WO2016190146A1 - Film for solar-cell back sheet, solar-cell back sheet including same, and solar cell - Google Patents
Film for solar-cell back sheet, solar-cell back sheet including same, and solar cell Download PDFInfo
- Publication number
- WO2016190146A1 WO2016190146A1 PCT/JP2016/064417 JP2016064417W WO2016190146A1 WO 2016190146 A1 WO2016190146 A1 WO 2016190146A1 JP 2016064417 W JP2016064417 W JP 2016064417W WO 2016190146 A1 WO2016190146 A1 WO 2016190146A1
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- WIPO (PCT)
- Prior art keywords
- film
- solar cell
- layer
- solar
- scs
- Prior art date
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Images
Classifications
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- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
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- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- 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
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- 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 film for a solar battery back sheet, a solar battery back sheet using the film, and a solar battery.
- FIG. 1 A typical configuration of a general solar cell is shown in FIG.
- a power generation element 3 is sealed with a transparent sealing material 2 such as EVA (ethylene-vinyl acetate copolymer), a transparent substrate 4 such as glass, and a resin sheet called a solar cell back sheet 1. It is configured by sticking together.
- Sunlight is introduced into the solar cell through the transparent substrate 4. Sunlight introduced into the solar cell is absorbed by the power generation element 3, and the absorbed light energy is converted into electric energy. The converted electric energy is taken out by a lead wire (not shown in FIG. 1) connected to the power generation element 3 and used for various electric devices.
- the solar battery back sheet 1 is a sheet member that is installed on the back side of the power generation element 3 with respect to the sun and is not in direct contact with the power generation element 3.
- the solar cell system and each member polyethylene-based, polyester-based, and fluorine-based resin films are mainly used. (See Patent Documents 1 to 3)
- a technique has been developed that improves the efficiency of the solar battery module by reflecting the light that has passed between the solar battery cells with the solar battery backsheet and taking it into the cells.
- JP-A-11-261085 Japanese Patent Laid-Open No. 11-186575 JP 2006-270025 A JP 2012-84670 A Japanese Patent No. 4766192
- Patent Document 4 in the proposal of forming a reflective layer with white beads and white binder on the surface of the substrate, by using white beads, bonding is performed at the time of EVA or solar cell sealing material production. There exists a subject that adhesiveness with the other member film which falls. Further, as proposed in Patent Document 5, a proposal for forming a highly reflective backsheet by forming a layer including a cavity can achieve a certain power generation efficiency improvement effect, but is still insufficient for improving the power generation efficiency of the solar cell module. There was a problem of being.
- the present invention provides a film for a solar battery back sheet that achieves both excellent output improvement effect and adhesion, a solar battery back sheet and a solar battery using the same. Is.
- the present invention is a void-containing polyester film having a porosity of 10% or more of the entire film, and in the cross section in the thickness direction of the polyester film, a line perpendicular to the surface direction is formed from one surface of the film to the other surface.
- the line connecting the one surface to the other surface is divided into four equal parts in the thickness direction (film thickness direction center point (C1 point), intermediate point between the film thickness direction center point and the film surface (C2- In each of the lines parallel to the plane direction of the film passing through each of (1 point) and (C2-2 point)) (divided horizontal line), the average area per cavity existing on the divided horizontal line passing through C1 is Sc.
- ( ⁇ m 2), Scs an average area per cavity present on dividing the horizontal line passing through the C2-1 points ( ⁇ m 2), per one cavity present on dividing the horizontal line passing through the C2-2 points Average area 'when a ( ⁇ m 2), (Sc / Scs), (Sc / Scs' Scs a) is at least one of 1.1 to 35 or less of, the polyester resin constituting the polyester film of terminal carboxyl It is a film for solar battery back sheets having a base amount of 35 equivalents / ton or less.
- the adhesiveness retention between the EVA resin which is a sealing material for solar battery cells and other member films to be bonded during backsheet processing ( Hereinafter, it is excellent in adhesion), and further, by mounting the solar cell back sheet of the present invention, a solar cell having higher power generation efficiency (hereinafter referred to as output improvement) than the conventional one can be provided.
- the film for solar battery backsheet of the present invention is a void-containing polyester film having a porosity of 10% or more of the entire film, and faces from one surface of the film to the other surface in a cross section in the thickness direction of the polyester film.
- a line perpendicular to the direction is drawn, and a line connecting the one surface to the other surface is divided into four equal parts in the thickness direction (film thickness direction center point (C1 point), film thickness direction center point and film surface
- the film for solar battery backsheet of the present invention is a void-containing polyester film having a porosity of 10% or more of the whole film, and has a polyester resin as a main component.
- the polyester resin as a main component means that the polyester resin is contained in an amount exceeding 50% by mass with respect to the resin constituting the polyester film of the present invention.
- the polyester resin used in the present invention is: 1) polycondensation of dicarboxylic acid or its ester-forming derivative (hereinafter collectively referred to as “dicarboxylic acid component”) and diol component, 2) carboxylic acid or carboxylic acid derivative in one molecule And a polycondensation of a compound having a hydroxyl group and 1) 2).
- the polymerization of the polyester resin can be performed by a conventional method.
- dicarboxylic acid component malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, dimer acid, eicosandioic acid, pimelic acid, azelaic acid, methylmalonic acid
- Aliphatic dicarboxylic acids such as ethylmalonic acid
- alicyclic dicarboxylic acids such as adamantane dicarboxylic acid, norbornene dicarboxylic acid, cyclohexane dicarboxylic acid, decalin dicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 4,4
- a dicarboxy compound obtained by condensing oxyacids such as l-lactide, d-lactide, hydroxybenzoic acid and the like, or a combination of a plurality of such oxyacids, at least one carboxy terminus of the dicarboxylic acid component described above Can also be used.
- aliphatic diols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol, Aromatic diols such as cyclohexanedimethanol, spiroglycol, isosorbide, bisphenol A, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 9,9'-bis (4-hydroxyphenyl) fluorene Group diols are typical examples. Moreover, these may be used independently or may be used in multiple types as needed. In addition, a dihydroxy compound formed by condensing a diol with at least one hydroxy terminal of the diol component described above can also be used.
- examples of the compound having a carboxylic acid or a carboxylic acid derivative and a hydroxyl group in one molecule include oxyacids such as l-lactide, d-lactide and hydroxybenzoic acid, and derivatives thereof, oligomers of oxyacids, dicarboxylic acids Examples thereof include those obtained by condensing an oxyacid with one carboxyl group of the acid.
- Polyester resins obtained from the above two components include polyethylene terephthalate, polyethylene-2,6-naphthalene dicarboxylate, polypropylene terephthalate, polybutylene terephthalate, poly-1,4-cyclohexylene dimethylene terephthalate and mixtures thereof.
- Polyethylene terephthalate and polyethylene-2,6-naphthalene dicarboxylate are preferred from the viewpoint of good film forming property, more preferably from the point that a film for a solar battery backsheet having better adhesion can be obtained. Most preferred is terephthalate.
- the polyester resin constituting the polyester film needs to have a terminal carboxyl group content of 35 equivalents / ton or less. It is preferably 30 equivalent / ton or less, more preferably 25 equivalent / ton or less, still more preferably 20 equivalent / ton or less, and particularly preferably 17 equivalent / ton or less.
- the film for solar cell backsheet of the present invention has 35 equivalents of the terminal carboxyl group amount of the polyester resin constituting the polyester film by controlling the size of the cavity contained in the film to a specific size as described later. It is possible to improve the adhesiveness even if it is less than / ton, and it is possible to achieve both excellent adhesiveness and heat-and-moisture resistance, and output improvement characteristics, which were difficult to achieve in the past.
- the lower limit of the terminal carboxyl group amount is not particularly limited as long as it does not impair the effects of the present invention, but is preferably 7 equivalents / ton or more, more preferably 11 amounts / ton or more.
- the amount of the terminal carboxyl group is less than 7 equivalents / ton, the polar end groups on the surface are insufficient, the absolute value of the adhesion strength becomes small, and the adhesion improving effect of the present invention may be insufficient.
- the intrinsic viscosity IV of the polyester resin constituting the polyester film is preferably 0.63 dl / g or more and 0.80 dl / g or less, more preferably 0.65 dl / g or more, and further preferably 0.67 dl / g or more.
- the intrinsic viscosity IV is less than 0.63 dl / g, the adhesiveness may decrease as a result of a decrease in the dispersibility of the nucleating agent that forms cavities. Moreover, the heat-and-moisture resistance of a polyester film may also fall.
- the intrinsic viscosity IV exceeds 0.80 dl / g, the extrudability of the polyester resin may deteriorate.
- the intrinsic viscosity IV of the polyester resin constituting the polyester film is 0.63 dl / g or more and 0.80 dl / g or less. Therefore, by setting the intrinsic viscosity IV of the polyester resin constituting the polyester film to 0.63 dl / g or more and 0.80 dl / g or less, a film for a solar battery back sheet having both adhesiveness, heat-and-moisture resistance, and workability is obtained. Can do.
- the number average molecular weight Mn of the polyester resin is preferably 8000 to 40,000, more preferably the number average molecular weight Mn is 9000 to 30000, and further preferably 10,000 to 20000.
- the number average molecular weight Mn is less than 8000, durability such as heat and moisture resistance and heat resistance may be lowered.
- the number average molecular weight Mn exceeds 40,000, the polymerization is difficult and the extrudability of the polyester resin may be deteriorated even if the polymerization is possible.
- the polyester resin preferably contains Mn or Na as a metal element. It is preferable that Mn is contained in the range of 50 to 200 ppm and Na is contained in the range of 10 to 80 ppm. It is more preferable that Mn and Na are included in the above range. When Mn or Na is contained in the above range in the polyester resin, hydrolysis of the film is suppressed, and a film for a solar battery back sheet that has both excellent heat and moisture resistance, adhesion, and output improvement can be obtained. .
- the polyester film of the present invention has a cavity inside.
- the “cavity” was obtained when the film was cut perpendicularly to the film surface direction without crushing the film in the thickness direction using a microtome, and the cut surface of the film was observed using an electron microscope.
- a cross-sectional area observed in the observation image represents a void having a size of 0.1 ⁇ m 2 or more.
- the polyester film of the present invention needs to have a porosity (a ratio of voids in the film cross section) of 10% or more. More preferably, the porosity is 15% or more, and further preferably 20% or more.
- the porosity of the entire film can be obtained from the area of the hollow portion in the observation image. Details of the method for measuring the porosity will be described later.
- the porosity is less than 10%, the reflectivity is insufficient and the output improvement is reduced. Moreover, when there are too few voids, stress concentrates at the adhesion interface with other member films, and the adhesion of the film for solar cell backsheet is reduced.
- the method for forming the cavities in the polyester film is not particularly limited, but a method of forming the cavities in the polyester film and then stretching it is preferable. It is difficult to control the structure of the cavity formed by the foaming agent or the like, and the adhesiveness of the solar battery backsheet film may be lowered.
- examples of the cavity nucleating agent include organic nucleating agents such as olefin resins that are incompatible with the polyester resin, and inorganic nucleating agents such as inorganic particles and glass beads.
- An organic nucleating agent is preferable as the cavity nucleating agent from the viewpoint that it is easy to incline the shape of the cavity in the thickness direction by a manufacturing method described later. By providing the hollow shape with an inclination in the thickness direction, the adhesion of the solar battery backsheet film can be enhanced.
- Organic nucleating agents include olefin resins, nylon 6, nylon 66, nylon 610, nylon 11, nylon 12, nylon 46, nylon MXD6, nylon 6T, and other polyamide resins, polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene- Styrene resins such as styrene copolymers, acrylic resins such as polymethyl methacrylate and polybutyl methacrylate, fluorine resins such as polytetrafluoroethylene and polyvinylidene fluoride, polyphenylene sulfide, polysulfone, polyethersulfone, polyarylate, poly Also used for super engineering plastics such as etherimide, or different types of polyester resins that are incompatible with the polyester resin of the polyester film of the present invention.
- olefin resins nylon 6, nylon 66, nylon 610, nylon 11, nylon 12, nylon 46, nylon MXD6, nylon 6T, and other polyamide resins
- Rukoto can.
- the olefin resin include aliphatic polyolefin resins such as polypropylene, polyethylene, high density polyethylene, low density polypropylene, ethylene-propylene copolymer, polymethylpentene, and cyclic polyolefin resins such as cycloolefin polymer and cycloolefin copolymer.
- an olefin-based resin having a Vicat softening point of 140 ° C. or higher is preferable as the organic nucleating agent from the viewpoint of excellent output improvement of the film for a solar battery backsheet by forming a fine cavity and improving the reflectivity.
- An olefin resin having a temperature of at least ° C is more preferable.
- the shape of the cavities may become too coarse, and the film adhesion for a solar battery backsheet and the output improvement may be reduced.
- the amount of the organic nucleating agent contained in the polyester film is preferably 1% by mass or more and 30% by mass or less, more preferably 4% by mass or more and 15% by mass or less, and still more preferably, with respect to the total mass of the polyester film. Is 8 mass% or more and 13 mass% or less.
- the amount of the organic nucleating agent contained in the polyester film is less than 1% by mass, the film for solar battery backsheet is excellent in adhesion, but may be inferior in output improvement due to decrease in reflectivity.
- the amount of the organic nucleating agent exceeds 30% by mass, although the output improvement is excellent, there are cases where there are too many cavities and the adhesion is poor.
- a dispersion aid when an organic nucleating agent is used, it is preferable to use a dispersion aid at the same time.
- a polyester elastomer or an amorphous polyester resin in which a polyether structure, a bent skeleton structure, a bulky cyclohexane skeleton structure, or the like is copolymerized is preferably used.
