CN101817228B - Preparation method and product of PVDF (Polyvinylidene Fluoride) based multi-layer co-bonding film - Google Patents
Preparation method and product of PVDF (Polyvinylidene Fluoride) based multi-layer co-bonding film Download PDFInfo
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- CN101817228B CN101817228B CN201010145240.2A CN201010145240A CN101817228B CN 101817228 B CN101817228 B CN 101817228B CN 201010145240 A CN201010145240 A CN 201010145240A CN 101817228 B CN101817228 B CN 101817228B
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Abstract
The invention discloses a preparation method and a product of a PVDF (Polyvinylidene Fluoride) based multi-layer co-bonding film. In the preparation method, modified resin containing a PVDF material is prepared through mixed flow and coextrusion by adopting a mutual dissolving and blending technology on fusants with high, middle and low lengths; and the PVDF based multi-layer co-bonding film is obtained through forming by a stretching process by adopting a multi-layer co-bonding technology of a multi-layer fluorine material. With the preparation method, the PVDF based multi-layer co-bonding film with favorable flexibility and high strength is developed through mutually dissolving, blending and modifying the PVDF material, thus, the mobility in the processing and film preparation process and the fluorine content of the material are increased, and the processibility and the weatherability of the film are improved.
Description
Technical field
The present invention relates to a kind of preparation method based on PVDF material, particularly a kind of multilayer based on PVDF preparation method of closely sealed film altogether.The invention still further relates to the product that above-mentioned preparation method obtains.
Background technology
Kynoar (PVDF) material has: 1, unrivaled weatherability and durability, excellent chemicals-resistant, solvent resistance, high-wearing feature, high mechanical properties; 2, there is good heat endurance, be easy to processing, be shaped and welding; 3, there is high polluting proofing property and do not support bacterium and conk function; 4, there is fire-retardant and low cigarette characteristic preferably, have the hypotonicity to most liquid and gas; 5, have high dielectric strength and volume resistance and can gamma ray resistant and the irradiation performance of electron beam.Therefore, PVDF material is widely used in various high-end occasions, is also the preferred material of photovoltaic back film.
Patent ZL03178633.2 has described coextrusion PVDF, adhesive composition and base material, directly obtains the material that is coated with PVDF and the adhesive composition between PVDF and base material, the homopolymers that its PVDF is PVDF.
Number of patent application is that 200780010818.X, 200910128532.2 patent document have been described PVDF multilayer films on a kind of PET of being attached to or PEN sheet material for photovoltaic module, its PVDF can be PVDF homopolymers and/or flexible PVDF, its membrane structure has added PMMA in preparation process, in its flexible PVDF preparation process, the fluorochemical monomers such as HFP are added, but a kind of flexible PVDF is only described in an embodiment, i.e. PVDF-HFP copolymer.
PVDF material is very poor to the adhesiveness of most of base materials, therefore need between PVDF and base material, place adhesive composition; In addition, the mobility of PVDF material is also slightly poor, therefore need in processing film-forming process, carry out modification to PVDF material.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of multilayer based on PVDF preparation method of closely sealed film altogether, this preparation method is to the PVDF material blending and modifying that dissolves each other, increase the mobility of its processing in film-forming process and the fluorine content of material, promote machinability and the weather resistance of film.The present invention also provides a kind of multilayer based on PVDF of preparing according to above-mentioned preparation method closely sealed film altogether.
For reaching above-mentioned technical purpose, technical scheme of the present invention is: a kind of multilayer based on PVDF is the preparation method of closely sealed film altogether, adopt the blending technology that dissolves each other of high, normal, basic melt length, be made by co-extrusion to fluorine-containing Kynoar (PVDF) material resin of modification through mixed flow; Utilize the multilayer closely sealed technology altogether of multilayer fluorine material, drawn technological forming, obtains this multilayer based on PVDF closely sealed film altogether.
The blending technology that dissolves each other that adopts high, normal, basic melt length, the resin obtaining has good mobility, compatibility, is easier to carry out follow-up common closely sealed technique.
