CN114806366A - Preparation method of transparent coating semi-finished product, wear-resistant photovoltaic transparent back plate with low water permeability - Google Patents
Preparation method of transparent coating semi-finished product, wear-resistant photovoltaic transparent back plate with low water permeability Download PDFInfo
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- CN114806366A CN114806366A CN202210313661.4A CN202210313661A CN114806366A CN 114806366 A CN114806366 A CN 114806366A CN 202210313661 A CN202210313661 A CN 202210313661A CN 114806366 A CN114806366 A CN 114806366A
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- wax powder
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- 230000035699 permeability Effects 0.000 title abstract description 6
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- 239000003795 chemical substances by application Substances 0.000 claims abstract description 53
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
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- 239000008199 coating composition Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- -1 phosphate ester Chemical class 0.000 description 4
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- ODJQKYXPKWQWNK-UHFFFAOYSA-L 3-(2-carboxylatoethylsulfanyl)propanoate Chemical compound [O-]C(=O)CCSCCC([O-])=O ODJQKYXPKWQWNK-UHFFFAOYSA-L 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 3
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- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
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- 238000005979 thermal decomposition reaction Methods 0.000 description 2
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- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
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- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
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- 239000002313 adhesive film Substances 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- 238000011056 performance test Methods 0.000 description 1
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- 239000002985 plastic film Substances 0.000 description 1
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- 239000011148 porous material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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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
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- 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
- C09D7/63—Additives non-macromolecular organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- 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
- H01L31/04—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 adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
- H01L31/049—Protective back sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention belongs to the technical field of photovoltaic back plates, and particularly relates to a preparation method of a transparent paint semi-finished product, a wear-resistant photovoltaic transparent back plate with low water permeability. The preparation method of the transparent paint semi-finished product comprises the following steps: preparing dispersion slurry, namely uniformly dispersing a solvent, a dispersing agent, modified wax powder and an inorganic UV (ultraviolet) auxiliary agent; wherein the drop melting point of the modified wax powder is 155-175 ℃, and the drop melting temperature is kept for 5-20 seconds; mixing and dispersing main body resin, a flatting agent, an adhesion promoter, an antioxidant and an organic UV (ultraviolet) auxiliary agent; adding the dispersion slurry and dispersing at high speed to form a semi-finished product of the coating. According to the photovoltaic transparent back plate, the structure and material cost are not increased, and the wear resistance and the water vapor transmittance of the composite back plate are achieved through the characteristic of hot melting and film forming of the modified wax powder; meanwhile, the weather resistance of the glass is not reduced through the formula design.
Description
The application is a divisional application with the name of 'outer layer transparent coating, photovoltaic transparent back plate and preparation method thereof' of application No. 2020116047361, filed 2020, 12 months and 30 days.
Technical Field
The invention belongs to the technical field of photovoltaic back plates, and particularly relates to an outer layer transparent coating, a photovoltaic transparent back plate and a preparation method thereof.
Background
The photovoltaic back plate is applied to the double-sided assembly, double-sided power generation can be achieved, and the photovoltaic back plate is a great trend of future assembly development. The conventional photovoltaic transparent back plate mainly has five structures of FPF, KPF, TPF, TPT and KPK, wherein F is a transparent fluorine coating, P is a transparent PET base film, T is a Tedlar transparent fluorine film of DuPont, and K is a PVDF transparent fluorine film. According to different requirements of customers, backboard manufacturers can provide backboards with different structures. For the selection of these five structures, the customer, in addition to the requirement of weather resistance, also puts requirements on the abrasion resistance of the outer layer (air surface) and the water vapor permeability of the back sheet. A backsheet containing T, K as the outer layer structure would be better than a F-structured fluorine coated backsheet in terms of abrasion resistance and moisture vapor transmission. However, the T, K layers of the back sheet have more adhesive layers, which increases the material cost of the back sheet; and the fluorine coating structure of FPF has lower material cost.
Disclosure of Invention
The invention provides an outer layer transparent coating, a photovoltaic transparent back plate and a preparation method thereof.
In order to solve the technical problems, the invention provides a coating which comprises the following raw materials in parts by mass: 73-100 parts of main body resin; 0.3-0.5 part of leveling agent; 4-8 parts of an adhesion promoter; 1-10 parts of modified wax powder; 0.15-0.30 part of dispersant; 0.15-0.60 part of antioxidant; 3-8 parts of an organic UV (ultraviolet) auxiliary agent; 0.1-0.5 part of inorganic UV auxiliary agent; 5-10 parts of a polyisocyanate curing agent; and 15-30 parts of a solvent.
