WO2012124926A2 - Particules de polymère fluoré cœur-écorce à revêtement de l'enveloppe de couche résistant aux intempéries à module solaire - Google Patents

Particules de polymère fluoré cœur-écorce à revêtement de l'enveloppe de couche résistant aux intempéries à module solaire Download PDF

Info

Publication number
WO2012124926A2
WO2012124926A2 PCT/KR2012/001677 KR2012001677W WO2012124926A2 WO 2012124926 A2 WO2012124926 A2 WO 2012124926A2 KR 2012001677 W KR2012001677 W KR 2012001677W WO 2012124926 A2 WO2012124926 A2 WO 2012124926A2
Authority
WO
WIPO (PCT)
Prior art keywords
shell
core
fluoropolymer
fluorine polymer
film
Prior art date
Application number
PCT/KR2012/001677
Other languages
English (en)
Korean (ko)
Other versions
WO2012124926A3 (fr
Inventor
하종욱
이수복
박인준
김수한
이광원
Original Assignee
한국화학연구원
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 한국화학연구원 filed Critical 한국화학연구원
Publication of WO2012124926A2 publication Critical patent/WO2012124926A2/fr
Publication of WO2012124926A3 publication Critical patent/WO2012124926A3/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F14/00—Homopolymers and 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
    • C08F14/18—Monomers containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
    • C08F259/08—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions 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; Compositions of derivatives of such polymers
    • C08L27/02—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on 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; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on 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; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/049—Protective back sheets
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to a fluoropolymer having a core-shell structure useful as a weatherability coating material of a solar cell module backsheet, wherein the core contains a copolymer unit of a functional comonomer having a perfluoroalkyl group.
  • -Shell fluoropolymer particles and a method of manufacturing the same. More specifically, it contains a core made of vinylidene fluoride (VDF) and at least one copolymerizable fluorinated monomer, and a functional perfluoroalkyl group-containing fluorine monomer copolymerizable with vinylidene fluoride.
  • VDF vinylidene fluoride
  • the present invention relates to a fluoropolymer particle having a shell composed of fluoropolymer.
  • the solar cell backsheet layer made of the coating material containing the fluorine polymer of the present invention has a high weather resistance due to its excellent chemical resistance, low water vapor permeability, electrical insulation, and ultraviolet (UV) light protection due to exposure to the surrounding environment. .
  • the solar cell module consists of an outer glass material, typically a solar cell encapsulated in a transparent protective package and a backsheet on the back.
  • the solar cell is made of a material including silicon for photovoltaic capture, cadmium indium selenide (CIS), cadmium indium gallium selenide (CIGS), quantum dots, and the like.
  • the backsheet on the backside of the solar cell module exposed to the environment not only has excellent long-term weather resistance, but also has excellent long-term weather resistance, as well as excellent vapor barrier and oxygen barrier properties and UV protection. It needs to be excellent in resistance.
  • the backsheet plays an important role in protecting against performance degradation of a silicon wafer (solar cell) caused by reaction with moisture, oxygen, or UV light.
  • the back sheet has a structure in which a polyester base film having excellent water vapor and oxygen barrier properties is encapsulated on both sides with a fluoropolymer film having excellent weather resistance in the form of a film laminated with three functional layers.
  • a polyester base film having excellent water vapor and oxygen barrier properties is encapsulated on both sides with a fluoropolymer film having excellent weather resistance in the form of a film laminated with three functional layers.
  • PET polyethylene terephthalate
  • Tedlar trade name
  • PVF polyvinyl fluoride
  • the polyethylene terephthalate is a polymer having excellent water vapor barrier properties and being relatively inexpensive, but its performance is easily degraded due to exposure to environmental effects such as UV rays, IR rays and ozone. This makes it possible to protect PET with Tedlar (PVF), which has excellent weather resistance. However, Tedlar films are relatively expensive and have poor resistance to water vapor.
  • PVF Tedlar
  • Typical solar cell backsheets are made of laminate films of PVF / PET / PVF layers.
  • the adhesion of PVF to PET is disadvantageous, and generally, the surface of the polymer is treated by corona discharge or a similar technique, or an adhesive is applied on PET to improve adhesion.
  • PVF / PET / PVF laminate film composites have conventionally been produced from preformed films of fluoropolymers, in particular PVF, attached to a polyester substrate.
  • laminating a preformed fluoropolymer film using an adhesive on a polymer substrate is complicated in the manufacturing process, and there is a problem that the laminate is separated again after many years of outdoor exposure.
