefin Elastomer: 62.72 wt% ethylene octene copolymer (melting point: 95°C, melt index: 1 g / 10 min, volume resistivity 6.0*10^15 ohm*cm), 20 wt% ethylene hexene copolymer (melting point: 91°C, melt index: 3 g / 10 min, volume resistivity 2.0*10^15 ohm*cm)

[0150] White Filler: 12 wt% titanium dioxide, 3 wt% barium sulfate

[0151] Peroxide Initiator: 0.75 wt% t-butyl peroxy maleate

[0152] Crosslinking Agent: 0.6 wt% tetra-vinyl tetramethyl cyclotetrasiloxane

[0153] Silane Coupling Agent: 0.5 wt% Vinyl triisopropenoxysilane

[0154] Antipolarization Aid: 0.3 wt% Barium phosphate

[0155] Light Stabilizer: 0.08 wt% 2-Hydroxy-4-dodecyloxybenzophenone

[0156] Antioxidant: 0.05 wt% n-Octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate

[0157] 3. High Adhesion Layer Formulation Design:

[0158] Matrix Resin: 60 wt% EVA (Melting Point: 66°C, Melt Index: 15 g / 10 min, VA: 33%), 25 wt% Ethylene Octene Copolymer (Melting Point: 55°C, Melt Index: 5 g / 10 min)

[0159] Tackifying Resin: 9 wt% Ethylene and Acrylic Acid (EAA) Copolymer, 5 wt% Terpene Resin

[0160] Peroxide Initiator: 0.35 wt% Tert-butyl Peroxy Maleate

[0161] Silane Coupling Agent: 0.65 wt% Vinyl triisopropenoxysilane

[0162] Example Formulation 7:

[0163] 1. Spill-Proof White Layer Formulation Design:

[0164] Inorganic Fiber Filaments: 25 wt% Quartz Fiber, 25 wt% Glass Fiber, 25 wt% Aluminum Oxide Fiber

[0165] Organic Fiber Filaments: 22 wt% Polypropylene Fiber

[0166] Silane Coupling Agent: 1.5 wt% Vinyl triethoxysilane, 1.5 wt% Vinyl trimethoxysilane

[0167] 2. Antipolarization Layer Formulation Design:

[0168] Polyolefin Elastomer: 50 wt% Ethylene Octene Copolymer (Melting Point: 85°C, Melt Index: 5 g / 10 min, Volume Resistivity 2.5*10^15 Ω*cm) 32.44 wt% Ethylene Octene Copolymer (Melting Point: 95°C, Melt Index: 1 g / 10 min, Volume Resistivity 6.0*10^15 Ω*cm)

[0169] White Filler: 10 wt% Titanium Dioxide, 5 wt% Barium Sulfate

[0170] Peroxide initiator: 0.5 wt% t-butylperoxy-2-ethylhexyl carbonate, 0.7 wt% t-amylperoxy 2-ethylhexyl carbonate

[0171] Crosslinking agent: 0.3 wt% trimethylenyl isocyanate

[0172] Silane coupling agent: 0.5 wt% vinyltriethoxysilane

[0173] Antipolarization aid: 0.5 wt% sodium diethyldithiocarbamate

[0174] Light stabilizer: 0.05 wt% 2-hydroxy-4-methoxybenzophenone

[0175] Antioxidant: 0.01 wt% 2,6-di-tert-butyl-4-methylphenol

[0176] 3. High adhesion layer formulation design:

[0177] Matrix resin: 83.5 wt% EVA (melting point: 75°C, melt index: 25 g / 10 min, VA: 28%)

[0178] Tackifying resin: 5 wt% ethylene and acrylic acid (EAA) copolymer, 5 wt% terpene resin, 5 wt% rosin resin

[0179] Peroxide initiator: 0.5 wt% t-amylperoxy 2-ethylhexyl carbonate

[0180] Silane coupling agent: 1 wt% vinyltriethoxysilane

[0181] Example formulation 8:

[0182] 1. Spill-proof white layer formulation design:

[0183] Inorganic fiber filaments: 35 wt% quartz fiber, 20 wt% alumina fiber, 15 wt% glass fiber

[0184] Organic fiber filaments: 28 wt% polyacrylonitrile fiber

[0185] Silane coupling agent: 1 wt% vinyltriethoxysilane, 1 wt% 3-methacryloxypropyl tris(trimethoxysiloxy)silane

[0186] 2. Antipolarization layer formulation design:

[0187] Polyolefin elastomer: 87.62 wt% ethylene octene copolymer (melting point: 95°C, melt index: 1 g / 10 min, volume resistivity 6.0*10^15 Ω*cm)

[0188] White filler: 10 wt% titanium dioxide

[0189] peroxide initiator: 1.5 wt% t-amyl peroxy 2-ethylhexyl carbonate

[0190] crosslinking agent: 0.2 wt% triallyl cyanurate

[0191] silane coupling agent: 0.4 wt% 3-methacryloxypropyl tris(trimethoxysiloxy)silane

[0192] anti-polarization aid: 0.08 wt% magnesium stearate, 0.1 wt% sodium stearate

[0193] light stabilizer: 0.1 wt% 2-cyano-3,3'-diphenyl acrylate isooctyl ester

[0194] antioxidant: 0.1 wt% 2,6-di-tert-butyl-4-methyl phenol

[0195] 3. High Adhesion Layer Formulation Design:

[0196] matrix resin: 90 wt% EVA (melting point: 58°C, melt index: 25 g / 10 min, VA: 33%)

[0197] tackifying resin: 9.2 wt% rosin resin

[0198] peroxide initiator: 0.3 wt% t-amyl peroxy 2-ethylhexyl carbonate

[0199] silane coupling agent: 0.5 wt% vinyl triethoxysilane

[0200] Example Formulation 9:

[0201] 1. Spill-Proof White Layer Formulation Design:

[0202] inorganic fiber filaments: 64 wt% quartz fiber

[0203] organic fiber filaments: 20 wt% polypropylene fiber, 15 wt% polyamide fiber

[0204] silane coupling agent: 1 wt% vinyl triethoxysilane

[0205] 2. Anti-Polarization Layer Formulation Design:

[0206] polyolefin elastomer: 58.16 wt% ethylene octene copolymer (melting point: 85°C, melt index: 5 g / 10 min, volume resistivity 2.5*10^15 ohm*cm), 30 wt% metallocene catalyzed polyethylene (melting point: 105°C, melt index: 5 g / 10 min, volume resistivity 3.0*10^16 ohm*cm)

[0207] white filler: 10 wt% titanium dioxide

[0208] Peroxide initiator: 0.9 wt% t-amyl peroxy 2-ethylhexyl carbonate

[0209] Crosslinking agent: 0.3 wt% pentaerythritol triacrylate

[0210] Silane coupling agent: 0.5 wt% vinyl trimethoxysilane

[0211] Antipolarization aid: 0.08 wt% magnesium stearate, 0.1 wt% sodium phosphate

[0212] Light stabilizer: 0.05 wt% 2-hydroxy-4-methoxybenzophenone

[0213] Antioxidant: 0.01 wt% 2,6-di-tert-butyl-4-methylphenol

[0214] 3. High bond layer formulation design:

[0215] Matrix resin: 40 wt% EVA (melting point: 75°C, melt index: 25 g / 10 min, VA: 28%), 40 wt% EVA (melting point: 58°C, melt index: 25 g / 10 min, VA: 33%)

[0216] Tackifying resin: 19.3 wt% ethylene and acrylic acid (EAA) copolymer

[0217] Peroxide initiator: 0.2 wt% t-amyl peroxy 2-ethylhexyl carbonate

[0218] Silane coupling agent: 0.5 wt% vinyl trimethoxysilane

[0219] Example formulation 10:

[0220] 1. Spill-proof white layer formulation design:

[0221] Inorganic fiber filaments: 60 wt% quartz fiber, 10 wt% glass fiber

[0222] Organic fiber filaments: 28 wt% polyamide fiber

[0223] Silane coupling agent: 2 wt% vinyl triacetoxysilane

[0224] 2. Antipolarization layer formulation design:

[0225] Polyolefin elastomer: 82.74 wt% ethylene octene copolymer (melting point: 85°C, melt index: 5 g / 10 min, volume resistivity 2.5*10^15 Ω*cm)

[0226] White filler: 8 wt% titanium dioxide, 5 wt% calcium carbonate, 2 wt% barium sulfate

[0227] Peroxide initiator: 0.5 wt% t-butyl peroxy 3,5,5-trimethylhexanoate

[0228] Crosslinking agent: 0.7 wt% ethoxylated pentaerythritol tetraacrylate

[0229] Silane coupling agent: 0.5 wt% vinyl triacetoxysilane

[0230] Anti-polarization aid: 0.5 wt% calcium phosphate

[0231] Light stabilizer: 0.05 wt% 2-hydroxy-4-methoxybenzophenone

[0232] Antioxidant: 0.01 wt% 2,6-di-tert-butyl-4-methylphenol

[0233] 3. High adhesive layer formulation design:

[0234] Matrix resin: 80 wt% EVA (melting point: 75°C, melt index: 25 g / 10 min, VA: 28%)

[0235] Tackifying resin: 18.8 wt% ethylene and acrylic acid (EAA) copolymer

[0236] Peroxide initiator: 0.45 wt% t-butyl peroxy 3,5,5-trimethylhexanoate

[0237] Silane coupling agent: 0.75 wt% vinyl triacetoxysilane

[0238] The preparation method of the double-glass white adhesive film in Example 1 to Example 10 includes the following steps:

[0239] S1. Preparation of the anti-overflow white layer: an acidic aqueous solution with a pH value of 4-5 is prepared, the silane coupling agent is slowly added into the acidic aqueous solution under stirring until it becomes transparent, and then filtered with gauze to obtain a cooling liquid; inorganic materials are melted and blown into fibers, dried after passing through the cooling liquid, and inorganic fibers are prepared; the inorganic fibers and organic fibers are woven by a weaving process to obtain the anti-overflow white layer.

[0240] S2. Preparation of the white anti-polarization layer and the high adhesive layer:

[0241] 1) Preparation of the white polyolefin masterbatch: the white filler and the polyolefin resin are uniformly mixed in a high-speed mixer, and then fed into a twin-screw extruder to prepare the white polyolefin masterbatch.

[0242] 2) Preparation of raw materials for the white anti-polarization layer and the high adhesive layer:

[0243] The polyolefin resin, white polyolefin masterbatch, peroxide initiator, crosslinking agent, silane coupling agent, light stabilizer, antioxidant, and anti-polarization aid were added to mixer 1 and dispersed and mixed for standby; the EVA resin, tackifying resin, peroxide initiator, and silane coupling agent were added to mixer 2 and dispersed and mixed for standby;

[0244] 3) Preparation of white anti-polarization layer and high adhesion layer: open the co-extrusion machine, set the main machine extrusion temperature to 65-90℃, and set the die temperature to 80-90℃; put the materials in step 3) mixer 1 and 2 into the hopper 1 and 2 respectively, pass through the distributor to make the white anti-polarization layer extrude on the rubber roller side and the high adhesion layer extrude on the steel roller side, and obtain the white anti-polarization layer and high adhesion layer respectively for standby.

[0245] S3 Place the anti-overflow white layer prepared in step S1 on the unwinding frame, and unwind while the adhesive film is being extruded, so that the adhesive film of step four and the anti-overflow white layer are cast together to form an anti-overflow white layer / white anti-polarization layer / high adhesion layer three-layer structure, and finally go through shaping, edge cutting, winding, packaging, and warehousing to obtain the double-glass white adhesive film.