Further, the host resin includes: one or more of FEVE fluororesin, polyester resin and hydroxy acrylic resin; the polyisocyanate curing agent comprises one or more of HDI tripolymer, H6XDI addition product and XDI addition product.
Further, the leveling agent comprises one or more of an acrylic leveling agent and an organic silicon leveling agent; the adhesion promoter comprises one or more of modified polyester resin, modified hydroxyl polyether resin, epoxy phosphate and coupling agent.
Further, the modified wax powder comprises one or more of modified PE wax powder, modified PP wax powder, modified PTFE wax powder, modified polyamide wax powder and a mixture thereof; the dispersant comprises one or more of a macromolecular type hyperdispersant, a controlled free radical type hyperdispersant, an anionic dispersant, a cationic dispersant and an electric neutral dispersant.
Further, the organic UV auxiliary agent comprises one or more of salicylic acid esters, benzophenones, benzotriazoles, substituted acrylonitrile and triazines; the inorganic UV auxiliary agent is one or a combination of more of nano zinc oxide and nano titanium dioxide.
Further, the antioxidant comprises one or more of hindered amine, hindered phenol, phosphite ester, thiodipropionate and mercaptan; the solvent is one or a combination of butyl acetate, xylene, ethyl acetate and propylene glycol methyl ether acetate.
In a second aspect, the present invention also provides a method for preparing a coating, comprising: preparing dispersion slurry, namely uniformly dispersing a solvent, a dispersing agent, modified wax powder and an inorganic UV (ultraviolet) auxiliary agent; mixing and dispersing main body resin, a flatting agent, an accelerating agent, an antioxidant and an organic UV (ultraviolet) auxiliary agent; adding the dispersion slurry and dispersing at a high speed to form a semi-finished paint product; adding a polyisocyanate curing agent into the paint semi-finished product; and stirring uniformly and adjusting viscosity to obtain the outer layer coating.
In a third aspect, the present invention also provides a photovoltaic backsheet comprising: the coating comprises a base material, an inner coating positioned on the surface of the base material and an outer coating positioned on the other surface of the base material.
Further, the coating is suitable for being formed by coating with the paint as described above; the main body resin and the polyisocyanate curing agent are heated, crosslinked and cured to form a net structure; and stable chemical bonds are formed among the adhesion promoter, the base material and the curing agent.
In a fourth aspect, the present invention also provides a method for preparing a photovoltaic back sheet, including: carrying out corona treatment on the uncoated surface of the base material; coating the surface of the uncoated side of the substrate with the coating as described above; baking; and coating corona treatment; wherein the baking temperature is matched with the boiling point of the solvent and the drop melting point of the modified wax powder.
The outer layer transparent coating, the photovoltaic transparent back plate and the preparation method thereof have the beneficial effects that under the condition that the structure and material cost are not increased, the wear resistance and the water vapor transmittance of the composite back plate are achieved through the characteristic of hot melting and film forming of the modified wax powder; meanwhile, the weather resistance of the coating is not reduced through the formula design.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
In order to make the aforementioned and other objects, features and advantages of the present invention comprehensible, preferred embodiments accompanied with figures are described in detail below.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a flow chart of a process for preparing the coating of the present invention;
fig. 2 is a schematic structural view of a photovoltaic transparent backsheet of the present invention;
fig. 3 is a process flow diagram for the preparation of a photovoltaic transparent backsheet of the present invention;
FIG. 4a is a schematic structural view of an FPF photovoltaic backsheet;
fig. 4b is a schematic structural diagram of a KPF photovoltaic backsheet;
fig. 4c is a schematic structural view of a TPF photovoltaic backsheet;
fig. 4d is a schematic structural view of a TPT photovoltaic backsheet;
fig. 4e is a schematic structural diagram of a KPK photovoltaic backsheet;
in the figure: the base material 10, P is a transparent PET base film 11, an outer layer coating 20, F is a transparent fluorine coating 21, T is a Tedlar transparent fluorine film 22 of DuPont, K is a PVDF transparent fluorine film 23, and an inner layer coating 30.
Detailed Description
To make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is apparent that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first part
The invention provides a coating (namely an outer layer transparent coating in the scheme), which comprises the following raw materials in parts by mass: 73-100 parts of main body resin; 0.3-0.5 part of leveling agent; 4-8 parts of an adhesion promoter; 1-10 parts of modified wax powder; 0.15-0.30 part of dispersant; 0.15-0.60 part of antioxidant; 3-8 parts of an organic UV (ultraviolet) auxiliary agent; 0.1-0.5 part of inorganic UV auxiliary agent; 5-10 parts of a polyisocyanate curing agent; and 15-30 parts of a solvent.
