CN116640521B - Long-acting self-cleaning transparent backboard and preparation method thereof - Google Patents

Long-acting self-cleaning transparent backboard and preparation method thereof Download PDF

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CN116640521B
CN116640521B CN202310921669.3A CN202310921669A CN116640521B CN 116640521 B CN116640521 B CN 116640521B CN 202310921669 A CN202310921669 A CN 202310921669A CN 116640521 B CN116640521 B CN 116640521B
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coating
fouling
parts
resin
transparent
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CN116640521A (en
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王同心
何张才
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Suzhou Hongdao New Material Co ltd
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Suzhou Hongdao New Material Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
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    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/48—Stabilisers against degradation by oxygen, light or heat
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
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    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
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    • H01—ELECTRIC ELEMENTS
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    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
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    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
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    • H01L31/042—PV modules or arrays of single PV cells
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    • H01L31/049—Protective back sheets
    • C—CHEMISTRY; METALLURGY
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Abstract

The invention belongs to the technical field of solar photovoltaic back plates, and particularly relates to a long-acting self-cleaning transparent back plate and a preparation method thereof. The long-acting self-cleaning solar cell backboard sequentially comprises an anti-fouling coating, a weather-resistant coating, a supporting substrate and a bonding coating from bottom to top, wherein the raw materials of the anti-fouling coating comprise main resin, anti-fouling filler, photoinitiator, organic solvent, silane coupling agent and auxiliary agent; wherein the antifouling filler comprises disulfide bond compound modified Al 2 O 3 And hexadecylpolysiloxane modified SiO 2 . The outer surface of the back plate is provided with a self-repairable wear-resistant anti-fouling coating, so that the back plate has long-acting self-cleaning performance, and the anti-implementation impact capability of the coated transparent back plate is improved.

Description

Long-acting self-cleaning transparent backboard and preparation method thereof
Technical Field
The invention belongs to the technical field of solar photovoltaic back plates, and particularly relates to a long-acting self-cleaning transparent back plate and a preparation method thereof.
Background
The photovoltaic backboard is used as a packaging material on the back of the photovoltaic module, can resist the erosion of the environment such as light, humidity and heat on materials such as a battery piece, an adhesive film and the like, plays an insulating protection role, and is a key raw material for prolonging the service life of the photovoltaic module.
In recent years, the photovoltaic Building Integrated (BIPV) market shows an expanding trend, and the transparent backboard becomes a new direction under the double requirements of weight reduction and double-sided power generation gain, so that head backboard enterprises enter the field of transparent backboard in a dispute manner. The transparent backboard is made of a fully transparent material, the weight of the transparent backboard is lighter, the installation and maintenance are convenient, and the assembly adopting the transparent backboard has more application scenes compared with the double-glass assembly. Meanwhile, as the back plate is mature in application, the transparent back plate is adopted to realize the production of the double-sided power generation assembly, and the factory building and equipment transformation cost is saved for assembly manufacturers, so that the back plate is favored in the industry.
At present, more and more transparent back plates adopt a coating type structure so as to meet the requirements of reliability and continuous cost reduction, and truly realize sustainable development of the photovoltaic industry. Conventional fluorine films have a very high surface energy, and their surfaces are easier to clean than glass, and dust or dirt can be easily blown away by wind or rain. The problems of insufficient sand falling impact resistance and dust shielding of the coated transparent backboard are gradually highlighted, and the influence on the power generation efficiency and the power generation capacity of the assembly is gradually highlighted.
Chinese patent application CN202210393613.0 discloses a preparation method and application of a transparent long-acting easy-cleaning flame-retardant anti-fouling coating for a photovoltaic panel. By adding the functional resin containing fluorine-silicon into the acrylic resin containing flame-retardant polyurethane, the super-hydrophobicity, high light transmittance, yellowing resistance, extremely high cleaning property and flame retardance of the coating are improved. But the sand drop impact resistance of the coated back plate cannot be improved, and the rest of the performances are required to be further improved.
Therefore, a long-acting self-cleaning transparent backboard with superhydrophobicity, high light transmittance, long-acting anti-fouling and high wear resistance needs to be developed to ensure the normal operation of the solar cell.
