CN103456817B - A kind of floride-free solar cell backboard and preparation method thereof - Google Patents

Abstract

The invention provides a fluorine-free multi-layer co-extruded solar cell backboard material. The backboard material is divided into three layers, namely a weather-resistant layer, an intermediate layer and an adhesive layer. Specifically, the weather-resistant layer is modified PC; The middle layer is modified PBT; the adhesive layer is modified PC, and the mixture of each layer is firstly extruded through a twin-screw extruder, and then co-extruded through a multi-layer co-extrusion device to obtain a backboard material. The fluorine-free multi-layer co-extruded solar battery back sheet of the present invention does not need to use fluorine-containing materials and adhesives, adopts multi-layer co-extrusion technology to realize the bonding between layer materials, has excellent physical properties and is low in price.

Description

A kind of fluorine-free solar battery back plate and preparation method thereof

technical field

The invention relates to solar battery equipment, in particular to a solar battery back plate material and a preparation method thereof.

Background technique

After the Tokyo Electric Power Fukushima Daiichi nuclear power plant accident, all walks of life rethink the development of renewable energy. As a clean, non-polluting renewable energy, solar energy has been paid more and more attention by people. The solar cell backsheet is located on the back of the solar cell panel, which protects and supports the cells and requires certain properties, such as insulation and water resistance. At present, the backplane products appearing on the market mainly include:

(1) One is a composite glued backsheet film, which is a composite fluorine film on both sides of a PET film, such as PVDF, ETFE or EVA film, with a three-layer structure, and the common one is a TPT structure.

(2) One is to coat the back sheet film, which is coated with fluororesin on both sides of the PET polyester film, and then dried and cured to form a film.

With the development of science and technology and the pressure of labor and raw material costs, the backplane has experienced a development process of double-fluorine backplane-single-fluorine backplane-fluorine-free backplane. The cost of double-fluorine backplane is the most expensive. In the process of practical application, during the application process of solar cell modules, after the solar ultraviolet rays pass through the tempered glass, battery sheet and EVA film, not many actually irradiate the surface of the solar backsheet, so as the fluorine in the traditional fluorine-containing backsheet The material has not really realized its value, and most of the fluorine materials widely used in the market currently use polyvinylidene fluoride. Research has found that during the process of film formation of polyvinylidene fluoride, the local temperature is too high, which will quickly produce HF The gas absorbs the calcium in human bones and damages the periosteum and bone. At the same time, the surface wettability of polyvinylidene fluoride is very poor, and it is difficult to bond with other plastic substrates without treatment. Therefore, it is of great significance to develop a new type of solar backsheet that is fluorine-free, has good insulation, water resistance, excellent aging resistance, and is easy to process.

Contents of the invention

The technical problem to be solved by the present invention is: in the existing solar battery backplane technology, the fluorine material has not been fully utilized, and the adhesion between the fluorine material and other plastics is poor, and HF gas which is harmful to the human body is easily produced .

For solving this technical problem, the technical scheme that the present invention adopts is:

The invention provides a new type of fluorine-free solar back sheet, the weather-resistant layer is polycarbonate layer (modified PC layer), the middle layer is polybutylene terephthalate (modified PBT layer), and the bonding layer In order to modify the polycarbonate layer (PC layer), there is no need to use fluorine-containing materials and adhesives, and the multi-layer co-extrusion technology is used to realize the bonding between the layer materials, which has excellent physical properties and low price.

Polycarbonate is a linear polycondensation polymer, which has the characteristics of good transparency, good thermoformability, excellent mechanical properties, high surface hardness, wear resistance, lubricity, high impact performance, and good insulation. The C=O in the chain has a certain polarity, which can be well bonded with polar polymer materials and improve the stiffness and tensile strength of the composite film.

The back sheet material is divided into 3 layers, which are weather-resistant layer, middle layer, and adhesive layer. plate material,

(1) The weather-resistant layer is modified PC, specifically, by weight, it consists of 100 parts of PC, 5-10 parts of UV shielding agent, 1-10 parts of UV absorber, and 0.5-1 part of light stabilizer , and 1 to 10 parts of modified polymer resin,

The UV shielding agent is mainly to improve the anti-ultraviolet effect of PC, prevent the degradation of PC polymer chains, and the aging of materials, such as TiO ₂ , ZnO, SiO ₂ , etc., have a long effective time and have good chemical and thermal stability. Non-toxic, non-irritating, and no chemical reaction with other additives, the surface-modified TiO ₂ , ZnO, SiO ₂ has good dispersion in the resin matrix and is not easy to agglomerate, such as R706 and R902 produced by DuPont wait,

The ultraviolet absorber is an ultraviolet absorber of benzophenones, benzotriazoles, substituted acrylonitriles and triazines, selected from UV-P, UV-O, UV-9 or UV-531,

Light stabilizers are mainly compounded with UV absorbers to achieve better anti-UV effects. The main components are hindered amines, such as AM-101, GW-540, 744, HPT, etc.