Optionally, the coating comprises the following raw materials in parts by weight: 85 parts of main resin; 0.4 part of a leveling agent; 5 parts of an adhesion promoter; 6 parts of modified wax powder; 0.2 part of a dispersant; 0.4 part of antioxidant; 5 parts of an organic UV (ultraviolet) auxiliary agent; 0.3 part of inorganic UV auxiliary agent; 8 parts of a polyisocyanate curing agent; and 20 parts of a solvent. In the scheme, the content units of the raw materials of the coating are parts by mass if no special description is provided.
Optionally, the host resin comprises: FEVE fluororesin, polyester resin and hydroxy acrylic resin. The main resin is the main film forming matter of the paint, is the continuous phase in the coating, can be cross-linked with the curing agent to form a network structure, and plays a main role in the physical and chemical properties of the coating. The reaction formula of the crosslinking reaction is
R-OH is main resin, and R' -NCO is curing agent.
Optionally, the polyisocyanate curing agent comprises one or more of HDI trimer, H6XDI adduct and XDI adduct. The polyisocyanate curing agent can react with OH of each component (such as main resin and adhesion promoter) in the coating due to NCO group, so that the coating is heated, crosslinked and cured to form a network structure.
Optionally, the leveling agent comprises one or more of an acrylic leveling agent and an organic silicon leveling agent. The leveling agent can influence the surface tension of a paint film, promote the paint to form a flat and uniform coating in the drying process, improve the permeability of the paint to a base material, and reduce appearance defects such as spots, marks and the like generated in the process of painting.
Optionally, the adhesion promoter includes one or more of modified polyester resin, modified hydroxy polyether resin, epoxy phosphate ester, and coupling agent. The adhesion promoter is PET adhesion promoter, and can form stable chemical bond with PET base material, so that the paint film can resist hot and humid erosion and is not easy to separate from the base material. Polar bonds such as hydroxyl, carboxyl, ketone, ether, carbonate and ester are formed on the PET base material after corona treatment, and Van der Waals force or chemical bonds are easily formed between epoxy, hydroxyl, ester, ether and the like in the adhesion promoter and the PET surface. Such as one of the reaction formulas
Optionally, the modified wax powder includes one or more of modified PE wax powder, modified PP wax powder, modified PTFE wax powder, modified polyamide wax powder, and mixtures thereof. The modified wax powder is added into the coating, and can be subjected to hot melting film forming under a specific temperature process (namely the temperature corresponding to the melting point of the modified wax powder, the melting point of the modified wax powder used in the invention is at a high temperature section, namely 155-175 ℃, and the melting temperature is kept for 5-20 seconds), so that the coating has a very low friction coefficient, the wear resistance of the coating is improved, and the water vapor barrier property of the coating is improved due to the film forming characteristic.
Optionally, the dispersant comprises one or more of a polymeric hyperdispersant, a controlled radical hyperdispersant, an anionic dispersant, a cationic dispersant and an electric neutral dispersant. One end of the active group of the dispersing agent can be adsorbed on the surface of the pigment and filler (such as modified wax powder and inorganic UV auxiliary agent) which are crushed into fine particles, and the other end is solvated to form an adsorption layer, so that charge repulsion is generated between the pigment and filler, and pigment and filler particles are dispersed and suspended in the coating for a long time to avoid re-flocculation, thereby ensuring the storage stability of the prepared coating system.
Optionally, the organic UV auxiliary agent includes one or more of salicylic acid esters, benzophenones, benzotriazoles, substituted acrylonitriles, triazines. The organic UV auxiliary agent can absorb ultraviolet rays, stabilize generated radicals (also referred to as "radicals" in chemistry, which means atoms or groups with unpaired electrons formed by the homogeneous cleavage of covalent bonds of molecules of a compound under external conditions such as photo-thermal conditions, etc., and the structure of the radicals is generally abbreviated as R.), and prevent organic components (such as host resin, modified wax powder, etc.) in the coating from being damaged and degraded by ultraviolet rays. Optionally, the inorganic UV auxiliary agent is one or a combination of more of nano zinc oxide and nano titanium dioxide. The inorganic UV auxiliary agent can shield ultraviolet rays, the size between nano particles is equal to or smaller than that of light waves, and the light absorption is obviously enhanced due to the size effect which causes the interval between a conduction band and a valence band to be increased.