- a form in which two or more kinds of dispersion aids are used in combination is also preferably used.
- the amount of the dispersion aid contained in the polyester film is preferably 1% by mass or more and 10% by mass or less, more preferably 2% by mass or more and 8% by mass or less, and still more preferably with respect to the total mass of the polyester film. It is 3 mass% or more and 6 mass% or less.
- the amount of the dispersion aid contained in the polyester film is less than 1% by mass, the effect as the dispersion aid is insufficient, and the adhesion may be lowered.
- the amount of the dispersion aid exceeds 10% by mass, the dispersibility may be excessively improved, and the adhesion may be lowered. Furthermore, there is a risk that the heat and humidity resistance of the polyester film may be lowered due to the decrease in crystallinity.
- the cavity in the observation image of the cross section in the thickness direction of the polyester film draws a line perpendicular to the surface direction from one surface of the film to the other surface, Three points dividing the line connecting one surface into four in the thickness direction (film thickness direction center point (C1 point), intermediate point between the film thickness direction center point and the film surface (C2-1 point), (C2-2 In the line parallel to the plane direction of the film passing through the point)) (divided horizontal line), the average area per cavity existing on the divided horizontal line passing through the point C1 is Sc ( ⁇ m 2 ), and the dividing through the point C2-1
- the average area per cavity existing on the horizontal line is Scs ( ⁇ m 2 )
- the average area per cavity existing on the divided horizontal line passing through the point C2-2 is Scs ′ ( ⁇ m 2 ), Sc / Scs)
- At least one of (Sc / Scs ′) is a polyester film of 1.1 to 35.
- they are 1.5 or more and 20 or less, More preferably, they are 2.0 or more and 15 or less, More preferably, they are 2.5 or more and 10 or less. Details of how to obtain Sc ( ⁇ m 2 ), Scs ( ⁇ m 2 ), and Scs ′ ( ⁇ m 2 ) will be described later.
- the size of the void contained in the film is at least one of (Sc / Scs) and (Sc / Scs ′) of 1.1 or more and 35 or less. It has been surprisingly found that the adhesion improves when the thickness direction is inclined so that It is not completely clear why this effect occurs, but the inventors presume as follows. If both (Sc / Scs) and (Sc / Scs') are less than 1.1 (the inclination of the size of the cavities contained in the film is small in the thickness direction), fine cavities are formed inside the polyester film.
- (Sc / Scs) and (Sc / Scs') indicate the shape of the cavity, the type of the cavity nucleating agent, the amount of the cavity nucleating agent, the amount of the dispersing agent, or the polyester resin after melt extrusion at the time of film production. It can be adjusted by the cooling rate. For example, by using an olefin resin having a Vicat softening point of 140 ° C. or higher as an organic nucleating agent, and increasing the amount of the cavity nucleating agent and the amount of the dispersion aid within a preferable range, the cavities can be uniformly refined and the The amount of cavities increases and (Sc / Scs) and (Sc / Scs') decrease.
- the film for solar cell backsheet of the present invention adjusts the type of the inner cavity nucleating agent, the amount of the cavity nucleating agent, the amount of the dispersing agent, or the cooling rate of the polyester resin after melt extrusion at the time of film production within a preferable range.
- at least one of the hollow (Sc / Scs) and (Sc / Scs') inside the polyester film is 1.1 to 35, and the solar cell back sheet has both excellent adhesion and improved output. It can be a film.
- both (Sc / Scs) and (Sc / Scs ′) are in the range of 1.1 to 35, the adhesion on both surfaces of the solar battery backsheet film is excellent. Even in a configuration in which one side of the film for solar battery backsheet is bonded to another member film and the other side is directly bonded to the solar battery cell, it is more preferable because excellent adhesion can be obtained on both surfaces of the film. .
- the film for solar battery backsheet of the present invention can increase the power generation output by reusing light by reflecting the light that has passed between the solar battery cells while diffusing with the solar battery backsheet.
- a form in which inorganic particles are contained in the polyester resin composition constituting the polyester film is preferable.
- the inorganic particles used here include calcium carbonate, magnesium carbonate, zinc carbonate, titanium oxide, zinc oxide, cerium oxide, magnesium oxide, barium sulfate, zinc sulfide, calcium phosphate, alumina, mica, mica, talc, clay, and kaolin. , Lithium fluoride, calcium fluoride, and the like.
- titanium oxide examples include crystalline titanium oxide such as anatase type titanium oxide and rutile type titanium oxide. From the viewpoint of increasing the difference in refractive index from the polyester used, titanium oxide having a refractive index of 2.7 or more is preferable, and at the same time, rutile type titanium oxide is used from the viewpoint of superior ultraviolet resistance. Further preferred. That is, the film for solar cell backsheets of this invention can improve output improvement more by making an inorganic particle be included in the polyester resin composition which comprises the polyester film which has the said cavity.
- the resin composition which comprises a polyester film contains an inorganic particle here, it has a laminated structure of 3 layers or more, and both surface layers (one surface layer is P2 layer) And the other surface layer is a P2 ′ layer) at least one resin composition contains inorganic particles and does not have a surface layer (this layer is a P1 layer) Is preferably a structure containing the above-described cavity nucleating agent, and more preferably a three-layer structure including P2 layer / P1 layer / P2 ′ layer.
- the porosity (Ps) of the P2 layer and the porosity (Ps ′) of the P2 ′ layer are preferably 5.0% or less, more preferably 4.0% or less, and still more preferably 3.5%. It is as follows. When either of the porosity (Ps) and (Ps ′) of the P2 layer and the P2 ′ layer exceeds 5.0%, the surface layer side may become unstable in the cavity area and the adhesion may be lowered. .
- the porosity (Ps) of the P2 layer and the porosity (Ps ′) of the P2 ′ layer are 5.0% or less, without reducing the adhesion,
- the reflectivity of the P1 layer and the diffusibility of the P2 layer or the P2 ′ layer can be utilized without canceling each other, and the output improvement can be further improved.
- process contamination by the cavity nucleating agent can be prevented during the production of the polyester film.
- the solar battery cell that expects the effect of the present invention Adhesion can be further improved by positioning the P2 layer or the P2 ′ layer that satisfies the above range on the side.
- the structure having the P2 layer or the P2 ′ layer containing the inorganic particles having ultraviolet resistance in the surface layer of the film for the solar battery backsheet of the present invention is effective for improving the output and for the solar battery backsheet by the ultraviolet rays hitting the solar battery cell.
- the laminated structure which has an inorganic particle in both the resin composition which comprises a P2 layer and a P2 'layer has the effect of the ultraviolet-ray resistance by the side of the said photovoltaic cell with respect to the reflected light of the ultraviolet ray which hits the back surface of a solar cell. It can also be demonstrated, and it can be said that it is a more preferable form.
- the main components of the P2 layer and the P2 ′ layer can be freely selected as long as the effects of the present invention are not impaired.
- a film for a solar battery back sheet having excellent adhesion between the P1 layer and the P2 layer interface can be obtained.
- an acrylic resin or the like as the main component of the P2 layer, it becomes possible to provide a P2 layer with a higher filling of inorganic particles on the P1 layer by a coating method, and to achieve both excellent adhesion and improved output. It can be set as the film for battery back sheets.
- the thickness of the P1 layer is T1 ( ⁇ m)
- the thickness of the P2 layer is T2 ( ⁇ m)
- the P2 ′ layer is W2 (mass%)
- the inorganic particle concentration contained in the resin composition constituting the P2 ′ layer is W2 ′ (mass). %)
- At least one of (T2 / T1) ⁇ W2 and (T2 ′ / T1) ⁇ W2 ′ preferably satisfies 0.35 or more and 1.50 or less. More preferably, they are 0.75 or more and 1.40 or less, More preferably, they are 0.90 or more and 1.20 or less.
- both (T2 / T1) ⁇ W2 and (T2 ′ / T1) ⁇ W2 ′ are less than 0.35, the diffusibility of the P2 layer and the P2 ′ layer is insufficient, and either layer is a solar cell. Even if it installs in the side, the output improvement property of the film for solar cell backsheets may fall.
- both (T2 / T1) ⁇ W2 and (T2 ′ / T1) ⁇ W2 ′ exceed 1.50, the diffusibility of the P2 layer and the P2 ′ layer becomes too strong, and the light reaches the P1 layer. However, the output improvement performance may be reduced.
- the inorganic particle concentration is preferably 10% by mass or less with respect to the total mass of the P1 layer, from the viewpoint of maintaining the excellent adhesion of the solar cell backsheet film. More preferably, it is more preferably 3% by weight or less.
- the inorganic particle content of the P1 layer exceeds 10% by mass, (Sc / Scs) or (Sc / Scs') of the polyester film becomes small, and the adhesion of the film for solar battery backsheet may be lowered.
- T1 / (T1 + T2 + T2 ′) indicating the ratio of the P1 layer to the total film thickness is preferably in the range of 0.6 or more and 0.99 or less, and the P2 layer and P2 ′ with respect to the total film thickness.
- T2 / (T1 + T2 + T2 ′) and T2 ′ / (T1 + T2 + T2 ′), which indicate the proportion of the layer, are preferably 0.01 or more and 0.2 or less.
- the film for solar cell backsheet of the present invention if necessary, other than the above-described hollow nucleating agent and inorganic particles, as long as the effect of the present invention is not impaired, a heat-resistant stabilizer, an oxidation-resistant stabilizer, an ultraviolet absorption Additives such as an agent, an ultraviolet stabilizer, an organic / inorganic lubricant, an organic / inorganic fine particle, a filler, a nucleating agent, a dye, and a coupling agent may be blended.
- an ultraviolet absorber is selected as an additive, the ultraviolet resistance of the solar cell backsheet film of the present invention can be further enhanced.
- the electrical insulation can be improved by adding an antistatic agent or the like.
- the total thickness of the solar cell backsheet film of the present invention is preferably 25 ⁇ m or more and 350 ⁇ m or less, more preferably 30 ⁇ m or more and 300 ⁇ m or less, and further preferably 50 ⁇ m or more and 260 ⁇ m or less.
- the film for solar battery backsheet of the present invention has a thickness of less than 25 ⁇ m, wrinkles may occur during bonding with other member films.
- the thickness is greater than 350 ⁇ m, the winding property may deteriorate.
- the thickness of the entire film is 45 ⁇ m or more, the effect of improving the adhesion due to the above-described deviation of the cavity area in the thickness direction can be remarkably obtained, and the output improvement effect can be obtained because the light reflectivity is good.
- it is 48 micrometers, More preferably, it is 50 micrometers or more.
- the film for solar cell backsheet of the present invention preferably has a thermal conductivity of 0.9 W / m ⁇ K or less, and more preferably 0.75 W / m ⁇ K or less.
- another film may be laminated on the surface opposite to the surface in close contact with the sealing material (hereinafter referred to as the air side surface).
- the thermal conductivity of the solar cell backsheet film can be lowered by increasing the porosity of the solar cell backsheet film.
- the polyester resin used as the raw material for the solar cell backsheet film of the present invention can be obtained by subjecting dicarboxylic acid or its ester derivative and diol to a transesterification or esterification reaction by a well-known method.
- reaction catalysts include alkali metal compounds, alkaline earth metal compounds, zinc compounds, lead compounds, manganese compounds, cobalt compounds, aluminum compounds, antimony compounds, titanium compounds, and phosphorus compounds.
- an alkali metal compound, a manganese compound, an antimony compound or a germanium compound, or a titanium compound is preferably added as a polymerization catalyst at any stage before the normal production method is completed, and the solar battery backsheet film is adhered.
- a sodium compound or a manganese compound from the viewpoint of further improving the properties.
- a manganese compound for example, when a manganese compound is taken as an example, it is preferable to add the manganese compound powder as it is.
- the terminal carboxyl group amount of the polyester resin is determined by heating at a temperature during polymerization or after polymerization of the polyester resin at a temperature of 190 ° C. to less than the melting point of the polyester resin under reduced pressure or an inert gas flow such as nitrogen gas.
- the so-called solid-state polymerization time can be controlled. Specifically, the amount of terminal carboxyl groups increases as the polymerization temperature increases, and the amount of terminal carboxyl groups decreases as the time of solid phase polymerization increases.
- the method for incorporating a cavity nucleating agent, inorganic particles, etc. into the film for solar cell backsheet of the present invention is to prepare master pellets prepared by melting and kneading raw materials in advance using a vent type biaxial kneading extruder or tandem type extruder. A blending method is preferred. At this time, since the master pellet receives a heat history, there is a concern that the heat deterioration is not a little progressed. Therefore, it is more preferable to prepare a master pellet containing the cavity nucleating agent and inorganic particles at a higher concentration, and mix and dilute them.
- a master pellet having a larger content than the content of the cavity nucleating agent to be contained in the polyester film is prepared in advance. It mixes with the polyester resin which is the main component of a polyester film, and adjusts to the target content.
- the method for producing a film for a solar battery backsheet according to the present invention is a method in which a raw material adjusted to have a polyester film composition is heated and melted in an extruder and extruded from a die cooled onto a cast drum to be processed into a sheet shape.
- the method (melt cast method) can be used.
- the film for solar battery backsheet of the present invention is preferably cooled at a cast drum temperature of 30 to 80 ° C., more preferably 40 to 70 ° C., and further preferably 45 to 60 ° C.
- the obtained sheet is led to a roll group heated to a temperature of 70 to 140 ° C., stretched in the longitudinal direction (longitudinal direction, that is, the traveling direction of the sheet), and cooled by a roll group having a temperature of 20 to 50 ° C. .