Disclosure of Invention
In order to overcome the defects, the invention provides a long-acting self-cleaning transparent backboard and a preparation method thereof. The outer surface of the back plate prepared by coating is a self-repairable wear-resistant and anti-fouling coating, so that the back plate has long-acting self-cleaning performance, and the sand falling resistance of the coated back plate is improved.
In order to solve the technical problems, the invention adopts the following technical scheme:
the long-acting self-cleaning transparent backboard comprises an anti-fouling coating, a weather-resistant coating, a supporting substrate and a bonding coating from bottom to top, wherein the raw materials of the anti-fouling coating comprise main resin, an anti-fouling filler, a photoinitiator, an organic solvent, a silane coupling agent and an auxiliary agent; wherein the anti-fouling filler comprises disulfide bond compound modified Al with the mass ratio of 1:5-5:1 2 O 3 And hexadecylpolysiloxane modified SiO 2 。
Preferably, the main resin comprises disulfide bond-containing polyurethane acrylic resin and organosilicon modified polyurethane acrylic ester, and the mass ratio of the two is 1:3-3:1.
Preferably, the preparation method of the polyurethane acrylic resin containing disulfide bonds comprises the steps of mixing an aromatic polyurethane acrylic acid ester oligomer and 4,4' -diaminodiphenyl disulfide, and reacting for 2-4 hours at 70-90 ℃ in a nitrogen atmosphere.
Preferably, the mass of the 4,4' -diaminodiphenyl disulfide is 1 to 10% of the mass of the aromatic urethane acrylate oligomer.
The disulfide bond-containing compound modified Al 2 O 3 The preparation method comprises the steps of reacting 2-hydroxyethyl disulfide with isocyanate methyltrimethoxysilane to prepare a siloxane compound containing disulfide bonds; then Al is added 2 O 3 Adding a disulfide bond-containing siloxane compound and a silane coupling agent KH550 hydrolysate into the dispersion liquid, and reacting to obtain the catalyst;
preferably, the molar ratio of the 2-hydroxyethyl disulfide to the isocyanate methyltrimethoxysilane is 1:1-5;
preferably, the Al 2 O 3 The preparation method of the dispersion liquid comprises the steps of adding nano Al 2 O 3 Adding ethanol/water mixed solution, and performing ultrasonic dispersion; the mass ratio of the ethanol to the water is 1:1;
preferably, the reaction is stirred at 70-90 ℃ for 4-8 hours; and after the reaction, centrifuging, separating and drying to obtain the catalyst.
The small particle size filler is modified Al containing disulfide bond compounds 2 O 3 ；
Preferably, the hexadecyl polysiloxane modified SiO 2 The preparation method of (C) comprises the steps of preparing hexadecyltrimethoxysilane, tetraethoxysilane and SiO 2 The catalyst is obtained through HCl catalytic reaction;
preferably, the reaction is carried out for 20-30 hours at 70-90 ℃ to obtain SiO 2 Modifying the suspension, adding SiO 2 And (3) centrifugally separating the modified suspension, washing with absolute ethyl alcohol, and drying to obtain the modified suspension.
The disulfide bond compound modifies Al 2 O 3 The particle size of the nano-particle anti-fouling filler is 30-50nm, the particle size ratio of the small particle size filler to the large particle size filler is reasonably designed, the agglomeration of the small particle size nano-particles is reduced, the gaps of the large particle size filler are filled with the small particle size nano-particles, and the proportion of the micron-sized and nano-sized anti-fouling filler particles is optimized, so that a high-compactness micro-nano concave-convex structure is realized, and the deposition and adhesion of sand dust and other pollutants are prevented.
The organic silicon modified polyurethane acrylic ester can be partially hydrolyzed in the curing process to generate silicon hydroxyl groups, and the silicon hydroxyl groups undergo condensation reaction to generate a silicon-oxygen-silicon siloxane structure, so that the organic silicon modified polyurethane acrylic ester can be combined with polyurethane acrylic resin for use, and the flexibility, weather resistance and wear resistance of the polyurethane acrylic resin can be fully combined, and the weather resistance, adhesive force and wear resistance of the anti-fouling coating can be improved.
