CN109651964B - Reworkable cross-linked weather-resistant polyolefin film for solar cell back panel - Google Patents
Reworkable cross-linked weather-resistant polyolefin film for solar cell back panel Download PDFInfo
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- CN109651964B CN109651964B CN201811141291.0A CN201811141291A CN109651964B CN 109651964 B CN109651964 B CN 109651964B CN 201811141291 A CN201811141291 A CN 201811141291A CN 109651964 B CN109651964 B CN 109651964B
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- C09J7/10—Adhesives in the form of films or foils without carriers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/06—Polyethene
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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
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
- C09J123/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C09J123/0815—Copolymers of ethene with aliphatic 1-olefins
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Abstract
A reworkable cross-linked weather-resistant polyolefin film comprises the following components: 100 parts by weight of a first polyolefin composition resin, 10 to 250 parts by weight of a second polyolefin composition resin, and 30 to 70 parts by weight of an elastic resin. The melting point of the first polyolefin composition resin is higher than that of the second polyolefin composition resin by 20 ℃ or more. The film of the present invention can be bonded to a solar cell module as a back sheet. When the film is torn off by heating, the film can be torn off more completely by virtue of the characteristic that the second polyolefin composition resin is slightly melted first but the first polyolefin composition resin is not melted yet. In addition, the elastic resin can increase the viscoelasticity, so that the film can be completely torn off from the battery module.
Description
Technical Field
The invention relates to a reworkable crosslinking weather-resistant polyolefin film and a preparation method thereof, in particular to a reworkable crosslinking weather-resistant polyolefin film for a solar cell back panel and a preparation method thereof.
Background
The solar cell module mainly comprises a glass cover plate, ethylene-vinyl acetate copolymer (EVA), a cell, a back plate, a junction box, a frame and the like. The solar cell back sheet not only provides support and protection effects for the cell, but also is a packaging material which is most directly contacted with the external environment in a large area in the above components, and the quality of the performance of the solar cell back sheet directly affects the power generation efficiency and the service life of the solar cell component, so the solar cell back sheet is one of important and indispensable components in the solar cell component.
Although great attention is usually paid to the durability of the solar cell back sheet in the production process to expect to reach the high standard of 25 years, the solar cell module is often exposed to complicated and harsh environments such as ice, snow, temperature, wind and ultraviolet radiation when being placed outdoors for a long time, and the aging of the solar cell back sheet material is inevitable. In addition, the solar cell backsheet may be mechanically damaged by an impact in the external environment.
For example, publication TW201341449 discloses a crosslinked weatherable polyolefin composition that can be made into a backsheet and applied to a solar cell. The back plate made of the crosslinking weather-resistant polyolefin composition has good weather resistance and mechanical strength, and has excellent strength with EVA for packaging. However, the polyolefin composition backing sheet has poor elasticity, so that it is difficult to perform rework.
In this case, in order to continue to effectively support and protect each of the solar cell modules, it is necessary to maintain the solar cell modules. If the solar cell back plate is damaged, the whole solar cell module is eliminated, which obviously does not meet the cost, so the solar cell back plate is generally torn off from the solar cell module and then a new solar cell back plate is attached again.
The methods commonly used for tearing off the solar cell back sheet at present mainly include a direct tearing method, an alcohol wiping method and a heating tearing method. The direct tearing method is time-consuming, and the adhesion is carried out after the repair, and the peeling strength with EVA is not enough, so that the direct tearing method is not adopted gradually. The alcohol wiping method has the advantages of high speed and high efficiency, but the peeling strength of the alcohol wiping method and the EVA is still less than 10N/cm after the alcohol wiping method is repaired and attached, and the alcohol wiping method is not ideal. The heating tearing method is a commonly used repairing method in most module factories at present, bonding is carried out after repairing, and the peeling strength of the heating tearing method and EVA can reach more than 40N/cm, so that the heating tearing method is an ideal scheme.
Generally, the heat tearing method is to heat the back sheet or glass (120 ℃ C. times.10 min.) with a heating table, or directly blow the back sheet or glass with a hot air gun (300-400 ℃ C.) and tear off the solar cell back sheet after the EVA is softened. In actual treatment, it is often found that after the solar cell back sheet is torn off, the adhesive residue of the solar cell back sheet is left on the EVA because the adhesion is too tight, and even because the adhesion is too large, the problem of large-area cell breakage and the like is caused in the tearing process, resulting in great loss.
Disclosure of Invention
The present invention is directed to provide a reworkable crosslinked weatherable polyolefin film for a solar cell back sheet and a method for manufacturing the same, which can mix a first polyolefin composition resin, a second polyolefin composition resin and an elastic resin having different melting points at a proper ratio. The reworkable crosslinking weather-resistant polyolefin film can be adhered to an EVA layer at the same time, and has high viscoelasticity, so that the adhesive residue is not easy to generate when being torn off.
In order to solve the above technical problems, one of the technical solutions of the present invention is to provide a reworkable crosslinked weatherable polyolefin film for a solar cell back sheet, which comprises a first polyolefin composition resin, a second polyolefin composition resin, and an elastic resin. The first polyolefin composition has a resin content of 100 parts by weight (PHR) and has a first melting point. The second polyolefin composition resin is contained in an amount of 10 to 250 parts by weight relative to 100 parts by weight of the first polyolefin composition resin, and has a second melting point. The first melting point is higher than the second melting point by more than 20 ℃. The elastic resin content is 30 to 70 parts by weight relative to 100 parts by weight of the first polyolefin composition resin.