- the both ends of the sheet are guided to a tenter while being held by clips, and are stretched in a direction (width direction) perpendicular to the longitudinal direction in an atmosphere heated to a temperature of 80 to 150 ° C.
- the draw ratio is preferably 2 to 30 times in terms of surface magnification, more preferably 4 to 25 times, and still more preferably 6 to 20 times.
- a cavity having an appropriate size can be formed in the polyester film of the present invention. If the surface magnification is less than twice, the cavity may be small and output improvement may be reduced. On the other hand, when the surface magnification exceeds 30 times, the cavity may become too large and the adhesion may be lowered. Also, it is not preferable from the viewpoint of excessive load on the film forming machine.
- the difference between the stretching ratios in the longitudinal direction (running direction during film formation) and the width direction of the film is preferably 4 times or less, more preferably 2 times or less, and still more preferably 1 time or less.
- the difference in the draw ratio exceeds 4 times, the shape of the cavity inside the polyester film is biased in one direction, and the adhesion may be lowered.
- the film for the solar battery backsheet of the present invention is a polyester film in which the difference in the draw ratio between the longitudinal direction (running direction during film formation) and the width direction of the film is 4 times or less, and the surface magnification is 2 times or more and 30 times.
- the set temperature at this time is preferably 150 ° C. or higher and 250 ° C. or lower, more preferably 170 ° C. or higher and 230 ° C. or lower, and further preferably 180 ° C. or higher and 220 ° C. or lower.
- heat setting is performed at less than 150 ° C., the thermal dimensional stability of the solar cell backsheet film is lowered, and there is a risk of problems such as curling during backsheet processing.
- heat setting is performed at a temperature exceeding 250 ° C., the hollow nucleating agent inside the film may flow and the desired reflection performance may not be obtained.
- the film for solar cell backsheets of the present invention has a P2 layer
- the raw material constituting the P1 layer and the raw material constituting the P2 layer are put into two different extruders, melted, and then merged
- a method of co-extrusion on a cast drum cooled from a die and processing it into a sheet (co-extrusion method), or a raw material constituting the P2 layer dissolved in a solvent after forming a polyester film having a P1 layer alone
- a method (coating method) in which the P2 layer is formed by applying a roll coating method, a dip coating method, a bar coating method, a die coating method, a gravure roll coating method and the like and then drying the solvent is preferably used.
- the solar cell backsheet film obtained by the above production method is excellent while maintaining the heat and moisture resistance, heat resistance, ultraviolet resistance, thermal dimensional stability, and workability of the conventional solar cell backsheet film. It is possible to achieve both adhesion and output improvement.
- the solar cell backsheet of this invention is a solar cell backsheet having the film for solar cell backsheet of the present invention and at least one functional layer.
- required by the measuring method mentioned later is 10 mm or less, and it is more preferable that it is 5 mm or less.
- the Young's modulus of the solar battery back sheet film is 4.0 GPa or less, and the Young's modulus of the solar battery back sheet is 4.0 GPa or less. Is preferred. More preferably, the Young's modulus of the solar cell backsheet film is 4.0 GPa or less, and the Young's modulus of the solar cell backsheet is more preferably 3.0 GPa or less.
- the lower limit of the Young's modulus of the solar cell backsheet film and the solar cell backsheet is not particularly limited as long as the function of the present invention is not impaired, but 0.5 GPa or more is sufficient.
- the solar battery back sheet By setting the Young's modulus of the solar battery back sheet to 4.0 GPa or less, when stacking the curl generated when the solar battery back sheet is stored in a roll state on the solar battery, the solar battery back sheet is caused by its own weight. Can be flattened.
- the method for setting the Young's modulus of the solar cell backsheet film in the above range is not particularly limited, but can be adjusted by the following method. For example, when the porosity in the polyester film for solar battery backsheet is increased or the draw ratio during film formation is decreased, the Young's modulus of the film for solar battery backsheet tends to be lowered.
- the Young's modulus of the film for solar battery back sheets tends to increase.
- the Young's modulus of the solar battery backsheet tends to be high when the Young's modulus of the film for solar battery backsheet used for the solar battery backsheet is high, and low when it is low.
- it can adjust with the Young's modulus of the layer laminated
- the functional layer of the solar battery backsheet of the present invention is preferably a layer containing at least one of polyethylene, polypropylene, and ethylene vinyl acetate copolymer, or a combination of a plurality of combinations, because the adhesion becomes good.
- the solar cell backsheet of the present invention by having the functional layer between the solar cell backsheet film and the encapsulant, it becomes possible to have good adhesion to the encapsulant.
- the thickness of the functional layer is preferably 30 ⁇ m or more and 300 ⁇ m or less, and 50 ⁇ m or more and 200 ⁇ m or less. It is more preferable that By setting the thickness of the layer to 30 ⁇ m or more, water vapor barrier properties and insulating properties are improved, and by setting the thickness to 300 ⁇ m or less, it is possible to suppress process contamination due to the protrusion of the functional layer B at the time of manufacturing a solar cell.
- the method of laminating the layer containing at least one of polyethylene, polypropylene, and ethylene vinyl acetate copolymer or a combination thereof with the film for solar cell backsheet of the present invention as a functional layer is not particularly limited.
- a method of directly laminating the film for solar cell backsheet of the present invention, and a method of laminating the film for solar cell backsheet of the present invention and a functional layer via an adhesive or the like within a range not inhibiting the effects of the present invention. can be mentioned.
- the functional layer of the backsheet of the present invention is composed of polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), ethylene-tetrafluoroethylene copolymer (ETFE), tetrafluoroethylene-hexafluoropolypropylene copolymer.
- a layer containing at least one of (FEP) or a combination thereof is preferable because the weather resistance of the backsheet can be improved.
- the functional layer is laminated on the air side surface of the film for solar battery backsheet of the present invention because deterioration due to ultraviolet rays can be suppressed.
- the functional layer preferably contains at least one of PVF and PVDF.
- the thickness of the functional layer is preferably 25 ⁇ m or more and 125 ⁇ m or less, and is 25 ⁇ m or more and 75 ⁇ m or less. It is more preferable. When the thickness of the layer is 25 ⁇ m or more, the weather resistance is improved, and when it is 125 ⁇ m or less, the workability of the solar battery back sheet is improved.
- the method of laminating the layer containing at least one of PVF, PVDF, PTFE, and ETFE as a functional layer on the film for solar cell backsheet of the present invention is not particularly limited. And a method of laminating the solar cell backsheet film of the present invention and a functional layer via an adhesive or the like within a range not impairing the effects of the present invention.
- the functional layer of the solar cell backsheet of the present invention is preferably a layer containing polyurethane, since the adhesion becomes good.
- the functional layer is located between the film for solar battery backsheet of the present invention and the sealing material, the adhesion with the sealing material is improved.
- the polyurethane here is a general term for polymers obtained from a compound having an isocyanate group and a compound having a hydroxyl group.
- the compound having a hydroxyl group examples include polyester polyols, polyether polyols, polyacrylic polyols, and fluorine-based polyols, and polyacrylic polyols and fluorine-based polyols are preferable from the viewpoint of heat and moisture resistance and weather resistance.
- the thickness of the functional layer is preferably 1 ⁇ m or more and 20 ⁇ m or less, and more preferably 2 ⁇ m or more and 10 ⁇ m or less.
- the weather resistance is improved by setting the thickness of the functional layer to 1 ⁇ m or more, and the workability of the backsheet is improved by setting the thickness to 20 ⁇ m or less.
- the method of laminating a layer containing polyurethane as a functional layer with the film for solar battery backsheet of the present invention is not particularly limited, but roll coating, gravure roll coating, kiss coating, and other coating methods, or The method of laminating by a printing method etc. is mentioned.
- the functional layer of the solar cell backsheet of this invention contains an inorganic compound. When the functional layer of the solar cell backsheet contains an inorganic compound, the water vapor barrier property of the solar cell backsheet is improved.
- silica and alumina are preferable, and silica is particularly preferable in terms of water vapor barrier property and heat and moisture resistance.
- the method for laminating the layer containing the inorganic compound as a functional layer with the film for solar cell backsheet of the present invention is not particularly limited, but the method for directly laminating the film for solar cell backsheet of the present invention or the present invention. Layers other than the polyester film obtained by laminating the film for solar cell backsheet of the present invention and the inorganic compound as long as the inorganic compound is laminated on the polyester film different from the film for solar cell backsheet of the present invention and the effect of the present invention is not impaired. And a method of laminating the layer via an adhesive or the like.
- the solar cell backsheet of the present invention is excellent in weather resistance and workability when a functional layer containing polyester is laminated with the film for solar cell backsheet of the present invention via an adhesive layer to form a solar cell backsheet. preferable.
- the thickness of the functional layer is preferably 25 ⁇ m or more and 188 ⁇ m or less, and more preferably 38 ⁇ m or more and 125 ⁇ m or less. It is possible to improve the weather resistance by increasing the thickness of the layer to 25 ⁇ m or more, and to improve the workability of the backsheet by reducing the thickness to 188 ⁇ m or less.
- the film for solar cell backsheets of this invention has a functional layer laminated
- porosity, (Sc / Scs), (Sc / Scs') are adhesive layers. And not including the functional layer.
- porosity, (Sc / Scs), (Sc / Scs') are adhesive layers.
- the center point in the direction of the thickness of the void-containing polyester film is C1, and C1 and the void-containing polyester film
- the intermediate points with the surface are (C2-1 point) and (C2-2 point).
- the solar cell of this invention mounts the said film for solar cell backsheets as it is.
- the solar battery back sheet is mounted.
- a structural example of the solar cell of the present invention is shown in FIG.
- a transparent substrate 4 such as glass and a solar cell back sheet 1
- a power generating element connected with a lead wire (not shown in FIG. 1) for taking out electricity is sealed with a transparent sealing material 2 such as EVA resin.
- a transparent sealing material 2 such as EVA resin.
- the present invention is not limited to this and can be used for any configuration.
- the solar battery back sheet 1 plays a role of protecting the power generation cell installed on the back surface of the sealing material 2 in which the power generation element is sealed.
- the solar battery backsheet is disposed so that the P2 layer is in contact with the sealing material 2 in terms of increasing the power generation efficiency of the solar battery.
- the power generating element 3 converts light energy of sunlight into electric energy, and is based on crystalline silicon, polycrystalline silicon, microcrystalline silicon, amorphous silicon, copper indium selenide, compound semiconductor, dye enhancement Arbitrary elements such as a sensitive system can be used in series or in parallel according to the desired voltage or current depending on the purpose. Since the transparent substrate 4 having translucency is located on the outermost surface layer of the solar cell, a transparent material having high weather resistance, high contamination resistance, and high mechanical strength characteristics in addition to high transmittance is used. In the solar cell of the present invention, the transparent substrate 4 having translucency can be made of any material as long as the above characteristics are satisfied. Examples thereof include glass, ethylene tetrafluoride-ethylene copolymer (ETFE), polyfluoride.
- ETFE ethylene tetrafluoride-ethylene copolymer
- Vinyl fluoride resin PVDF
- PVDF polyvinylidene fluoride resin
- TFE polytetrafluoroethylene resin
- FEP tetrafluoroethylene-hexafluoropropylene copolymer
- CFE polytrifluoroethylene chloride resin
- Fluorinated resins such as polyvinylidene fluoride resin, olefinic resins, acrylic resins, and mixtures thereof.
- glass it is more preferable to use a tempered glass.
- stretched the said resin uniaxially or biaxially from a viewpoint of mechanical strength is used preferably.
- the adhesiveness with EVA resin etc. which are the sealing materials of an electric power generation element, it is also preferably performed to give the surface a corona treatment, a plasma treatment, an ozone treatment, and an easy adhesion treatment. .
- the sealing material 2 for sealing the power generating element covers the surface of the power generating element with resin and fixes it, protects the power generating element from the external environment, and has a light-transmitting base material for the purpose of electrical insulation.
- a material having high transparency, high weather resistance, high adhesion, and high heat resistance is used to adhere to the backsheet and the power generation element. Examples thereof include ethylene-vinyl acetate copolymer (EVA), ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA) resin, ethylene-methacrylic acid copolymer (EMAA), Ionomer resins, polyvinyl butyral resins, and mixtures thereof are preferably used.
- the film for solar cell backsheet of the present invention on a solar cell as a solar cell backsheet, even when placed outdoors for a long period of time compared to conventional solar cells, Adhesiveness is maintained, and further, power generation efficiency can be increased.
- the solar cell of the present invention can be suitably used for various applications without being limited to outdoor use and indoor use such as a solar power generation system and a power source for small electronic components.
- the indicator at the time of titration used phenol red, and the place where it changed from yellowish green to light red was set as the end point of titration. If there is an insoluble matter such as inorganic particles in the solution in which the measurement sample is dissolved, the solution is filtered to measure the mass of the insoluble matter, and the value obtained by subtracting the mass of the insoluble matter from the measurement sample mass is measured. The following correction was made.
- fluorescent X-ray analysis method fluorescent X-ray analyzer (model number: 3270) manufactured by Rigaku Corporation) is used. Quantification was carried out by atomic absorption spectrometry (manufactured by Tadate Corporation: Polarized Zeeman atomic absorption photometer 180-80, frame: acetylene-air).
- a line perpendicular to the film thickness direction is drawn for each observed image, and the line is divided into four equal points (film thickness direction center point (C1 point), intermediate point between the film thickness direction center point and the film surface)
- a line parallel to the thickness direction is drawn on the film passing through (C2-1 point) and (C2-2 point).