Optionally, the antioxidant comprises one or more of hindered amine, hindered phenol, phosphite ester, thiodipropionate and mercaptan. The antioxidant can delay or inhibit the polymer formed by crosslinking and curing of the coating from proceeding through a thermal decomposition process, thereby preventing the aging of the polymer and prolonging the service life of the polymer.
Optionally, the solvent is one or a combination of butyl acetate, xylene, ethyl acetate and propylene glycol methyl ether acetate. The solvent can well dissolve the organic reactant to form a homogeneous system, so that the reaction is smoothly carried out.
Further, referring to fig. 1, the present invention also provides a preparation method of the coating, including: preparing dispersion slurry, namely uniformly dispersing the solvent, the dispersant, the modified wax powder and the inorganic UV auxiliary agent; mixing and dispersing main body resin, a flatting agent, an accelerating agent, an antioxidant and an organic UV (ultraviolet) auxiliary agent; adding the dispersion slurry and dispersing at a high speed to form a semi-finished paint product; adding a polyisocyanate curing agent into the paint semi-finished product; and uniformly stirring and adjusting viscosity to obtain the outer layer transparent coating.
Specifically, the preparation method of the coating comprises the following steps:
(1) preparing dispersion slurry: mixing and uniformly stirring a solvent and a dispersant, and sequentially adding a small amount of modified wax powder and an inorganic UV (ultraviolet) auxiliary agent for multiple times; in the process of adding the powder, the rotating speed of the stirrer is increased to 1500-2000 rpm and kept for 20-30min, so that the powder is uniformly dispersed.
(2) Preparing a semi-finished paint product: mixing and dispersing the main body resin, the leveling agent, the PET adhesion promoter, the antioxidant and the organic UV auxiliary agent at a high speed, adding the dispersion slurry prepared in the step (1), and dispersing at a high speed for 30-60min to obtain a semi-finished coating;
(3) and (3) coating finished product: and adding a polyisocyanate curing agent into the semi-finished paint, uniformly stirring and adjusting viscosity to obtain the paint.
Further, referring to fig. 2, the present invention also provides a photovoltaic back sheet (i.e., a photovoltaic transparent back sheet) comprising: a substrate 10, an inner coating 30 on one surface of the substrate 10, and an outer coating 20 on the other surface of the substrate.
Alternatively, the substrate may be, for example, but not limited to, a PET monocoat (i.e., PET monocoat is PET coated with an inner coating on the inside of the substrate, where the inner coating forms the inner coating 30). In this case, the inside of the substrate 11 is coated with an inner coating 30 to contact EVA, and the outside of the substrate 11 is coated with an outer coating 20 to contact air.
Further, the coating is suitable for being formed by coating with the paint as described above; the main body resin and the polyisocyanate curing agent are heated, crosslinked and cured to form a net structure; and stable chemical bonds are formed among the accelerator, the base material and the curing agent.
Further, referring to fig. 3, the invention also provides a preparation method of the photovoltaic back sheet, which comprises the following steps: carrying out corona treatment on the uncoated surface of the base material; coating an outer layer coating on the surface of the uncoated side of the substrate; baking at high temperature; performing corona treatment on the coating to obtain a photovoltaic transparent back panel FPF; the baking temperature is matched with the boiling point of the solvent and the drop melting point of the modified wax powder, namely the baking temperature needs to reach the drop melting point of the modified wax powder on the premise of realizing solvent volatilization, so that the wax powder is hot-melted into a film. Solvents of different boiling points are selected according to the baking temperature to ensure that the coating is not sticky, has sufficient cross-linking curing and the temperature and time for hot-melting the wax powder into a film.
Optionally, referring to fig. 3, according to the film thickness requirement, coating the coating on the surface of the uncoated surface of the corona-treated PET single-coated product, baking the coating in a low-medium-high temperature section oven to complete curing and film-forming of the coating, and performing corona treatment to obtain the photovoltaic transparent back plate.
The second part
Example 1
(1) Preparing dispersion slurry: mixing 10 parts of butyl acetate, 10 parts of ethyl acetate and 0.2 part of macromolecular hyper-dispersant, uniformly stirring, and sequentially adding 5 parts of modified PP wax powder and 0.2 part of nano zinc oxide for a plurality of times in small amount; in the adding process, the rotating speed of the stirrer is increased to 2000 revolutions per minute and kept for 30 minutes, and the dispersion is uniform.