  • U.S. Patent Nos. 3,133,854, 5,139,878, and 6,632,518 disclose primers and adhesives capable of making durable laminate structures from preformed films. These processes require the formation of at least one adhesive layer, or one primer and one adhesive layer before the actual lamination step, which requires heat and pressure in the lamination step to produce laminates using preformed fluoropolymer films. It is expensive and requires a lot of investment. In addition, the preformed fluoropolymer film must have a sufficient thickness to impart the strength required in the manufacturing process and subsequent processes, such that the laminate contains a fluoropolymer layer thicker than the thickness required as an effective protective layer.
  • US Patent Publication No. 2009/0260677 discloses a film coated with a fluorine polymer that can improve the disadvantage of the process for producing a laminate with a pre-fabricated fluoropolymer film.
  • US Pat. No. 7,803,867 discloses an aqueous fluoropolymer coating composition capable of imparting improved durability, fouling resistance, water repellency, reflectivity, and the like. The technique relates to an aqueous fluoropolymer coating comprising an acrylic modified fluoropolymer, wherein the aqueous fluoropolymer having an interpenetrating network type morphology as a dispersion in the form of an acrylic modified fluoropolymer is polyvinyl chloride.
  • PVDF lidene fluoride
  • PVDF lidene fluoride
  • U. S. Patent No. 6,635, 714 discloses fluoropolymer-acrylic compositions prepared by polymerizing vinylidene fluoride (VDF) and optionally perhalogenated comonomers for weather resistance.
  • U.S. Patent No. 5,646,201 discloses an aqueous dispersion of a fluorine-containing copolymer obtained by seed polymerization of (meth) acrylic acid ester in the presence of seed particles prepared by copolymerizing VDF and chlorotrifluoroethylene (CTFE). Started.
  • compositions containing such conventional fluorine polymers are not yet satisfactory to replace weatherable fluoropolymer laminate materials (PVF films) for backsheets, and research on such weatherable fluoropolymer coating materials as the demand for solar cells grows rapidly. Is more required.
  • PVF films weatherable fluoropolymer laminate materials
  • the back sheet of the solar cell module generally has a structure in which a polyester base film having excellent water vapor and oxygen barrier properties is wrapped on both sides with a weather resistant fluoropolymer laminate film.
  • Fluoropolymer laminate film mainly uses PVF film.
  • An object of the present invention is to provide a new weather-resistant fluoropolymer coating material that can replace the PVF film used in the manufacture of the back sheet of the solar cell module.
  • the present inventors have prepared a method for producing fluoropolymer particles having improved weatherability and moisture resistance without changing the bulk physical properties of the original fluoropolymers, the core-shell containing a functional comonomer containing a small amount of perfluoroalkyl group in the shell
  • the discovery of copolymerization techniques has led to the completion of the present invention.
  • the core-shell structured fluoropolymer particles containing perfluoroalkyl groups in the shell according to the present invention are useful as weather-resistant coating materials to replace PVF fluoropolymer laminates used in solar cell backsheets, and compared with conventional laminate technology.
  • the manufacturing process of the sheet can be shortened and the manufacturing cost can be improved.
  • the present invention provides a core-shell structured fluoropolymer particles to be used as a weather-resistant coating material of the back sheet of the solar cell module.
  • the fluoropolymer particles of the core-shell structure of the present invention contain a small amount of perfluoroalkyl groups on the shell side.
  • Fluoropolymer of the perfluoroalkyl group containing core-shell structure on the shell side which concerns on this invention is manufactured by the core-shell polymerization method which contains a fluorovinyl ether copolymerization monomer in a shell.
  • the present invention provides core-shell structured fluoropolymer particles having a fluoropolymer shell containing a perfluoroalkyl group.
  • the fluoropolymer of the perfluoroalkyl group-containing core-shell structure on the shell side is prepared by a core-shell polymerization method including a fluorovinyl ether copolymer monomer represented by the following formula (1) on the shell side.
  • the present invention provides a core-shell fluoropolymer particle comprising (a) a core made of a fluoropolymer and (b) a shell having a perfluoroalkyl group introduced therein using a fluorovinylether comonomer represented by the following formula (1).
  • CF 2 CFOCF 2 CF 2 R f
  • R f is a C 1 ⁇ C 3 perfluoroalkyl or perfluoroalkoxy group, more preferably -CF 3 or -OCF 3 .
  • the fluoropolymer consists of polymerization of vinylidene fluoride, vinyl fluoride or a fluorine comonomer copolymerizable therewith, and the fluorine comonomer comprises tetrafluoroethylene, hexafluoropropylene or chlorotrifluoroethylene.
  • the fluoropolymer of the perfluoroalkyl group-containing core-shell structure on the shell side according to the present invention imparts excellent weather resistance without changing the bulk physical properties of the fluoropolymer.
  • the fluorovinyl ether comonomer represented by the formula (1) provides a shell containing perfluoroalkyl group having excellent low surface energy characteristics, thereby improving moisture resistance and antifouling property without impairing the physical properties of the original fluorine polymer. Long-term weather resistance in Esau can be significantly improved.