- the number of cavities to be traced if there are less than 20 cavities on the divided horizontal line in the observation image, all cavities are traced, and if there are 20 or more cavities, the center of gravity of the cavities is It is assumed that 20 cavities close to the points C1, C2-1, and C2-2 are selected and traced.
- the film side for the solar battery backsheet of the present invention was horizontally fixed, and the peel strength when the peeled portion was subjected to a peel test at 180 ° peel at a speed of 200 mm / min. was measured, and the adhesion of the solar cell backsheet film was determined as follows.
- peel strength When peel strength is 6N / 15mm or more: A When peel strength is 4N / 15mm or more and less than 6N / 15mm: B When peel strength is 2N / 15mm or more and less than 4N / 15mm: C When peel strength is 1N / 15mm or more and less than 2N / 15mm: D When peel strength is less than 1 N / 15 mm: E Adhesiveness is good from A to D, and among them, A is the best.
- the wet heat resistance was determined as follows.
- A When the breaking elongation after the wet heat test is 40% or more and less than 60% of the breaking elongation before the wet heat test: B When the breaking elongation after the wet heat test is 20% or more and less than 40% of the breaking elongation before the wet heat test: C When the breaking elongation after the wet heat test is 10% or more and less than 20% of the breaking elongation before the wet heat test: D When the breaking elongation after the wet heat test is less than 10% of the breaking elongation before the wet heat test: E The wet heat resistance is good in A to D, and A is the best among them.
- UV resistance color change during UV treatment test
- b value Color tone (b value) measurement Based on JIS-Z-8722 (2000), a spectroscopic color difference meter SE-2000 (manufactured by Nippon Denshoku Industries Co., Ltd., light source halogen lamp 12V4A, 0 ° to ⁇ 45 °)
- the test was done so that an ultraviolet test light might hit the surface of the P2 layer side.
- the functional layer B is provided on the surface opposite to the surface having the functional layer B, and in Examples 38 to 44 and 47 to 49, The test was conducted so that the ultraviolet test light hits the surface having the functional layer B ′ in 54 to 56.
- Thermal conductivity is 0.08 W / m ⁇ K or less: A Thermal conductivity is over 0.08 W / m ⁇ K and 0.12 W / m ⁇ K or less: B Thermal conductivity exceeds 0.12 W / m ⁇ K and 0.14 W / m ⁇ K or less: C Thermal conductivity exceeds 0.14 W / m ⁇ K: D The thermal conductivity is good from A to B, and A is the best among them.
- Solar cell characteristic evaluation (7-1) Solar cell output improvement evaluation
- the flux “HOZAN H722” is applied to the front and back silver electrode portions of the polycrystalline silicon solar cell “Gintech G156M3”.
- a wiring material “copper foil SSA-SPS0.2 ⁇ 1.5 (20) manufactured by Hitachi Cable, Ltd.” cut into a length of 155 mm on the front and back silver electrodes was applied with a dispenser, and the cell on the front side Place the wire 10 mm away from one end of the wire on the end of the wiring material and the back side to be symmetrical with the front side, and use the soldering iron to bring the soldering iron into contact from the back side of the cell so that the front and back sides are simultaneously Solder welding was performed to produce 1 cell strings.
- the longitudinal direction of the wiring material protruding from the cell of the produced 1 cell string and the longitudinal direction of the extraction electrode “copper foil A-SPS0.23 ⁇ 6.0 manufactured by Hitachi Cable, Ltd.” cut into 180 mm are shown. Placed vertically, the flux was applied to the portion where the wiring material and the extraction electrode overlapped, and solder welding was performed, thereby producing strings with extraction electrodes. At this time, the short-circuit current was measured according to the standard state of JIS C8914: 2005, and the power generation performance of the cell alone was obtained.
- 190 mm ⁇ 190 mm glass (3.2 mm thick white plate heat-treated glass for solar cells manufactured by Asahi Glass Co., Ltd.) as a cover material
- 190 mm ⁇ 190 mm ethylene vinyl acetate (Sanvik sealing material 0.5 mm as a front side sealing material) Thickness)
- strings with extraction electrodes that have been evaluated for power generation performance of a single cell
- 190 mm x 190 mm ethylene vinyl acetate 0.5 mm thick sealant manufactured by Sunvic
- 190 mm x 190 mm The film for solar cell backsheet of the present invention was stacked and fixed in order, and the glass was set so as to be in contact with the hot plate of the vacuum laminator, the hot plate temperature was 145 ° C., the vacuum was drawn for 4 minutes, the press was 1 minute, and the holding time.
- the strings with extraction electrodes were set so that the glass surface was on the cell surface side.
- the film for solar battery backsheets of this invention was a structure which has P2 layer on the single side
- the obtained solar cell module was subjected to measurement of a short-circuit current measured according to the standard state of JIS C8914: 2005, and the power generation performance of the solar cell equipped with the solar cell backsheet of the present invention was obtained.
- the adhesion of the solar cells was determined as follows by checking how many of the ten solar cells had the sheet peeled off visually. When peeling does not occur in all solar cells: A When the sheet is peeled from one or more than four solar cells among the produced solar cells: B When sheets are peeled from 4 or more and less than 8 solar cells among the produced solar cells: C When 8 or more sheets of the produced solar cells are peeled from the solar cells: D When peeling occurs in all solar cells: E Adhesiveness of the solar cell is good from A to D, and among them, A is the best.
- Young's modulus When Young's modulus is 2.0 GPa or less: A When Young's modulus exceeds 2.0 GPa and is 3.0 GPa or less: B When Young's modulus is more than 3.0 GPa and 4.0 GPa or less: C When Young's modulus exceeds 4.0 GPa: D The Young's modulus is good from A to C, and A is the best among them.
- the average value of the four curl heights obtained in step 1 was taken, and the curl height evaluation was determined as follows from the average value of the curl heights obtained.
- the average curl height is less than 5 mm: A Average value of curl height is 5 mm or more and less than 10 mm: B The average curl height is 10 mm or more and less than 15 mm: C The average curl height is 15 mm or more: D The curl height is good in A to C, and A is the best among them.
- Water vapor transmission rate is less than 0.5 g / m 2 / day: A Water vapor transmission rate is 0.5 g / m 2 / day or more and less than 1.0 g / m 2 / day: B Water vapor transmission rate is 1.0 g / m 2 / day or more and less than 2.0 g / m 2 / day: C Water vapor transmission rate is 2.0 g / m 2 / day or more and less than 3.0 g / m 2 / day: D Water vapor transmission rate is 3.0 g / m 2 / day or more: E The water vapor barrier properties A to D are good, and A is the best among them.
- PET raw material A 100 parts by mass of dimethyl terephthalate, 57.5 parts by mass of ethylene glycol, 0.03 parts by mass of manganese acetate tetrahydrate and 0.03 parts by mass of antimony trioxide were melted at 150 ° C. in a nitrogen atmosphere. While stirring this melt, the temperature was raised to 230 ° C. over 3 hours to distill methanol, and the transesterification reaction was completed.
- an ethylene glycol solution (pH 5.0) in which 0.005 parts by mass of phosphoric acid and 0.021 parts by mass of sodium dihydrogen phosphate dihydrate were dissolved in 0.5 parts by mass of ethylene glycol was added. .
- the intrinsic viscosity of the polyester composition at this time was less than 0.2.
- the polymerization reaction was performed at a final temperature of 285 ° C. and a degree of vacuum of 0.1 Torr to obtain polyethylene terephthalate having an intrinsic viscosity of 0.52 and a terminal carboxyl group amount of 15 equivalents / ton.
- the obtained polyethylene terephthalate was dried and crystallized at 160 ° C. for 6 hours.
- PET-a polyethylene terephthalate having an intrinsic viscosity of 0.82 and a terminal carboxyl group amount of 10 equivalents / ton.
- the obtained polyethylene terephthalate composition had a glass transition temperature of 82 ° C. and a melting point of 255 ° C.
- PET raw material B A polyethylene terephthalate (PET-b) having an intrinsic viscosity of 0.85 and a terminal carboxyl group amount of 6 equivalents / ton was obtained except that the solid phase polymerization time was 10 hours.
- PET raw material C A polyethylene terephthalate (PET-c) having an intrinsic viscosity of 0.79 and a terminal carboxyl group content of 15 equivalents / ton was obtained except that the final temperature of the polymerization reaction was 290 ° C.
- PET raw material D PET-d
- PET-d polyethylene terephthalate
- PET raw material E A polyethylene terephthalate (PET-e) having an intrinsic viscosity of 0.75 and a terminal carboxyl group content of 28 equivalents / ton was obtained except that the final temperature of the polymerization reaction was 300 ° C.
- PET raw material F As the reaction catalyst, 0.03 parts by mass of magnesium acetate dihydrate instead of manganese acetate, and after completion of the transesterification reaction, the same procedure as in PET raw material A was performed except that only 0.005 parts by mass of phosphoric acid was added. Polyethylene terephthalate (PET-f) having a terminal carboxyl group amount of 10 equivalents / ton was obtained.
- PET raw material G A polyethylene terephthalate (PET-g) having an intrinsic viscosity of 0.76 and a terminal carboxyl group content of 24 equivalents / ton was obtained except that the final temperature of the polymerization reaction was 297 ° C.
- PET raw material H A polyethylene terephthalate (PET-h) having an intrinsic viscosity of 0.65 and a terminal carboxyl group amount of 34 equivalents / ton was obtained except that the final temperature of the polymerization reaction was 305 ° C.
- Hollow nucleant master pellet B In place of PET resin A, 2. 6. Except for using the PET resin B obtained in the above section.
- the hollow nucleating agent master pellet B was produced by the same composition and method as the hollow nucleating agent master pellet A of the item.
- Hollow nucleant master pellet C In place of PET resin A, the above 3. 6. Except for using the PET resin C obtained in the above section.
- the hollow nucleating agent master pellet C was produced by the same composition and method as the hollow nucleating agent master pellet A of the item.
- Hollow core master pellet D In place of PET resin A, the above 4. 6. Except for using the PET resin D obtained in the above section.
- the hollow nucleating agent master pellet D was produced by the same composition and method as the hollow nucleating agent master pellet A of the item.
- Hollow core master pellet F In place of PET resin A, 5. 6. Except for using the PET resin F obtained in the above section.
- the hollow nucleating agent master pellet F was produced by the same composition and method as the hollow nucleating agent master pellet A.
- PMP polymethylpentene
- TPX registered trademark
- TPE polyester-based elastomer
- Hytrel registered trademark
- PET resin A PET-a
- PP polypropylene
- Noblen registered trademark
- Titanium oxide master pellet 100 parts by mass of PET resin A (PET-a) obtained according to the above and 100 parts by mass of rutile-type titanium oxide particles (TiO 2 ) having an average particle diameter of 210 nm are melt-kneaded in a vented 290 ° C. extruder, and oxidized. A titanium master pellet was prepared.
- Barium sulfate master pellet 100 parts by mass of PET resin A (PET-a) obtained according to the above and 100 parts by mass of barium sulfate particles (BaSO 4 ) having an average particle size of 1.5 ⁇ m were melt-kneaded in a vented 290 ° C. extruder, and sulfuric acid was added. Barium master pellets were prepared.
- Polyethylene vinyl acetate copolymer film Polyethylene in which 50 parts by mass of polyethylene vinyl acetate (vinyl acetate content 5% by mass) and 30% by mass of titanium dioxide having a number average secondary particle size of 0.25 ⁇ m are dispersed as inorganic particles. 50 parts by mass of master chips (containing 30% by mass of titanium dioxide with respect to the total amount of master chips) were supplied to an extruder heated to a temperature of 190 ° C., and a polyethylene vinyl acetate film extruded from a T die was used.
- PVF film “Tedlar” (registered trademark) manufactured by DuPont was used.
- PVDF film Arkema “Kyner” (registered trademark) was used.
- ETFE Film Daikin Industries, Ltd. “Neofluon” (registered trademark) EF series was used.
- Urethane coating agent (coating agent a, coating agent b)
- coating agent a “Halshybrit” (registered trademark) polymer UV-G301 (solid content concentration: 40), which is an acrylic coating agent manufactured by Nippon Shokubai Co., Ltd., is prepared according to the formulation shown in the main agent column of Table 9. (Mass%) were mixed together with colored pigment Titanium Co., Ltd. titanium oxide particles JR-709 and a solvent, and the mixture was dispersed using a bead mill.
- polyester plasticizer “Polysizer” (registered trademark) W-220EL manufactured by DIC Corporation is added as a plasticizer to obtain a main component of coating agent a for resin layer formation having a solid content concentration of 51 mass%. It was.
- “Desmodur” (registered trademark) N3300 (solid content concentration: 100 mass%) manufactured by Sumika Bayer Urethane Co., Ltd., which is a nurate-type hexamethylene diisocyanate resin shown in Table 10. Is added in an amount calculated in advance such that the mass ratio with the resin layer forming main agent is 100/4, and is further calculated in advance so that the solid content concentration is 20% by mass. Diluent: n-propyl acetate was weighed and stirred for 15 minutes to obtain a coating agent a having a solid concentration of 20% by mass.
- coating agent b As preparation of coating agent b, “Takenate” (registered trademark) D120N manufactured by Mitsui Chemicals, Inc., which is a hydrogenated xylylene diisocyanate shown in Table 11, and “Zeffle” (registered trademark) GK570 manufactured by Daikin Industries, Ltd.
- the diluent shown in Table 10 was blended in an amount calculated in advance so that the mass ratio to the resin layer forming main agent was 65/12, and further calculated in advance so that the solid content concentration was 20% by mass: N-Butyl acetate was weighed and stirred for 15 minutes to obtain a coating agent b having a solid content of 20% by mass.