(2) Preparing a semi-finished paint product: 88 parts of FEVE fluororesin (Dajin GK570), 0.3 part of organic silicon flatting agent, 2 parts of modified polyester resin, 3 parts of epoxy resin, 0.3 part of hindered phenol antioxidant, 4 parts of benzotriazole and 1 part of salicylate are mixed and dispersed at high speed, then the dispersion slurry prepared in the step (1) is added, and the high-speed dispersion is carried out for 30min, thus obtaining the semi-finished product of the coating.
(3) And (3) coating finished product: adding 8 parts of HDI curing agent (Corsichun N3300) into the semi-finished paint product, and uniformly stirring and adjusting viscosity to obtain the finished paint product.
(4) Coating the finished coating on the surface of the PET single-coated product subjected to corona treatment, baking the PET single-coated product through a low-temperature section, medium-temperature section and high-temperature section baking oven to finish curing and film forming of the coating, and carrying out corona treatment to obtain the photovoltaic transparent back plate.
Example 2
(1) Preparing dispersion slurry: mixing 11 parts of propylene glycol methyl ether acetate, 11 parts of ethyl acetate and 0.3 part of high-molecular type hyper-dispersant, uniformly stirring, and sequentially adding 5 parts of modified PP wax powder, 2 parts of modified PTFE wax powder, 0.1 part of nano zinc oxide and 0.05 part of nano titanium dioxide for a few times; and in the adding process, the rotating speed of the stirrer is increased to 2000 revolutions per minute and is kept for 30 minutes, and the dispersion is uniform.
(2) Preparing a semi-finished paint product: 96 parts of FEVE fluororesin (Changxing 41011), 0.4 part of acrylic acid leveling agent, 4.8 parts of epoxy resin, 0.2 part of coupling agent, 0.3 part of hindered phenol antioxidant, 4 parts of benzotriazole and 1 part of salicylate are mixed and dispersed at high speed, then the dispersion slurry prepared in the step (1) is added, and the high-speed dispersion is carried out for 30min, thus obtaining a semi-finished product of the coating;
(3) and (3) coating finished product: 8.2 parts of HDI curing agent (Corsichun N3300) is added into the semi-finished paint product, and the paint product is obtained after uniform stirring and viscosity adjustment.
(4) Coating the finished coating on the surface of the PET single-coated product subjected to corona treatment, baking the PET single-coated product through a low-temperature section, medium-temperature section and high-temperature section baking oven to finish curing and film forming of the coating, and carrying out corona treatment to obtain the photovoltaic transparent back plate.
Example 3
(1) Preparing dispersion slurry: 26 parts of butyl acetate and 0.25 part of macromolecular hyper-dispersant are mixed and stirred uniformly, and 5 parts of modified PE/PP wax powder and 0.2 part of nano zinc oxide are sequentially added for a plurality of times in small amount; in the adding process, the rotating speed of the stirrer is increased to 2000 rpm and kept for 20min, so that the dispersion is uniform.
(2) Preparing a semi-finished paint product: 69 parts of FEVE fluororesin (Dajin GK570), 23 parts of hydroxy acrylic resin, 0.35 part of acrylic flatting agent, 5 parts of PET adhesion promoter epoxy resin, 0.3 part of phosphate, 0.4 part of hindered phenol antioxidant, 2.5 parts of benzotriazole and 2.5 parts of triazine are mixed and dispersed at high speed, then the dispersion slurry prepared in the step (1) is added, and the high-speed dispersion is carried out for 40min, thus obtaining the semi-finished product of the coating.
(3) And (3) coating finished product: 9.4 parts of HDI curing agent (Corsichun N3300) is added into the semi-finished paint product, and the paint is obtained after uniform stirring and viscosity adjustment.
(4) Coating the finished coating on the surface of the PET single-coated product subjected to corona treatment, baking the PET single-coated product through a low-temperature section, medium-temperature section and high-temperature section baking oven to finish curing and film forming of the coating, and carrying out corona treatment to obtain the photovoltaic transparent back plate.
Example 4
(1) Preparing dispersion slurry: mixing 15 parts of propylene glycol methyl ether acetate and 0.3 part of an electrically neutral dispersant, uniformly stirring, and sequentially adding 10 parts of modified PTFE wax powder and 0.5 part of nano zinc oxide for a few times; in the adding process, the rotating speed of the stirrer is increased to 1800 rpm and kept for 20min, so that the dispersion is uniform.