The coating main resin polyurethane acrylic resin (SAC) contains disulfide bond and Al modified by disulfide bond compound 2 O 3 After ultraviolet curing and heating, the filler is crosslinked through disulfide bond exchange reaction and double bonds to form a rough surface with a firm micro-nano structure. The anti-fouling coating provided by the invention can be hydrophobic and oleophobic, and has excellent super amphiphobicity and self-repairing performance. By disulfide exchange reaction, al 2 O 3 The filler and SAC reform the complete coating through covalent bonds in the self-repairing process, and the damaged coating surfaceCan be repaired again, and the superhydrophobicity is recovered, so that the anti-fouling coating has long-lasting anti-fouling capability.
Cetyl polysiloxane modified SiO 2 The particles are transparent powder with high chemical inertia and high hardness, so that the hardness of the backboard is increased, and the abrasion resistance and scratch resistance of the backboard are improved and the light transmittance is not influenced after the hexadecyl polysiloxane is adopted for modification.
Preferably, the photoinitiator is selected from any one or more of benzophenone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxycyclohexyl phenyl ketone, alpha-amine alkyl phenyl ketone, 2,4, 6-trimethyl benzoyl diphenyl phosphine oxide, bis (2, 4, 6-trimethyl benzoyl) phenyl phosphine oxide, 2- (o-chlorophenyl) -4, 5-diphenyl imidazole dimer and 9-phenyl acridine;
preferably, the organic solvent is one or more of ethanol, n-butanol, ethyl acetate, butyl acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, xylene and butanone;
preferably, the silane coupling agent is selected from one or more of vinyl trimethoxy silane, vinyl tri (beta-methoxyethoxy) silane, vinyl triisopropoxy silane, vinyl triethoxy silane, gamma-methacryloxypropyl trimethoxy silane and vinyl triacetoxy silane;
preferably, the auxiliary agent comprises one or two of a leveling agent and a dispersing agent.
Preferably, the raw materials of the anti-fouling layer comprise the following components in percentage by weight: 30-50% of main resin, 5-10% of anti-fouling filler, 1-5% of photoinitiator, 30-60% of organic solvent, 1-5% of silane coupling agent and 1-8% of auxiliary agent.
Preferably, the raw materials of the weather-resistant coating comprise: 30-60 parts of main resin, 1-20 parts of filler, 1-20 parts of curing agent, 20-60 parts of solvent, 0.1-5 parts of ultraviolet auxiliary agent and 0.5-10 parts of other auxiliary agents, wherein the other auxiliary agents comprise at least one of flatting agent, dispersing agent, catalyst and coupling agent.
The host resin comprises one or more of acrylic resin, polyester resin and epoxy resin.
The filler comprises pigment and other inorganic fillers, wherein the other inorganic fillers are selected from one or more of scratch-resistant powder, transparent powder, silica powder, glass powder and extinction powder, and the inorganic fillers have excellent effects of improving mechanical properties such as anti-rolling, scratch resistance and anti-press printing of the backboard.
The curing agent is one or more of aromatic isocyanate curing agent, aliphatic isocyanate curing agent and blocked isocyanate curing agent.
The dispersing agent is an anionic dispersing agent and/or a high molecular dispersing agent; the leveling agent is one or more of polyacrylate leveling agent, polyether modified polysiloxane leveling agent and reactive polysiloxane leveling agent; the catalyst is an organotin catalyst; the coupling agent is a silane coupling agent.
The organic solvent is one or more of ethanol, n-butanol, ethyl acetate, butyl acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, xylene and butanone.
Preferably, the support substrate is a single-layer or multi-layer film layer of at least one material selected from polyethylene naphthalate film, polypropylene terephthalate film, polyethylene terephthalate film, polybutylene terephthalate film, polycarbonate film, silicon copolymer modified polycarbonate film, polymethyl methacrylate film, polyimide; the support substrate may have a thickness of 100 to 800. Mu.m, preferably 150 to 300. Mu.m.
Preferably, the bonding coating comprises the following components in parts by weight: 40-60 parts of main resin, 20-40 parts of solvent, 1-5 parts of curing agent, 1-5 parts of modifying auxiliary agent, 0.5-5 parts of down-conversion material, 1-5 parts of extinction powder and 0.5-5 parts of other auxiliary agent.
The host resin comprises one or more of acrylic resin, polyester resin and epoxy resin.
The down-conversion material is Ca 2 V 2 O 7 :7％Yb 3+ 、SrMoO 4 :10％Yb 3+ 、YVO 4 :1％Tm 3+ 、CYP:15％Ce 3+ One or more of them.