Preferably, the first polyolefin composition resin is a high melting point polypropylene resin with a melt flow index of 0.3-20 and a melting point of 150-170 ℃; the second polyolefin composition resin is one or a combination of more than two of high-density polyethylene resin, linear low-density polyethylene resin, low-density polyethylene resin and low-melting point polypropylene resin with a melt flow index of between 3 and 20 and a melting point of between 110 and 150 ℃, wherein the content of the high-density polyethylene resin is 0 to 50 parts by weight relative to 100 parts by weight of the first polyolefin composition resin, the content of the linear low-density polyethylene resin is 0 to 100 parts by weight relative to 100 parts by weight of the first polyolefin composition resin, the content of the low-density polyethylene resin is 0 to 50 parts by weight relative to 100 parts by weight of the first polyolefin composition resin, and the content of the low-melting point polypropylene resin is 0 to 50 parts by weight relative to 100 parts by weight of the first polyolefin composition resin; the elastic resin is one or the combination of more than two of polyolefin elastomer, ethylene vinyl acetate copolymer EVA and ethylene olefin copolymer.
In order to further enhance the weather resistance, the reworkable crosslinked weather-resistant polyolefin film can be further added with fluorine-containing resin. Preferably, the reworkable crosslinked weather-resistant polyolefin film further comprises a fluororesin in an amount of 0.5 to 15 parts by weight relative to 100 parts by weight of the first polyolefin composition resin, wherein the fluororesin is selected from one or a combination of two or more of Polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), Ethylene-tetrafluoroethylene copolymer (ETFE), Polychlorotrifluoroethylene (PCTFE), and Ethylene-polychlorotrifluoroethylene copolymer (ECTFE).
Preferably, the fluororesin is polytetrafluoroethylene having a molecular weight of 25 to 100 ten thousand.
In order to increase the processability of the reworkable crosslinking weather-resistant polyolefin film and make the reworkable polyolefin film easier to rework, a fluorine-containing processing aid can be further added. Preferably, the reworkable crosslinked weather-resistant polyolefin film further comprises a PPA fluorine-containing processing aid in an amount of 0.1 to 1 part by weight based on 100 parts by weight of the first polyolefin composition resin.
Preferably, the reworkable crosslinked weather-resistant polyolefin film further comprises a crosslinking agent, a crosslinking assistant, a lubricant, an assistant, an antioxidant and a pigment, wherein the content of the crosslinking agent is 0.3-15 PHR relative to 100PHR of the first polyolefin composition resin, and the crosslinking agent is an organic peroxide crosslinking agent(ii) a The content of the crosslinking assistant is 0-6 PHR relative to 100PHR of the first polyolefin composition resin, and the crosslinking assistant is selected from diolefins with two terminal carbon-carbon double bonds, trienes with two terminal carbon-carbon double bonds, tetraenes with two terminal carbon-carbon double bonds (An alkadiene, alkatriene, or alkatetraene compound and comprising at least two branched carbon-carbon double bonds), Triallyl isocyanurate (TAIC), Trimethylolpropane Triacrylate (TMPTA) and nano titanium dioxide (TiO PTA)2) One or a combination of two or more of them; the content of the lubricant is 0.3 to 45PHR relative to 100PHR of the first polyolefin composition resin; the content of the auxiliary agent is 0.3-240 PHR relative to 100PHR of the first polyolefin composition resin; the content of the antioxidant is 0.3-15 PHR relative to 100PHR of the first polyolefin composition resin, and the antioxidant is selected from phenol antioxidants or triphenyl phosphite antioxidants; the content of the colorant is 0 to 105PHR relative to 100PHR of the first polyolefin composition resin.
Preferably, the reworkable crosslinked weatherable polyolefin film has a reflectance of greater than 65% for light having a wavelength of 420 to 650 nm.
In order to solve the above technical problems, another technical solution adopted by the present invention is to provide a method for preparing a cross-linked weatherable polyolefin film, comprising the following steps: premixing a first polyolefin composition resin, a second polyolefin composition resin and an elastic resin by a mixer to form a mixture, wherein the content of the second polyolefin composition resin is 10-250 parts by weight relative to 100 parts by weight of the first polyolefin composition resin, the melting point of the first polyolefin composition resin is higher than that of the second polyolefin composition resin by more than 20 ℃, and the content of the elastic resin is 30-70 parts by weight relative to 100 parts by weight of the first polyolefin composition resin; uniformly mixing the mixture by a kneader; gelatinizing and crosslinking the components of the mixture with a roller; preparing the gelled mixture into a sheet by a calender; and cooling and shaping the sheet body by a cooling wheel set.
Preferably, in the step of performing preliminary stirring to form the mixture, a fluororesin is further compounded in an amount of 0.5 to 15 parts by weight with respect to 100 parts by weight of the first polyolefin composition resin, the fluororesin being selected from one or a combination of two or more of polyvinylidene fluoride, polytetrafluoroethylene, an ethylene-tetrafluoroethylene copolymer, polychlorotrifluoroethylene, and an ethylene-polychlorotrifluoroethylene copolymer.
Preferably, the fluororesin is a powder having an average particle size of 3 to 10 μm, and the fluororesin is polytetrafluoroethylene having a molecular weight of 25 to 100 ten thousand.
In order to increase the processability of the reworkable crosslinking weather-resistant polyolefin film and make the reworkable polyolefin film easier to rework, a fluorine-containing processing aid can be further added. Preferably, the reworkable crosslinked weather-resistant polyolefin film further comprises a PPA fluorine-containing processing aid in an amount of 0.1 to 1 part by weight based on 100 parts by weight of the first polyolefin composition resin.
