CN105895722A - Polyvinylidene fluoride (PVDF) thin film for single-sided frosted and high-reflection solar backplate and preparation method of PVDF thin film - Google Patents

Polyvinylidene fluoride (PVDF) thin film for single-sided frosted and high-reflection solar backplate and preparation method of PVDF thin film Download PDF

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Publication number
CN105895722A
CN105895722A CN201610353453.1A CN201610353453A CN105895722A CN 105895722 A CN105895722 A CN 105895722A CN 201610353453 A CN201610353453 A CN 201610353453A CN 105895722 A CN105895722 A CN 105895722A
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layer
thin film
pvdf
solar energy
polyvinylidene fluoride
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CN105895722B (en
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唐超
李华
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Suzhou Gutai New Material Co Ltd
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Suzhou Golden Technology Material Co Ltd
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • 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
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/416—Reflective
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention belongs to the technical field of an optical film, in particular relates to a polyvinylidene fluoride (PVDF) thin film for a single-sided frosted and high-reflection solar backplate and a preparation method of the PVDF thin film. The PVDF thin film comprises an outer layer, an intermediate layer, an inner layer and a light reflection layer which are formed by melting extrusion and are sequentially combined from one side to the other side, the materials of the outer layer and the inner layer are polyvinylidene fluoride, one surface, far away from the intermediate layer, of the outer layer is a frosted surface, and the material of the light reflection layer is a crylic acid grafted polyvinylidene fluoride copolymer. The preparation method comprises the following steps of allowing the raw materials of the outer layer, the intermediate layer, the inner layer and the light reflection layer thin film to sequentially pass through an extruding machine, a multi-layer co-extrusion machine head, a cooling roller and a traction winding mechanism for combination and formation, wherein the cooling roller comprises a polishing roller and an embossing roller. In the technical scheme provided by the invention, the PVDF film layer is modified by introducing crylic acid graft, the problem of EVA bonding is solved, the reflective rate of a surface, close to EVA, of a backlight film is also improved, and the light utilization degree is improved.

