WO2013125799A1 - Fluorine-based polymer composition for back sheet of solar cell module and method for manufacturing back sheet comprising same for solar cell module - Google Patents

Fluorine-based polymer composition for back sheet of solar cell module and method for manufacturing back sheet comprising same for solar cell module

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Publication number
WO2013125799A1
WO2013125799A1 PCT/KR2013/000716 KR2013000716W WO2013125799A1 WO 2013125799 A1 WO2013125799 A1 WO 2013125799A1 KR 2013000716 W KR2013000716 W KR 2013000716W WO 2013125799 A1 WO2013125799 A1 WO 2013125799A1
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Prior art keywords
polymer
solar
step
composition
cell
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PCT/KR2013/000716
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French (fr)
Korean (ko)
Inventor
하종욱
이수복
박인준
이광원
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한국화학연구원
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04Coating
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J179/00Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
    • C09J179/04Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09J179/08Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L31/00Semiconductor devices sensitive to infra-red radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus peculiar to the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04Semiconductor devices sensitive to infra-red radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus peculiar to the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042PV modules or arrays of single PV cells
    • H01L31/048Encapsulation of modules
    • H01L31/049Protective back sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J2327/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/16Homopolymers or copolymers of vinylidene fluoride
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy

Abstract

The present invention relates to a fluorine-based polymer composition for the back sheet of a solar cell module, and to a method for manufacturing a back sheet comprising same for a solar cell module, and more particularly, to a fluorine-based polymer composition for the back sheet of a solar cell module characterized by comprising a fluorine polymer and an adhesive polymer binder resin, wherein the fluorine polymer is a homopolymer of vinylidene fluoride (VDF), a copolymer of VDF, or a combination thereof; and the adhesive polymer binder resin comprises polyamic acid. According to the invention, the fluorine-based polymer composition for the back sheet of a solar cell module has excellent strength of adhesion to the base material so that the formation of an additional adhesive layer on the material beforehand is not necessary, thus simplifying the manufacturing process for the back sheet. The back sheet for a solar cell module manufactured using the composition is characterized by having excellent durability and weather resistance.

Description

【Specification 】

- the title of the invention;

Method of manufacturing a solar cell back sheet of a fluorine-based polymer for the base compositions and the back sheet for solar cells comprising the same modeul

[Technology]

The invention relates to a method for manufacturing a back sheet of a fluorine-based polymer composition for the back of the solar cells 7, the parent sheet and a solar cell comprising the same parent.

[Background Art]

Solar mode used outdoors have a high durability and weather resistance is required in such configuration and material structure. In particular, because the role of the solar cell modeul back surface is exposed to the environment, the backsheet so that the solar cell can be maintained over 25 years of long-term properties in harsh environments, as well as long-term weather resistance excellent, blocking of water vapor and oxygen resistance and UV it is necessary to excel resistance. Further, the back sheet is the key to protection from degradation of the silicon wafer caused by the banung as moisture and oxygen or UV rays.

In general, the structure of the back sheet is a film form a stacked into three functional layers. More specifically, the back sheet is a polyester-based base film to wrap on both sides (encapsulate) structure with a fluorine-based polymer film.

To the polyester substrate has a high moisture and oxygen barrier properties of polyethylene terephthalate (PET) has been mainly used. In addition, a polyethylene terephthalate in the surrounding on both sides the fluorine polymer film is polyvinyl fluoride (PVF) of the US Dew pungsa Raise the Te film have been primarily used.

A typical solar cell back sheet is made of polyvinyl fluoride / polyethylene terephthalate / polyvinyl laminate film of Lai DE layer.

Polyethylene terephthalate is a problem that has excellent water vapor barrier properties and is relatively inexpensive, but performance of the environmental impact caused by the ultraviolet rays, infrared rays and ozone easily lowered. Accordingly, the Te film Raise weather resistance is excellent polyvinyl fluoride film was bonded to both sides of a polyethylene terephthalate film complements the weather resistance of the back sheet.

However, the rim Raise film is a relatively expensive matter unsatisfactory resistance to water vapor. In addition, fluorinated polymer, such as the Te Raise film there is a disadvantage that the adhesion to polyethylene terephthalate good general process the polymer surface with a technique such as corona discharge, or is used by applying the adhesive on the polyethylene terephthalate film .

The sub-total block polymer is used to produce a pre-loaded form. At this time, it contains a fluorine-based polymer film production process and post-process, a thick fluorine-based polymer layer as above, and should have a thickness that is cheungbun a thickness, which results in an efficient requires a protective layer to give the strength required for the pre-formed. In addition, there is a problem that because the laminate was formed an adhesive layer in advance on the substrate required many expensive requires heat and pressure. A technique related to a conventional back sheet for solar cells may modeul following techniques are known as. Republic of Korea Patent Application Publication No. 1 lead 2011 eu No. 0,030,857 (Published: 24.03.2011) that is related to additional surface treatment sealant film having excellent adhesion between the solar cell back sheet of for without the backsheet polyamide on one surface of the substrate and forming a coating layer containing a resin, another aspect is directed to a back sheet which is prepared by forming a vinylidene fluoride polymer coating layer (Patent Document