Preferably, the modifying aid is vinyl terminated dimethyl (siloxane and polysiloxane).
The down-conversion material is Ca 2 V 2 O 7 :7％Yb 3+ Or CYP 15% Ce 3+ 。
Preferably, the other auxiliary agent is at least one of a light stabilizer, a leveling agent and a dispersing agent.
Preferably, the weather-resistant coating liquid is prepared by: adding main resin, filler, curing agent, ultraviolet auxiliary agent and other auxiliary agents into solvent according to the proportion, and mixing to obtain uniformly mixed coating liquid, namely weather-proof coating liquid.
Preferably, the bond coat coating liquid is prepared: the main resin, the curing agent, the modifying auxiliary agent, the down-conversion material, the extinction powder and other auxiliary agents are added into the solvent according to the proportion and mixed to obtain the uniformly mixed coating liquid, namely the bonding coating liquid.
Preferably, the anti-fouling coating is prepared by: adding the main resin, the anti-fouling filler, the photoinitiator, the silane coupling agent and other auxiliary agents into an organic solvent according to the proportion, and mixing to obtain a uniformly mixed coating liquid, namely the anti-fouling coating liquid.
Preferably, the preparation method of the long-acting self-cleaning transparent backboard comprises the following steps:
(1) Corona treatment is carried out on the inner surface of the supporting substrate, the adhesive coating liquid is coated, the transparent coating is obtained after curing for 0.5 to 5 minutes in a drying tunnel at the temperature of 100 to 200 ℃, and the adhesive coating is formed after curing, and the thickness is 6 to 15 mu m;
(2) Carrying out corona treatment on the outer surface of the supporting substrate, coating weather-proof coating liquid, and curing in a drying tunnel at 100-200 ℃ for 0.5-5min to obtain a transparent coating, wherein the thickness of the weather-proof coating is 10-20 mu m;
(3) And spraying an anti-fouling coating liquid on the surface of the weather-resistant coating, and forming an anti-fouling coating after ultraviolet curing to finish the preparation of the anti-fouling transparent backboard, wherein the thickness is 1-5 mu m.
Compared with the prior art, the invention has the beneficial effects that:
(1) The inventionThe transparent back plate contains self-repairable anti-fouling coating, and the main resin of the coating contains disulfide bond in polyurethane acrylic resin (SAC) and Al modified by disulfide bond-containing compound 2 O 3 After ultraviolet curing and heating, the filler is crosslinked through disulfide bond exchange reaction and double bonds to form a rough surface with a firm micro-nano structure. The anti-fouling coating provided by the invention can be hydrophobic and oleophobic, and has excellent super amphiphobicity and self-repairing performance. By disulfide exchange reaction, al 2 O 3 The filler and SAC form a complete coating again through covalent bonds in the self-repairing process, the damaged coating surface can be repaired again, and the superhydrophobicity is recovered, so that the backboard has a long-acting anti-fouling function.
(2) The antifouling filler of the antifouling coating of the invention is modified Al containing disulfide bond compound 2 O 3 And hexadecylpolysiloxane modified SiO 2 The composition of the (2) obtains a concave-convex micro-nano structure through reasonable particle size control and mass fraction control, so that the coating has excellent hydrophobic and oleophobic performance, ensures the anti-fouling capability of the transparent backboard, maintains the high light transmittance of the backboard, can enhance the wear resistance of the backboard, and improves the sand falling resistance of the coated backboard.
(3) The main resin of the anti-fouling coating is a composition of polyurethane acrylic resin (SAC) containing disulfide bonds and organosilicon modified polyurethane acrylic ester (OSC), and the material characteristics of the two resins can be combined to realize no fluorination of the coating, ensure the weather resistance of the anti-fouling coating, improve the adhesive force of the anti-fouling coating to the weather-resistant coating and improve the wear resistance and impact resistance of the coating.
(4) In addition, the invention carefully combines the raw materials of the bonding coating and the weather-resistant coating, and particularly adopts specific modifying auxiliary agent and main resin, so that the hydrophobicity, yellowing value and sand falling resistance of the outer coating of the backboard device are obviously improved.
Drawings
Fig. 1 is a schematic structural view of a long-acting self-cleaning transparent back plate according to the present invention.