Description

One side frosted height reflected solar energy backboard PVDF thin film and preparation method
Technical field
The invention belongs to blooming technical field, be specifically related to a kind of one side frosted height reflected solar energy backboard and use PVDF thin film and preparation method thereof.
Background technology
Solar panel is mainly made up of header board, solar battery sheet and backboard, and wherein header board is to have height The safety glass of light transmittance, solar battery sheet is by EVA (polyethylene-polyvinyl acetate copolymer) glued membrane Encapsulating, solar energy backboard is positioned at the back side of solar panel, and cell piece rises protection and supporting role, needs There is reliable insulating properties, water preventing ability, resistance to ag(e)ing.Solar energy backboard typically has three-decker, outward Layer protective layer needs have good environment resistant erosiveness and adhesive property preferable with internal layer, because of fluorine-containing thin The weatherability of film highlights, and therefore outer protective layer is generally PVF (polyvinyl fluoride), PVDF (poly-inclined difluoro Ethylene), PTFE (politef) and THV (tetrafluoroethene, hexafluoropropene and vinylidene fluoride poly- Compound), intermediate layer film needs have good insulating properties, is typically chosen in PET (polyester) thin film, Internal layer needs have good adhesive property, excellent uvioresistant ability and higher luminous reflectance with encapsulating EVA Rate；The selection of internal layer is generally fluoropolymer membrane or the big class of EVA film two, although EVA film relatively fluoropolymer membrane is compared to be had Low price and the good feature of caking property, but its anti-ultraviolet property and in the protective value in intermediate layer but There is critical defect, so fluoropolymer membrane or the main selection of inner layer material, but fluoropolymer membrane exists viscous with EVA The problem that knot power is less.Surface grafting, plasma treatment high reflecting rate surface
Chinese patent CN103101268A discloses a kind of frosting polyvinylidene difluoride film and preparation method thereof, This patent is adjusted by component and the content of polyvinylidene fluoride layer so that the polyvinylidene difluoride film of preparation Surface be frosting, thus strengthen and the cohesive force of EVA.But meanwhile because of surface gloss significantly under Fall, causes the luminous reflectance of solar energy backboard to decline to a great extent, and on the one hand reduces the utilization rate of light, the opposing party Face luminous energy can be caused assembly to generate heat by solar energy backboard absorption, reduces service life.
Summary of the invention
The invention provides a kind of one side frosted height reflected solar energy backboard PVDF thin film and preparation method thereof, In order to solve the problem that current solar energy backboard cannot take into account EVA cohesive force and highly reflective.
In order to solve above-mentioned technical problem, the technical scheme is that described one side frosted height reflects the sun Can backboard PVDF thin film, including four layers of melted co-extrusion formed from side to opposite side compound successively outside Layer, intermediate layer, internal layer and reflector layer, the material of described outer layer and internal layer is Kynoar, described outside Layer is frosting away from the one side in intermediate layer, and the material of described reflector layer is that acrylic acid-grafted Kynoar is total to Polymers (PVDF-g-P (AA)).
The surface modification of general pvdf membrane, after being all film forming, by chemically or physically method at pvdf membrane Modifying surface, typically can improve surface adhesion after graft modification, the method for modifying that the present invention provides It is first to carry out PVDF grafting, then by four layers of co-extrusion film forming, namely adds a Modified Membrane layer, The most foresighted improve with EVA cohesive force while, reflector layer relatively internal layer PVDF Thin film is compared surface gloss and is improve, and turbidity diminishes, it is thus achieved that the combination property of back side film more excellent.
Owing to reflector layer glossiness is too high, light pollution can be produced when depositing, therefore backboard membrane outer layer is set to Frosting, on the one hand can increase the cohesive force with intermediate layer, it is possible to so that one surface of backboard membrane is the most soft With, it is easy to deposit.
Further, described acrylic acid-grafted polyvinylidene fluoride copolymer is existed by the method for radical polymerization Graft acrylic acid on PVDF polymer molecule.
Further, in described acrylic acid-grafted polyvinylidene fluoride copolymer, acrylic acid-grafted rate is 0.5%-0.8%.
Further, the raw material of described reflector layer includes acrylic acid-grafted polyvinylidene fluoride copolymer and uvioresistant Line agent, described outer layer raw material includes polyvinylidene fluoride resin, delustering agent and ultraviolet (UV) resistant agent.
Further, described ultraviolet (UV) resistant agent be particle diameter be the titanium dioxide of 20-50 μm, described delustering agent is silicon Diatomaceous earth or silicon dioxide.
Present invention also offers the preparation method of above-mentioned one side frosted height reflected solar energy backboard PVDF thin film, Comprise the steps: that the raw material of outer layer, intermediate layer, internal layer and reflector layer thin film sequentially passes through extruder, many Layer co-extruding machine head, chill roll group and traction winding mechanism composite molding；Described chill roll group include polishing roll and Knurling rolls, described polishing roll is for the sizing of the surface of reflector layer, and described knurling rolls are for the sizing of the surface of outer layer.
Polishing roll has high surface gloss, can further improve the surface light reflection rate of reflector layer, described pressure Flower roller may further ensure that the frosted finish effect of superficies.
Further, during coextrusion mold, thin film first passes through polishing roll and forms the sizing of reflector layer surface High bright finish, is then forming matte surface by knurling rolls to superficies sizing.
Further, described multi-layer co-extruded head includes outer layer head, intermediate layer head, internal layer head and anti- Photosphere head, the head temperature of described reflector layer head is 200-220 DEG C.
Further, the raw material of the described reflector layer thin film temperature when entering reflector layer head exists 180-200℃。
By controlling entrance temperature and head temperature, can effectively control the crystal structure composition of reflector layer, enter One step improves the surface gloss of reflector layer.