Preferably, in the step of performing preliminary stirring to form the mixture, a crosslinking agent, a crosslinking assistant, a lubricant, an assistant, and a coloring material are also mixed. Wherein the content of the cross-linking agent is 0.3-15 PHR relative to 100PHR of the first polyolefin composition resin, and the cross-linking agent is an organic peroxide cross-linking agent; the content of the crosslinking auxiliary agent is 0-6 PHR relative to 100PHR of the first polyolefin composition resin, and the crosslinking auxiliary agent is selected from one or a combination of more than two of diene, triene compound, tetraene compound, TAIC, trimethylolpropane triacrylate and nano-scale titanium dioxide with two terminal carbon-carbon double bonds; the content of the lubricant is 0.3 to 45PHR relative to 100PHR of the first polyolefin composition resin; the content of the auxiliary agent is 0.3-240 PHR relative to 100PHR of the first polyolefin composition resin; the content of the coloring material is 0 to 105PHR relative to 100PHR of the first polyolefin composition resin.
Preferably, the operating temperature of the rolling mill and the calender is between 130 and 220 ℃.
The invention adopts another technical scheme that a using method of the cross-linking weather-resistant polyolefin film is provided, and the cross-linking weather-resistant polyolefin film is used as a back plate of a solar cell.
One of the advantages of the invention is that the reworkable crosslinked weatherable polyolefin film provided by the present invention can be manufactured by the technical scheme of "mixing the elastic resin and the first polyolefin composition resin and the second polyolefin composition resin with different melting points" and "the melting point of the first polyolefin composition resin is higher than the melting point of the second polyolefin composition resin by more than 20 ℃, so that the reworkable crosslinked weatherable polyolefin film does not have too strong adhesion with the EVA layer because the first polyolefin composition resin is not melted when the back sheet is processed and reworked at a temperature around the second melting point, and the film has elasticity due to the existence of the elastic resin and can be torn off more completely. In addition, the present invention can achieve both the above-mentioned property of being able to be peeled off and the adhesiveness to the EVA layer by the technical means of "the content of the second polyolefin composition resin is 10 to 250 parts by weight with respect to 100 parts by weight of the first polyolefin composition resin, and the content of the elastic resin is 30 to 70 parts by weight with respect to 100 parts by weight of the first polyolefin composition resin".
For a better understanding of the features and technical content of the present invention, reference should be made to the following detailed description of the invention and accompanying drawings, which are provided for purposes of illustration and description only and are not intended to limit the invention.
Drawings
FIG. 1 is a flow chart of a method for manufacturing a reworkable crosslinked weatherable polyolefin film according to an embodiment of the present invention.
Detailed Description
The following is a description of the embodiments of the reworkable crosslinked weatherable polyolefin film for solar cell back sheet disclosed in the present invention by specific examples, and those skilled in the art can understand the advantages and effects of the present invention from the disclosure in the present specification. The invention is capable of other and different embodiments and its several details are capable of modification in various other respects, all without departing from the spirit and scope of the present invention. The drawings of the present invention are for illustrative purposes only and are not intended to be drawn to scale. The following embodiments will further explain the related art of the present invention in detail, but the disclosure is not intended to limit the scope of the present invention.
Referring to fig. 1, fig. 1 is a schematic flow chart illustrating a process for manufacturing a reworkable crosslinked weatherable polyolefin film according to an embodiment of the present invention. The invention relates to a method for preparing a repairable cross-linking weather-resistant polyolefin film, which is characterized in that a first polyolefin composition resin (with high melting point), a second polyolefin composition resin (with low melting point) and an elastic resin (with good elasticity) with different melting points are mixed with each other and mixed according to a proper proportion (the content of the second polyolefin composition resin is 10-250 parts by weight relative to 100 parts by weight of the first polyolefin composition resin, and the content of the elastic resin is 30-70 parts by weight relative to 100 parts by weight of the first polyolefin composition resin), so that the repairable cross-linking weather-resistant polyolefin film can be adhered to an EVA layer at the same time, and has the characteristic of difficult adhesive residue when torn off. The specific process comprises the following main steps:
s100: premixing a first polyolefin composition resin, a second polyolefin composition resin and an elastic resin in a mixer to form a mixture, wherein the content of the second polyolefin composition resin is 10 to 250 parts by weight relative to 100 parts by weight of the first polyolefin composition resin, the melting point of the first polyolefin composition resin is higher than that of the second polyolefin composition resin by 20 ℃ or higher, and the content of the elastic resin is 30 to 70 parts by weight relative to 100 parts by weight of the first polyolefin composition resin;
s102: uniformly mixing the mixture by a kneader;
s104: gelatinizing and crosslinking the components of the mixture by a rolling machine;
s106: preparing the gelled mixture into a sheet by a calender; and
s108: and introducing the sheet body into a cooling wheel set for cooling and shaping.
More specifically, the process for producing a reworkable crosslinked weatherable polyolefin film of the present invention comprises premixing a first polyolefin composition resin (having a high melting point), a second polyolefin composition resin (having a low melting point) and an elastic resin (having excellent elasticity) in an appropriate ratio at a low temperature by using a mixer (step S100). Wherein, the first polyolefin composition resin can be a high melting point polypropylene resin with a melt flow index of 0.3-20 and a melting point of 150-170 ℃. The second polyolefin composition resin may be High Density Polyethylene (HDPE), Linear Low Density Polyethylene (LLDPE), Low Density Polyethylene (LDPE), or Low melting point polypropylene (LDPE) with a melt flow index of 3-20 and a melting point of 110-150 ℃, and the second polyolefin composition resin may be one or a combination of two or more of polyolefin elastomer (TPO), ethylene vinyl acetate copolymer (EVA), and ethylene olefin copolymer.