In the figure: 1-anti-fouling coating, 2-weather-resistant coating, 3-supporting substrate and 4-bonding coating.
Detailed Description
The present invention will be described in further detail with reference to the following examples, which are not intended to limit the present invention, but are merely illustrative of the present invention. The experimental methods used in the following examples are not specifically described, but the experimental methods in which specific conditions are not specified in the examples are generally carried out under conventional conditions, and the materials, reagents, etc. used in the following examples are commercially available unless otherwise specified.
Wherein, the polyurethane acrylic resin SAC containing disulfide bonds is obtained after being modified by commercial products, and the preparation method is as follows: aromatic urethane acrylate oligomer (Zhan Xin resin, model EBECRYL 204) and chain extender 4,4' -diaminodiphenyl disulfide (5 wt% of oligomer) were added to a urethane prepolymer solution (Ji Ning Duo chemical Co., ltd., model LD 1227) and reacted at 80℃for 3 hours under nitrogen atmosphere to obtain SAC.
Silicone modified urethane acrylate OSC is a commercially available product from a new resin of the skian type EBECRYL8890.
Disulfide bond containing compound modified Al 2 O 3 For self-making, the preparation method is as follows:
(1) Weigh 5g of nano Al 2 O 3 (Jikang, model SS-LY 30) in a 250ml round bottom flask, adding 200ml ethanol/water mixture (ethanol: water=1:1, mass ratio) into the flask, and performing ultrasonic dispersion for 30min to obtain Al 2 O 3 And (3) a dispersion.
(2) The 2-hydroxyethyl disulfide and isocyanate methyltrimethoxysilane are reacted for 2 hours at 80 ℃ according to the mol ratio of 1:2, so as to obtain the siloxane compound containing disulfide bonds. 0.15g of the silane coupling agent gamma-aminopropyl triethoxysilane KH550 was weighed, 4g of deionized water was added, and the pH was adjusted to approximately 3 with glacial acetic acid, allowing the silane coupling agent to hydrolyze well.
(3) To Al 2 O 3 Adding the 0.1g disulfide bond siloxane compound and KH550 hydrolysate into the dispersion, stirring at constant temperature of 80 ℃ for 6 hours, centrifuging after the reaction is finished, washing with absolute ethyl alcohol for 4 times, drying in an oven at 80 ℃ for 24 hours, and grinding for later use.
Cetyl polysiliconeAlkane modified SiO 2 For self-making, the preparation method is as follows:
(1) Hexadecyltrimethoxysilane (HDTMS), tetraethoxysilane (TEOS) and SiO 2 Particle (Anhuixin Crystal material, high purity spherical SiO) 2 1-3 micron specification) is prepared by HCl catalytic reaction, and SiO is formed after 24 hours of reaction at 80 DEG C 2 Modifying the suspension.
(2) SiO is made of 2 The modified suspension is centrifugally separated, washed by absolute ethyl alcohol for 4 times, dried in an oven at 80 ℃ for 24 hours and ground for standby.
The product name of the hydroxy acrylic resin is the chemical hypomer fs-2820.
Unsaturated polyester resin, the manufacturer is Changxing chemical and the model is ETERSET 2736.
The hydrogenated bisphenol A type epoxy resin is prepared by complexing a new material in Shanghai, and the model is EP-4080E.
Vinyl-terminated dimethyl (siloxane and polysiloxane) is prepared by the manufacturer of Shanghai drum ministerial biotechnology.
Hexamethylene diisocyanate trimer, manufactured by Kogyo under the model Desmodur N3300.
Example 1
1) The anti-fouling coating liquid comprises the following components in percentage by mass:
the preparation method comprises the following steps: mixing the above materials uniformly.
2) The bonding coating comprises the following components in percentage by mass:
main resin 50%: 30% of hydroxy acrylic resin, 10% of unsaturated polyester resin and 10% of hydrogenated bisphenol A epoxy resin;
the preparation method comprises the following steps: mixing the above materials uniformly.