(2) Preparing a semi-finished paint product: and (3) mixing 73 parts of polyester resin, 0.3 part of acrylic acid leveling agent, 4 parts of epoxy phosphate, 0.15 part of phosphite ester and 3 parts of benzophenone, dispersing at a high speed, adding the dispersion slurry prepared in the step (1), and dispersing at a high speed for 30min to obtain a semi-finished product of the coating.
(3) And (3) coating finished product: and adding 5 parts of HDI tripolymer into the semi-finished paint, uniformly stirring and adjusting viscosity to obtain the paint.
(4) Coating the finished coating on the surface of the PET single-coated product subjected to corona treatment, baking the PET single-coated product through a low-temperature section, medium-temperature section and high-temperature section baking oven to finish curing and film forming of the coating, and carrying out corona treatment to obtain the photovoltaic transparent back plate.
Example 5
(1) Preparing dispersion slurry: 30 parts of dimethylbenzene and 0.15 part of anionic dispersant are mixed and stirred uniformly, and 5 parts of modified polyamide wax powder and 0.1 part of nano titanium dioxide are sequentially added for a plurality of times in small amount; in the process of adding the powder, the rotating speed of the stirrer is increased to 1500 revolutions per minute and kept for 30 minutes, so that the powder is uniformly dispersed.
(2) Preparing a semi-finished paint product: mixing and dispersing 100 parts of hydroxyl acrylic resin, 0.5 part of acrylic flatting agent, 8 parts of modified hydroxyl polyether resin, 0.6 part of thiodipropionate and 8 parts of benzophenone at a high speed, adding the dispersion slurry prepared in the step (1), and dispersing at a high speed for 60min to obtain a semi-finished paint product.
(3) And (3) coating finished product: and adding 10 parts of H6XDI addition product into the semi-finished paint product, uniformly stirring and adjusting viscosity to obtain the paint.
(4) Coating the finished coating on the surface of the PET single-coated product subjected to corona treatment, baking the PET single-coated product through a low-temperature section, medium-temperature section and high-temperature section baking oven to finish curing and film forming of the coating, and carrying out corona treatment to obtain the photovoltaic transparent back plate.
Third part
In this section, the photovoltaic transparent back sheet prepared in examples 1 to 3 and the existing back sheet (FPF back sheet, KPF back sheet) were subjected to performance testing, and the testing results are shown in table 4. Wherein the amounts of the components in the coating in the photovoltaic transparent back sheet in examples 1-3 are shown in tables 1-3, respectively.
(1) In example 1, paint formulation, stirring, coating and baking were carried out in the formulation ratios shown in table 1. The stirring speed is 2000 r/min, and the stirring time is 60 min; the highest temperature of the oven is 165 ℃, and the baking time is 2 min; the corona strength was 4.5 kW.
Table 1 coating composition of example 1
| Type (B) | Specific composition/ratio | Amount per part by mass |
| Resin of main body | FEVE fluororesin (Dajin GK570) | 88 |
| Leveling agent | Organic silicon leveling agent | 0.3 |
| PET adhesion promoter | Modified polyester resin: epoxy resin 2:3 | 5 |
| Modified wax powder | Modified PP wax powder | 5 |
| Dispersing agent | High molecular type super dispersant | 0.2 |
| Antioxidant agent | Hindered phenol antioxidant | 0.3 |
| Organic UV auxiliaries | Benzotriazoles: salicylic acid esters ═ 4:1 | 5 |
| Inorganic UV auxiliary agent | Nano zinc oxide | 0.2 |
| Polyisocyanate curing agent | HDI curing agent (Kesichuang N3300) | 8 |
| Solvent(s) | Butyl acetate: ethyl acetate ═ 1:1 | 20 |
(2) In example 2, coating preparation, stirring, coating and baking were carried out in the formulation ratios shown in table 2. The stirring speed is 2000 r/min, and the stirring time is 60 min; the highest temperature of the oven is 170 ℃, and the baking time is 1.5 min; the corona strength was 4.5 kW.
Table 2 coating composition of example 2
(3) In example 3, coating formulation, stirring, coating and baking were carried out in the formulation ratios shown in table 3. The stirring speed is 2000 r/min, and the stirring time is 60 min; the highest temperature of the oven is 160 ℃, and the baking time is 2 min; the corona strength was 4.5 kW.