One). The polyamide-based resin comprising a Fuji Kasei (Fuji kasei)'s TXM78-A, TXM78-C, Thorn ide series, Uni Kema one or more selected from the group consisting of MACR0MELT 6901 of PRIADIT2053 and henkelsa's (Uni cheraa) and that is characterized. However, the invention is a method for improving the adhesion of the film to form the polyamide-based resin on a surface of a substrate package, a fluorine-based polymer resin is the adhesive strength between being attached to form a separate bonding layer, a fluorine-based polymer resin and substrate sikineunde improvement is limited. Republic of Korea Patent Publication No. 10-2008-0078179 No. (Published: 27.08.2008) relates to a method of manufacturing the back sheet to be used for protection of the solar Sal, laminating a fluorine polymer compound, a polyvinyl fluoride film to a polyester film by case so that by applying a super strong adhesive the UR in a precise coating amount attached to the force on the can, durability, moisture resistance, heat resistance, UV improve the properties and flatness made on the back sheet is used as a protective sheet for solar cells to be is (Patent Document 2).. However, the backsheet in order to improve the adhesion of the polyvinyl fluoride film to the polyester film, to be carried out each time to form one of the functional layers such as adhesive layer is corona treated first. In addition, the pressing process is required to increase the adhesive force of the UR, there is a problem that the production steps increases, including a step to press the the final laminated substrate. Republic of Korea Patent Registration Patent 10-0612411 (date: 08.07.2006) relates to a process of manufacturing the back sheet for solar cell modeul the step of unwinding a polyethylene terephthalate film in the take-up reulreo (step 1); The step of applying an adhesive to one side of a polyethylene terephthalate film unwound in said step 1 (step 2); Passing the adhesive-coated polyethylene terephthalate film in the second step has a different temperature condition of the heating chamber into a plurality of continuously arranged (step 3); Cooling the third stage of the polyethylene te Lev 1 de-rate film (step 4); The step of unwinding a rolled rim Raise film and by pressing the "adhesive coated surface of the rim by the unwinding of the film Raise gaapreul multiple cooling of step 4, a polyethylene terephthalate film laminated (step 5); Relates to a solar cell back sheet modeul a manufacturing process characterized in that comprising a (Patent Document 3); and Te Raise the film is a polyethylene terephthalate film bonded to the step of winding the reulreo (step 6). However, the method of manufacturing the back sheet is a step of forming an adhesive layer of Te Raise film prior to lamination to the polyethylene terephthalate film be followed first. Moreover, it includes a step of aging for a long period of time of 60 to 80 hours, the prepared backsheet long manufacturing time, the manufacturing process is complicated problem. Republic of Korea Patent Publication No. 10-2011-0010386 No. (Publication date: 2011.02 0.01) is directed to a solar cell back sheet and a production method thereof, a) a base layer 2) is coated on at least one surface on the substrate layer, the adhesive layer containing a urethane-based adhesive agent, and 3) is coated on the adhesive layer, fluoride vinylidene relates to dengye method for manufacturing a solar cell back sheet thereof comprises a fluorine-based coating layer comprising a polymer and a solar cell comprising the same (Patent Document 4), but the invention is the base layer prior to the formation of the fluorine-based coating layer after be preceded by the step of forming an adhesive layer hamye drying the formed adhesive layer at a high temperature of 160 ° C, the need for a separate process to the process is a complicated problem nyaenggak The. The invention backsheet by coating a fluorine polymer is polyvinyl fluoride (PVF) of interest level yet satisfactory hagieneun replacing the backsheet with a laminate film is not, there is a worldwide solar cell demand class height and the production cost is cheaper is the actual circumstances that there is a need for a back sheet material for weather resistance and durability, new and improved solar modeul is increasing. The physical properties required for the solar cell backsheet may be secured durability and weatherability properties have excellent adhesion between the material and the material itself. Thus, the present inventors to solve the problems as described above, the fluorinated polymer composition comprising the fluorinated polymer and the adhesive polymer binder resin is not necessary to pre-form a separate adhesive layer to a substrate is excellent in adhesion to a substrate backsheet and to shorten the manufacturing process, to find out that it can control the thickness of the thin layer composition is coated on a substrate it is possible to reduce the fluorinated polymeric material cost and completed the present invention.

(Patent Document 1) KR 10-2011-0030857 A (2011.03.24 1, 5 p)

(Patent Document 2) KR 10-2008-0078179 A (2008.08.27, 2 p)

(Patent Document 3) KR 10-0612411 B1 (2006.08.07, 5 eu 7).

(Patent Document 4) KR 10-2011-0010386 A (2011.02.01, 2 p)

[Detailed Description of the Invention]

[SUMMARY]

The purpose of the present invention to provide a fluorinated polymer composition for the back sheet of a solar cell model.

A further object of the present invention to provide a method for manufacturing a solar cell modeul back sheet using the composition.

[Technical Solution]

In order to solve the above problems, the present invention is a fluorine polymer and adhesive

"Comprises a polymer binder resin, the fluorine polymer is vinylidene, fluoride (VDF) homopolymer, vinylidene fluoride copolymer, or a combination of a; Adhesive polymer binder resin provides a backsheet fluorinated polymer composition of the solar cell base comprising a polyamic acid (acid Polyamic).

The invention also common summing uniformly adding a solvent to the fluorinated polymer composition (step 1); The step of coating the common compound prepared in Step 1, on one side or both sides of a polyethylene terephthalate, polyethylene naphthalate, or a combination of the substrate (step 2); And a step (step 3) heating the coated substrate is a common compound in Step 2; provides a method of producing a backsheet for a solar cell module comprising a.

[Advantageous Effects]

Fluorinated polymer composition produced in the present invention is excellent in adhesion to the substrate, it is not necessary to pre-form a separate adhesive layer to the substrate it is possible to shorten the back sheet manufacturing process. Further, the tank is coated on a base material. This For be thin to control the thickness of the Dangerous it can not only reduce the raw materials cost of the fluorinated polymer, the solar cell produced using the composition modeul backsheet excellent durability and weatherability characteristics have.

[Brief description of drawings]

1 is a schematic diagram showing a cross-sectional shape of the back sheet for solar cells according to the invention modeul.