As mentioned above, the melting point of the first polyolefin composition resin is higher than the melting point of the second polyolefin composition resin by more than 20 ℃, so as to ensure the convenience of the subsequent processing operation, in terms of the material selection, the melting point of the first polyolefin composition resin may be higher than the melting point of the second polyolefin composition resin by 30 ℃, or even the melting point of the first polyolefin composition resin is higher than the melting point of the second polyolefin composition resin by 40 ℃ to 50 ℃.
Wherein the content of the high-density polyethylene resin is 0 to 50 parts by weight relative to 100 parts by weight of the first polyolefin composition resin, the content of the linear low-density polyethylene resin is 0 to 100 parts by weight relative to 100 parts by weight of the first polyolefin composition resin, the content of the low-density polyethylene resin is 0 to 50 parts by weight relative to 100 parts by weight of the first polyolefin composition resin, and the content of the low-melting polypropylene resin is 0 to 50 parts by weight relative to 100 parts by weight of the first polyolefin composition resin.
The elastic resin is preferably a polyolefin elastomer (TPO). The content of the elastomer resin is 30 to 70 parts by weight relative to 100 parts by weight of the first polyolefin composition resin.
In the present invention, a fluororesin may be mixed in the preliminary stirring step to form a mixture, and the fluororesin to be added may be one or a combination of two or more selected from PVDF, PTFE, ETFE, PCTFE, and ECTFE. The addition of the fluororesin (the fluororesin with the resin content of 0.2-5 PHR relative to 100PHR of the first polyolefin composition) in a proper proportion enables the prepared crosslinking weather-resistant polyolefin film to have good weather resistance, and the proper mixing of the first polyolefin composition resin and the fluororesin can also generate better tensile property.
In addition, in the present invention, in the step of performing preliminary stirring to form a mixture, a fluorine-containing auxiliary may be further mixed. The content of the fluorine-containing auxiliary agent is 0.1 to 1PHR relative to 100PHR of the first polyolefin composition resin. When the first polyolefin composition resin, the fluorine-containing auxiliary agent and the fluororesin are properly mixed with each other, the crosslinked weather-resistant polyolefin film can further have better tensile property, weather resistance and reworkability.
In addition, in order to make the fluororesin and the fluorine-containing auxiliary agent sufficiently and uniformly dispersed in the first polyolefin composition resin to avoid the occurrence of pitted surface and the like of the product due to uneven dispersion of the components, the fluororesin used in the preferred embodiment of the present invention is a powder having an average particle size of 3 to 10 μm, more preferably 4.5 to 8 μm. Further, in a preferred embodiment of the present invention, the fluororesin is polytetrafluoroethylene having a molecular weight of 25 to 100 ten thousand. In addition, the fluorine-containing auxiliary is selected from the class having good compatibility with polyolefin resins, and preferably, PPA processing aid is selected.
In order to enable the first polyolefin composition resin, the second polyolefin composition resin, the elastic resin, the fluororesin and the fluorine-containing auxiliary agent to be sufficiently crosslinked and gelled in the subsequent process and facilitate the subsequent processing procedure, in a preferred embodiment of the present invention, additives such as a crosslinking agent, a crosslinking auxiliary agent, a lubricant, an auxiliary agent, an antioxidant and a coloring material may be added in advance in the step of premixing. Wherein the content of the crosslinking agent is 0.3 to 15PHR relative to 100PHR of the first polyolefin composition resin; the content of the crosslinking auxiliary agent is 0-6 PHR relative to 100PHR of the first polyolefin composition resin; the content of the lubricant is 0.3 to 45PHR relative to 100PHR of the first polyolefin composition resin; the content of the auxiliary agent is 0.3-240 PHR relative to 100PHR of the first polyolefin composition resin; the content of the antioxidant is 0.3-15 PHR relative to 100PHR of the first polyolefin composition resin, and the antioxidant is selected from phenol antioxidants or triphenyl phosphite antioxidants; the content of the coloring material is 0 to 105PHR relative to 100PHR of the first polyolefin composition resin.
The crosslinking agent used in the present invention is an organic peroxide crosslinking agent which starts to decompose when the temperature rises to the decomposition temperature of the peroxide and reacts with the polyolefin resin to crosslink into a network structure. The organic peroxide has a half-life of 10 minutes at a decomposition temperature in the range of 110 to 220 ℃.
Specifically, the following compounds may be employed: succinic acid peroxide (110 ℃), benzoyl peroxide (110 ℃), 2-ethylhexanoic acid tert-butylperoxide (113 ℃), p-chlorobenzoyl peroxide (115 ℃), isobutyric acid peroxide (115 ℃), isopropylcarbonic acid peroxide (135 ℃), lauric acid peroxide (140 ℃), 2, 5-dimethyl-2, 5-di (benzoyl peroxide) hexane (140 ℃), peracetic acid tert-butyl ester (140 ℃), phthalic acid peroxide di-tert-butyl ester (140 ℃), maleic acid peroxide tert-butyl ester (140 ℃), cyclohexanone peroxide (145 ℃), benzoic acid tert-butyl ester (145 ℃), dicumyl peroxide (150 ℃), 2, 5-dimethyl-2, 5-di (tert-butyl-peroxide) hexane (155 ℃), benzoic acid, 2, 5-dimethyl-2, 5-di (tert-butyl-peroxide) hexane (155 ℃), and mixtures thereof, T-butyl peroxy (155 ℃), t-butyl hydroperoxide (158 ℃), di-t-butyl peroxide (160 ℃), 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexyne (170 ℃) and α, α' -bis-t-butylperoxy-1, 4-diisopropylbenzene (160 ℃). To select α, α' -bis-tert-butylperoxy-1, 4-diisopropylbenzene and 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexyne. The temperatures indicated in the above parentheses are the decomposition temperatures corresponding to the half-lives of the individual compounds of 10 minutes. In order to avoid the problem that the uniformity and quality of the product are affected by the crosslinking reaction in the former process (in the process of operation of a mixer or a kneader) or the difficulty of the latter process is increased, an organic peroxide crosslinking agent with higher decomposition temperature can be adopted to ensure that the former process can be controlled below the decomposition temperature, thereby improving the stability of the physical property and the appearance quality in batches.