Table 3 coating composition of example 3
| Type (B) | Specific composition/ratio | Amount per part by mass |
| Host resin | FEVE fluororesin (gold GK 570): hydroxyacrylic resin 69: 23 | 92 |
| Leveling agent | Acrylic acid leveling agent | 0.35 |
| PET adhesion promoter | Epoxy resin: phosphoric acid esters ═ 5:0.3 | 5.3 |
| Modified wax powder | Modified PE/PP wax powder | 5 |
| Dispersing agent | Macromolecular type hyperdispersant | 0.25 |
| Antioxidant agent | Hindered phenol antioxidant | 0.4 |
| Organic UV auxiliaries | Benzotriazoles: triazines 1:1 | 5 |
| Inorganic UV auxiliary agent | Nano zinc oxide | 0.2 |
| Polyisocyanate curing agent | HDI curing agent (Kesichuang N3300) | 9.4 |
| Solvent(s) | Acetic acid butyl ester | 26 |
(4) As can be seen from the test results table 4, the FPFs of examples 1, 2, and 3 have the same structure, but the wear resistance is much higher than that of the FPF coating type backplane, and the water vapor transmission rate is lower than that of the FPF backplane; compared with KPF type back plates, the wear resistance and the water vapor transmission rate are close to the results of KPF composite type back plates. Compared with an FPF (flexible printed circuit) coated back plate and a double-sided coating, the FPF coated back plate has the advantages that the wear resistance of the outer coating of the transparent back plate and the water vapor transmittance are improved by coating the coating on the outer side of a transparent PET (polyethylene terephthalate) single-coated product through the characteristic of baking and film forming of modified wax powder, and the improvement of the performance is realized by a glue composite film; the baking temperature of the double-sided coating type backboard is generally within the range of 90-170 ℃, the drop melting point of the modified wax powder used in the invention is in a high temperature section, namely 155-175 ℃, the front section of the baking oven is used for solvent volatilization, and the rear section is used for full curing and crosslinking and film forming of the modified wax powder; because the density of the modified wax powder is 0.80-0.95 g/cubic centimeter mostly and less than 1.0-2.0 g/cubic centimeter of the density of the main resin, when the baking temperature is higher than the drop melting point temperature, the modified wax powder tends to float upwards and form a film on the surface of the coating after hot melting.
Table 4 photovoltaic backsheet Performance test results
In summary, in the prior art solutions, as shown in fig. 4a to fig. 4e, the conventional photovoltaic transparent back sheet mainly has five structures, namely FPF, KPF, TPF, TPT, and KPK, and the inner side of the photovoltaic transparent back sheet contacts EVA, and contacts EVA to perform heating vacuum lamination packaging; one F-coat on the FPF is in contact with EVA and the other is on the outside, and there is an abrasion resistance requirement for the F-coat in contact with air, and air. The adhesive has four structures of KPF, TPF, TPT and KPK, and has better wear resistance and water vapor permeability due to the existence of fluorine film, but has complex structure and high cost. Wherein, referring to fig. 4a, the photovoltaic transparent back sheet of FPF structure comprises a transparent PET base film 11, transparent fluorine coatings 21 on both surfaces of the transparent PET base film 11; the two transparent fluorine coatings 21 are respectively bordered by the photovoltaic packaging adhesive film and outside air. Referring to fig. 4b, the photovoltaic transparent back plate with KPF structure comprises a transparent PET base film 11, a transparent fluorine coating 21 and a PVDF transparent fluorine film 23 respectively located on two surfaces of the transparent PET base film 11; the transparent fluorine coating 21 is bordered by an EVA surface, and the PVDF transparent fluorine film 23 is bordered by air. Referring to fig. 4c, the photovoltaic transparent back sheet of the TPF structure includes a transparent PET base film 11, transparent fluorine coatings 21 respectively disposed on two surfaces of the transparent PET base film 11, and Tedlar transparent fluorine films 22 of dupont; the transparent fluorine coating 21 borders the EVA face, and the Tedlar transparent fluorine film 22 of DuPont borders the air. Referring to fig. 4d, the photovoltaic transparent back plate with the KPK structure comprises a transparent PET base film 11, and PVDF transparent fluorine films 23 respectively located on two surfaces of the transparent PET base film 11; the PVDF transparent fluorine film 23 is respectively connected with the EVA surface and the air. Referring to fig. 4e, the photovoltaic transparent back sheet of the TPT structure includes a transparent PET base film 11, and dupont Tedlar transparent fluorine films 22 respectively disposed on both surfaces of the transparent PET base film 11; the Tedlar transparent fluorine film 22 of DuPont is respectively connected with the EVA surface and the air. The fluorine coating in the FPF structure is coated on the surface of PET and is baked at high temperature, a solvent can form a solvent volatilization channel on the surface of the coating, and once the coating is crosslinked, pores generated by