The fluorine-containing PVDF material resin of above-mentioned modification, refer to a kind of take vinylidene (VDF) as main binary, ternary and/or quadripolymer, it is 55～65% VDF that this copolymer often comprises percentage by weight, comprises percentage by weight and be the fluorine-containing comonomer that 0～15% nano-powder material and percentage by weight are 20～35%.
Above-mentioned nano-powder material is metal oxide, and it can be one or more mixtures in silica, titanium dioxide and/or alchlor, preferred, selects titanium dioxide; Described fluorine-containing comonomer comprises one or more mixtures in tetrafluoroethene (TFE), hexafluoropropene (HFP), CTFE (CTFE).
The above-mentioned common closely sealed technology of multilayer of utilizing multilayer fluorine material is the copolymerization fluorine material film based on PVDF by several layers, be bonded in basement membrane both sides through compoiste adhering technique, form multi-layer compound film, be respectively from top to down copolymerization fluorine material film, basement membrane, the multilayer copolymerization fluorine material film based on PVDF of multilayer based on PVDF, do not comprise composite tie layer; Above-mentioned several layers refer to two-layer, three layers, four layers or five layers, described two-layer, three layers, four layers or five layers of number of plies that refers to that basement membrane is one-sided; Described multilayer refers to total number of plies of final thin-film material, does not comprise composite tie layer.
The above-mentioned copolymerization fluorine material film thickness based on PVDF is 5～30 μ m, and preferred thickness is 10～18 μ m.
One or more in described compoiste adhering technique use polyester, polyurethane, epoxy resin, polyacrylate material are as binding agent.
Described basement membrane is PET, PEN and/or PET-PEN composite, preferred, selects PET material as basement membrane.
The above-mentioned multilayer based on PVDF is closely sealed method for manufacturing thin film altogether, is made by the stretched technique of multi-layer compound film and sided corona treatment.Preferably, drawing process is biaxial tension.Stretched technological forming, product has excellent mechanical stretch performance and anti-electrical breakdown capability.
For making preparation technology more stable, the quality of preparing product is more outstanding, and above-mentioned mixed flow adopts twin-screw multiterminal evacuation mixed flow equipment to carry out.
According to the above-mentioned multilayer based on the PVDF multilayer based on PVDF that altogether prepared by the preparation method of closely sealed film closely sealed film altogether, its gross thickness is 100～900 μ m.
Preparation method of the present invention is by blending and modifying that PVDF material is dissolved each other; develop and there is good flexibility and the high-intensity multilayer based on PVDF for the protection of photovoltaic module closely sealed film altogether; increase mobility in processing film-forming process and the fluorine content of material, promoted machinability and the weather resistance of film.Adopt the modified fluoride-containing material resin based on PVDF, in film-forming process, can increase the mobility of this modified resin, thereby be easier to accomplish multilayer sealing property altogether; In addition, by the modification to PVDF, increase the fluorine content of modification PVDF resin, thereby strengthened machinability and the weatherability of this resin material, be more conducive to be applied on photovoltaic module.
The specific embodiment
Embodiment 1
Adopt twin-screw multiterminal evacuation mixed flow equipment, at the temperature of 250 ℃ by the VDF that is 60% by percentage by weight, percentage by weight is TFE that 15% nano-titanium dioxide powder and percentage by weight are 25% blending and modifying that dissolves each other, and is made by co-extrusion to modification PVDF material resin through mixed flow.
Use film extruder, at the temperature of 245 ℃, above-mentioned modification PVDF material resin basis being become to thickness is the copolymerization fluorine material film based on PVDF of 5 μ m.
Utilize the multilayer closely sealed technology altogether of multilayer fluorine material, be raw material by the copolymerization fluorine material film based on PVDF of above-mentioned acquisition, take PET as basement membrane, selection polyester material is adhesive, compound through biaxial tension, dry type, obtaining thickness is the multilayer of 100 μ m based on PVDF closely sealed film altogether.
Embodiment 2
Adopt twin-screw multiterminal evacuation mixed flow equipment, the VDF that is 65% by percentage by weight at the temperature of 250 ℃, percentage by weight is HFP that 15% nano silica powder and percentage by weight are 20% blending and modifying that dissolves each other, and is made by co-extrusion to modification PVDF material resin through mixed flow.