3) The weather-resistant coating comprises the following components in percentage by mass:
main resin 50%: 30% of hydroxy acrylic resin, 10% of unsaturated polyester resin and 10% of hydrogenated bisphenol A epoxy resin;
and (3) filling: siO (SiO) 2 5% of extinction powder;
curing agent: hexamethylene diisocyanate trimer 5%;
solvent: 5% of dimethylbenzene,
25% of propylene glycol methyl ether acetate;
ultraviolet auxiliary agent: 3% of 2-hydroxy-4-n-octoxybenzophenone,
2% of bis (1, 2, 6-pentamethyl-4-piperidinyl) -sebacate;
other auxiliaries: the dispersant is BYK-P-104s 2%;
the leveling agent is BYK358N 2%;
dioctyltin dilaurate 1%.
The preparation method comprises the following steps: mixing the above materials uniformly.
The preparation method of the transparent backboard comprises the following steps:
first, a bond coat is prepared
The inner surface of 275 mu m support substrate polyethylene terephthalate (PET) is coated with a bonding coating liquid by adopting corona treatment, and the bonding coating is formed after curing for 5min at 170 ℃ and has the thickness of 12 mu m.
Second step, preparing weather-proof coating
The outer surface of the PET supporting substrate is subjected to corona treatment, a weather-proof coating liquid is coated, and the weather-proof coating is formed after curing for 5min at 150 ℃ and has the thickness of 10 mu m.
Third step, preparing the anti-fouling coating
And (3) coating an anti-fouling coating liquid on the surface of the weather-resistant coating, curing the anti-fouling coating for 120s under a UV lamp with the wavelength of 365nm, and preparing the transparent backboard by the dry thickness of the anti-fouling coating of 1 mu m, wherein the structural schematic diagram is shown in figure 1.
Example 2
1) The anti-fouling coating liquid comprises the following components in percentage by mass:
2) The bonding coating comprises the following components in percentage by mass:
3) The weather-resistant coating comprises the following components in percentage by mass:
main resin 60%: 30% of a hydroxy acrylic resin; 20% of unsaturated polyester resin; 10% of hydrogenated bisphenol A epoxy resin;
and (3) filling: siO (SiO) 2 3% of extinction powder;
curing agent: hexamethylene diisocyanate trimer 2%;
solvent: xylene 5% and propylene glycol methyl ether acetate 20%;
ultraviolet auxiliary agent: 3% of ultraviolet absorber 2-hydroxy-4-n-octoxybenzophenone,
2% of hindered amine light stabilizer bis (1, 2, 6-pentamethyl-4-piperidinyl) -sebacate;
other auxiliaries: the leveling agent is BYK358N 4 percent,
Dioctyltin dilaurate 1%.
The preparation method of the transparent backboard comprises the following steps:
first, preparing a bonding coating:
and (3) carrying out corona treatment on the inner surface of the PET supporting substrate with the thickness of 300 mu m, coating the bonding coating liquid, and curing at 150 ℃ for 5min to form a bonding coating with the thickness of 15 mu m.
Second step, preparing weather-proof coating
The outer surface of the PET supporting substrate is subjected to corona treatment, a weather-proof coating liquid is coated, and the weather-proof coating is formed after curing for 5min at 150 ℃ and has the thickness of 20 mu m.
Third step, preparing the anti-fouling coating
And (3) coating an anti-fouling coating liquid on the surface of the weather-resistant coating, curing the anti-fouling coating for 120 seconds under a UV lamp with the wavelength of 365nm, and preparing the transparent backboard by the dry thickness of the anti-fouling coating being 3 mu m.
Example 3
1) The anti-fouling coating liquid comprises the following components in percentage by mass:
2) The bonding coating comprises the following components in percentage by mass:
main resin 55%: 30% of hydroxy acrylic resin, 15% of unsaturated polyester resin and 10% of hydrogenated bisphenol A epoxy resin;
3) The weather-resistant coating comprises the following components in percentage by mass:
main resin 40%: 20% of a hydroxy acrylic resin; 10% of unsaturated polyester resin; 10% of hydrogenated bisphenol A epoxy resin;
and (3) filling: siO (SiO) 2 3% of extinction powder;
curing agent: hexamethylene diisocyanate trimer 2%;
solvent: xylene 5% and propylene glycol methyl ether acetate 45%;
ultraviolet auxiliary agent: 3% of ultraviolet absorber 2-hydroxy-4-n-octoxybenzophenone,
2% of hindered amine light stabilizer bis (1, 2, 6-pentamethyl-4-piperidinyl) -sebacate;
other auxiliaries: the dispersant is BYK-P-104s 2%; the leveling agent is BYK358N 2% and dioctyltin dilaurate 1%.