2 is a brief schematic view showing a method of manufacturing a back sheet for solar cells according to the invention modeul.

[Best mode for practicing the invention;

¾ invention includes a fluorine polymer and the adhesive polymer resin binder,

The fluorine polymer is vinylidene fluoride (VDF) of ¾ dock polymer, vinylidene fluoride copolymer, or a combination thereof, and; Adhesive polymer binder resin provides a backsheet fluorinated polymer composition of the solar cell base comprising a polyamic acid (acid Polyamic). Furthermore, the present invention common summing stage uniformly by adding a solvent to the composition (step 1);

The step of coating the common compound prepared in Step 1, on one side or both sides of a polyethylene terephthalate, polyethylene naphthalate, or a combination of the substrate (step 2); And

It provides a method of making solar cell back sheet comprising a modeul; (step 3) heating the coated substrate is a common compound in the above step 2. Hereinafter, the present invention will be described in detail. The present invention (hereinafter called hereinafter composition.) Fluorine-containing polymer composition for the back sheet of a solar cell mode according to the comprises a fluorine polymer and the adhesive polymer binder resin, a fluorine polymer is vinylidene fluoride (VDF) contained in the composition a homopolymer, vinylidene fluoride copolymer, or a combination thereof, and;, the adhesive polymeric binder resin comprises a polyamic acid (acid polyamic). In the present invention, the fluorine polymer contained in the composition prevents degradation of the substrate due to the external environment and acts as a supplement to the durability and weather resistance of the back sheet, an adhesive polymeric binder resin of the composition in the coating and curing process of the composition improves the adhesion to the base material ", it serves to strengthen the coating composition layer to the substrate. The composition according to the present invention because it has excellent adhesion to a base material including a fluorine polymer and the adhesive polymer binder resin, it is not necessary to pre-form a separate adhesive layer to the substrate it is possible to shorten the back sheet manufacturing process, the coating on the substrate It can control the thickness of the thinner composition that it has an advantage capable of reducing the raw material cost of the fluorinated polymer. The composition is coated on a base material, the base material include polyethylene terephthalate (polyethylene terephthalate, PET), polyethylene naphthalate (polyethylene; naphthalate, PEN) or, but can use a polyester resin comprising a common compound of the materials limited not, the person skilled in the art to be freely selected depending on the function or use of the produced backsheet. Further, the fluorine polymer contained in the composition according to the invention uses a common compound of exclusive authentication copolymer, vinylidene fluoride copolymer or the material of vinylidene fluoride (VDF), specifically speaking solely of vinylidene fluoride polymer; Common compound of the copolymer of vinylidene fluoride and other fluorine-based monomer; And common compound of vinylidene fluoride homopolymer and a vinylidene fluoride copolymer; uses. In the case of using a common compound of vinylidene homopolymer, vinylidene fluoride copolymer or the material of the fluoride as a fluorine polymer contained in the composition according to the invention, a vinylidene fluoride 60 with respect to the total mol number of the fluorine polymer and - preferably included in 90 mol%, more preferably it contained by 80 ~ 90 mol%. When the vinylidene fluoride comprises less than 60 mol%, based on the total molar number of the fluorine polymer, there is a problem can not exert the effects associated with the durability and weather resistance, stir drying characteristics required for solar cell back sheet. Further, as the fluorine polymer of vinylidene fluoride and other fluorine-containing monomers common in the case of using the compounds, the ratio of the other fluorine-containing monomers than vinylidene fluoride, based on the total molar number of the fluorine polymer having difficulty in the solvent selected for high to coat the composition on the substrate there is a problem. In the present invention, the vinylidene fluoride copolymer can be used a fluorinated comonomer containing a vinyl ether or fluoro Lodi dioxole (fluorodioxole) fluoroalkyl roeul repin, fluoro. The fluorinated comonomers include tetrafluoroethylene (TFE), a hex-fluoro-propylene (HFP), chlorotrifluoroethylene with ethylene (CTFE), trifluoro-ethylene, butyl ethylene, purple as isobutylene, perfluoro hex-fluoro by Luo as propyl vinyl ether (PPVE), perfluoroalkyl vinyl ether (PEVE), perfluoro methyl vinyl ether (PMVE), perfluoro-2, 2-dimethyl-1,3-dioxole (PDD) and purple from the group comprising 2-methylene-eu eu -4-methyl-1,3-dioxolane (PMD) by Luo can be selected at least one kind. Furthermore, the composition according to the invention comprises an adhesive polymeric binder resin. In the present invention, the adhesive polymeric binder resin is preferably included in the fluorine polymer and the adhesive 4 to 50 parts by weight based on the total weight of the polymeric binder resin ¾ which heunhap the solvent in manufacturing a composition, comprising 10 to 40% by weight it is further preferred that. The adhesive polymeric binder resin is contained in excess of the fluorine polymer and the adhesive agent when included as less than 4 wt ¾ based on the total weight of the polymer binder resin, and the problem is not the adhesive force of the composition and the substrate cheungbun, 50% by weight If there is a problem that the durability and weather resistance poor to lower the physical properties of the composition. The compositions according to the present invention includes a polyamic acid as the adhesive polymer resin binder. Polyamic acid the polyimide time at 30 ° C as a precursor of (poly imide) is Ν, O-dimethyl-Ν- theta imide dissolved in 0.5 wt% (Ν, Ν-dimthylacetamide) has an inherent viscosity of at least 0.1, N- methylpiperidin-tease has a characteristic such as viscosity, such as money (N- methylpyrrolodone) a condensing reagent (coalescing agent) and furfuryl alcohol (furfuryl alcohol) which is soluble in lowering agent. In addition, polyamine acids generally imidization as resin advanced by about 50%, when cured up the condensed banung of carboxylic acid groups and amine groups are imidized banung proceeds to a further feature for improving the durability of adhesion and coating of the base material there is.