  • the fluoropolymer particles of the core-shell structure of the present invention are prepared by a polymerization reaction process in which a fluorovinyl ether comonomer is added together with a fluorine monomer at the end of polymerization of a fluorine monomer to form a shell containing a fluorovinyl ether comonomer. do.
  • the polymerization process is a water dispersion polymerization process such as emulsion (dispersion) polymerization and suspension polymerization including seed polymerization (seed polymerization).
  • the fluoropolymer particles of the core-shell structure of the present invention include those dispersed in powder, pellet or liquid phase.
  • the fluoropolymer particles of the core-shell structure according to the present invention are characterized by having an average particle diameter in the range of 10-500 nm when produced by water dispersion polymerization.
  • the polymerization product dispersion can be used directly and the surfactant can be added to the dispersion or concentrated or stabilized by known methods.
  • Other materials may be mixed into the dispersion for use in the form of a dispersion, and the dispersion mixed mixture may be co-coagulated with a dry blend or filled resin. At this time, the solid content of the dispersion is characterized in that 5-70%.
  • the core-shell structured fluoropolymer particles of the present invention may be recovered by a method of vigorously stirring after adding an electrolyte selectively from the water-dispersed polymer or by drying a solid at room temperature after cooling.
  • the polymerization process is performed in order to form a core-shell particle structure, in which the shell of the particles is at least in the core by the presence of a fluorovinyl ether monomer which is not present in the core. Distinct from parts. Preferably, no fluorovinyl ether monomer is included in the core.
  • the core-shell interface is regarded as the boundary between a polymer containing a fluorovinyl ether monomer and a polymer containing no fluorovinyl ether monomer, wherein the shell portion in the particle It is characterized in that 1 to 25% by weight. When the shell portion is 1% or less, there is no effect of improving weather resistance due to the core-shell structure, and when it is 25% by weight or more, physical properties such as mechanical strength are lowered, which is not preferable.
  • Fluorovinyl ether monomers are included in the shell of the particles to impart a pendant side group containing perfluoroalkyl groups.
  • the content of the fluorovinyl ether monomer in the fluoropolymer particles of the present invention is characterized in that 0.01 to 5% by weight.
  • the content of the fluorovinyl ether monomer is 0.01% by weight or less, there is no effect of introducing a perfluoroalkyl group, and thus the weather resistance improvement effect does not appear.
  • the content of the fluorovinyl ether monomer is 5% by weight or more, physical properties such as mechanical strength are lowered, which is not preferable.
  • the core-shell structure can be formed by terminating the polymerization to form the core and starting to inject the fluorovinyl ether monomer from the polymerization point for constructing the shell and continuing the addition until the end of the polymerization.
  • polyvinylidene fluoride and polyvinyl fluoride and fluorinated polymer copolymers of vinylidene fluoride (VDF) and vinyl fluoride (VF) are suitable.
  • the fluoropolymer copolymer of each of VDF and VF preferably contains 60 mol% or more of VF and VDF, respectively.
  • the comonomer used in the manufacture of the VF copolymer or VDF copolymer of the present invention is preferably a fluorine-based comonomer.
  • fluorinated comonomers examples include tetrafluoroethylene (TFE), hexafluoropropylene (HFP), chlorotrifluoroethylene (CTFE), trifluoroethylene, hexafluoroisobutylene, perfluorobutylethylene, purple Luoropropyl vinyl ether, perfluoroethyl vinyl ether, perfluoromethyl vinyl ether, perfluoro-2,2-dimethyl-1,3-dioxol and perfluoro-2-methylene-4-methyl-1 , 3-dioxolane and the like.
  • TFE tetrafluoroethylene
  • HFP hexafluoropropylene
  • CTFE chlorotrifluoroethylene
  • trifluoroethylene hexafluoroisobutylene
  • perfluorobutylethylene purple Luoropropyl vinyl ether, perfluoroethyl vinyl ether, perfluoromethyl vinyl ether, perfluoro
  • the water dispersion emulsion polymerization of the fluorine-based monomer is carried out according to a conventional method used in the prior art.
  • the emulsion polymerization step is carried out by dispersing the fluorine monomer using a fluorine-based surfactant.
  • the amount of the fluorine-based surfactant is different depending on the required physical properties such as the solid content and particle size of the produced fluorine polymer, it is preferable that the fluorine polymer is 0.01 to 2% by weight based on the amount of fluorine polymer having good physical properties.
  • the aqueous dispersion obtained after the polymerization reaction contains 10-50% by weight of fluoropolymer particles.
  • the water dispersion polymerization process of the present invention is carried out according to a conventional method, it is generally carried out in a pressure of 20 ⁇ 120 °C, 5 ⁇ 50 bar, in this case, the pH of the reactant for the water dispersion polymerization reaction is 5 ⁇ It is suitable that it is a condition of 10.