- Laminating adhesive As a laminating adhesive, 36 parts by mass of a dry laminating agent “Dick Dry” (registered trademark) TAF-300 manufactured by DIC Corporation, and a TAF hardener manufactured by DIC Corporation containing hexamethylene diisocyanate resin as a main component as a curing agent. 3 parts by weight of AH-3 and 30 parts by weight of ethyl acetate were weighed and stirred for 15 minutes to obtain a coating agent c as a laminating adhesive having a solid content concentration of 30% by weight.
- a dry laminating agent “Dick Dry” registered trademark
- TAF hardener manufactured by DIC Corporation containing hexamethylene diisocyanate resin as a main component as a curing agent.
- 3 parts by weight of AH-3 and 30 parts by weight of ethyl acetate were weighed and stirred for 15 minutes to obtain a coating agent c as a laminating adhesive having a solid content concentration of 30% by weight.
- Example 1 In order to obtain the composition shown in Table 1, 77.5 parts by mass of PET raw material A (PET-a) vacuum-dried at 180 ° C. for 2 hours as a raw material constituting the P1 layer and 22.5 parts of the hollow nucleating agent master pellet A were obtained. On the other hand, 72 parts by mass of PET raw material A (PET-a) vacuum-dried at 180 ° C. for 2 hours as a raw material constituting the P2 layer and 28 parts by mass of titanium oxide master pellets were mixed, Each was melted and discharged in two different extruders heated to 280 ° C., merged so as to be laminated with P2 / P1 / P2 in a feed block, and then co-extruded from a T die.
- the co-extruded molten sheet was closely cooled and solidified by an electrostatic application method on a drum maintained at a surface temperature of 50 ° C. to obtain an unstretched sheet.
- a three-fold speed difference is created between the roll heated to a temperature of 88 ° C. and the roll adjusted to a temperature of 25 ° C.
- the tenter is guided to a preheating zone at a temperature of 80 ° C. in the tenter, and subsequently in a heating zone maintained at 90 ° C. in a direction perpendicular to the longitudinal direction (width) Direction). Subsequently, heat treatment was carried out at 220 ° C. for 20 seconds in a heat treatment zone in the tenter, and further uniformly cooled while performing relaxation treatment in the 4% width direction to form a polyester film.
- the overall porosity was 21%
- the porosity of the surface layer was 2.5% for both Ps and Ps ′
- the cavity area ratio was confirmed ( Both (Sc / Scs) and (Sc / Scs') were 3.5.
- the polymer properties were measured, the intrinsic viscosity IV was 0.70 dl / g, the terminal carboxyl group amount was 14 equivalents / ton, and the metal elements contained 69 ppm of Mn, 241 ppm of Sb, and 29 ppm of Na.
- the film had excellent adhesion, wet heat resistance, ultraviolet resistance, and thermal conductivity. Furthermore, as a result of evaluating the characteristics of the solar cell, it was found that it has excellent output improvement and adhesion.
- Examples 2 to 11 Except for changing the composition of the P1 layer as shown in Table 1, using the amount of the hollow nucleating agent master pellet and the hollow nucleating agent master pellets G to I, or mixing the titanium oxide master pellet used in the P2 layer with the P1 layer. Obtained the film for solar cell backsheets similarly to Example 1.
- Example 12 As shown in Table 3, a solar cell backsheet film was obtained in the same manner as in Example 1 except that the PET resin as the main component of the P1 layer and the P2 layer was changed to PET-b to f as shown in Table 3.
- Examples 12 to 15 are in a good range although the adhesion is inferior to that of Example 1. I understood it.
- the heat and humidity resistance decreased with a decrease in intrinsic viscosity IV and an increase in the amount of terminal carboxyl groups. It was also found that the thermal conductivity was excellent as in Example 1.
- the output improvement was reduced with the increase in the amount of terminal carboxyl groups as compared with Example 1, the adhesion was in a good range.
- Example 16 is inferior to Example 1 in terms of the intrinsic viscosity and the amount of terminal carboxyl groups, the adhesion of the solar battery backsheet, the output improvement of the solar battery, and the adhesion are inferior, but it is in a good range. I understood.
- Examples 17 to 25 A solar battery backsheet film was obtained in the same manner as in Example 1 except that the lamination ratio and film configuration of the solar battery backsheet, the amount of inorganic particles in the P2 layer, and the casting temperature were changed as shown in Table 3.
- Example 25 was smaller than Example 1 in both (Sc / Scs) and (Sc / Scs').
- the polymer characteristics were the same as in Example 1.
- the thickness of the P1 layer was T1 ( ⁇ m), and the thickness of the P2 layer was T2 ( ⁇ m), the adhesiveness is inferior to that of Example 1 as (T1 / T2) ⁇ W2 increases when the concentration of inorganic particles contained in the resin composition constituting the P2 layer is W2 (mass%). It was found to be in a good range. Further, the ultraviolet resistance was lowered as the concentration of inorganic particles in the P2 layer was lowered. The thermal conductivity was excellent as in Example 1.
- Example 25 has the adhesion of the solar cell back sheet which is very excellent similarly to Example 1, and the output improvement property and adhesion of a solar cell, a cavity nucleating agent adheres on a process roll at the time of film forming. I found out that
- Example 26 As shown in Table 3, a solar cell backsheet film was obtained in the same manner as in Example 1 except that a high concentration of inorganic particles was added to the P1 layer in the P1 layer single film configuration.
- Example 27 Since barium sulfate particles are used as the inorganic particles of the P2 layer, barium sulfate master pellets are used, and the discharge rate of the extruder is adjusted so that the lamination ratio (P2: P1: P2) of the polyester film is 1: 1: 1. Obtained the film for solar cell backsheets similarly to Example 3. When the cavity area ratio of the obtained solar cell backsheet film was confirmed, as shown in Table 4, both (Sc / Scs) and (Sc / Scs') were smaller than Example 3. About the obtained solar cell backsheet film, as a result of evaluating the solar cell backsheet characteristics, it was found that the film for the solar cell backsheet had good adhesion although it was inferior to Example 3. The thermal conductivity was excellent as in Example 1. Furthermore, as a result of evaluating the solar cell characteristics, it was found that the solar cell characteristics were inferior to those of Example 3 but had good adhesiveness, and there was no problem in terms of output improvement.
- Example 28 As shown in Table 3, a solar cell backsheet film was obtained in the same manner as in Example 1 except that the PET resin as the main component of the P1 layer and the P2 layer was changed to PET-g as shown in Table 3.
- Example 29 to 31 A film for a solar battery back sheet was obtained in the same manner as in Example 1 except that the line speed was changed during film formation and the total thickness of the film was changed as shown in Table 3.
- Examples 32 to 44 Using the coating material c prepared as the laminating adhesive on one surface of the P2 layer of the film for solar battery backsheet obtained in Example 1, it was applied using a wire bar and at a temperature of 80 ° C. for 45 seconds. The dried adhesive layer was formed so that the thickness of the coating film after drying was 5.0 ⁇ m. Next, the functional layer B shown in Table 5 was laminated
- Example 45 to 49 In the same manner as in Examples 32 to 44, the functional layer B shown in Table 6 was laminated on the adhesive layer and aged at a temperature of 40 ° C. for 3 days to obtain a solar cell backsheet.
- the solar cell backsheets shown in Examples 45 to 49 had good adhesion, moist heat resistance, and ultraviolet resistance, and had a large Young's modulus and curl height, but had excellent water vapor barrier properties. . Moreover, it was excellent in the solar cell characteristic.
- Examples 50 to 53 Using one of the P2 layers of the solar cell backsheet film obtained in Example 1, the thickness of the functional layer B after drying becomes the thickness shown in Table 6, using a wire bar according to Table 6, and paint a The coating material b was applied and dried at a temperature of 100 ° C. for 60 seconds to produce solar cell backsheet films (in Examples 50 to 53, porosity, (Sc / Scs), (Sc / Scs) ') was determined based on a laminated film including the functional layer B). When the obtained solar cell backsheet film was evaluated as a solar cell backsheet, both the backsheet characteristics and the solar cell characteristics were excellent.
- Example 54 Using the coating material c prepared as the laminating adhesive on one surface of the P2 layer of the film for solar battery backsheet obtained in Example 1, it was applied using a wire bar and at a temperature of 80 ° C. for 45 seconds. The dried adhesive layer was formed so that the thickness of the coating film after drying was 5.0 ⁇ m. Next, the functional layer B ′ shown in Table 6 was laminated on the adhesive layer and aged at a temperature of 40 ° C. for 3 days. Furthermore, using the coating material c prepared as a laminating adhesive on the other P2 layer on which the functional layer B ′ is not laminated, it is applied using a wire bar, dried at a temperature of 80 ° C.
- the adhesive layer for lamination was formed so that the thickness of the coating film was 5.0 ⁇ m.
- the functional layer B shown in Table 6 was laminated on the laminating adhesive layer and aged at a temperature of 40 ° C. for 3 days to obtain a solar cell backsheet.
- the obtained solar cell backsheets shown in Examples 54 and 55 had good adhesion, wet heat resistance, and ultraviolet resistance, and were excellent in Young's modulus, curl height, and water vapor barrier properties. Moreover, it was excellent in the solar cell characteristic.
- Example 56 Using one of the P2 layers of the solar cell backsheet film obtained in Example 1, the thickness of the functional layer B after drying becomes the thickness shown in Table 6, using a wire bar according to Table 6, and paint a Was applied and dried at a temperature of 100 ° C. for 60 seconds to obtain a solar battery backsheet film having a functional layer B. Further, using a coating c prepared as a laminating adhesive on one P2 layer on which the functional layer B is not laminated, it is applied using a wire bar, dried at a temperature of 80 ° C. for 45 seconds, and dried. The adhesive layer for lamination was formed so that the film thickness was 5.0 ⁇ m.
- a functional layer B ′ shown in Table 6 was laminated on the laminating adhesive layer and aged at a temperature of 40 ° C. for 3 days to obtain a solar cell backsheet.
- the solar cell back sheet shown in Example 56 was excellent in water vapor barrier property, although Young's modulus and curl height were large. Moreover, the solar cell characteristics were also excellent.
- Example 1 A solar cell backsheet film was obtained in the same manner as in Example 1 except that the amount of the hollow nucleating agent in the P1 layer was 3% by mass. When the porosity of the obtained film for solar battery back sheets was confirmed, it was found that the porosity of the entire film was 9%, which was out of the scope of the present invention. Furthermore, it turned out that the film for solar cell backsheets obtained by the comparative example 1 is a solar cell backsheet inferior in adhesiveness and heat conductivity. Moreover, it turned out that it is a solar cell inferior to an output improvement property and adhesiveness also about a solar cell characteristic.
- the solar cell backsheet films obtained in Comparative Examples 1 to 4 were solar cell backsheets having poor adhesion.
- the comparative example 6 is a solar cell backsheet with inferior thermal conductivity.
- the solar cell backsheet film was found to be a solar cell backsheet with poor adhesion and thermal conductivity. Moreover, it turned out that it is a solar cell inferior to an output improvement property and adhesiveness also about a solar cell characteristic.
- Example 8 A solar cell backsheet film was obtained in the same manner as in Example 1 except that the PET resin, which is the main component of the P1 layer and P2 layer, was changed to PET-h.
- the film for solar cell backsheets obtained by the comparative example 8 is a solar cell backsheet inferior in adhesiveness and heat-and-moisture resistance. Moreover, it turned out that it is a solar cell in which both an output improvement property and adhesiveness are inferior also about the solar cell characteristic.
- Comparative Example 9 Pre-heated unstretched sheet obtained by extruding and cooling from a T-die with a P1 layer single-layer structure during film formation with a roll group heated to a temperature of 70 ° C, and then placed at a position 15 mm away from both surfaces of the sheet A solar cell backsheet film was obtained in the same manner as in Comparative Example 2, except that the film was heated for 0.72 seconds at an output of 50 W / cm with the infrared heater and stretched three times in the longitudinal direction (longitudinal direction). When the cavity area ratio of the obtained solar cell backsheet film was confirmed, unlike Comparative Example 2, the cavity area in the thickness direction was biased.
- the average area per cavity is only small, and at a depth of 25 to 75% of the total film thickness, there is a difference in the average area per cavity.
- (Sc / Scs) and (Sc / Scs ′) were 1.0.
- the film for solar battery back sheet obtained in Comparative Example 9 was found to be a solar battery back sheet having poor adhesion. Moreover, it turned out that it is a solar cell in which both an output improvement property and adhesiveness are inferior also about the solar cell characteristic.
- Example 10 A solar battery back sheet was laminated in the same manner as in Example 32 except that the film for Comparative Example 6 was used, and the functional layer B shown in Table 9 was laminated and aged at a temperature of 40 ° C. for 3 days. did.
- the obtained solar cell back sheet was inferior in Young's modulus and curl height.
- the solar cell characteristic although adhesiveness was improved from the comparative example 6, it was a solar cell with inferior output improvement.
- Example 11 A solar battery back sheet was laminated in the same manner as in Example 42 except that the film of Comparative Example 6 was used, and the functional layer B shown in Table 9 was laminated and aged at a temperature of 40 ° C. for 3 days. did.
- the obtained solar cell back sheet was inferior in Young's modulus and curl height. Moreover, it was a solar cell inferior to adhesiveness and output improvement about a solar cell characteristic.
- the solar cell backsheet film of the present invention By mounting the solar cell backsheet film of the present invention on a solar cell as a solar cell backsheet, adhesion to the solar cell backsheet even when placed outdoors for a long period of time compared to conventional solar cells Can be maintained, and the power generation efficiency can be increased.