The modified polymer resin is a modified polyolefin, which can greatly reduce the water absorption of PC and improve the hydrolysis resistance of its film, such as HD900P, PC-33C or TRD-428P;

(2) The middle layer is modified PBT, specifically, by weight, it consists of 80-90 parts of PBT, 5-10 parts of anti-ultraviolet shielding agent, and 1-5 parts of anti-hydrolysis agent,

The anti-ultraviolet shielding agent is mainly to improve the anti-ultraviolet effect of PBT, prevent the degradation of PBT polymer chains, and the aging of materials, such as TiO ₂ , ZnO, SiO ₂ , etc., which have a long effective time and have good chemical stability and thermal stability. Stability, non-toxic, non-irritating, and no chemical reaction with other additives, surface modified TiO ₂ , ZnO, SiO ₂ have good dispersion in the resin matrix and are not easy to agglomerate, such as R706 produced by DuPont, R902 etc.,

The anti-hydrolysis agent is polycarbodiimide, which has good compatibility with polyester. It can repair the polymer chain of polyester under high temperature conditions, prevent and reduce the degradation of polymer chain, and effectively maintain the polymer chain. The molecular weight of the material maintains the physical and mechanical properties of the material;

(3) The bonding layer is modified PC, specifically, by weight, it is composed of 80-90 parts of PC and 10-20 parts of polyolefin copolymer,

Polyolefin copolymers are selected from one or both of ethylene ethyl acrylate copolymer (EEA), ethylene-methyl acrylate copolymer (EMA), ethylene-(meth)acrylic acid copolymer (EMAA, EAA) blends.

The present invention also provides a method for preparing the above-mentioned solar backsheet material. The mixture of the above-mentioned weather-resistant layer, intermediate layer, and adhesive layer is added to a twin-screw extruder to melt, and each melt passes through its own flow channel in the The multi-layer co-extrusion device merges in the die head, co-extrudes through the die head, and is extruded by cooling rolls, cooled, reheated, and re-cooled to prepare a multi-layer fluorine-free back sheet.

The beneficial effects of the present invention are: compared with the prior art, the patent of the present invention does not use fluorine-containing resins, and adopts multi-layer co-extrusion to prepare solar battery back sheets without using adhesives, and is suitable for PC and PBT. After modification, the fluorine-free backsheet structure obtained by co-extrusion has better mechanical properties, excellent adhesion between layers, excellent weather resistance and hydrolysis resistance, which ensures the service life of solar cells. The method is simple, the continuous production is fast, the cost is greatly reduced, and the method has very good application prospects.

Description of drawings

Figure 1: Schematic diagram of the structure of the solar backsheet prepared in Example 1. In order from top to bottom, the first layer is a weather-resistant layer, modified PC; the second layer is a structural reinforcement layer, modified PBT; the third layer is an adhesive layer, modified PC.

Detailed ways

Example 1

In parts by weight: Mix 100 parts of PC (Taiwan Chimei PC-110), 5 parts of titanium dioxide (Ti-Pure R902), 1 part of UV-P, 0.5 parts of AM-101 and 5 parts of modified polymer resin HD900P , put the mixture into a twin-screw extruder (manufactured by Guangzhou Putong Experimental and Analytical Instrument Co., Ltd., the length-to-diameter ratio of the screw is 44:1, the speed of the main engine is 120r/min, and the speed of feeding is 140r/min), and the melt is extruded to Splitter die head, extruder temperature setting: barrel temperature (°C): 170, 230, 250, 260; die head (°C): 270, 280, 280.

In parts by weight: Mix 80 parts of PBT (U.S. DuPont SK605), 5 parts of titanium dioxide (Ti-Pure R902) and 1 part of polycarbodiimide (Shanghai Union Chemical Co., Ltd.), and add the mixture to the twin-screw In the extruder (manufactured by Qidong Dingjia Machinery Equipment Co., Ltd.), melt to the splitter die head, and the temperature of the extruder is set as follows: barrel temperature (°C): 200, 220, 240, 270; die head (°C): 270, 260, 250.

In parts by weight: Mix 80 parts of PC (Taiwan Chimei PC-110) and 20 parts of EAA (US Dow 3150) evenly, and put the mixture into a twin-screw extruder (manufactured by Guangzhou Putong Experimental Analysis Instrument Co., Ltd. ), melted to the split die head, and the temperature of the extruder is set as follows: barrel temperature (°C): 170, 230, 250, 260; die head (°C): 270, 280, 280.