The crosslinking assistant is selected from diolefins with two terminal carbon-carbon double bonds, trienes with two terminal carbon-carbon double bonds, tetraolefins with two terminal carbon-carbon double bonds (alkadiene, alkatriene, or alkatetraene compound and compound at least two terminal carbon-carbon double bonds), TAIC crosslinking assistant, TMPTA crosslinking assistant and nano TiO 22One or a combination of two or more of them. More specifically, one or more crosslinking aids such as 1,9-decadiene (1,9-decadiene), 1,7-octadiene (1,7-octadiene), 1,5-hexadiene (1,5-hexadiene), 1,4-pentadiene (1,4-pentadiene), 1,3-butadiene (1,3-butadiene), 1,3,5-hexatriene (1,3,5-hexatriene), and 2,3-dimethyl-1,3-butadiene (2,3-dimethyl-1,3-butadiene) can be used. Furthermore, nanoscale TiO2Can also be used as another crosslinking assistant, and the function of the crosslinking assistant is to promote the resin and the crosslinking agent to properly perform crosslinking reaction in a roller machine at the working temperature of 150-220 ℃, without additionally irradiating by radiation to improve the crosslinking degree. By adding nano-sized TiO2The resulting polyolefin film can be made uniform in appearance and physical properties, and can exhibit an excellent crosslinking effect when used in combination with the above-mentioned crosslinking assistant such as diolefin.
The auxiliary agent is one or mixture of ultraviolet absorbent and filler. Wherein, the content of the ultraviolet absorbent is 0.3-9 PHR relative to 100PHR of the first polyolefin composition resin, and the function is to eliminate free radicals generated in the ultraviolet irradiation process, thereby preventing chain growth and reducing the occurrence of photodegradation or photooxidation. Generally, the ultraviolet absorber is a Hindered Amine compound, and the Hindered Amine can be converted into a corresponding nitroxide radical after absorbing Light energy in an oxygen state, thereby capturing a radical generated in polymer degradation, and has a regeneration function in a Light stabilization process, thereby inhibiting a chain reaction. On the other hand, the content of the filler is 0.3 to 90PHR relative to 100PHR of the first polyolefin composition resin, and is selected from one or more than two of calcium carbonate, clay, talcum powder, mica powder, limestone and silica powder.
The characteristics of the lubricant, and the lubricant selected for use in the preferred embodiment of the present invention, are further described in the relevant sections below.
The antioxidant can be selected from phenolic antioxidants and Triphenyl phosphites, and sometimes two or more antioxidants are used, which can produce a significant synergistic effect. Wherein, the phenolic antioxidant can prevent the growth of a chain and can utilize the steric hindrance effect to prevent the oxidation reaction from going on; triphenyl phosphites are able to form stable compounds with oxygen atoms, decompose hydrogen peroxide compounds and terminate free radical chain reactions, thereby preventing chain reactions from occurring.
The colorant can be added according to the color requirement of the product. In practice, the colorant may be added by using an organic colorant, an inorganic colorant or a mixture of inorganic and organic colorants, and the colorant (i.e., 0PHR) may be omitted if it is not particularly required. The pigment is selected from carbon black and titanium dioxide (TiO)2) Phthalocyanine green, phthalocyanine blue, cobalt blue, ketone red, mercury cadmium red, cadmium yellow, chrome yellow, azo yellow, chrome green, ultramarine, Fe2O3Brown, etc. Due to micron-sized TiO2The film has strong shielding force (more than 0.1 μm), so that the film can be used as a coloring material, and the reflectance of a polyolefin film can be improved when the film is added in a proper amount, thereby being beneficial to improving the conversion efficiency of the solar cell to light energy and improving the power generation efficiency of the solar cell; furthermore, a proper amount of micron-sized TiO is added2The weather resistance of the polyolefin film can be improved, so that the service life of the solar cell is prolonged; furthermore, TiO in micron order2Can also strongly absorb the cross-linking agent to promote the cross-linking agent to be uniformly dispersed in the resin, thereby avoiding the occurrence of black spots in the product and being beneficial to the finishingAnd the quality of the product is improved.
Returning to the flow steps of the preferred embodiment of the present invention, in the aforementioned step S100, the first polyolefin composition resin, the second polyolefin composition resin, the elastic resin, the fluororesin, the fluorine-containing auxiliary agent, and the aforementioned various additives are first added to a mixer, and preliminary stirring is performed under low temperature conditions to form a mixture. Next, the mixture is uniformly kneaded with a kneader at a low temperature lower than the decomposition temperature of the crosslinking agent (step S102).
After the mixture is sufficiently kneaded and mixed by the kneader, it is fed into a roll mill so that the mixture can be preliminarily gelled and crosslinked by the roll mill (step S104). At this time, the operating temperature of the calender is controlled to be 130 to 220 c (depending on the selected crosslinking agent) in order for the crosslinking agent to function.