Use film extruder, at the temperature of 245 ℃, above-mentioned modification PVDF material resin basis being become to thickness is the copolymerization fluorine material film based on PVDF of 10 μ m.
Utilize the multilayer closely sealed technology altogether of multilayer fluorine material, be raw material by the copolymerization fluorine material film based on PVDF of above-mentioned acquisition, take PEN as basement membrane, selecting polyester-polyurethane composite is adhesive, compound through simple tension, dry type, obtaining thickness is the multilayer of 900 μ m based on PVDF closely sealed film altogether.
Embodiment 3
Adopt twin-screw multiterminal evacuation mixed flow equipment, the VDF that is 60% by percentage by weight at the temperature of 250 ℃, percentage by weight is TFE that 15% nanometer alchlor powder and the percentage by weight HFP that is 10% and percentage by weight are 15% blending and modifying that dissolves each other, and is made by co-extrusion to modification PVDF material resin through mixed flow.
Use film extruder, declining the temperature of 245 ℃, to become thickness be the copolymerization fluorine material film based on PVDF of 15 μ m on above-mentioned modification PVDF material resin basis.
Utilize the multilayer closely sealed technology altogether of multilayer fluorine material, be raw material by the copolymerization fluorine material film based on PVDF of above-mentioned acquisition, take PET as basement membrane, selection polyurethane material is adhesive, through four-way stretch, dry type is compound, obtaining thickness is the multilayer of 350 μ m based on PVDF closely sealed film altogether.
Embodiment 4
Adopt twin-screw multiterminal evacuation mixed flow equipment, the VDF that is 55% by percentage by weight at the temperature of 250 ℃, percentage by weight is CTFE that nano titanium oxide-alchlor powder of 10% and the percentage by weight HFP that is 20% and percentage by weight are 15% blending and modifying that dissolves each other, and is made by co-extrusion to modification PVDF material resin through mixed flow.
Use film extruder, declining the temperature of 245 ℃, to become thickness be the copolymerization fluorine material film based on PVDF of 18 μ m on above-mentioned modification PVDF material resin basis.
Utilize the multilayer closely sealed technology altogether of multilayer fluorine material, be raw material by the copolymerization fluorine material film based on PVDF of above-mentioned acquisition, take PET-PEN composite as basement membrane, selection epoxy resin is adhesive, compound through multi tension, dry type, obtaining thickness is the multilayer of 380 μ m based on PVDF closely sealed film altogether.
Embodiment 5
Adopt twin-screw multiterminal evacuation mixed flow equipment, at the temperature of 250 ℃, by the VDF that is 65% by percentage by weight, and the percentage by weight CTFE that is 35% the blending and modifying that dissolves each other, is made by co-extrusion to modification PVDF material resin through mixed flow.
Use film extruder, declining the temperature of 245 ℃, to become thickness be the copolymerization fluorine material film based on PVDF of 22 μ m on above-mentioned modification PVDF material resin basis.
Utilize the multilayer closely sealed technology altogether of multilayer fluorine material, be raw material by the copolymerization fluorine material film based on PVDF of above-mentioned acquisition, take PET as basement membrane, selection polyacrylate material is adhesive, compound through biaxial tension, dry type, obtaining thickness is the multilayer of 450 μ m based on PVDF closely sealed film altogether.
Embodiment 6
Adopt twin-screw multiterminal evacuation mixed flow equipment, at the temperature of 250 ℃ by the VDF that is 55% by percentage by weight, percentage by weight is TFE that nano silicon-alchlor powder of 10% and the percentage by weight CTFE that is 15% and percentage by weight are 20% blending and modifying that dissolves each other, and is made by co-extrusion to modification PVDF material resin through mixed flow.
Use film extruder, declining the temperature of 245 ℃, to become thickness be the copolymerization fluorine material film based on PVDF of 30 μ m on above-mentioned modification PVDF material resin basis.
Utilize the multilayer closely sealed technology altogether of multilayer fluorine material, be raw material by the copolymerization fluorine material film based on PVDF of above-mentioned acquisition, take PEN as basement membrane, selection polyester-polyurethane-epoxy resin composite material is adhesive, compound through biaxial tension, dry type, obtaining thickness is the multilayer of 700 μ m based on PVDF closely sealed film altogether.