- the solar cell of the present invention can be suitably used for various applications without being limited to outdoor use and indoor use such as a solar power generation system and a power source for small electronic components.
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Abstract
Description
従来の太陽電池バックシートにおいては、太陽電池セル同士の間を通過した光を太陽電池バックシートで反射させ、セルに取り込むことにより太陽電池モジュールの効率を向上させる技術が開発されている。具体的に、基材表面に白色ビーズと白色バインダーにより反射層を形成し、モジュール効率を向上させる技術や、空洞を含む層を形成することにより高反射の太陽電池バックシートを提供する技術(特許文献4、5参照)が提案されている。 A typical configuration of a general solar cell is shown in FIG. In the solar cell, a
In the conventional solar battery backsheet, a technique has been developed that improves the efficiency of the solar battery module by reflecting the light that has passed between the solar battery cells with the solar battery backsheet and taking it into the cells. Specifically, a technology that improves the module efficiency by forming a reflective layer with white beads and a white binder on the surface of the substrate, and a technology that provides a highly reflective solar cell backsheet by forming a layer containing cavities (patent)
以下本発明の太陽電池バックシート用フィルムについて説明する。 The film for solar battery backsheet of the present invention is a void-containing polyester film having a porosity of 10% or more of the entire film, and faces from one surface of the film to the other surface in a cross section in the thickness direction of the polyester film. A line perpendicular to the direction is drawn, and a line connecting the one surface to the other surface is divided into four equal parts in the thickness direction (film thickness direction center point (C1 point), film thickness direction center point and film surface One of the cavities existing on the divided horizontal line passing through the point C1 in each of the lines (divided horizontal lines) parallel to the plane direction of the film passing through each of the intermediate points (points C2-1 and C2-2) the average area per Sc (μm 2), Scs an average area per cavity present on dividing the horizontal line passing through the C2-1 points (μm 2), dividing the horizontal line passing through the C2-2 points 'When the (μm 2), (Sc / Scs), (Sc / Scs' Scs the average area per cavity that exists is 35 or less, at least one of 1.1 or more of) the polyester film It is characterized by satisfy | filling that the amount of terminal carboxyl groups of the polyester resin to comprise is 35 equivalent / tons or less.
The solar cell backsheet film of the present invention will be described below.
ここで(Sc/Scs)と(Sc/Scs’)のいずれもが、1.1以上35以下の範囲にあると、太陽電池バックシート用フィルムの両表面で密着性が優れるため、例えば本発明の太陽電池バックシート用フィルムの片面を他の部材フィルムと張り合わせて、もう片面を太陽電池セルに直接、張り合わせるような構成においても、フィルム両表面で優れた密着性が得られることからより好ましい。 When the values of (Sc / Scs) and (Sc / Scs') are different and only one of them is in the range of 1.1 to 35, the (Sc / Scs) or By positioning the surface in which (Sc / Scs ′) is in a preferable range, adhesion and output improvement can be further improved. For example, when only (Sc / Scs) is 1.1 or more and 35 or less, the solar battery back sheet film arranged so that the sealing material is located on the film surface side close to Scs is improved in adhesion and output. Can be made compatible.
Here, when both (Sc / Scs) and (Sc / Scs ′) are in the range of 1.1 to 35, the adhesion on both surfaces of the solar battery backsheet film is excellent. Even in a configuration in which one side of the film for solar battery backsheet is bonded to another member film and the other side is directly bonded to the solar battery cell, it is more preferable because excellent adhesion can be obtained on both surfaces of the film. .
ここで用いる無機粒子としては、例えば、炭酸カルシウム、炭酸マグネシウム、炭酸亜鉛、酸化チタン、酸化亜鉛、酸化セリウム、酸化マグネシウム、硫酸バリウム、硫化亜鉛、リン酸カルシウム、アルミナ、マイカ、雲母、タルク、クレー、カオリン、フッ化リチウム、およびフッ化カルシウムなどが挙げられる。更にこれらの中でもポリエステル樹脂との加工が容易な観点から、炭酸カルシウム、炭酸マグネシウム、酸化チタン、酸化亜鉛、硫酸バリウムが好ましく、太陽電池バックシート用フィルムの耐紫外線性を同時に高められる観点から酸化チタンがより好ましい。また酸化チタンとしては、例えばアナタース型酸化チタンおよびルチル型酸化チタンのような結晶型の酸化チタンを挙げることができる。用いられるポリエステルとの屈折率の差を大きくするという観点からは、屈折率が2.7以上の酸化チタンであることが好ましく、同時に耐紫外線性により優れる観点から、ルチル型酸化チタンを用いることが更に好ましい。
すなわち、本発明の太陽電池バックシート用フィルムは、前記の空洞を有するポリエステルフィルムを構成するポリエステル樹脂組成物に無機粒子を含有させることで、出力向上性をより高めることができる。 The film for solar battery backsheet of the present invention can increase the power generation output by reusing light by reflecting the light that has passed between the solar battery cells while diffusing with the solar battery backsheet. Here, from the viewpoint of increasing the light diffusibility, a form in which inorganic particles are contained in the polyester resin composition constituting the polyester film is preferable.
Examples of the inorganic particles used here include calcium carbonate, magnesium carbonate, zinc carbonate, titanium oxide, zinc oxide, cerium oxide, magnesium oxide, barium sulfate, zinc sulfide, calcium phosphate, alumina, mica, mica, talc, clay, and kaolin. , Lithium fluoride, calcium fluoride, and the like. Further, among these, calcium carbonate, magnesium carbonate, titanium oxide, zinc oxide, and barium sulfate are preferable from the viewpoint of easy processing with a polyester resin, and titanium oxide from the viewpoint of simultaneously improving the ultraviolet resistance of the film for solar battery backsheet. Is more preferable. Examples of titanium oxide include crystalline titanium oxide such as anatase type titanium oxide and rutile type titanium oxide. From the viewpoint of increasing the difference in refractive index from the polyester used, titanium oxide having a refractive index of 2.7 or more is preferable, and at the same time, rutile type titanium oxide is used from the viewpoint of superior ultraviolet resistance. Further preferred.
That is, the film for solar cell backsheets of this invention can improve output improvement more by making an inorganic particle be included in the polyester resin composition which comprises the polyester film which has the said cavity.
なお、P2層の空隙率(Ps)およびP2’層の空隙率(Ps’)のいずれか一方のみが5.0%以下を満たすフィルムである場合は、本発明の効果を期待する太陽電池セル側に上記範囲をみたすP2層あるいはP2’層を位置させることにより、より密着性を高めることができる。
本発明の太陽電池バックシート用フィルムの表層に前記の耐紫外線性を有する無機粒子を含有するP2層あるいはP2’層を有する構成は出力向上効果と、太陽電池セルに当たる紫外線による太陽電池バックシート用フィルムの変色を抑制するといった耐紫外線性を両立することができるためより好ましい形態といえる。またP2層とP2’層を構成する樹脂組成物の両方に無機粒子を有する積層構成は、前記の太陽電池セル側の耐紫外線性の効果を、太陽電池の背面に当たる紫外線の反射光に対しても発揮することが可能となり、更に好ましい形態といえる。 In addition, when inorganic particles are contained in the P2 layer and the P2 ′ layer, they may become a cavity nucleating agent and the surface layer may contain a small amount of cavities. At this time, the porosity (Ps) of the P2 layer and the porosity (Ps ′) of the P2 ′ layer are preferably 5.0% or less, more preferably 4.0% or less, and still more preferably 3.5%. It is as follows. When either of the porosity (Ps) and (Ps ′) of the P2 layer and the P2 ′ layer exceeds 5.0%, the surface layer side may become unstable in the cavity area and the adhesion may be lowered. . In the film for solar cell backsheet of the present invention, the porosity (Ps) of the P2 layer and the porosity (Ps ′) of the P2 ′ layer are 5.0% or less, without reducing the adhesion, The reflectivity of the P1 layer and the diffusibility of the P2 layer or the P2 ′ layer can be utilized without canceling each other, and the output improvement can be further improved. Furthermore, process contamination by the cavity nucleating agent can be prevented during the production of the polyester film.
In addition, when only one of the porosity (Ps) of the P2 layer and the porosity (Ps ′) of the P2 ′ layer is a film that satisfies 5.0% or less, the solar battery cell that expects the effect of the present invention Adhesion can be further improved by positioning the P2 layer or the P2 ′ layer that satisfies the above range on the side.
The structure having the P2 layer or the P2 ′ layer containing the inorganic particles having ultraviolet resistance in the surface layer of the film for the solar battery backsheet of the present invention is effective for improving the output and for the solar battery backsheet by the ultraviolet rays hitting the solar battery cell. It can be said to be a more preferable form because it can achieve both UV resistance such as suppressing discoloration of the film. Moreover, the laminated structure which has an inorganic particle in both the resin composition which comprises a P2 layer and a P2 'layer has the effect of the ultraviolet-ray resistance by the side of the said photovoltaic cell with respect to the reflected light of the ultraviolet ray which hits the back surface of a solar cell. It can also be demonstrated, and it can be said that it is a more preferable form.
本発明の太陽電池バックシート用フィルムが前記のP2層および/またはP2’層を有する構成をとる場合、P1層の厚みをT1(μm)、P2層の厚みをT2(μm)、P2’層の厚みをT2’(μm)、P2層を構成する樹脂組成物に含まれる無機粒子濃度をW2(質量%)、P2’層を構成する樹脂組成物に含まれる無機粒子濃度をW2’(質量%)としたとき、(T2/T1)×W2、(T2‘/T1)×W2’のうち少なくとも一方が0.35以上1.50以下を満たすことが好ましい。より好ましくは、0.75以上1.40以下であり、さらに好ましくは0.90以上1.20以下である。 The main components of the P2 layer and the P2 ′ layer (hereinafter sometimes expressed as the P2 layer in a unified manner) can be freely selected as long as the effects of the present invention are not impaired. For example, by using the same polyester resin as the P1 layer as the main component of the P2 layer, a film for a solar battery back sheet having excellent adhesion between the P1 layer and the P2 layer interface can be obtained. Further, by using an acrylic resin or the like as the main component of the P2 layer, it becomes possible to provide a P2 layer with a higher filling of inorganic particles on the P1 layer by a coating method, and to achieve both excellent adhesion and improved output. It can be set as the film for battery back sheets.
When the film for solar battery backsheet of the present invention has the above-described P2 layer and / or P2 ′ layer, the thickness of the P1 layer is T1 (μm), the thickness of the P2 layer is T2 (μm), and the P2 ′ layer. Is T2 ′ (μm), the inorganic particle concentration contained in the resin composition constituting the P2 layer is W2 (mass%), and the inorganic particle concentration contained in the resin composition constituting the P2 ′ layer is W2 ′ (mass). %), At least one of (T2 / T1) × W2 and (T2 ′ / T1) × W2 ′ preferably satisfies 0.35 or more and 1.50 or less. More preferably, they are 0.75 or more and 1.40 or less, More preferably, they are 0.90 or more and 1.20 or less.
次に、本発明の太陽電池バックシート用フィルムの製造方法について例を挙げて説明する。これは一例であり、本発明は、かかる例によって得られる物のみに限定して解釈されるものではない。 (Method for producing film for solar battery back sheet)
Next, an example is given and demonstrated about the manufacturing method of the film for solar cell backsheets of this invention. This is an example, and the present invention should not be construed as being limited to the product obtained by such an example.
ここで本発明の太陽電池バックシート用フィルムはキャストドラム温度を30以上80℃以下で冷却することが好ましく、より好ましくは40℃以上70℃以下、更に好ましくは45℃以上60℃以下である。キャストドラムの温度を30℃未満の場合、溶融押出されたフィルムの冷却速度が速すぎて、ポリエステルフィルムの(Sc/Scs)あるいは(Sc/Scs’)が小さくなり好ましい範囲を外れる場合がある。一方でキャストドラムの温度が80℃を超えると、ポリエステル樹脂の結晶化が進行しすぎて延伸時に破れが発生する場合がある。 Next, the method for producing a film for a solar battery backsheet according to the present invention is a method in which a raw material adjusted to have a polyester film composition is heated and melted in an extruder and extruded from a die cooled onto a cast drum to be processed into a sheet shape. The method (melt cast method) can be used.
Here, the film for solar battery backsheet of the present invention is preferably cooled at a cast drum temperature of 30 to 80 ° C., more preferably 40 to 70 ° C., and further preferably 45 to 60 ° C. When the temperature of the cast drum is less than 30 ° C., the cooling rate of the melt-extruded film is too fast, and the (Sc / Scs) or (Sc / Scs ′) of the polyester film may become small and deviate from the preferred range. On the other hand, when the temperature of the cast drum exceeds 80 ° C., crystallization of the polyester resin proceeds too much, and tearing may occur during stretching.
次に、本発明の太陽電池バックシートについて説明する。本発明の太陽電池バックシートは、本発明の太陽電池バックシート用フィルムと少なくとも1層以上の機能層を有する太陽電池バックシートであることが重要である。中でも、後述する測定方法により求められる太陽電池バックシートのカール高さが10mm以下であることが好ましく、5mm以下であることがより好ましい。太陽電池バックシートのカール高さを10mm以下とすることで、カールによって発生する位置ずれやセル割れの発生率が減少し、太陽電池の生産性を向上することが可能となる。 (Solar cell back sheet)
Next, the solar cell backsheet of this invention is demonstrated. It is important that the solar cell backsheet of the present invention is a solar cell backsheet having the film for solar cell backsheet of the present invention and at least one functional layer. Especially, it is preferable that the curl height of the solar cell backsheet calculated | required by the measuring method mentioned later is 10 mm or less, and it is more preferable that it is 5 mm or less. By setting the curl height of the solar battery back sheet to 10 mm or less, it is possible to reduce the occurrence rate of misalignment and cell cracks caused by curling, and to improve the productivity of the solar battery.