Further, the temperature of described polishing roll is 25-35 DEG C, temperature 20-30 DEG C of described knurling rolls.
The technical scheme that the present invention provides, by introducing acrylic graft-modified pvdf membrane layer, not only solves The adhesion problem of EVA, also makes the reflecting rate in the face that backlight film presses close to EVA increase, improves light Availability, and four layers of co-extrusion film are easy to process, and layer is strong with interlayer adhesion, and therefore stable performance exists Solar energy Backplane area has wide market prospect.
Accompanying drawing explanation
The figure of the expressing technique of Fig. 1 one side of the present invention frosted height reflected solar energy backboard PVDF thin film Solve explanation.
Shown in figure:
1-extruder, 2-flat roll, 3-knurling rolls, 4-traction winding mechanism, the 5-one side frosted height reflection sun Can backboard PVDF thin film.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is carried out concrete introduction.
The preparation of acrylic acid-grafted polyvinylidene fluoride copolymer PVDF-g-P of embodiment 1 (AA)
In four-hole boiling flask, add 40mL DMF, 2g PVDF powder is dissolved in DMF solution, heating, It is passed through nitrogen 30min with except air, adds acrylic acid AA (mass fraction is 10%), heating in water bath 70 DEG C, After 30min, add initiator B PO 0.1g, react 5h, after reaction terminates, at room temperature cool down, use 50mL Dehydrated alcohol precipitates, and to remove acrylate homopolymer and impurity, is then vacuum dried 24h, obtains PVDF-g-P (AA), percent grafting=(grafting post-consumer polymer amount-grafting prepolymer amount)/grafting prepolymer amount=0.8%.
Embodiment 2
Outer layer is frosting polyvinylidene difluoride film, and each component of outer layer raw material is: the titanium dioxide of 1 weight portion (particle diameter 20 μm), the silicon dioxide of 1 weight portion and the polyvinylidene fluoride resin melt blending of 50 weight portions.
Intermediate layer is polymethyl methacrylate film, and concrete configuration method refers to existing PMMA thin film Type method.
Internal layer is polyvinylidene difluoride film, and each component of internal layer raw material is: the titanium dioxide (particle diameter of 1 weight portion 20 μm) and the polyvinylidene fluoride resin melt blending of 50 weight portions.
Reflector layer is acrylic acid modified polyvinylidene difluoride film, and each component of reflector layer raw material is: 1 weight portion Titanium dioxide (particle diameter 20 μm) and the embodiment 1 of 50 weight portions in preparation PVDF-g-P (AA) melt Melt blended.
As it is shown in figure 1, above layers raw material sequentially pass through extruder (not shown), multi-layer co-extruded head 1, Polishing roll 2, knurling rolls 3 and traction winding mechanism 4 composite molding obtain described one side frosted height reflected solar energy Backboard PVDF thin film 5.
The most multi-layer co-extruded head 1 includes outer layer head, intermediate layer head, internal layer head and reflector layer head, The head temperature of described reflector layer head controls at 220 DEG C.
The melt blending material of the described reflector layer raw material temperature when entering reflector layer head is at 200 DEG C.
The temperature of described polishing roll controls at 35 DEG C, the temperature of described knurling rolls 25 DEG C.
Controlling each layer raw material extrusion capacity and rate of extrusion by vacuumatic measuring pump, extrusion capacity is directly proportional to thickness, Each layer thickness can be adjusted as required.
The each layer thickness of the present embodiment is outer layer 10 μm, and intermediate layer is 10 μm, internal layer 5 μm, reflector layer 5 μm.
Embodiment 3
Outer layer is frosting polyvinylidene difluoride film, and each component of outer layer raw material is: the titanium dioxide of 5 weight portions (particle diameter 50 μm), the silicon dioxide of 5 weight portions and the polyvinylidene fluoride resin melt blending of 50 weight portions.
Intermediate layer is polymethyl methacrylate film, and concrete configuration method refers to existing PMMA thin film Type method.
Internal layer is polyvinylidene difluoride film, and each component of internal layer raw material is: the titanium dioxide (particle diameter of 5 weight portions 50 μm) and the polyvinylidene fluoride resin melt blending of 50 weight portions.
Reflector layer is acrylic acid modified polyvinylidene difluoride film, and each component of reflector layer raw material is: 5 weight portions Titanium dioxide (particle diameter 50 μm) and the embodiment 1 of 50 weight portions in preparation PVDF-g-P (AA) melt Melt blended.
As it is shown in figure 1, above layers raw material sequentially pass through extruder (not shown), multi-layer co-extruded head 1, Polishing roll 2, knurling rolls 3 and traction winding mechanism 4 composite molding obtain described one side frosted height reflected solar energy Backboard PVDF thin film 5.
The most multi-layer co-extruded head 1 includes outer layer head, intermediate layer head, internal layer head and reflector layer head, The head temperature of described reflector layer head controls at 200 DEG C.
The melt blending material of the described reflector layer raw material temperature when entering reflector layer head is at 180 DEG C.
The temperature of described polishing roll controls at 25 DEG C, the temperature of described knurling rolls 20 DEG C.
It is then passed through the solar energy backboard membrane after biaxial tension obtains accordingly.
Controlling each layer raw material extrusion capacity and rate of extrusion by vacuumatic measuring pump, extrusion capacity is directly proportional to thickness, Each layer thickness can be adjusted as required.
The each layer thickness of the present embodiment is outer layer 10 μm, and intermediate layer is 10 μm, internal layer 5 μm, reflector layer 5 μm.
Comparative example 1
Include that outer layer, intermediate layer and internal layer, described outer layer and internal layer are polyvinylidene fluoride resin successively, in Interbed PMMA, three layers are prepared by three-layer co-extruded casting technique.
The raw material of its ectomesoderm and internal layer includes 50 weight portion Kynoar, 1 weight portion titanium dioxide and 100 The mixed solution that the N,N-dimethylformamide (DMF) of weight portion configures.
The raw material in intermediate layer is the ethyl acetate solution of polymethyl methacrylate.
Above-mentioned raw materials is by three-layer co-extruded casting film-forming and biaxial tension, it is thus achieved that comparative example solar energy backboard membrane, Concrete technology is implemented with reference to prior art.
Comparative example 2
For frosting polyvinylidene difluoride film, concrete preparation process sees Chinese patent CN103101268A's Embodiment 1.
Embodiment 2-3 and comparative example testing result see table 1
Table 1