* 45. In addition, carboxylic acid groups or amine groups which can be the surface of the hydrogen-bonding of the polyester substrate to contribute to the improved adhesion to the substrate, In addition, the esterification banung or already polyester by encoding banung contained in the polyamic acid possible chemical bond with the substrate surface, so it can improve the adhesion to the substrate greatly. In addition, the composition according to the invention as an adhesive polymeric binder resin replicon amide imide (Polyamide imide, PAD, polyimide (Polyimi de, PI), polyphenylene sulfide (Polypheny lene sulfide, PPS), polyether sulfone (Polyether sulfone , PES), polyarylene-ether ketone (Polyary lene- etherketone), replicon imide (polyether imi de), polyphenylene oxide (Polyphnylene oxide), poly ether ketone, silicone and epoxy (meth) acrylic resin containing may further include a binder resin, at least one member selected from the group. in the case where the composition according to the invention comprises a common compound of the polyamine acid and a binder resin with an adhesive polymeric binder resin, polyamine acids on the total weight of the adhesive polymer binder resin "About preferably included as less than 50 weight ¾ ~ 100% by weight. polyamic acid adhesive polymeric binder If not the total that is heunhap to less than 50% by weight prepared for the weight has a problem reduced or falls durable adhesion to the base material of the composition. In addition, the composition according to the invention a dehydrating agent and already for chemical curing of the polyamic acid the catalyst may further comprise encoding.

Thus, the present invention is a chemically curing proceeds imidization method by the adhesive polymer binder resin, already proceeding imidization by heating in order to progress the imidation of "polyamic acid method of thermal curing and the dehydrating agent and the imidization catalyst to be included in the At the same time it can be done. In the present invention, the dehydrating agent is contained in the composition may contain 5-23 parts by weight based on the total weight of the composition, the dehydrating agent is, for example, can be used for acid anhydride (acid anhydride) such as acetic anhydride. In the present invention, the imidization catalyst may be included as part 0.05 to 2 parts by weight based on the total weight of the polyamic acid contained in the composition, the imidization catalyst is, for example, isoquinoline (isoquinoline) contained in the composition, beta-can be used a tertiary amine, such as picoline (β -picol ine) and pyridine. Furthermore, the degree of imidization of polyamic acid, the polyamic acid contains the molecular weight, the polyamic acid is already banung condition of encoding in accordance with the film thickness and the curing method of the composition that included in the composition may vary. Further, in the present invention: The composition may further comprise a particle barrier for blocking additive and the oxygen and water, such as pigments, fillers, light stabilizers. In the present invention, the additive is in the solar cell modeul possible to improve the power generation efficiency and properties of the solar cell, as in additives, pigments by selecting, for example, titanium oxide, silica, alumina and one or more of calcium carbonate It can be used. In the present invention, wherein the barrier particles are mica in solar modeul as can improve the moisture barrier properties of the composition, the barrier particles are coated with an oxide layer, such as for example, iron oxide, titanium oxide particles, can be used by selecting the glass flakes (glass flake) particles, stainless steel pool Lake (stainless steel flake) particles and aluminum flakes (flake aluminium) 1 or more kinds of particles. Furthermore, the present invention common summing stage uniformly by adding a solvent to the composition (step 1);

The step of coating the common compound prepared in Step 1, on one side or both sides of a polyethylene terephthalate, polyethylene naphthalate, or a combination of the substrate (step 2); And

It provides a method of making solar cell back sheet comprising a modeul; (step 3) heating the coated substrate is a common compound in the above step 2. Hereinafter, a method of manufacturing a back sheet for solar cell modeul according to the present invention will be described in more detail step by step. In the present invention, step 1 is a step common to sum the composition and the solvent. A method of manufacturing a back sheet for solar cell modeul according to the present invention, information about the composition and the solvent is heunhap the specific description thereof is identical as described above will be omitted.

The composition and the solvent to be heunhap acetone (Acetone), methyl ethyl ketone (methylethylketone)

. Tetrahydrofuran (tetrahydrofuran, THF) of common compounds, isophorone (isophorone), dimethylacetamide (dimethyl acetamide), propylene carbonate (propylene carbonate), - butyl pyrrolidone lactone (eu butyrolactone) and N 一-methylpyrrolidone ( N- methyl pyrrolidone) and dimethyl sulfonyl oxide (but can be used dimethylsulfoxide) alone or the combined common traces of compound, was relatively lower than the boiling point of the composition, the bubble does not occur in the film formation and drying of the composition, the composition comprising If the solvent is to help unggyeol (coalescence) of the fluorine polymer it is not limited to that.

In the present invention, the composition being heunhap and the solvent is available in a solution (solution) or a dispersion liquid (dispersion) type. More specifically, the composition may be provided in solution or dispersion form according to the solvent to be used as a fluorine type polymer in the composition.

In the present invention, a fluorine polymer in the composition is heunhap the solvent is preferably 10 to 50% by weight relative to the total weight of water heunhap of the composition and the solvent. If the fluorine polymer in the composition contained the heunhap to less than 10 wt% based on the total weight of water, if contained, and have a problem that is not economical because a lot of energy consumption to evaporate the solvent, and more than 50% by weight, the solution viscosity of to the excessively increased formation of high-quality coating layer it is difficult. Heunhap concentration of water produced in the step 1 and the need to adjust the viscosity according to the working characteristics, the viscosity may vary depending upon the other components and the process equipment and processing conditions of the composition.