なお、太陽電池バックシート用フィルムのヤング率を上記の範囲とする方法は特に制限されるものではないが、以下の方法などで調整することができる。例えば、太陽電池バックシート用ポリエステルフィルム中の空隙率を高くしたり、製膜時の延伸倍率を低くすると、太陽電池バックシート用フィルムのヤング率は低くなる傾向にある。また、太陽電池バックシート用ポリエステルフィルム中の空隙率を低くしたり、製膜時の延伸倍率を高くすると、太陽電池バックシート用フィルムのヤング率は高くなる傾向にある。また、太陽電池バックシートのヤング率は、太陽電池バックシートに用いる太陽電池バックシート用フィルムのヤング率が高いと高くなり、低いと低くなる傾向がある。それ以外にも、太陽電池バックシート用フィルムに積層する層のヤング率により調整することができる。 By setting the Young's modulus of the solar battery back sheet to 4.0 GPa or less, when stacking the curl generated when the solar battery back sheet is stored in a roll state on the solar battery, the solar battery back sheet is caused by its own weight. Can be flattened.
The method for setting the Young's modulus of the solar cell backsheet film in the above range is not particularly limited, but can be adjusted by the following method. For example, when the porosity in the polyester film for solar battery backsheet is increased or the draw ratio during film formation is decreased, the Young's modulus of the film for solar battery backsheet tends to be lowered. Moreover, when the porosity in the polyester film for solar battery back sheets is lowered or the stretching ratio at the time of film formation is increased, the Young's modulus of the film for solar battery back sheets tends to increase. Further, the Young's modulus of the solar battery backsheet tends to be high when the Young's modulus of the film for solar battery backsheet used for the solar battery backsheet is high, and low when it is low. In addition, it can adjust with the Young's modulus of the layer laminated | stacked on the film for solar cell backsheets.
ポリエチレン、ポリプロピレン、エチレンビニルアセテート共重合体のうちの少なくとも1つ、あるいは複数の組み合わせを含む層を機能層として本発明の太陽電池バックシート用フィルムと積層する方法は、特に限られるものではないが、本発明の太陽電池バックシート用フィルムに直接積層する方法や、本発明の効果を阻害しない範囲で、本発明の太陽電池バックシート用フィルムと機能層を接着剤などを介して積層する方法が挙げられる。 The functional layer of the solar battery backsheet of the present invention is preferably a layer containing at least one of polyethylene, polypropylene, and ethylene vinyl acetate copolymer, or a combination of a plurality of combinations, because the adhesion becomes good. In particular, in the solar cell backsheet of the present invention, by having the functional layer between the solar cell backsheet film and the encapsulant, it becomes possible to have good adhesion to the encapsulant. Among these, it is particularly preferable to use polyethylene from the viewpoint of weather resistance and water vapor barrier properties. When a layer including at least one of polyethylene, polypropylene, and ethylene vinyl acetate copolymer or a combination thereof is used as a functional layer, the thickness of the functional layer is preferably 30 μm or more and 300 μm or less, and 50 μm or more and 200 μm or less. It is more preferable that By setting the thickness of the layer to 30 μm or more, water vapor barrier properties and insulating properties are improved, and by setting the thickness to 300 μm or less, it is possible to suppress process contamination due to the protrusion of the functional layer B at the time of manufacturing a solar cell.
The method of laminating the layer containing at least one of polyethylene, polypropylene, and ethylene vinyl acetate copolymer or a combination thereof with the film for solar cell backsheet of the present invention as a functional layer is not particularly limited. , A method of directly laminating the film for solar cell backsheet of the present invention, and a method of laminating the film for solar cell backsheet of the present invention and a functional layer via an adhesive or the like within a range not inhibiting the effects of the present invention. Can be mentioned.
PVF、PVDF、ETFE、FEPのうちの少なくとも1つ、あるいは複数の組み合わせを含む層を機能層とする場合、機能層の厚みは25μm以上、125μm以下であることが好ましく、25μm以上75μm以下であることがより好ましい。当該層の厚みを25μm以上とすることで耐候性が向上し、125μm以下とすることで太陽電池バックシートの加工性が向上する。 The functional layer of the backsheet of the present invention is composed of polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), ethylene-tetrafluoroethylene copolymer (ETFE), tetrafluoroethylene-hexafluoropolypropylene copolymer. A layer containing at least one of (FEP) or a combination thereof is preferable because the weather resistance of the backsheet can be improved. In particular, it is preferable that the functional layer is laminated on the air side surface of the film for solar battery backsheet of the present invention because deterioration due to ultraviolet rays can be suppressed. From the viewpoint of weather resistance, the functional layer preferably contains at least one of PVF and PVDF.
When a layer including at least one of PVF, PVDF, ETFE, and FEP or a combination thereof is used as a functional layer, the thickness of the functional layer is preferably 25 μm or more and 125 μm or less, and is 25 μm or more and 75 μm or less. It is more preferable. When the thickness of the layer is 25 μm or more, the weather resistance is improved, and when it is 125 μm or less, the workability of the solar battery back sheet is improved.
ポリウレタンを含む層を機能層とする場合、機能層の厚みは1μm以上、20μm以下であることが好ましく、2μm以上10μm以下であることがより好ましい。ポリウレタンを含む層を機能層とした場合、機能層の厚みを1μm以上とすることで耐候性が向上し、20μm以下とすることでバックシートの加工性が向上する。
ポリウレタンを含む層を機能層として本発明の太陽電池バックシート用フィルムと積層する方法は、特に限られるものではないが、ロールコート法、グラビアロールコート法、キスコート法、およびその他のコート法、あるいは印刷法等によって積層する方法が挙げられる。
また、本発明の太陽電池バックシートの機能層は、無機化合物を含むことが好ましい。太陽電池バックシートの機能層が無機化合物を含むことで、太陽電池バックシートの水蒸気バリア性が向上する。機能層が含む無機化合物としては、シリカや、アルミナが好ましく、水蒸気バリア性、耐湿熱性の面で特にシリカをが好ましい。
無機化合物を含む層を機能層として本発明の太陽電池バックシート用フィルムと積層する方法としては特に限られるものではないが、本発明の太陽電池バックシート用フィルムに直接積層する方法や、本発明の太陽電池バックシート用フィルムと異なるポリエステルフィルムに無機化合物を積層し、本発明の効果を阻害しない範囲で、本発明の太陽電池バックシート用フィルムと無機化合物を積層したポリエステルフィルム以外の層(機能層)を接着剤などを介して積層する方法が挙げられる。 The functional layer of the solar cell backsheet of the present invention is preferably a layer containing polyurethane, since the adhesion becomes good. In particular, when the functional layer is located between the film for solar battery backsheet of the present invention and the sealing material, the adhesion with the sealing material is improved. The polyurethane here is a general term for polymers obtained from a compound having an isocyanate group and a compound having a hydroxyl group. Examples of the compound having an isocyanate group include trimethylene diisocyanate (TDI), hexamethylene diisocyanate (HDI), methylene bis (4,1-phenylene) = diisocyanate (MDI), 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate. (IPDI), xylylene diisocyanate (XDI) and other diisocyanates, trimethylolpropane adducts of these diisocyanates, isocyanurates that are trimers of these diisocyanates, burette conjugates of these diisocyanates, polymeric diisocyanates, etc. Of these, HDI is preferred from the viewpoint of color tone. Examples of the compound having a hydroxyl group include polyester polyols, polyether polyols, polyacrylic polyols, and fluorine-based polyols, and polyacrylic polyols and fluorine-based polyols are preferable from the viewpoint of heat and moisture resistance and weather resistance.
When a layer containing polyurethane is used as the functional layer, the thickness of the functional layer is preferably 1 μm or more and 20 μm or less, and more preferably 2 μm or more and 10 μm or less. When the layer containing polyurethane is a functional layer, the weather resistance is improved by setting the thickness of the functional layer to 1 μm or more, and the workability of the backsheet is improved by setting the thickness to 20 μm or less.
The method of laminating a layer containing polyurethane as a functional layer with the film for solar battery backsheet of the present invention is not particularly limited, but roll coating, gravure roll coating, kiss coating, and other coating methods, or The method of laminating by a printing method etc. is mentioned.
Moreover, it is preferable that the functional layer of the solar cell backsheet of this invention contains an inorganic compound. When the functional layer of the solar cell backsheet contains an inorganic compound, the water vapor barrier property of the solar cell backsheet is improved. As the inorganic compound contained in the functional layer, silica and alumina are preferable, and silica is particularly preferable in terms of water vapor barrier property and heat and moisture resistance.
The method for laminating the layer containing the inorganic compound as a functional layer with the film for solar cell backsheet of the present invention is not particularly limited, but the method for directly laminating the film for solar cell backsheet of the present invention or the present invention. Layers other than the polyester film obtained by laminating the film for solar cell backsheet of the present invention and the inorganic compound as long as the inorganic compound is laminated on the polyester film different from the film for solar cell backsheet of the present invention and the effect of the present invention is not impaired. And a method of laminating the layer via an adhesive or the like.
次に、本発明の太陽電池について説明する。本発明の太陽電池は、前記の太陽電池バックシート用フィルムをそのまま搭載する。もしくは前記の太陽電池バックシートを搭載することを特徴とする。
本発明の太陽電池の構成例を図1に示す。電気を取り出すリード線(図1には示していない)を接続した発電素子をEVA樹脂などの透明な封止材2で封止したものに、ガラスなどの透明基板4と太陽電池バックシート1として貼り合わせて構成されるが、これに限定されず任意の構成に用いることができる。 (Solar cell)
Next, the solar cell of the present invention will be described. The solar cell of this invention mounts the said film for solar cell backsheets as it is. Alternatively, the solar battery back sheet is mounted.
A structural example of the solar cell of the present invention is shown in FIG. As a
(1)ポリマー特性
(1-1)末端カルボキシル基量(表中ではCOOH量と記載する。)
末端カルボキシル基量については、Mauliceの方法に準じて、以下の方法にて測定した。(文献:M.J. Maulice, F. Huizinga, Anal.Chim.Acta,22 363(1960))
測定試料2gをo-クレゾール/クロロホルム(質量比7/3)50mLに温度80℃にて溶解し、0.05NのKOH/メタノール溶液によって滴定し、末端カルボキシル基濃度を測定し、当量/ポリエステル1tの値で示した。なお、滴定時の指示薬はフェノールレッドを用いて、黄緑色から淡紅色に変化したところを滴定の終点とした。なお、測定試料を溶解させた溶液に無機粒子などの不溶物がある場合は、溶液を濾過して不溶物の質量測定を行い、不溶物の質量を測定試料質量から差し引いた値を測定試料質量とする補正を実施した。 [Measurement method and evaluation method of characteristics]
(1) Polymer characteristics (1-1) Amount of terminal carboxyl groups (in the table, described as COOH amount)
The terminal carboxyl group amount was measured by the following method according to the method of Malice. (Reference: M. J. Malice, F. Huizinga, Anal. Chim. Acta, 22 363 (1960))
2 g of a measurement sample was dissolved in 50 mL of o-cresol / chloroform (
オルトクロロフェノール100mlに、測定試料を溶解させ(溶液濃度C(測定試料質量/溶液体積)=1.2g/ml)、その溶液の25℃での粘度をオストワルド粘度計を用いて測定した。また、同様に溶媒の粘度を測定した。得られた溶液粘度、溶媒粘度を用いて、下記式(4)により、[η]を算出し、得られた値をもって固有粘度(IV)とした。
ηsp/C=[η]+K[η]2・C ・・・(4)
(ここで、ηsp=(溶液粘度/溶媒粘度)―1、Kはハギンス定数(0.343とする)である。)
なお、測定試料を溶解させた溶液に無機粒子などの不溶物がある場合は、以下の方法を用いて測定を行った。
(i)オルトクロロフェノール100mLに測定試料を溶解させ、溶液濃度が1.2g/mLよりも濃い溶液を作成する。ここで、オルトクロロフェノールに供した測定試料の質量を測定試料質量とする。
(ii)次に、不溶物を含む溶液を濾過し、不溶物の質量測定と、濾過後の濾液の体積測定を行う。
(iii)濾過後の濾液にオルトクロロフェノールを追加して、(測定試料質量(g)-不溶物の質量(g))/(濾過後の濾液の体積(mL)+追加したオルトクロロフェノールの体積(mL))が、1.2g/100mLとなるように調整する。
(例えば、測定試料質量2.0g/溶液体積100mLの濃厚溶液を作成したときに、該溶液を濾過したときの不溶物の質量が0.2g、濾過後の濾液の体積が99mLであった場合は、オルトクロロフェノールを51mL追加する調整を実施する。((2.0g-0.2g)/(99mL+51mL)=1.2g/mL))
(iv)(iii)で得られた溶液を用いて、25℃での粘度をオストワルド粘度計を用いて測定し、得られた溶液粘度、溶媒粘度を用いて、上記式(C)により、[η]を算出し、得られた値をもって固有粘度(IV)とする。 (1-2) Intrinsic viscosity IV
The measurement sample was dissolved in 100 ml of orthochlorophenol (solution concentration C (measurement sample mass / solution volume) = 1.2 g / ml), and the viscosity of the solution at 25 ° C. was measured using an Ostwald viscometer. Similarly, the viscosity of the solvent was measured. [Η] was calculated by the following formula (4) using the obtained solution viscosity and solvent viscosity, and the obtained value was defined as the intrinsic viscosity (IV).