  • the water dispersion polymerization may use an initiator to initiate free radical polymerization of the fluorine monomer.
  • the initiators include commonly used peroxides, azo compounds, or redox based initiators.
  • the amount of the initiator is preferably 0.05 to 0.5% by weight based on the amount of fluoropolymer.
  • the water dispersion polymerization may use a chain transfer agent (chain transfer agent).
  • chain transfer agents include esters such as diethylmalonate, ethers such as dimethyl ether, methyl t-butyl ether, alkanes such as ethane, propane and n-pentane, halogenated hydrocarbons such as CCl 4 , CHCl 3 and CH 2 Cl 2 And carbon fluoride compounds such as CH 2 FCF 3 (HCFC-134a).
  • the solid content of the fluoropolymer polymer in the dispersed phase in the aqueous dispersion polymerization is preferably in the range of 10 to 50% by weight, and the particle size of the fluorine polymer is in the range of 10 to 500 nm. It is desirable to have.
  • the fluorine polymer includes separating the polymer in the solid form from the dispersed phase by aggregation if desired.
  • the present invention provides a fluoropolymer coating composition comprising the above-mentioned core-shell fluoropolymer particles in the form of a solution or dispersion.
  • the solvent is a typical solution or dispersion is used that has a high boiling point to avoid the generation of bubbles during the film formation / drying process.
  • solvents are needed to assist in the coagulation of fluoropolymers.
  • the polymer concentration of the coating composition should be adjusted to have a good workability viscosity, depending on the specific polymer, the other components of the composition and the process equipment and conditions used.
  • the fluorine polymer coating composition is a solution
  • the fluorine polymer is preferably 10 to 25% by weight based on the total weight of the composition, and 25 to 50% by weight in the case of the dispersion.
  • the polymer form in the coating composition is determined by the type of fluoropolymer and the solvent used, PVF is normally present in dispersion form and PVDF is present in dispersion or solution form depending on the solvent used.
  • PVDF can form solutions at room temperature in polar organic solvents such as ketones, esters and ethers. Suitable examples of solvents include acetone, methyletetyl ketone (MEK) and tetrahydrofuran (THF), isophorone, dimethyl acetamide, propylene carbonate, y-butylolactone, N-methylpyrrolidone and dimethylsulfooxide And the like.
  • the copolymers of VF and VDF may be used in the form of dispersions or solutions.
  • the preparation of the dispersions may use the methods described in US Pat. Nos. 2,419,008, 2,510,783 and 2,599,300.
  • the fluoropolymer coating composition in the form of a dispersion may be ground in a suitable solvent.
  • the milling may typically use a ball mill.
  • the content of the adhesive polymer in the coating composition is characterized in that 1 to 40% by weight.
  • the fluoropolymer coating composition according to the present invention can be used to prepare a coating film.
  • the fluorine polymer coating composition may be coated by applying to the substrate in a liquid phase without the need to prepare a pre-formed film.
  • the coating method may be cast, immersion, spray and coating, and the like, but is not limited thereto.
  • the coating film may be formed by casting a dispersion on the base film using a known method such as spray, roller, knife, curtain, and gravure coating device. have.
  • the dry coating thickness of the cast dispersion preferably ranges from 2.5 ⁇ m to 250 ⁇ m.
  • the solution or dispersion is dried by removing the solvent and thermally condensed to form a fluoropolymer coating on the base film.
  • the fluorine polymer is in the form of a solution
  • the composition may be coated by air drying at room temperature by coating the base film. At this time, a drying temperature is 25-200 degreeC.
  • a drying temperature is 25-200 degreeC.
  • the fluoropolymer coating composition may be completely attached to the base film, and may promote the interaction between the functional group of the adhesive polymer and the functional group of the polymer base film.
  • the temperature may vary depending on the adhesive polymer used and the functional group of the base film, and should be higher than the temperature required for the fluorine polymer in the form of dispersion to condense.
  • the solvent is removed and heated to a sufficiently high temperature to allow the fluoropolymer particles to condense into a continuous film. At this time, it is preferable that temperature is 150 degreeC-250 degreeC.
  • the solvent assists condensation and causes condensation at lower temperatures than when no solvent is used. Therefore, the conditions for coagulating the polymer may vary depending on the thickness of the fluoropolymer, cast dispersion and base film used.
  • the residence time of the composition in the oven is 1 to 10 minutes, it is preferable to control the temperature from 150 ° C to 250 ° C to condense the film. More preferably, it is 160 to 220 degreeC.
  • the oven air temperature is different from the temperature of the fluoropolymer coating, and the temperature of the fluoropolymer coating is lower than the oven temperature.