Further, the step 1 can be used to separate the milling device to heunhap the composition and the solvent, but on the, "may be combined uniformly common to the composition and a solvent, the composition and heunhap process the heunhap water physical and chemical characteristics produced in the solvent do not change the present invention it is not limited thereto. Further, the step 1 according to the present invention is a vinylidene fluoride homopolymer, vinylidene fluoride copolymer, or the combined the material traces further comprising the step of producing fluorine polymer, through the steps for the total number of moles of the fluorine polymer You may adjust the amount of vinylidene fluoride.

Method for preparing the fluorine polymer is so commonly known, a person skilled in the art can be easily produced. Further, Step 2 according to the invention is a method comprising coating the common compounds (compounds of the composition and the common solvent) the substrate prepared in Step 1. A substrate on which is coated the common compound is a polyethylene terephthalate (polyethylene terephthalate, PET), polyethylene naphthalate (polyethylene naphthalate, PEN) or, but can use a polyester resin comprising a common compound of the materials are not limited to, Therefore, the function or purpose of the back sheet is made one of ordinary skill in the art can be selected free topge.

In the present invention, the back sheet for solar cell modeul, but can be coated with a common compound prepared in Step 1, on one side or both sides of a base material, the base material in order to increase the strength, weather resistance, UV resistance and moisture barrier properties of the backsheet it is the coating on both surfaces is preferred. As a method for coating a common compound prepared in step 1 to the base material, but can take advantage of a known method such as casting, dipping, spraying, and coating in the art, there is possible to uniformly coat a common compound to the substrate limited no.

Further, the above method may be performed using conventional coating apparatus such as a spray coating device, a coating device, a knife coating apparatus and a curtain coating device. Further, the steps of step 3 is heated to the common compound is coated substrate according to the invention, it consists of a drying step and a curing step. The drying step is common to the process of evaporation of the solvent that has been contained in the compound, drying of the common compounds the coated substrate may be made from 25 ~ 200 ° C relative to the temperature of the heater 3 to 15 minutes, of the substrate the temperature should be kept below the heating device. Further, the temperature of the substrate should be maintained at a temperature capable of promoting interaction with functional period of the functional group and the base material of the adhesive polymer resin in the binder composition in order to ensure that the fluorine polymer is completely adhered to the substrate in the composition. Further, the curing step is a step of traces to be performed after the process of evaporation of the solvent that has been contained in the compound, unggyeol (coalescence) of the fluorine polymer particles in the composition in a continuous film form. At this time, the curing may take place for 1 to 30 minutes at 150 ~ 250 ° C, based on the silver is in the heating device, the temperature of the coating composition to the substrate is lower than the heating device. At this time, the conditions for unggyeol the composition may vary according to the operating conditions such as the thickness of the fluorine-type of polymer, solvent and substrate used.

[Mode for Carrying out the invention]

It will be described in more detail through the following examples of the present invention. However the examples are not limited by the examples of this disclosure, it may make the present invention to illustrate the invention.

<Example 1> Preparation of solar cell backsheet for modeul 1

Step 1: Preparation of fluorine polymer

In the DI water 620 mi in 1000 mi pressure half equipped with a stirrer unggi, and then pressurized to 5 atm by feeding nitrogen gas, and by an operation for degassing repeated five times to remove the air made to the pressure half unggi in vacuo .

Perfluoroalkyl of 20% by weight in the vacuum pressure half unggi octanoic acid ammonium salt solution (Aldrich) and 6.3 mi of chloroform (Junsei) was added to 1.0 m.

Raising the pressure of silver is half unggi to 80 ° C, vinylidene fluoride (Apollo Scientific Co.) added to the pressure Raise to 300 psig, 0.2% ammonium sulfate solution is added to a 10 ml buffer (APS, Ammonium Persulfate, Junsei) the It was added.

After the initial reaction the 5 psi pressure drop occurred, the 0.2% while maintaining the pressure in the anti-unggi to 300 psig ammonium persulfate solution (initiator solution, Junsei) was begun to supply at a rate of 0.6 m ^ / rnin. Banung after the start, vinylidene fluoride after a total of 205 g is turned on, the supply of all the raw materials was stopped and the product was recovered by lowering the pressure of the semi unggi is solid content of the product 25.0%. After dilution of the product with deionized water in the same amount was cooled to ungjip.

Was collected by filtration and the ungjip fluorine polymer solid then was washed three times with deionized yieunsu of 1000 ml and dried with 50 ° C to obtain a polyvinylidene fluoride powder. Step 2: "Preparation of a back sheet for solar cell modeul

The polyvinylidene fluoride powder 30 g, polyamic acid (PAA, Solvay Advanced Polymers Inc., Toron AI-10) prepared in Step 1 7 g, acetic acid anhydride and 3 g, and isoquinoline 0.2 g All isophorone solvent was suspended in 50 g .

The suspension mulol glass beads (glass bead, diameter = 4 讓) were combined uniformly common for 30 minutes by a ball mill to prepare a device that contains a fluorine-based polymer composition solution.

The composition solution using a knife (draw knife) pulling of 0.125 mm dukkae was coated on a polyethylene terephthalate film (SKC Inc., skyrol SG00L, thickness 250) substrate. After this, 150 "for 5 minutes evaporated solvent in the air C, and cured within 10 minutes at a Bon Festival heated to 200 ° C.

At this time, the thickness of the coating was measured composition was 25 m. <Example 2> Preparation of solar cell backsheet for modeul 2

According to the first embodiment. Vinylidene fluoride and chloro-tetrafluoroethane as beulso polymer in step 1, ethyl (. CTFE), respectively 80: was prepared for a solar cell modeul backsheet in the same manner as in Example 1 except for using a 20 weight ratio.