[0246] The adhesive films prepared in Comparative Examples 1-10 and the adhesive film of Comparative Example 1 (white film not using inorganic fibers and organic fibers, treated by pre-crosslinking scheme) were detected according to the national standard GBT 29848-2018 Ethylene-vinyl acetate copolymer (EVA) adhesive film for photovoltaic module packaging, and the performances were compared, and the performances were as follows:

[0247]

[0248] In addition, it should be understood that although the present specification is described in terms of embodiments, not every embodiment contains only one independent right scheme, and the description of the specification is only for the sake of clarity, and those skilled in the art should consider the specification as a whole, and the technical schemes in each embodiment can also be appropriately combined to form other embodiments that those skilled in the art can understand.

Claims

1. A double glass white adhesive film, characterized by: The anti-overflow white layer, the white anti-polarization layer and the high adhesion layer are sequentially stacked from top to bottom, The anti-overflow white layer is a reticular structure film, and its composition comprises: 50-75 parts by weight of inorganic fibers, 20-50 parts by weight of organic fibers, and 0.2-3 parts by weight of silane coupling agent; The inorganic fibers are laid flat in the warp and weft directions of the anti-overflow white layer without interweaving, and the organic fibers are interwoven with the inorganic fibers in the warp and weft directions; The fiber monofilament diameter is 1-30 microns, the inorganic fibers are modified by the silane coupling agent, the fibers are high-transmittance fibers with a light transmittance of greater than or equal to 92% in the 380-1100 nm wavelength band, and the anti-overflow white layer has a mesh number of 200-1000 meshes; The inorganic fibers are one or more of high-purity silica fibers, quartz fibers, glass fibers and alumina fibers, and the organic fibers are one or more of polypropylene fibers, polyacrylonitrile fibers, polyamide fibers and polyester fibers; The composition of the white anti-polarization layer comprises: 80-95 parts by weight of polyolefin elastomer resin, 5-15 parts by weight of white filler, 0.1-1.5 parts by weight of peroxide initiator, 0.3-1.5 parts by weight of crosslinking agent, 0.05-0.5 parts by weight of silane coupling agent, 0.05-0.5 parts by weight of anti-polarization aid, 0.01-0.2 parts by weight of light stabilizer, and 0.01-0.15 parts by weight of antioxidant; The composition of the high adhesion layer comprises: 80-95 parts by weight of base resin, 5-20 parts by weight of tackifying resin, 0.1-1.5 parts by weight of peroxide initiator, and 0.5-1.0 parts by weight of silane coupling agent.

2. The double glass white adhesive film according to claim 1, characterized in that: The thickness of the anti-overflow white layer is 50-120 microns, the thickness of the white anti-polarization layer is 150-300 microns, and the thickness of the high adhesion layer is 100-150 microns.

3. The double glass white adhesive film according to claim 1, wherein: The polyolefin elastomer resin is selected from one or more of ethylene-octene copolymer, ethylene-hexene copolymer, ethylene-butene copolymer and metallocene-catalyzed polyethylene, the polyolefin elastomer resin has a melt index of 1-10 g / 10 min, a melting point of 55-105°C, and a volume resistivity of greater than or equal to 1×10^15 Ω·cm.