After the mixture is preliminarily gelatinized and cross-linked in the roll mill, the gelatinized mixture is formed into a sheet by a calender (step S106). At this time, the operating temperature of the calender is controlled between 130 ℃ and 220 ℃, so that the mixture is continuously gelatinized and crosslinked in the process of being calendered into a sheet by the calender, and the prepared product has good physical properties because of being fully gelatinized and crosslinked. Specifically, a higher temperature than that in the previous step may be used in this step to assist the decomposition of the crosslinking agent and to accelerate the progress of the crosslinking reaction. In addition, the production speed of the sheet body output by the calender is controlled to be 10-120 meters per minute, and the thickness of the sheet body is controlled to be 0.05 mm-1.0 mm, so that the uniform and sufficient crosslinking degree of the product is ensured.
It is worth mentioning that when the film of the present invention is applied to other different purposes, the film can be imprinted according to the actual requirement, and at this time, the sheet body made by the calender can be introduced into an embossing wheel set so as to press the required lines on the sheet body through the embossing wheel set. Since the preferred embodiment is mainly applied to a solar cell back sheet, the embossing step may not be performed in principle, however, if it is necessary to form optical microstructures on the surface of the sheet body in order to improve the reflection efficiency, the embossing step may be optionally performed.
On the other hand, since the polyolefin material has an increased viscosity in a high-temperature molten state, a phenomenon of sticking a wheel is likely to occur during the process of processing and molding, and the torque increases to make it difficult to process. In order to avoid the above situation, the preferred embodiment of the present invention adds a proper amount of lubricant, and adopts a way of matching the internal lubricant and the external lubricant. Wherein the external lubricant comprises C12-18 fatty acid series and fatty acid ester series, preferably stearic acid; the lubricant with both inside and outside comprises fatty acid amide, metal alkali and organosilicon lubricant; the internal lubricant includes fatty acid having a carbon number of 20 or more, paraffin hydrocarbon series, and the like. In the embodiment, the matching of the lubricants with different internal and external characteristics is utilized, so that the polyolefin resin is not adhered to the metal wheel surface of the adhesive tape machine, and the polyolefin resin is easily compatible with the lubricant and is easy to gel. As described above, in a preferred embodiment of the present invention, the content of the lubricant is 0.3 to 45PHR with respect to 100PHR of the first polyolefin composition resin. Wherein, the external lubricant accounts for 40-70% of the total amount of the lubricant, and the rest 30-60% is the internal lubricant or the lubricant with both internal and external parts.
It should be noted that, in order to avoid electrostatic sparking of the accumulated material (BANK) during the roll pressing of the crosslinked polyolefin on the surface of the laminator, it is also conceivable to add an antistatic agent to the initial mixture, thereby imparting conductivity to the surface of the polyolefin resin to eliminate the sparking. Specifically, one or more of ethoxylated glycerol fatty acid esters, phosphate esters, fatty amine derivatives, and other alcohol derivatives such as alkyl phosphate and polyethylene glycol stearate can be used as the antistatic agent of the present invention.
Returning to the main process steps of the present invention, after the sheet is made by the calender, the sheet is introduced into the cooling wheel set so that the sheet can be sufficiently cooled and shaped (step S108), and the final product is coiled and stored, thus completing the preparation procedure of the reworkable crosslinked weather-resistant polyolefin film of the present invention.
[ examples ]
The ingredients according to table 1 were taken and added to the mixer. The mixture is formed by pre-stirring in a mixer under low temperature conditions, then is mixed by a kneader, and is sent to a rolling mill to be gelatinized and crosslinked at 175 ℃. Then, the resulting mixture was rolled by a calender at 210 ℃ to give a sheet having a thickness of 0.06mm at 105 m/min.
[ comparative example ]
The ingredients according to table 1 were taken and added to the mixer. Pre-stirring by a mixer under low temperature to form a mixture, then mixing by a kneader, and then feeding into a rolling mill to gelatinize and crosslink at 180 ℃. Then, the mixture was rolled by a calender at 220 ℃ and 105 m/min to give a sheet having a thickness of 0.06 mm.
The comparative examples further illustrate the properties of the elastomer resin not added, and are compared with examples.
TABLE 1
| Example (parts by weight) | Comparative example (parts by weight) | |
| A first polyolefin composition resin | 100 | 100 |
| Second polyolefin composition resin | 200 | 200 |
| Elastic resin | 32 | 0 |
| Fluororesin | 2 | 2 |
| Fluorine-containing auxiliary agent | 0.2 | 0.2 |
| Crosslinking agent | 3 | 3 |
| Crosslinking aid | 0.5 | 0.5 |
| Lubricant agent | 0.5 | 0.5 |
| Auxiliary agent | 1 | 1 |
| Antioxidant agent | 1 | 1 |
[ evaluation items ]
Table 2 lists the test methods provided by the inspection standard for insulating back sheets for crystalline silicon solar cell modules in GB/T310342014, and by evaluating the various physical properties of the foregoing examples, it can be found that the obtained parameter values all meet the expected criterion values:
TABLE 2
In addition, table 3 additionally lists different test methods, and for various physical property evaluations of the examples of the present invention, the following test methods were respectively used for evaluation:
1. tensile strength (psi), elongation (%): the evaluation was carried out using the test ASTM D638M.