Claims (10)

1. an one side frosted height reflected solar energy backboard PVDF thin film, it is characterised in that include four layers The outer layer being combined successively from side to opposite side, intermediate layer, internal layer and the reflector layer that melted co-extrusion is formed, institute The material stating outer layer and internal layer is Kynoar, and described outer layer is frosting away from the one side in intermediate layer, The material of described reflector layer is acrylic acid-grafted polyvinylidene fluoride copolymer.
A kind of one side frosted height reflected solar energy backboard PVDF thin film, its Being characterised by, described acrylic acid-grafted polyvinylidene fluoride copolymer passes through the method for radical polymerization at poly-inclined fluorine Graft acrylic acid on ethylene molecule.
A kind of one side frosted height reflected solar energy backboard PVDF thin film, its Being characterised by, in described acrylic acid-grafted polyvinylidene fluoride copolymer, acrylic acid-grafted rate is 0.5%-0.8%.
A kind of one side frosted height reflected solar energy backboard PVDF thin film, its Being characterised by, the raw material of described reflector layer includes acrylic acid-grafted polyvinylidene fluoride copolymer and ultraviolet (UV) resistant agent, Described outer layer raw material includes polyvinylidene fluoride resin, delustering agent and ultraviolet (UV) resistant agent.
A kind of one side frosted height reflected solar energy backboard PVDF thin film, its Be characterised by, described ultraviolet (UV) resistant agent be particle diameter be the titanium dioxide of 20-50 μm, described delustering agent is kieselguhr Or silicon dioxide.
6. the preparation side of the arbitrary described one side frosted height reflected solar energy backboard PVDF thin film of claim 1-5 Method, it is characterised in that comprise the steps: that the raw material of outer layer, intermediate layer, internal layer and reflector layer thin film depends on Secondary through extruder, multi-layer co-extruded head, chill roll group and traction winding mechanism composite molding；Described cooling Roller group includes polishing roll and knurling rolls, and described polishing roll is used for the sizing of the surface of reflector layer, described knurling rolls Shape in the surface of outer layer.
The preparation side of one side frosted height reflected solar energy backboard PVDF thin film the most according to claim 6 Method, it is characterised in that during coextrusion mold, thin film first passes through polishing roll to reflector layer surface sizing shape Become high bright finish, then by knurling rolls, superficies sizing is formed matte surface.
The preparation side of one side frosted height reflected solar energy backboard PVDF thin film the most according to claim 7 Method, it is characterised in that described multi-layer co-extruded head include outer layer head, intermediate layer head, internal layer head and Reflector layer head, the head temperature of described reflector layer head is 200-220 DEG C.
The preparation side of one side frosted height reflected solar energy backboard PVDF thin film the most according to claim 8 Method, it is characterised in that the raw material of the described reflector layer thin film temperature when entering reflector layer head exists 180-200℃。
The preparation of one side frosted height reflected solar energy backboard PVDF thin film the most according to claim 8 Method, it is characterised in that the temperature of described polishing roll is 25-35 DEG C, temperature 20-30 DEG C of described knurling rolls.
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CN111070654A (en) * 2019-12-27 2020-04-28 宜兴市光辉包装材料有限公司 Preparation method of single-side matte PVC heat-shrinkable label film by film blowing method

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CN111070654B (en) * 2019-12-27 2021-08-24 宜兴市光辉包装材料有限公司 Preparation method of single-side matte PVC heat-shrinkable label film by film blowing method

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