  • the coating layer prepared by using the coating composition containing perfluoroalkyl group-containing fluoropolymer particles having a perfluoroalkyl group-containing core-shell structure on the shell side according to the present invention has excellent low surface energy characteristics and water resistance, since the perfuluroalkyl group is oriented at the outermost side. Antifouling properties.
  • the coating layer having such characteristics is not only greatly improved in weather resistance compared to the conventional fluorine polymer film, but also can easily control the thickness of the coating layer, thereby optimizing the use of expensive fluorine polymer to improve the manufacturing cost of the backsheet. There is this.
  • the coating layer manufacturing process using the composition containing the core-shell structured fluorine polymer particles according to the present invention can reduce the energy cost required compared to the lamination process for forming a conventional fluorine polymer film and shorten the process can do.
  • the coating is placed in a weather tester (Sunshine Weather-o-meter; Suga Shikenki Co.) and exposed to Xenon lamp light (exposure intensity: 3 SUN, environment: black panel temperature 85 ° C / humidity 50% RH).
  • the accelerated weathering test is carried out with a repeated shower for 8 minutes every 2 hours and after 1000 hours the change in gloss is measured using a gloss meter. It determines as follows according to the glossiness measurement result.
  • the coating is placed in an environmental test machine and held for 1000 hours under a temperature of 85 ° C./85% RH, and the number of pinholes formed on the surface is measured.
  • the number of pinholes is determined as follows.
  • 620ml deionized water was added to a 1000ml pressure reactor equipped with a stirrer, pressurized to 5atm using nitrogen gas, and then degassed five times to remove air, and then 20% by weight of perfluorooctanoic acid ammonia under vacuum. 6.3 ml of an aqueous salt solution and 1.0 ml of chloroform were added. The temperature of the reactor was raised to 80 ° C., and vinylidene fluoride (VDF) was added to raise the pressure to 300 psig. Then, 10 ml of 2 g / L ammonium percellate (APS) aqueous solution was added thereto.
  • VDF vinylidene fluoride
  • the initiator aqueous solution was started at 0.6 ml / min while maintaining the pressure in the reactor at 300 psig.
  • the dispersion was diluted with the same amount of deionized water and then frozen and coagulated.
  • the agglomerated fluoropolymer solid was collected by filtration, washed three times with 1000 ml of deionized water, and then dried at 50 ° C.
  • the powdered solid was suspended in isophorone solvent to prepare a 25 wt% fluoropolymer dispersion.
  • This dispersion is coated onto a 2.0 mm thick PTFE (10 cm ⁇ 20 cm) using a 0.4 mm thick draw knife.
  • the coated PTFE was dried in an oven at 200 ° C. for 10 minutes to prepare a core-shell structured fluoropolymer coating.
  • the fluoropolymer coating of the core-shell structure thus prepared was subjected to the weather resistance test and the moisture resistance test by the method described above.
  • the gloss after the weathering test was measured at 96% of the gloss before the test.
  • the specimens after the moisture resistance test had no pinholes and no difference in appearance from the test. From this, it was confirmed that weather resistance and moisture resistance were good.
  • the resulting fluoropolymer solid was FTIR analyzed by 19F NMR and found to contain 1.9 wt.% FVE 2 monomer.
  • Example 1 Using this, a coating film was prepared in the same manner as in Example 1 to evaluate weather resistance and moisture resistance. The results are shown in Table 1 below.
  • Example 2 The same procedure as in Example 1 was conducted except that vinyl fluoride (VF) was used instead of vinylidene fluoride (VDF). The resulting fluoropolymer solid was FTIR analyzed by 19 F NMR and found to contain 2.0 wt% FVE 2 monomer.
  • VF vinyl fluoride
  • VDF vinylidene fluoride
  • Example 1 Using this, a coating film was prepared in the same manner as in Example 1 to evaluate weather resistance and moisture resistance. The results are shown in Table 1 below.
  • the resulting fluoropolymer solid was FTIR analyzed by 19 F NMR and found to contain 2.1 wt% FVE 1 monomer.
  • Example 1 Using this, a coating film was prepared in the same manner as in Example 1 to evaluate weather resistance and moisture resistance. The results are shown in Table 1 below.
  • the resulting fluoropolymer solid was FTIR analyzed by 19F NMR and found to contain 0.5% by weight of FVE 2 monomer.
  • Example 1 Using this, a coating film was prepared in the same manner as in Example 1 to evaluate weather resistance and moisture resistance. The results are shown in Table 1 below.
  • the core-shell structure is not the same as in Example 1 except that a fluorovinyl ether monomer is added. Fluoropolymer was prepared.
  • Comparative Example 1 was vinylidene fluoride (VDF)
  • Comparative Example 2 was vinyl fluoride (VF)
  • VDF / CTFE 80: 20 weight ratio
  • the coating was prepared in the same manner as in Example 1 to evaluate the weatherability and moisture resistance. The results are shown in Table 1 below.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Computer Hardware Design (AREA)
  • Electromagnetism (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Paints Or Removers (AREA)
  • Photovoltaic Devices (AREA)
  • Laminated Bodies (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