2. Surface tension: the evaluation was carried out using the ASTM D2578 test.
3. Heating and shrinking: evaluation was carried out by JIS-B0601 test.
TABLE 3
[ advantageous effects of the embodiments ]
One of the benefits of the invention is that the reworkable cross-linked weather-resistant polyolefin film provided by the invention, the method can lead the prepared reworkable crosslinking weather-resistant polyolefin film to be capable of being reworked through the technical proposal of mixing a first polyolefin composition resin, a second polyolefin composition resin and an elastic resin with different melting points and the technical proposal of mixing the first polyolefin composition resin, the second polyolefin composition resin and the elastic resin, leading in weather-resistant fluororesin and adding easy-reworkable fluorine-containing auxiliary agent, when the second polyolefin composition resin is processed at a temperature around the melting point of the second polyolefin composition resin and the reworkable crosslinked weather-resistant polyolefin film is bonded to a solar cell module and used as a back sheet, since the first polyolefin composition resin is not yet melted, it does not have too strong adhesion to the EVA layer and can be removed relatively completely. The reworkable crosslinking weather-resistant polyolefin film for the solar cell back plate can be conveniently replaced after the solar cell back plate is used for a long time, and in the initial assembly and processing process, if part of products are not aligned during attachment and need to be torn off and reworked, the phenomenon that residual glue is left on the crosslinking weather-resistant polyolefin film or the crosslinking weather-resistant polyolefin film is damaged or even other components of a solar cell assembly are damaged due to too strong adhesion can be avoided.
The disclosure is only a preferred embodiment of the invention, and is not intended to limit the scope of the claims, so that all technical equivalents and modifications using the contents of the specification and drawings are included in the scope of the claims.
Claims (9)
1. A reworkable cross-linked weather-resistant polyolefin film for a solar cell back sheet, comprising:
100 parts by weight of a first polyolefin composition resin, said first polyolefin composition resin having a first melting point;
a second polyolefin composition resin in an amount of 10 to 250 parts by weight relative to 100 parts by weight of the first polyolefin composition resin, the second polyolefin composition resin having a second melting point, the first melting point being higher than the second melting point by 20 ℃ or higher; and
an elastic resin in an amount of 30 to 70 parts by weight relative to 100 parts by weight of the first polyolefin composition resin;
wherein the elastic resin is a polyolefin elastomer;
the reworkable cross-linked weather-resistant polyolefin film for the solar cell back panel is processed and attached to the solar cell module at the temperature of the second melting point to serve as the back panel, and the first polyolefin composition resin is not melted;
before the reworking, the peeling force between the solar cell back plate of the reworkable crosslinking weather-resistant polyolefin film and an encapsulated EVA film layer of the solar cell module is more than or equal to 40N/cm;
and the stripping force between the solar cell back plate of the reworkable cross-linked weather-resistant polyolefin film and an encapsulated EVA film layer of the solar cell module after the reworking is more than or equal to 40N/cm.
2. The reworkable crosslinked weatherable polyolefin film for a solar cell backsheet according to claim 1, wherein:
the first polyolefin composition resin is a high-melting-point polypropylene resin with a melt flow index of 0.3-20 and a melting point of 150-170 ℃;
the second polyolefin composition resin is one or a combination of two or more of a high density polyethylene resin, a linear low density polyethylene resin, a low density polyethylene resin, and a low melting point polypropylene resin having a melt flow index of 3 to 20 and a melting point of 110 to 150 ℃, wherein the content of the high density polyethylene resin is 0 to 50 parts by weight based on 100 parts by weight of the first polyolefin composition resin, the content of the linear low density polyethylene resin is 0 to 100 parts by weight based on 100 parts by weight of the first polyolefin composition resin, the content of the low density polyethylene resin is 0 to 50 parts by weight based on 100 parts by weight of the first polyolefin composition resin, and the content of the polypropylene resin is 0 to 50 parts by weight based on 100 parts by weight of the first polyolefin composition resin.
3. The reworkable cross-linked weatherable polyolefin film for a solar cell backsheet according to claim 1, further comprising: and a fluororesin in an amount of 0.5 to 15 parts by weight based on 100 parts by weight of the first polyolefin composition resin, the fluororesin being one or a combination of two or more selected from the group consisting of polyvinylidene fluoride, polytetrafluoroethylene, an ethylene-tetrafluoroethylene copolymer, polychlorotrifluoroethylene, and an ethylene-polychlorotrifluoroethylene copolymer.
4. The reworkable crosslinked weather-resistant polyolefin film for a solar cell backsheet according to claim 3, wherein the fluororesin is polytetrafluoroethylene having a molecular weight of 25 to 100 ten thousand.
5. The reworkable crosslinked weatherable polyolefin film for a solar cell back sheet according to claim 1, wherein the fluorine-containing additive is PPA processing additive, and the content thereof is 0.1 to 1 part by weight relative to 100 parts by weight of the resin content of the first polyolefin composition.
6. The reworkable cross-linked weatherable polyolefin film for a solar cell backsheet according to claim 1, further comprising:
a crosslinking agent in an amount of 0.3 to 15 parts by weight based on 100 parts by weight of the first polyolefin composition resin, wherein the crosslinking agent is an organic peroxide crosslinking agent;
0-6 parts by weight of a crosslinking assistant per 100 parts by weight of the first polyolefin composition resin, wherein the crosslinking assistant is one or a combination of two or more selected from diolefins with two terminal carbon-carbon double bonds, triolefins with two terminal carbon-carbon double bonds, tetraolefins with two terminal carbon-carbon double bonds, triallyl isocyanurate, trimethylolpropane triacrylate and nano-scale titanium dioxide;
a lubricant in an amount of 0.3 to 45 parts by weight relative to 100 parts by weight of the first polyolefin composition resin;
an auxiliary agent in an amount of 0.3 to 240 parts by weight based on 100 parts by weight of the first polyolefin composition resin;
an antioxidant in an amount of 0.3 to 15 parts by weight relative to 100 parts by weight of the first polyolefin composition resin, the antioxidant being selected from a phenol antioxidant or a triphenyl phosphite antioxidant; and
and a colorant in an amount of 0 to 105 parts by weight based on 100 parts by weight of the first polyolefin composition resin.