volatilization exist permanently, so that the fluorine coating basically has no barrier to water vapor; in the aspect of abrasion resistance, the fluorine coating has a lower abrasion resistance because of limited urethane bonds formed by a crosslinking reaction and a crosslinking density and a molecule arrangement density which are lower than those of the fluorine film. The outer layer transparent coating, the photovoltaic transparent back plate and the preparation method thereof adopt FPF structures, the inner layer coating contacting EVA is coated on the inner side of the base material, the coating contacting air is coated on the outer side of the base material to form the outer layer coating, and the wax powder in the formula is hot-melted to form a film at the corresponding dripping temperature by changing the formula design of the coating; because the density of the modified wax powder is small, the modified wax powder has the tendency of floating upward after high-temperature hot melting, and a compact plastic film is easily formed on the surface of the outer coating; the modified wax powder has poor UV resistance, and a proper amount of organic UV absorbent, stabilizer, inorganic nano zinc oxide and titanium oxide are required to be added; the addition of the antioxidant is also necessary, so that the thermal decomposition of the modified wax powder and other materials is avoided, the wear resistance of the outer coating is improved, and the water vapor transmittance is reduced.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (7)
1. A preparation method of a transparent paint semi-finished product is characterized by comprising the following steps:
preparing dispersion slurry, namely uniformly dispersing a solvent, a dispersing agent, modified wax powder and an inorganic UV (ultraviolet) auxiliary agent; wherein
The drop melting point of the modified wax powder is 155-175 ℃, and the drop melting temperature is kept for 5-20 seconds;
mixing and dispersing main body resin, a flatting agent, an adhesion promoter, an antioxidant and an organic UV (ultraviolet) auxiliary agent;
adding the dispersion slurry and dispersing at high speed to form a semi-finished product of the coating.
2. A photovoltaic backsheet, comprising:
the coating comprises a base material, an inner coating positioned on the surface of the base material and an outer coating positioned on the other surface of the base material; wherein
The outer coating comprises the following raw materials in parts by mass:
73-100 parts of main body resin;
4-8 parts of an adhesion promoter;
1-10 parts of modified wax powder;
3-8 parts of an organic UV (ultraviolet) auxiliary agent;
5-10 parts of a polyisocyanate curing agent; and
15-30 parts of a solvent; wherein
The melting point of the modified wax powder is 155-175 ℃, and the melting temperature is kept for 5-20 seconds.
3. The photovoltaic backsheet according to claim 2,
the main body resin and the polyisocyanate curing agent are heated, crosslinked and cured to form a net structure.
4. The photovoltaic backsheet according to claim 2,
and stable chemical bonds are formed among the adhesion promoter, the base material and the curing agent.
5. A method for preparing a photovoltaic back sheet, comprising:
carrying out corona treatment on the uncoated surface of the substrate coated with the inner layer coating;
coating the surface of the uncoated surface of the substrate with a coating; the coating comprises 1-10 parts of modified wax powder; the drop melting point of the modified wax powder is 155-175 ℃, and the drop melting temperature is kept for 5-20 seconds;
baking; and
coating corona treatment; wherein
The baking temperature is matched with the boiling point of the solvent and the drop melting point of the modified wax powder.
6. The production method according to claim 5,
the coating further comprises: the coating comprises main resin, a flatting agent, an adhesion promoter, a dispersing agent, an antioxidant, an organic UV auxiliary agent, an inorganic UV auxiliary agent, a polyisocyanate curing agent and a solvent.
7. The method according to claim 5,
the modified wax powder comprises one or more of modified PE wax powder, modified PP wax powder, modified PTFE wax powder, modified polyamide wax powder and a mixture thereof; the dispersant comprises one or more of a macromolecular type hyperdispersant, a controlled free radical type hyperdispersant, an anionic dispersant, a cationic dispersant and an electric neutral dispersant.
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| DE102022120917A1 (en) | 2022-08-18 | 2024-02-29 | Hanwha Q Cells Gmbh | Back element, solar module and use of a dye |
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| CN113372771A (en) * | 2021-06-21 | 2021-09-10 | 常州回天新材料有限公司 | High-wear-resistance transparent coating for photovoltaic back plate and preparation method thereof |
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| CN116144227A (en) * | 2022-12-29 | 2023-05-23 | 苏州赛伍应用技术股份有限公司 | Non-fluorine weather-proof paint and application thereof |
| CN117247588B (en) * | 2023-11-02 | 2024-02-09 | 宁波长阳科技股份有限公司 | Coating composition for enhancing adhesive force of transparent polyimide film and application thereof |
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