The preparation method of the transparent backboard comprises the following steps:
first, preparing a bonding coating:
and (3) carrying out corona treatment on the inner surface of the PET supporting substrate with the thickness of 300 mu m, coating the bonding coating liquid, and curing at 150 ℃ for 5min to form a bonding coating with the thickness of 10 mu m.
Second step, preparing weather-proof coating
The outer surface of the PET supporting substrate is subjected to corona treatment, a weather-proof coating liquid is coated, and the weather-proof coating is formed after curing for 3min at 160 ℃, wherein the thickness of the weather-proof coating is 15 mu m.
Third step, preparing the anti-fouling coating
And (3) coating an anti-fouling coating liquid on the surface of the weather-resistant coating, curing the anti-fouling coating for 120 seconds under a UV lamp with the wavelength of 365nm, wherein the dry thickness of the anti-fouling coating is 4 mu m, and thus, the transparent backboard is prepared.
Comparative example 1
The comparative example differs from example 1 in the composition and mass percent of the anti-coating liquid, specifically:
the remainder remained the same as in example 1.
Comparative example 2
The comparative example differs from example 1 in the composition and mass percent of the anti-fouling coating liquid, specifically:
the remainder remained the same as in example 1.
Comparative example 3
The comparative example differs from example 1 in the composition and mass percent of the bond coat, specifically:
main resin 50%: 30% of hydroxy acrylic resin and 20% of unsaturated polyester resin;
the remainder remained the same as in example 1.
Comparative example 4
The comparative example differs from example 1 in the composition and mass percent of the weatherable coating, specifically:
main resin: 50% of a hydroxy acrylic resin;
and (3) filling: 5%;
curing agent: hexamethylene diisocyanate trimer 5%;
solvent: xylene 5% and propylene glycol methyl ether acetate 25%;
ultraviolet auxiliary agent: 3% of ultraviolet absorber 2-hydroxy-4-n-octoxybenzophenone,
2% of hindered amine light stabilizer bis (1, 2, 6-pentamethyl-4-piperidinyl) -sebacate;
other auxiliaries: the dispersant is BYK-P-104s 2%; the leveling agent is BYK358N 2% and dioctyltin dilaurate 1%. The remainder remained the same as in example 1.
Experiment one the following assays were performed using photovoltaic back sheets prepared in examples 1-3 and comparative examples 1-4.
Outer coating hydrophobicity: the contact angle of the anti-fouling coating was tested with reference to standard GBT 30693-2014.
Adhesion of the anti-fouling coating: the measurements were carried out according to the cross-hatch test method of GB/T928-1998 color paint and varnish paint films.
Light transmittance of the anti-fouling coating: the anti-fouling coating was tested for total light transmittance (abbreviated as transmittance or light transmittance) according to the standard of JISK7105-1981 test method for optical Properties of plastics.
Sand falling test: the anti-sand dropping property of the outer coating is tested according to the standard of GB/T31034-2014 insulating back plate for crystalline silicon solar cell module.
QUV aging: according to the standard of GB/T31034-2014 insulating backboard for crystalline silicon solar cell module, an ultraviolet aging lamp is used for treatment, the accumulated ultraviolet energy reaches 240 kwh/square meter, and a sample is taken out to observe the appearance yellowing value delta b of the transparent backboard.
And (3) wet heat aging treatment: according to the standard of GB/T31034-2014 insulating backboard for crystalline silicon solar cell module, the temperature and humidity of a high-temperature high-humidity box body are set to be 85 ℃, the humidity is 85%, the accumulation time is 2000 hours, and a sample is taken out to test the hydrophobicity and the light transmittance of the anti-fouling coating.