Une enveloppe de couche à module solaire comprend généralement une structure dont les deux côtés d'un film à base de polyester constituent une excellente barrière contre la vapeur d'eau et l'oxygène et est entourée d'un film laminé de polymère fluoré résistant aux intempéries, ce film utilisant principalement un film de fluorure de polyvinyle (PVF). Pour répondre aux exigences du marché mondial pour un matériau de revêtement de polymère fluoré peu coûteux à résistance aux intempéries plutôt que pour un film PVF existant, l'invention propose un nouveau matériau de revêtement de polymère fluoré résistant aux intempéries permettant de remplacer le film PVF existant. Cette invention concerne des particules de polymère fluoré à structure cœur-écorce utilisées en tant que matériau de revêtement résistant aux intempéries pour une enveloppe de couche à module solaire. Plus particulièrement, les particules de polymère fluoré à structure cœur-écorce comprennent une petite quantité d'un groupe perfluoroalkyle du côté écorce. Plus spécifiquement, l'invention concerne un polymère fluoré cœur-écorce qui comprend (a) un cœur formé de polymère fluoré et (b) une écorce dans laquelle un groupe perfluoroalkyle est introduit au moyen de comonomère fluorovinyléther.
PCT/KR2012/001677 2011-03-11 2012-03-08 Particules de polymère fluoré cœur-écorce à revêtement de l'enveloppe de couche résistant aux intempéries à module solaire WO2012124926A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2011-0021756 2011-03-11
KR1020110021756A KR101281736B1 (ko) 2011-03-11 2011-03-11 태양전지 모듈 백시트의 내후성 코팅용 코어-쉘 불소고분자 입자