The above-mentioned melts pass through their respective flow channels, meet in the die head of the multi-layer co-extrusion device, co-extrude through the die head, and pass through the extrusion of the cooling roll, cooling, secondary heating (temperature 80°C), and re-cooling to prepare A multi-layer fluorine-free back sheet was obtained, which was rolled up for use.

Example 2

In parts by weight: Mix 100 parts of PC (Germany Bayer 2407), 10 parts of titanium dioxide (Ti-Pure R706), 10 parts of UV-O, 1 part of AM-101 and 10 parts of modified polymer resin PC-33C , put the mixture into the twin-screw extruder (manufactured by Guangzhou Putong Experimental and Analytical Instrument Co., Ltd.), melt and extrude to the split die head, and the temperature of the extruder is set as: Barrel temperature (°C): 200, 220, 240, 270 ; Die (°C): 270, 260, 250.

In parts by weight: Mix 90 parts of PBT (Nippon Polyplastics 3116), 10 parts of titanium dioxide (Ti-Pure R902), and 5 parts of polycarbodiimide (Shanghai Union Chemical Co., Ltd.), and add the mixture to In the twin-screw extruder (manufactured by Qidong Dingjia Machinery Equipment Co., Ltd.), the molten ester splitting die head, the temperature of the extruder is set as follows: barrel temperature (°C): 200, 220, 240, 270; die head (°C): 270, 260,250.

In parts by weight: Mix 90 parts of PC (Bayer 2407, Germany) and 10 parts of EVA (DuPont 1075A, USA) evenly, and put the mixture into a twin-screw extruder (manufactured by Guangzhou Putong Experimental Analysis Instrument Co., Ltd.), Melting to the split die head, the temperature of the extruder is set as follows: barrel temperature (°C): 200, 220, 240, 270; die head (°C): 270, 260, 250.

The above-mentioned melts pass through their respective flow channels, merge in the die head of the multi-layer co-extrusion device, co-extrude through the die head, and pass through the extrusion of the cooling roll, cooling, secondary heating (heating temperature 80°C), and re-cooling A multi-layer fluorine-free back sheet is prepared and rolled up for use.

Example 3

In parts by weight: Mix 100 parts of PC (Samsung 1100R), 6 parts of zinc oxide, 5 parts of UV-0, 0.7 parts of GW-540 and 10 parts of modified polymer resin TRD-428P, and add the mixture to the double In the screw extruder (manufactured by Guangzhou Putong Experimental Analysis Instrument Co., Ltd.), the melt is extruded to the splitter die, and the temperature of the extruder is set as follows: barrel temperature (°C): 200, 220, 240, 270; die head (°C) : 270, 260, 250.

In parts by weight: Mix 85 parts of PBT (U.S. DuPont SK602), 10 parts of titanium dioxide and 2 parts of polycarbodiimide (Shanghai Youen Chemical Co., Ltd.), and put the mixture into a twin-screw extruder (Qidongding Manufactured by Jia Machinery Equipment Co., Ltd.), the molten ester splitting die head, the temperature of the extruder is set as follows: barrel temperature (°C): 200, 220, 240, 270; die head (°C): 270, 260, 250.

In parts by weight: Mix 80 parts of PC (Samsung 1100R) and 20 parts of EMAA (U.S. DuPont 7940) evenly, put the mixture into a twin-screw extruder (manufactured by Guangzhou Putong Experimental Analysis Instrument Co., Ltd.), melt To the split die head, the temperature of the extruder is set as follows: barrel temperature (°C): 200, 220, 240, 270; die head (°C): 270, 260, 250.

The above-mentioned melts pass through their respective flow channels, merge in the die head of the multi-layer co-extrusion device, co-extrude through the die head, and pass through the extrusion of the cooling roll, cooling, secondary heating (heating temperature 80°C), and re-cooling A multi-layer fluorine-free back sheet is prepared and rolled up for use.

Example 4

In parts by weight: Mix 100 parts of PC (Bayer 2407, Germany), 5 parts of silica, 1 part of UV-9, 0.5 parts of 744 and 10 parts of modified polymer resin HD900P, and add the mixture to the twin-screw extruder In the extruder (manufactured by Guangzhou Putong Experimental Analysis Instrument Co., Ltd.), the melt is extruded to the split die head, and the temperature of the extruder is set as follows: barrel temperature (°C): 200, 220, 240, 270; die head (°C): 270 , 260, 250.