The results of the above performance tests are shown in table 1 below:
table 1 back panel performance test data
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The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (5)

1. The long-acting self-cleaning transparent backboard is characterized in that the backboard is sequentially provided with an anti-fouling coating, a weather-resistant coating, a supporting substrate and a bonding coating from bottom to top, wherein the raw materials of the anti-fouling coating comprise main resin, anti-fouling filler, a photoinitiator, an organic solvent, a silane coupling agent and an auxiliary agent; wherein the anti-fouling filler comprises disulfide bond compound modified Al with the mass ratio of 1:5-5:1 2 O 3 And hexadecylpolysiloxane modified SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The disulfide bond compound modifies Al 2 O 3 The particle size of the particles is 30-50nm;
the main resin comprises polyurethane acrylic resin containing disulfide bonds and organosilicon modified polyurethane acrylic ester in a mass ratio of 1:3-3:1;
the hexadecyl polysiloxane modified SiO 2 The preparation method of (C) comprises the steps of preparing hexadecyltrimethoxysilane, tetraethoxysilane and SiO 2 The catalyst is obtained through HCl catalytic reaction;
the raw materials of the anti-fouling coating comprise the following components in percentage by weight: 30-50% of main resin, 5-10% of anti-fouling filler, 1-5% of photoinitiator, 30-60% of organic solvent, 1-5% of silane coupling agent and 1-8% of auxiliary agent;
the weather-resistant coating comprises the following raw materials in parts by weight: 30-60 parts of main resin, 1-20 parts of filler, 1-20 parts of curing agent, 20-60 parts of solvent, 0.1-5 parts of ultraviolet auxiliary agent and 0.5-10 parts of other auxiliary agents, wherein the main resin is compounded by acrylic resin, polyester resin and epoxy resin;
the bonding coating comprises the following components: 40-60 parts of main resin, 20-40 parts of solvent, 1-5 parts of curing agent, 1-5 parts of modifying auxiliary agent, 0.5-5 parts of down-conversion material, 1-5 parts of extinction powder and 0.5-5 parts of light stabilizer; the main body resin is a mixture of hydroxy acrylic resin, unsaturated polyester resin and hydrogenated bisphenol A epoxy resin.
2. The transparent back sheet according to claim 1, wherein the preparation method of the disulfide bond-containing urethane acrylic resin comprises mixing an aromatic urethane acrylate oligomer and 4,4' -diaminodiphenyl disulfide, and reacting at 70-90 ℃ for 2-4 hours under nitrogen atmosphere to obtain the transparent back sheet.
3. The transparent backsheet according to claim 1, wherein the disulfide bond containing compound modified Al 2 O 3 The preparation method comprises the steps of reacting 2-hydroxyethyl disulfide with isocyanate methyltrimethoxysilane to prepare a siloxane compound containing disulfide bonds; then Al is added 2 O 3 Adding a disulfide bond-containing siloxane compound and a silane coupling agent KH550 hydrolysate into the dispersion liquid, and reacting to obtain the final product.
4. The long-acting self-cleaning transparent backsheet according to claim 1, wherein the modifying aid is vinyl-terminated dimethyl (siloxane and polysiloxane); the down-conversion material is Ca 2 V 2 O 7 :7％Yb 3+ Or CYP 15% Ce 3+ 。
5. A method of making a long-lasting, self-cleaning transparent backsheet according to any one of claims 1-4, comprising the steps of:
(1) Corona treatment is carried out on the inner surface of the supporting substrate, coating liquid prepared from raw materials of the bonding coating is coated, the transparent coating is obtained after curing for 0.5 to 5 minutes in a drying tunnel at the temperature of 100 to 200 ℃, and the bonding coating is formed after curing, wherein the thickness of the bonding coating is 6 to 15 mu m;
(2) Carrying out corona treatment on the outer surface of a supporting substrate, coating a coating liquid prepared from weather-proof coating raw materials, and curing in a drying tunnel at 100-200 ℃ for 0.5-5min to obtain a transparent coating, wherein the thickness of the weather-proof coating is 10-20 mu m;
(3) And (3) spraying a coating liquid prepared from the anti-fouling coating raw material on the surface of the weather-resistant coating, and forming an anti-fouling coating after ultraviolet curing, wherein the thickness is 0.5-3 mu m, thus completing the preparation of the anti-fouling transparent backboard.
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CN116179046A (en) * 2022-12-27 2023-05-30 浙江中聚材料有限公司 Weather-resistant coating material applied to photovoltaic backboard and preparation process thereof

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CN115505325A (en) * 2022-03-22 2022-12-23 武汉中科先进材料科技有限公司 Self-repairing self-cleaning dual-curing coating for photovoltaic glass and preparation method thereof
CN114773512A (en) * 2022-06-21 2022-07-22 苏州易昇光学材料有限公司 High-wear-resistance fluorocarbon resin and coating for solar backboard using same
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