<Example 3> Preparation of the back sheet for solar cell modeul 3

Of Example 1 propylene to vinylidene fluoride and the hex-fluoro-fluorinated polymer in the step of (HFP), respectively 80: 20 in the same manner as in Example 1 except that a weight ratio of the solar cell back sheet for modeul of It was prepared. <Example 4> Preparation of the back sheet for solar cell modeul 4

Example 1 Ethylene with vinylidene denpol fluoride and tetrafluoroethylene as a fluorinated polymer in the step of (TFE), respectively 90: Use in a weight ratio of 10, except that a dehydrating agent and is not already in use for encoding the catalyst in step 2, It was prepared a solar cell modeul backsheet in the same manner as in example 1.

<Example 5> Preparation of the back sheet for solar cell modeul 5

In the example except for using a weight ratio of 20 and 8 minutes in a heated Bon Festival to 200 ° C cured: Example 1 Step 2, a polyamine acid and polyether sulfone (PES) with an adhesive polymeric binder resin in each of 80 of the in the same manner as in 1 was prepared for solar cell back sheet modeul.

<Example 6> Preparation of the back sheet for solar cell modeul 6

"Example 1 vinylidene in step 1, and fluorine polymer fluoride with chlorotetrafluoroethane ¾ the ethyl Luo, respectively 80: Use in a weight ratio of 20, and a polyamine with an adhesive polymeric binder resin in the step 2, acid polyether sulfone, each 90 : it was prepared in a heated oven at 10 180 ° C, using a weight ratio of in the same manner as in example 1, except that curing for 10 minutes modeul solar cell back sheet.

<Example 7> Preparation of the back sheet for solar cell module 7

Example 1 Vinyl propylene fluoride, and hex-fluoro-fluorine polymer in step 1, each of the 80: used in a weight ratio of 20 and without the use of a dehydrating agent and the imidization catalyst in step 2, the polyamine acid with an adhesive polymeric binder resin polyether sulfone 60, respectively: a in the same manner as in example 1, except that curing for 15 minutes in a heated oven at 200 ° C using a weight ratio of 40 for the solar battery back-sheet modeul was prepared.

<Example 8> Preparation of the back sheet for solar cell modeul 8

Vinylidene fluoride (VDF) instead of vinylidene fluoride with tetrafluoroethylene and ethylene, respectively 90 in the step 1 in Example 1 with an adhesive polymeric binder resin in the step 2 using a weight ratio of 10, a polyamine acid polyethersulfone respectively 80: was prepared for a solar battery back-sheet modeul in the same manner as in example 1, except that curing for 5 minutes in a heated oven at 20 200 ° C, using a weight ratio of.

<Example 9> Preparation of the back sheet for solar cell modeul 9

In Example 1, without using the dehydrating agent and the imidization catalyst in step 2, a polyamic acid and a (meth) acrylic resin (Acryl) with an adhesive polymeric binder resin were 50: Use in a weight ratio of 50 heated to 180 ° C in the same manner as in example 1, except that curing for 5 minutes in an oven to prepare a solar cell back sheet modeul.

<Example 10> Preparation of solar cell backsheet for modeul 10

In Step 1 of Example 1 in a fluorine polymer of vinylidene fluoride and chloro ethyl tetrafluoroethylene, respectively 80: to use a weight ratio of 20, and a dehydrating agent and without already using encoding catalyst in step 2, the adhesive polymeric binder resin polyamine acid and (meth) acrylic resin, each 60: was prepared in example 1 in the same manner as in the sun for battery modeul backsheet except that curing for 5 minutes in an oven heated to 40 200 ° C, using a weight ratio of.

<Example 11> Preparation of the back sheet for solar cell 11 modeul

Example 1 Vinyl propylene fluoride, and hex-fluoro-fluorine polymer in step 1, each of the 80: used in a weight ratio of 20 and without the use of a dehydrating agent and the imidization catalyst in step 2, the polyamine acid with an adhesive polymeric binder resin It was prepared a solar cell modeul backsheet in the same manner as in example 1 except that curing for 5 minutes at a heating to 180 ° C by using a weight ratio of 30 Bon Festival: (meth) acrylic resin 70, respectively.

<Example 12> Preparation of the back sheet for solar cell 12 modeul

In Step 1 of Example 1 in a fluorine polymer of vinylidene fluoride and tetra-pole ethylene respectively 90 to Luo: as used in a weight ratio of 10, and a dehydrating agent and without already using encoding catalyst in step 2, the adhesive polymeric binder resin polyamine acid and (meth) acrylic resin was prepared in example 1 in the same manner as the solar cell back sheet for modeul except that each was used at a weight ratio of 60 to 40 cured for 3 minutes in a heated oven at 180 V.

<Example 13> Preparation of the back sheet for solar cell 13 modeul

To the first embodiment of acetic anhydride the vinylidene fluoride (VDF) a fluorine polymer in step 1, 35 g of use, and dehydration in the step 2, the zero 1 g, to the isoquinoline by 0.06 g, adhesive polymeric binder resin imidization catalyst 2 g of polyamic acid was prepared a solar cell back sheet for modeul in the same manner as in example 1 except for using.

<Example 14> Preparation 14 of the back sheet for solar cell modeul

To the first embodiment of acetic anhydride the vinylidene fluoride (VDF) a fluorine polymer in step 1 of 33 g, and the dehydration in the step 2, the zero using 2 g, with isoquinoline to 0.12 g, the adhesive polymeric binder resin imidization catalyst in the same manner as in example 1 except that the polyamic acid 4 g were prepared for solar cell back sheet modeul. <Example 15> Preparation 15 of the solar cell back sheet for modeul

Isoquinoline to Example 1 Step 1 of vinylidene fluoride (VDF) the 28 g used, and in step 2 the zero dehydration of acetic acid anhydride and a fluorine polymer in a 5 g, imidization catalyst 0.30 g, with an adhesive polymeric binder resin a, except that the pulley amine acid 10 g in the same manner as in example 1 to prepare a back sheet for solar cell modeul.