Publications (2)

Publication Number Publication Date
WO2012124926A2 true WO2012124926A2 (fr) 2012-09-20
WO2012124926A3 WO2012124926A3 (fr) 2012-11-08

Family

ID=46831169

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2012/001677 WO2012124926A2 (fr) 2011-03-11 2012-03-08 Particules de polymère fluoré cœur-écorce à revêtement de l'enveloppe de couche résistant aux intempéries à module solaire

Country Status (2)

Country Link
KR (1) KR101281736B1 (fr)
WO (1) WO2012124926A2 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102530988B1 (ko) * 2022-06-29 2023-05-11 주식회사 엘엑스엠엠에이 흐름성과 응집성이 개선된 코어쉘형 불소계 수지 입자 및 제조 방법

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4908410A (en) * 1989-01-27 1990-03-13 E. I. Du Pont De Nemours And Company Modified polytetrafluoroethylene fine powder and preparation thereof
US5494752A (en) * 1992-07-09 1996-02-27 Daikin Industries, Ltd. Composite microparticle of fluorine containing resins
US5780552A (en) * 1996-09-13 1998-07-14 E. I. Du Pont De Nemours And Company Fluoropolymers having core/shell structure with functional units in the shell
US7763680B2 (en) * 2005-11-18 2010-07-27 E.I. Du Pont De Nemours And Company Melt-fabricable core/shell perfluoropolymer

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4908410A (en) * 1989-01-27 1990-03-13 E. I. Du Pont De Nemours And Company Modified polytetrafluoroethylene fine powder and preparation thereof
US5494752A (en) * 1992-07-09 1996-02-27 Daikin Industries, Ltd. Composite microparticle of fluorine containing resins
US5780552A (en) * 1996-09-13 1998-07-14 E. I. Du Pont De Nemours And Company Fluoropolymers having core/shell structure with functional units in the shell
US7763680B2 (en) * 2005-11-18 2010-07-27 E.I. Du Pont De Nemours And Company Melt-fabricable core/shell perfluoropolymer

Also Published As

Publication number Publication date
KR101281736B1 (ko) 2013-07-04
KR20120103856A (ko) 2012-09-20
WO2012124926A3 (fr) 2012-11-08

Similar Documents

Publication Publication Date Title
US8048518B2 (en) Fluoropolymer coated films useful for photovoltaic modules
AU2007338713B2 (en) Crosslinkable vinyl fluoride copolymer coated film and process for making same
JP5449136B2 (ja) フルオロポリマー被膜フィルム、それの形成方法、およびフルオロポリマー液体組成物
US7981478B2 (en) Fluoropolymer coating compositions containing adhesive polymers and substrate coating process
TWI491508B (zh) 多層膜及其製造方法
CN103703571B (zh) 用于太阳能电池的环保型背板及其制备方法
JP6075802B2 (ja) 水分散組成物、親環境光電池モジュール用バックシート及びその製造方法
WO2012124926A2 (fr) Particules de polymère fluoré cœur-écorce à revêtement de l'enveloppe de couche résistant aux intempéries à module solaire
KR101373580B1 (ko) 고차단성 코팅층 함유 태양전지 모듈용 백시트
KR101282028B1 (ko) 태양전지 모듈 백시트의 내후성 코팅용 불소고분자-퍼플루오로알킬기 함유 아크릴 입자
KR20130135780A (ko) 다층 필름 및 이를 포함하는 광전지 모듈

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12757941

Country of ref document: EP

Kind code of ref document: A2

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12757941

Country of ref document: EP

Kind code of ref document: A2