Above-described embodiment does not limit the present invention in any way, and every employing is equal to replaces or technical scheme that the mode of equivalent transformation obtains all drops in protection scope of the present invention.
Claims (3)
1. the preparation method of closely sealed film altogether of the multilayer based on PVDF; it is characterized in that: adopt twin-screw multiterminal evacuation mixed flow equipment; at the temperature of 250 ℃ by the VDF that is 55-65% by percentage by weight; percentage by weight is that the nano-powder material of 0-15% and percentage by weight are the fluorine-containing comonomer of the 20-35% blending and modifying that dissolves each other, and is made by co-extrusion to modification PVDF material resin through mixed flow; Use film extruder, above-mentioned modification PVDF material resin is extruded into the copolymerization fluorine material film based on PVDF that thickness is 5-30 μ m at the temperature of 245 ℃; Utilize the multilayer closely sealed technology altogether of multilayer fluorine material, be raw material by the copolymerization fluorine material film based on PVDF of above-mentioned acquisition, take PET, PEN or PET-PEN composite as basement membrane, one or more in selection polyester material, polyurethane material, epoxy resin, polyacrylate material are adhesive, compound through biaxial tension and dry type, obtaining thickness is the multilayer of 100-900 μ m based on PVDF closely sealed film altogether.
2. the multilayer based on the PVDF according to claim 1 preparation method of closely sealed film altogether, is characterized in that: described nano-powder material is one or more mixtures in silica, titanium dioxide or alchlor.
3. the multilayer based on the PVDF according to claim 1 preparation method of closely sealed film altogether, is characterized in that: described fluorine-containing comonomer is one or more mixtures in tetrafluoroethene, hexafluoropropene or CTFE.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010145240.2A CN101817228B (en) | 2010-04-12 | 2010-04-12 | Preparation method and product of PVDF (Polyvinylidene Fluoride) based multi-layer co-bonding film |
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| CN201010145240.2A CN101817228B (en) | 2010-04-12 | 2010-04-12 | Preparation method and product of PVDF (Polyvinylidene Fluoride) based multi-layer co-bonding film |
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| CN101817228B true CN101817228B (en) | 2014-06-18 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| FR2982796A1 (en) * | 2011-11-23 | 2013-05-24 | Arkema France | Manufacturing fluorinated film useful for protecting back sheet of photovoltaic panel, comprises coextruding fluorinated film with layer of nonfluorinated polymer with mineral loads, and then delaminating layer of nonfluorinated polymer |
| CN106147088A (en) * | 2015-04-13 | 2016-11-23 | 江苏昊华光伏科技有限公司 | High-performance drip, fog dispersal PVDF composite canopy film |
| CN106147089A (en) * | 2015-04-13 | 2016-11-23 | 江苏昊华光伏科技有限公司 | High intensity PVDF agricultural mulching |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050137351A1 (en) * | 2003-12-17 | 2005-06-23 | 3M Innovative Properties Company | Polymer electrolyte membranes crosslinked by direct fluorination |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050137351A1 (en) * | 2003-12-17 | 2005-06-23 | 3M Innovative Properties Company | Polymer electrolyte membranes crosslinked by direct fluorination |
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Effective date of registration: 20161017 Address after: 215500, No. 28, light loop road, Xinzhuang Town, Jiangsu, Changshou City Patentee after: Jinagsu Haohua Photovoltaic Technology Co., Ltd. Patentee after: Gong Fugen Address before: 215500, No. 28, light loop road, Xinzhuang Town, Jiangsu, Changshou City Patentee before: Jinagsu Haohua Photovoltaic Technology Co., Ltd. |
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Effective date of registration: 20170830 Address after: 215500, No. 28, light loop road, Xinzhuang Town, Jiangsu, Changshou City Patentee after: Jinagsu Haohua Photovoltaic Technology Co., Ltd. Address before: 215500, No. 28, light loop road, Xinzhuang Town, Jiangsu, Changshou City Co-patentee before: Gong Fugen Patentee before: Jinagsu Haohua Photovoltaic Technology Co., Ltd. |
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