<Example 16> Preparation of the back sheet for solar cell 16 modeul

To the first embodiment of vinylidene fluoride (VDF) to 25 g using, dehydrating agent anhydride in step 2, acetic acid as a fluorine polymer in step 1 of 6 g, to the isoquinoline by 0.36 g, adhesive polymeric binder resin imidization catalyst , except that the polyamic acid 12 g was prepared in the "solar cell modeul backsheet in the same manner as in example 1. <Example 17> Preparation of the back sheet for solar cell 17 modeul

Isoquinoline to Example 1 Step 1 vinylidene denpol fluoride (VDF) the 20 g used, and acetic anhydride dehydrating agent in step 2, a fluorine polymer in a 8 g, imidization catalyst 0.51 g, adhesive polymeric binder resin It was prepared as for example 1, a solar cell modeul backsheet in the same manner, except that the polyamic acid 17 g.

<Comparative Example 1> Preparation 18 in solar cell back sheet for modeul

Example 1 a dehydrating agent, for imidation catalyst and an adhesive polymeric binder resin and that is not the solar cell in the same manner as in Example 1 except for using modeul backsheet in Step 2 was prepared in the.

<Comparative Example 2> Preparation of the back sheet for solar cell 19 modeul

Except for using the above-described embodiment in the steps of 12 to a dehydrating agent and without already using encoding catalyst, the adhesive polymer binder resin, (meth) acrylic, but in Example 1 By a method similar to that of the solar cell modeul backsheet It was.

<Comparative Example 3> Preparation of solar cell backsheet for modeul 20

Example 1 stage, without the use of a dehydrating agent and the imidization catalyst in 2, was prepared in Example 1 in the same manner as the solar cell back sheet for modeul except that only with polyethersulfone with an adhesive polymeric binder resin. <Comparative Example 4> Preparation of the back sheet for solar cell 21 modeul

Example 1 a fluorine polymer in step 1, the ethyl-vinyl-laden fluoride and chloro-tetrafluoroethane, respectively 80: Use in a weight ratio of 20, and the dehydrating agent in step 2, that is not already used for imidation catalyst, the adhesive polymeric binder resin except that was prepared in example 1 and a solar cell back sheet modeul 'in the same way.

<Comparative Example 5> Preparation of the back sheet for solar cell 22 modeul

Example. 1 with a fluorine polymer in step 1, the propylene to vinylidene fluoride and the hex-Fluoro of each 80: Use in a weight ratio of 20, and, and is carried out except in step 2, the dehydrating agent, it has not been used for encoding the catalyst, the adhesive polymeric binder resin in the same manner as in example 1 to prepare a back sheet for solar cell modeul.

<Comparative Example 6> Preparation of the back sheet for solar cell 23 modeul

Example 1 Step 1 vinylidene denpol fluoride and tetrafluoroethylene as a fluorinated polymer in the ethylene, respectively 90: is used in a weight ratio of 10, the dehydrating agent in step 2, that is not already used for imidation catalyst, the adhesive polymeric binder resin It was prepared, except for the solar cell modeul backsheet in the same manner as in example 1. <Experimental Example 1> solar cell back sheet of the adhesive strength evaluation fluorinated polymer composition 1

In order to measure the adhesion between the polyester film base and, the composition prepared according to the present invention was measured by T-PEEL TEST way, the results are shown in Table 1 below.

In addition, high temperature humidification conditions to evaluate the durability of the coating layer is the adhesive strength was measured with respect to a specimen kept for 10 days (Ndo: 85 ¾: 80 ° C, relative humidity).

To, Table 1 shows the ttaron Examples and Comparative Examples in terms of this invention, Table 2 shows the peel strength measurement results therefrom.

[Table 1]

[Table 2]

In the present invention, the dehydrating agent and the imidization was already performing a chemical curing and thermal curing using the imidation catalyst or at the same time, performs only the thermosetting adhesive with a polymeric binder resin, polyamic acid.

Referring to Examples 1 to 12 of Table 1, the (termed hereinafter, the fluorine-based polymer composition.) Invention the fluorinated polymer composition for the back sheet of a solar cell mode according to the though did not form a separate adhesive layer on a base material though exhibited a peel strength of at least 0.5 kg f / cm even at a high temperature humidity conditions.

On the other hand, referring to Comparative Examples 1 to 6, an adhesive polymer fluorinated polymer composition containing no binder resin did not show adhesion to the substrate, and the adhesive can be a binder with a polymeric binder resin, but the fluorine-containing polymer prepared by using a composition comprises from about relative to the base

The 0.1 eoteuna indicate the peel strength of about kg f / cm, Ko Un humidity conditions it can be seen that the adhesive strength does not appear.

In addition, embodiments Referring to 13-17, based on the total weight of the amount of adhesive polymer binder resin contained in the composition of the raw materials (fluorine and branched "adhesive polymer binder resin, a dehydrating agent and the imidization catalyst) is heunhap the solvent as it indicated that the adhesive strength is improved when it was embedded in 10-50% by weight.

Therefore, the fluorinated polymer composition according to the invention From the results of the above are excellent in adhesion to the base material does not need to form a separate adhesive layer by including a common compound of the polyamic acid or polyamic acid and a binder resin as an adhesive polymeric binder resin solar modeul for the backsheet it can be seen that to shorten the manufacturing process.