4. The double-glass white adhesive film according to claim 1, characterized in that: The white filler is selected from one or more of titanium dioxide, barium sulfate, calcium carbonate and zinc white; The peroxide initiator is composed of one or more of tert-butyl peroxy-2-ethylhexyl carbonate, tert-amyl peroxy-2-ethylhexyl carbonate, 1,1-bis(tert-butyl)peroxy cyclohexane, 2,5-dimethyl-2,5-bis(tert-butyl peroxy)hexane, tert-butyl peroxy maleate, tert-butyl peroxy 3,5,5-trimethylhexanoate, tert-butyl peroxy acetate and benzoyl peroxide. The crosslinking agent is selected from one or more of triallyl isocyanurate, triallyl cyanurate, trimethylolethane isocyanurate, tripropylene glycol diacrylate, 1,6-hexanediol diacrylate, dipropylene glycol diacrylate, neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, polyethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated glyceryl triacrylate, bis-trimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, pentaerythritol triacrylate, trivinyltrimethylcyclotrisiloxane, tetra-vinyltetramethylcyclotetrasiloxane, penta-vinylpentamethylcyclopentasiloxane; The silane coupling agent is selected from one or more of 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltris(trimethoxysiloxy)silane, vinylmethyldiethoxysilane, vinylmethyldimethoxysilane, vinyltriacetoxysilane, vinyltriisopropenoxysilane, vinyltris(2-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane; The anti-polarization aid is selected from one or more of metal stearate, alkali metal salt of alkyl sulfonic acid, phosphoric acid or dithiocarbamic acid, polyacrylamide and xanthate; The light stabilizer is selected from one or more of 2,2,6,6-tetramethylpiperidine-4-one, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-decyloxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-hydroxy-4-methoxybenzophenone, phenyl salicylate, 2-cyano-3,3'-diphenylacrylic acid iso-octyl ester, sebacic acid bis-2,2,6,6-tetramethylpiperidinyl alcohol ester, polybutanedioic acid (4-hydroxyethyl-2,2,6,6-tetramethyl-1-piperidinylethanol) ester; The antioxidant is selected from one or more of 2,6-di-tert-butyl-4-methylphenol, butylated hydroxyltoluene, n-octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], triethylene glycol bis-3-(2-tert-butyl-4-hydroxy-5-methyl-phenyl)propionate, 1,6-hexanediol-3-(3,5-di-tert-butyl-4-hydroxy-phenyl)propionate, dilauryl thiodipropionate, triphenyl phosphite, tris(nonylphenyl)phosphite, diphenyl-octyl phosphite, distearyl pentaerythritol phosphite; The base resin is selected from one or more of copolymer of ethylene and vinyl acetate, ethylene octene copolymer, ethylene butene copolymer, with a melt index of 5-30 g / 10 min and a melting point of 55-80℃; The tackifying resin is selected from one or more of ethylene and acrylic acid copolymer, terpene resin, rosin resin.

5. The method for preparing a double-glass white adhesive film as described in claim 1, characterized in that, The preparation method comprises the following steps: S1: preparing the anti-overflow white layer: an acid aqueous solution with a pH value of 4-5 is prepared, a silane coupling agent is slowly added into the acid aqueous solution under stirring until the solution becomes transparent, and then the solution is filtered through gauze to obtain a cooling solution; inorganic materials are melted and blown into fibers, the fibers are dried after being cooled in the cooling solution to obtain inorganic fibers, and the inorganic fibers and organic fibers are woven through a weaving process to obtain the anti-overflow white layer; S2: preparing the white anti-polarization layer and the high-adhesion layer; S3: casting the prepared anti-overflow white layer, white anti-polarization layer and high-adhesion layer to form a three-layer structure of anti-overflow white layer / white anti-polarization layer / high-adhesion layer, and then shaping to obtain the double-glass white adhesive film.

6. The method for preparing a double-glass white adhesive film according to claim 5, characterized in that, The step S2 of preparing the white anti-polarization layer and the high-adhesion layer specifically comprises the following steps: 1) preparing the white polyolefin masterbatch: white fillers and polyolefin elastomer resins are uniformly mixed in a high-speed mixer, and then fed into a twin-screw extruder to prepare the white polyolefin masterbatch; 2) preparing raw materials for the white anti-polarization layer and the high-adhesion layer: polyolefin elastomer resins, white polyolefin masterbatch, peroxide initiators, crosslinking agents, silane coupling agents, light stabilizers, antioxidants, and anti-polarization additives are added into a mixer 1 for dispersion mixing; base resins, tackifying resins, peroxide initiators, and silane coupling agents are added into a mixer 2 for dispersion mixing, and the base resins are EVA resins; 3) preparing the white anti-polarization layer and the high-adhesion layer: a co-extrusion machine is opened, the extrusion temperature of the main machine is set to 65-90℃, and the die temperature is set to 80-90℃; the materials in the mixer 1 and 2 in step 2) are respectively fed into the material bins 1 and 2, the white anti-polarization layer is extruded on the rubber roller side through a distributor, and the high-adhesion layer is extruded on the steel roller side, to obtain the white anti-polarization layer and the high-adhesion layer respectively.

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