In parts by weight: Mix 80 parts of PBT (U.S. DuPont SK605), 5 parts of zinc oxide and 1 part of polycarbodiimide evenly, and put the mixture into a twin-screw extruder (manufactured by Qidong Dingjia Machinery Equipment Co., Ltd.) Among them, the molten ester splitting die head, the temperature of the extruder is set as follows: barrel temperature (°C): 200, 220, 240, 270; die head (°C): 270, 260, 250.

In parts by weight: Mix 85 parts of PC (Bayer 2407, Germany) and 15 parts of EMA (DuPont E403, USA) evenly, and add the mixture into a twin-screw extruder (manufactured by Guangzhou Putong Experimental Analysis Instrument Co., Ltd.), Melting to the split die head, the temperature of the extruder is set as follows: barrel temperature (°C): 200, 220, 240, 270; die head (°C): 270, 260, 250.

The above-mentioned melts pass through their respective flow channels, merge in the die head of the multi-layer co-extrusion device, co-extrude through the die head, and pass through the extrusion of the cooling roll, cooling, secondary heating (heating temperature 80°C), and re-cooling A multi-layer fluorine-free back sheet is prepared and rolled up for use.

The performance test of the solar backsheets prepared in Examples 1-4:

Tensile strength and elongation at break are tested according to the ASTM D882 standard; UVB aging is tested according to the aging time of 3000h, 0.68W/ ^m2 test conditions, to observe whether there is any color difference; the peel strength test method is tested according to the ASTM D1876 standard; weather resistance test According to the GB/T13448-2006 standard test, the test conditions are: keep warm for 1000h at a temperature of 85°C and a humidity of 85%, and observe whether there is any yellowing change. The test results are shown in Table 1.

Table 1

Inspired by the above-mentioned ideal embodiment according to the present invention, through the above-mentioned description content, relevant workers can make various changes and modifications within the scope of not departing from the technical idea of the present invention. The technical scope of the present invention is not limited to the content in the embodiments, and must be determined according to the scope of the claims.

Claims (10)

1. a floride-free solar cell backboard, is characterized in that: described backboard is floride-free multi-layer co-extruded solar cell backboard, and back veneer material is divided into 3 layers, is respectively weathering layer, intermediate layer, tack coat,

Weathering layer is the PC of modification, specifically, counts by weight, by the PC of 100 parts, and 5 ~ 10 parts of ultraviolet light screeners, 1 ~ 10 part of ultraviolet absorber, 0.5 ~ 1 part of light stabilizer, and 1 ~ 10 part of modify polymeric resins composition;

Intermediate layer is the PBT of modification, specifically, counts by weight, by the PBT of 80 ~ 90 parts, and the uvioresistant screener of 5 ~ 10 parts, the hydrolysis-resisting agent composition of 1 ~ 5 part;

Tack coat is the PC of modification, specifically, counts by weight, by the PC of 80 ~ 90 parts, and the polyolefin copolymers composition of 10 ~ 20 parts.

2. floride-free solar cell backboard as claimed in claim 1, is characterized in that: in described weathering layer, ultraviolet light screener is selected from R706 or R902.

3. floride-free solar cell backboard as claimed in claim 1, is characterized in that: in described weathering layer, and ultraviolet absorber is the ultraviolet absorber of benzophenone class, benzotriazole, the fine class of replacement propylene or triazines.

4. floride-free solar cell backboard as claimed in claim 1, is characterized in that: in described weathering layer, ultraviolet absorber is UV-P, UV-O, UV-9 or UV-531.

5. floride-free solar cell backboard as claimed in claim 1, is characterized in that: the light stabilizer in described weathering layer, is selected from AM-101, GW-540,744 or HPT.

6. floride-free solar cell backboard as claimed in claim 1, is characterized in that: in described weathering layer, modify polymeric resins is the modifier of TPO.

7. floride-free solar cell backboard as claimed in claim 1, is characterized in that: in described weathering layer, modify polymeric resins is HD900P, PC-33C or TRD-428P.

8. floride-free solar cell backboard as claimed in claim 1, is characterized in that: in described intermediate layer, hydrolysis-resisting agent is polycarbodiimide.

9. floride-free solar cell backboard as claimed in claim 1, is characterized in that: the polyolefin copolymers in described tack coat is selected from ethylene ethyl acrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-methacrylic acid copolymer or ethylene-acrylic acid copolymer.

10. the preparation method of the floride-free solar cell backboard as described in any one of claim 1 to 9, it is characterized in that: described method is, respectively by the batch mixing of weathering layer, intermediate layer, tack coat, add melting in double screw extruder, each melt is converged in the die head of multi-layer co-extruded device by respective runner, through die head coextrusion, through chill roll extruding, cooling, post bake, cool again, prepare the floride-free backboard of multilayer.