[Industrial Applicability]

Fluorinated polymer composition produced in the present invention is excellent in adhesion to the substrate, it is not necessary to pre-form a separate adhesive layer to the substrate it is possible to shorten the back sheet manufacturing process. In addition, it is possible to thin to control the thickness of the composition to be coated on the base material can be achieved which is capable of reducing the raw material cost of the fluorine polymer O country, the solar cell back sheet for modeul manufactured using the composition because it has excellent durability and weatherability characteristics , it may be useful in the manufacture of a solar cell back sheet base.

Claims

[Claims] 2δ WO 2013/125799 PCT / KR2013 / 000716
[Claim 1]
Includes a fluorine polymer and the adhesive polymer resin binder,
The fluorine polymer is a homopolymer of vinylidene fluoride (VDF), vinyl fluoride copolymer, or a combination thereof, and; Adhesive polymer binder resin block Subtotal polymer composition for the back of the solar cell base comprising a polyamic acid (Polyamic acid) sheet.
[Claim 2]
The method of claim 1 wherein the adhesive polymeric binder resins include polyamide, deuyi imide (Polyamide imide, PAI), polyimide (Po ly imi de, PI) polyphenylene sulfide (Polypheny 1 ene sulfide, PPS), polyether sulfone (polyether sulfone, PES), polyarylene-ether ketone (Polyarylene- etherketone), polyether imide (Po lyether imi de), polyphenylene oxide (Polyphnylene oxide), poly ether ketone, silicone and epoxy (meth) acrylic resin back of the solar cell base sheet fluorinated polymer composition which further comprises a binder resin, at least one member selected from the group including.
[Claim 3]
The method of claim 1, wherein the composition is a coating for the substrate,
Wherein the substrate is a polyethylene terephthalate (polyethylene terephthalate, PET), polyethylene naphthalate (po lyethy 1 ene naphthalate, PEN) or back of the solar cell model, characterized in that the combination of a fluorinated polymer sheet composition.
[Claim 4]
The method of claim 1, wherein the fluorine polymer contained in the composition is vinylidene fluoride (VDF) homopolymer and vinylidene fluoride (VDF) copolymers, respectively 60 ~ 90 mol% and 10 ~ 40 mo is heunhap 1% the back of the solar cell model, characterized in sheet fluorinated polymer composition.
[5.]
The method of claim 1, wherein the vinylidene denpul fluoride (VDF) ethylene (CTFE), trifluoroacetic comonomers include propylene (HFP), chlorotrifluoroethylene with ethylene (TFE), hex pool Luo tetrafluoroethylene copolymer ethylene, hex-fluoro-isobutylene, perfluorobutyl ethylene, perfluoro-propyl vinyl ether (PPVE), perfluoroalkyl vinyl ether (PEVE), perfluoro methyl vinyl ether (PMVE), perfluoro -2 to , 2-dimethyl-1,3-dioxole (PDD), and that the tokjing that at least one member selected from the group comprising 2-methylene-4-methyl-1,3-dioxolane (PMD) perfluoroalkyl The backsheet fluorinated polymer composition of the solar cell model.
[6.]
The method of claim 1, wherein the adhesive polymer resin binder is a fluorine polymer and the adhesive 4, based on the total weight of the polymer binder resin in the composition backsheet fluorinated polymer composition of the solar cell module, characterized in that contained in 50% by weight.
[7.]
Claim 2 wherein the adhesive polymeric binder polyamine acids total adhesive polymer binder resin component 50 parts by weight of at least ¾ to 100% by weight less than that of the solar battery back-sheet according to claim all the fluorinated polymer in the composition of the resin.
[8.]
The method of claim 1, wherein the composition is the dehydrating agent and but already further comprising an encoding catalyst, the dehydrating agent is 5 with respect to the total weight of the composition, - and an amount of 23 parts by weight, the imidization catalyst is included in the composition pole total of Ria acid the backsheet fluorinated polymer composition of the solar cell model, characterized in that an amount of 0.05 to 2 parts by weight based on the weight.
[9.]
The summing a uniform common solvent is added to the composition according to claim 1 (step 1);
The step of coating the mixture prepared in step 1 to the polyethylene terephthalate, one side or both sides of a polyethylene naphthalate, or a combination of the substrate (step 2); And
Heating the coated substrate is a common compound in the above step 2 (step 3); solar modeul back method of producing a sheet comprising a. [10.]
The back sheet for solar cell modeul prepared by the method of claim 9.
PCT/KR2013/000716 2012-02-21 2013-01-29 Fluorine-based polymer composition for back sheet of solar cell module and method for manufacturing back sheet comprising same for solar cell module WO2013125799A1 (en)

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KR101512435B1 (en) * 2013-12-17 2015-04-16 한국화학연구원 Back sheet for solar cell and solar cell comprising thereof
WO2015093763A1 (en) * 2013-12-17 2015-06-25 한국화학연구원 Solar cell fluorinated coating composition, fluorinated multilayer film, and solar cell comprising same

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US6417284B1 (en) * 1999-09-30 2002-07-09 Nexpress Solutions Llc Adhesion priming composition for fluoropolymer coatings
KR20070108159A (en) * 2005-02-28 2007-11-08 가부시키가이샤 가네카 Method for producing polyimide film
JP2011503851A (en) * 2007-11-08 2011-01-27 中国楽凱フィルム集団公司China Lucky Film Group Corporation Backsheet and its manufacturing method for solar cell

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KR20070108159A (en) * 2005-02-28 2007-11-08 가부시키가이샤 가네카 Method for producing polyimide film
JP2011503851A (en) * 2007-11-08 2011-01-27 中国楽凱フィルム集団公司China Lucky Film Group Corporation Backsheet and its manufacturing method for solar cell

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