7. The reworkable cross-linked weatherable polyolefin film for a solar cell backsheet according to claim 1, wherein the reworkable cross-linked weatherable polyolefin film has a reflectance of light with a wavelength of 420 to 650nm of greater than 65%.
8. A using method of a reworkable crosslinked weather-resistant polyolefin film for a solar cell back sheet is characterized by comprising the following steps: providing a reworkable crosslinked weatherable polyolefin film for a solar cell back sheet, the reworkable crosslinked weatherable polyolefin film for a solar cell back sheet comprising:
100 parts by weight of a first polyolefin composition resin, said first polyolefin composition resin having a first melting point;
a second polyolefin composition resin in an amount of 10 to 250 parts by weight relative to 100 parts by weight of the first polyolefin composition resin, the second polyolefin composition resin having a second melting point, the first melting point being higher than the second melting point by 20 ℃ or higher; and
an elastic resin in an amount of 30 to 70 parts by weight relative to 100 parts by weight of the first polyolefin composition resin;
wherein the elastic resin is a polyolefin elastomer;
processing at the temperature of the second melting point, and attaching the reworkable crosslinked weather-resistant polyolefin film for the solar cell back panel to a solar cell module to be used as a back panel, wherein the first polyolefin composition resin is not melted; and
repairing: tearing off the solar cell back plate of the reworkable cross-linked weather-resistant polyolefin film for the solar cell back plate, and then re-attaching the solar cell back plate of the reworkable cross-linked weather-resistant polyolefin film for the solar cell back plate;
before the repairing, the stripping force between the solar cell backboard of the repairable crosslinking weather-resistant polyolefin film for the solar cell backboard and an encapsulated EVA film layer of the solar cell module is more than or equal to 40N/cm;
and the stripping force between the solar cell backboard of the reworkable crosslinking weather-resistant polyolefin film for the solar cell backboard and an encapsulated EVA film layer of the solar cell module after the reworking is not less than 40N/cm.
9. The use method of the reworkable crosslinked weather-resistant polyolefin film for a solar cell back sheet according to claim 8, wherein:
the first polyolefin composition resin is a high-melting-point polypropylene resin with a melt flow index of 0.3-20 and a melting point of 150-170 ℃;
the second polyolefin composition resin is one or a combination of two or more of a high density polyethylene resin, a linear low density polyethylene resin, a low density polyethylene resin, and a low melting point polypropylene resin having a melt flow index of 3 to 20 and a melting point of 110 to 150 ℃, wherein the content of the high density polyethylene resin is 0 to 50 parts by weight based on 100 parts by weight of the first polyolefin composition resin, the content of the linear low density polyethylene resin is 0 to 100 parts by weight based on 100 parts by weight of the first polyolefin composition resin, the content of the low density polyethylene resin is 0 to 50 parts by weight based on 100 parts by weight of the first polyolefin composition resin, and the content of the polypropylene resin is 0 to 50 parts by weight based on 100 parts by weight of the first polyolefin composition resin.
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| CN201811141291.0A Expired - Fee Related CN109651964B (en) | 2017-10-11 | 2018-09-28 | Reworkable cross-linked weather-resistant polyolefin film for solar cell back panel |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928425A (en) * | 2010-09-02 | 2010-12-29 | 苏州赛伍应用技术有限公司 | Resin composition and solar batter component containing the same |
| JP5075281B2 (en) * | 2010-10-06 | 2012-11-21 | 積水化学工業株式会社 | Flexible solar cell module |
| CN103214715A (en) * | 2013-04-03 | 2013-07-24 | 南亚塑胶工业股份有限公司 | Crosslinking weather resistance polyolefin composite applicable to adhesive tape machine processing and manufactured adhesive tape and method thereof |
| CN104371227A (en) * | 2014-11-06 | 2015-02-25 | 浙江比例包装股份有限公司 | Fluorine-containing plastic processing assistant and preparation method thereof |
| CN205944114U (en) * | 2016-08-24 | 2017-02-08 | 苏州中来光伏新材股份有限公司 | Solar cell back sheet and subassembly thereof |
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| CN102585731B (en) * | 2011-12-28 | 2014-03-05 | 广州鹿山新材料股份有限公司 | Polyolefin packaging glue film composite and application thereof |
| JP6191252B2 (en) * | 2013-06-07 | 2017-09-06 | 大日本印刷株式会社 | Encapsulant composition and encapsulant for solar cell module |
-
2017
- 2017-10-25 CN CN201711014438.5A patent/CN109651978A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928425A (en) * | 2010-09-02 | 2010-12-29 | 苏州赛伍应用技术有限公司 | Resin composition and solar batter component containing the same |
| JP5075281B2 (en) * | 2010-10-06 | 2012-11-21 | 積水化学工業株式会社 | Flexible solar cell module |
| CN103214715A (en) * | 2013-04-03 | 2013-07-24 | 南亚塑胶工业股份有限公司 | Crosslinking weather resistance polyolefin composite applicable to adhesive tape machine processing and manufactured adhesive tape and method thereof |
| CN104371227A (en) * | 2014-11-06 | 2015-02-25 | 浙江比例包装股份有限公司 | Fluorine-containing plastic processing assistant and preparation method thereof |
| CN205944114U (en) * | 2016-08-24 | 2017-02-08 | 苏州中来光伏新材股份有限公司 | Solar cell back sheet and subassembly thereof |
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| CN109651978A (en) | 2019-04-19 |
| TW201915074A (en) | 2019-04-16 |
| CN109651964A (en) | 2019-04-19 |
| TWI679235B (en) | 2019-12-11 |
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