ηsp / C = [η] + K [η] 2 · C (4)
(Where ηsp = (solution viscosity / solvent viscosity) −1, K is the Huggins constant (assuming 0.343))
In addition, when there existed insoluble matters, such as inorganic particles, in the solution in which the measurement sample was dissolved, the measurement was performed using the following method.
(I) A measurement sample is dissolved in 100 mL of orthochlorophenol to prepare a solution having a solution concentration higher than 1.2 g / mL. Here, let the mass of the measurement sample used for orthochlorophenol be the measurement sample mass.
(Ii) Next, the solution containing insoluble matter is filtered, and the mass of the insoluble matter is measured, and the volume of the filtrate after filtration is measured.
(Iii) Adding orthochlorophenol to the filtrate after filtration, (measurement sample mass (g) −mass of insoluble matter (g)) / (volume of filtrate after filtration (mL) + added orthochlorophenol The volume (mL) is adjusted to 1.2 g / 100 mL.
(For example, when a concentrated solution having a measurement sample mass of 2.0 g / solution volume of 100 mL was prepared, the mass of insoluble matter when the solution was filtered was 0.2 g, and the filtrate volume after filtration was 99 mL Adjust to add 51 mL of orthochlorophenol ((2.0 g-0.2 g) / (99 mL + 51 mL) = 1.2 g / mL))
(Iv) Using the solution obtained in (iii), the viscosity at 25 ° C. is measured using an Ostwald viscometer, and using the obtained solution viscosity and solvent viscosity, η] is calculated, and the obtained value is defined as intrinsic viscosity (IV).
Mg、Mn、Sb金属元素量については蛍光X線分析法(理学電機(株)製蛍光X線分析装置(型番:3270))にて、Na金属元素については原子吸光分析法(曰立製作所製:偏光ゼーマン原子吸光光度計180-80。フレーム:アセチレンー空気)にて定量を行った。 (1-3) Metal Element Content Regarding the Mg, Mn, and Sb metal element amounts, the fluorescent X-ray analysis method (fluorescent X-ray analyzer (model number: 3270) manufactured by Rigaku Corporation) is used. Quantification was carried out by atomic absorption spectrometry (manufactured by Tadate Corporation: Polarized Zeeman atomic absorption photometer 180-80, frame: acetylene-air).
(2-1)フィルム断面の観察
ミクロトームやCP(クロスセクションポリッシャ)断面加工を用いて、本発明の太陽電池バックシート用フィルムを厚み方向に潰すことなく、フィルム面方向に対して垂直に切断、断面出しを行った。次いで、走査型電子顕微鏡(SEM)(日本電子(株)電界放射走査型電子顕微鏡“JSM-6700F”)を用いてサンプルの切断面を観察した画像を得た。
(2-2)フィルム全体の空隙率の測定
(2-1)の手法を任意でフィルムサンプル中で異なる箇所を計5箇所選択し、フィルムの長手方向、及び幅方向でフィルム断面を切断した計10箇所について、フィルムの厚み方向全体が観察できる最大の倍率で観察した画像を準備する。次いで、それぞれの空洞部分のみ透明なフィルム上にトレースし、イメージアナライザー(ニレコ株式会社製:ルーゼックスIID)を用いて測定した空洞面積と、観察画像内の全体のフィルム断面積との比を算出し、10箇所の平均値をフィルム全体の空隙率とした。
(2-3)フィルム表層の空隙率(Ps)、(Ps’)の測定
3層以上の積層フィルムについては、フィルム表層の空隙率(Ps)、(Ps’)を以下の方法にて測定した。すなわち(2-2)と同様に作製した計10箇所の観察断面について、フィルム表層(P2層およびP2’層)の表層全体を視野内で観察できる最大の倍率で観察した画像を準備し、同様にイメージアナライザーを用いて面積比を算出し、10箇所の平均値をフィルム表層の空隙率とした。
(2-4)各水平線上に存在する空洞の空洞面積の測定
(2-2)と同様に作製した計10箇所の観察断面について、フィルムの厚み方向全体が観察できる最大の倍率で観察した画像を準備する。次いで、それぞれの観察画像についてフィルムの厚み方向に垂直な線を引き、その線を4等分する3点(フィルム厚み方向中心点(C1点)、フィルム厚み方向中心点とフィルム表面との中間点(C2-1点)、(C2-2点)とする)を通るフィルムに厚み方向に平行な線(分割水平線)を引く。次いで、分割水平線上に存在する空洞部分のみ透明なフィルム上にトレースし、イメージアナライザーを用いて各水平線上に存在する空洞の平均面積を求めた。
尚、トレースする空洞の個数については、観察画像内の分割水平線上に存在する空洞が20個未満の場合はすべての空洞についてトレースし、20個以上の空洞が存在する場合は空洞の重心が、C1点、C2-1点、C2-2点に近い空洞20個を選択してトレースを行うこととする。
(2-5)平均空洞面積比(Sc/Scs)、(Sc/Scs’)の算出
(2-4)によって得られた平均面積について、C1点を通る分割水平線上に存在する空洞1個当たりの平均面積をSc(μm2)、C2-1点を通る分割水平線上に存在する空洞1個当たりの平均面積をScs(μm2)、C2-2点を通る分割水平線上に存在する空洞1個当たりの平均面積をScs’(μm2)として、空洞面積比(Sc/Scs)あるいは(Sc/Scs’)を算出し、計10箇所の平均値を本発明の平均空洞面積比(Sc/Scs)、(Sc/Scs’)とした。 (2) Cavity area ratio (2-1) Observation of film cross section Using microtome or CP (cross section polisher) cross section processing, the film for solar cell backsheet of the present invention is not crushed in the thickness direction but in the film surface direction. On the other hand, cutting and sectioning were performed vertically. Next, an image obtained by observing the cut surface of the sample was obtained using a scanning electron microscope (SEM) (JEOL Co., Ltd. field emission scanning electron microscope “JSM-6700F”).
(2-2) Measurement of the porosity of the entire film A total of five different locations in the film sample were arbitrarily selected in the method of (2-1), and the cross section of the film was cut in the longitudinal and width directions of the film. About 10 places, the image observed by the maximum magnification which can observe the whole thickness direction of a film is prepared. Next, only each cavity is traced on a transparent film, and the ratio of the cavity area measured using an image analyzer (manufactured by Nireco Corporation: Luzex IID) and the total film cross-sectional area in the observed image is calculated. The average value at 10 locations was defined as the porosity of the entire film.
(2-3) Measurement of porosity (Ps) and (Ps ′) of film surface layer For three or more layers of laminated films, the porosity (Ps) and (Ps ′) of the film surface layer were measured by the following method. . In other words, for the observation cross-sections in a total of 10 places prepared in the same manner as in (2-2), images were prepared by observing the entire surface layer of the film surface layer (P2 layer and P2 ′ layer) at the maximum magnification that can be observed within the field of view. The area ratio was calculated using an image analyzer, and the average value at 10 locations was defined as the porosity of the film surface layer.
(2-4) Measurement of cavity area of cavities existing on each horizontal line Images observed at the maximum magnification at which the entire thickness direction of the film can be observed with respect to a total of 10 observation cross sections produced in the same manner as in (2-2) Prepare. Next, a line perpendicular to the film thickness direction is drawn for each observed image, and the line is divided into four equal points (film thickness direction center point (C1 point), intermediate point between the film thickness direction center point and the film surface) A line parallel to the thickness direction (divided horizontal line) is drawn on the film passing through (C2-1 point) and (C2-2 point). Subsequently, only the cavity portions present on the divided horizontal lines were traced on a transparent film, and the average area of the voids present on each horizontal line was determined using an image analyzer.
As for the number of cavities to be traced, if there are less than 20 cavities on the divided horizontal line in the observation image, all cavities are traced, and if there are 20 or more cavities, the center of gravity of the cavities is It is assumed that 20 cavities close to the points C1, C2-1, and C2-2 are selected and traced.
(2-5) Calculation of the average cavity area ratio (Sc / Scs), (Sc / Scs ′) (2-4), the average area per cavity existing on the divided horizontal line passing through point C1 average area of the Sc (μm 2), Scs an average area per cavity present on dividing the horizontal line passing through the C2-1 points (μm 2), the
(3-1)貼り合わせサンプルの作製
本発明の太陽電池バックシート用フィルム、太陽電池バックシートに、厚さ125μm二軸延伸ポリエステルフィルム“ルミラー”(登録商標)X10S(東レ(株)製)を接着剤(“タケラック”(登録商標)A310(三井武田ケミカル(株)製)90質量部、“タケネート”(登録商標)A3(三井武田ケミカル(株)製)10質量部を混合したもの)にて貼り合わせた後、40℃に温度調整した恒温槽で48hrエージングを行った。
(3-2)密着性評価
(3-1)で得られたサンプルについて、高度加速寿命試験装置プレッシャークッカー(エスペック(株)製)にて、温度120℃、相対湿度100%の条件下にて48時間処理を行った後、本発明の太陽電池バックシート用フィルム側を水平に固定して、貼り合わせた部分を200mm/分の速度で180°剥離にて剥離試験を実施した際の剥離強度を測定し、太陽電池バックシート用フィルムの密着性を以下のように判定を行った。
剥離強度が6N/15mm以上の場合:A
剥離強度が4N/15mm以上、6N/15mm未満の場合:B
剥離強度が2N/15mm以上、4N/15mm未満の場合:C
剥離強度が1N/15mm以上、2N/15mm未満の場合:D
剥離強度が1N/15mm未満の場合:E
密着性はA~Dが良好であり、その中でもAが最も優れている。 (3) Adhesion Evaluation (3-1) Preparation of Bonded Sample A 125 μm-thick biaxially stretched polyester film “Lumirror” (registered trademark) X10S (Toray 90 parts by mass of adhesive ("Takelac" (registered trademark) A310 (manufactured by Mitsui Takeda Chemical)), 10 parts by mass of "Takenate" (registered trademark) A3 (manufactured by Mitsui Takeda Chemical) ) And then aged for 48 hours in a thermostatic chamber adjusted to 40 ° C.
(3-2) Adhesion evaluation The sample obtained in (3-1) was subjected to a highly accelerated life test apparatus pressure cooker (manufactured by Espec Corp.) at a temperature of 120 ° C. and a relative humidity of 100%. After performing the treatment for 48 hours, the film side for the solar battery backsheet of the present invention was horizontally fixed, and the peel strength when the peeled portion was subjected to a peel test at 180 ° peel at a speed of 200 mm / min. Was measured, and the adhesion of the solar cell backsheet film was determined as follows.
When peel strength is 6N / 15mm or more: A
When peel strength is 4N / 15mm or more and less than 6N / 15mm: B
When peel strength is 2N / 15mm or more and less than 4N / 15mm: C
When peel strength is 1N / 15mm or more and less than 2N / 15mm: D
When peel strength is less than 1 N / 15 mm: E
Adhesiveness is good from A to D, and among them, A is the best.
本発明の太陽電池バックシート用フィルム、太陽電池バックシートを測定片の形状10mm×200mmに切り出した後、高度加速寿命試験装置プレッシャークッカー(エスペック(株)製)にて、温度125℃、相対湿度100%RHの条件下にて48時間処理を行い、その後、ASTM-D882(1997)に基づいて破断伸度を測定した。なお、測定はチャック間50mm、引っ張り速度300mm/min、測定回数n=5とし、また、シートの長手方向、幅方向のそれぞれについて測定した後、その平均値を湿熱試験後の破断伸度とした。得られた湿熱試験後の破断伸度から、耐湿熱性を以下のように判定した。
湿熱試験後の破断伸度が湿熱試験前の破断伸度の60%以上の場合:A
湿熱試験後の破断伸度が湿熱試験前の破断伸度の40%以上60%未満の場合:B
湿熱試験後の破断伸度が湿熱試験前の破断伸度の20%以上40%未満の場合:C
湿熱試験後の破断伸度が湿熱試験前の破断伸度の10%以上20%未満の場合:D
湿熱試験後の破断伸度が湿熱試験前の破断伸度の10%未満の場合:E
耐湿熱性はA~Dが良好であり、その中でもAが最も優れている。 (4) Moisture and heat resistance evaluation After cutting out the film for solar cell backsheet of the present invention and the solar cell backsheet into a measurement piece shape of 10 mm × 200 mm, using a highly accelerated life test apparatus pressure cooker (manufactured by ESPEC Corporation), The treatment was performed for 48 hours under the conditions of a temperature of 125 ° C. and a relative humidity of 100% RH, and then the elongation at break was measured based on ASTM-D882 (1997). Note that the measurement was performed between the chuck 50 mm, the pulling speed 300 mm / min, the number of measurements n = 5, and after measuring for each of the longitudinal direction and the width direction of the sheet, the average value was defined as the breaking elongation after the wet heat test. . From the elongation at break after the obtained wet heat test, the wet heat resistance was determined as follows.
When the breaking elongation after the wet heat test is 60% or more of the breaking elongation before the wet heat test: A
When the breaking elongation after the wet heat test is 40% or more and less than 60% of the breaking elongation before the wet heat test: B
When the breaking elongation after the wet heat test is 20% or more and less than 40% of the breaking elongation before the wet heat test: C
When the breaking elongation after the wet heat test is 10% or more and less than 20% of the breaking elongation before the wet heat test: D
When the breaking elongation after the wet heat test is less than 10% of the breaking elongation before the wet heat test: E
The wet heat resistance is good in A to D, and A is the best among them.
(5-1)色調(b値)測定
JIS-Z-8722(2000)に基づき、分光式色差計SE-2000(日本電色工業(株)製、光源 ハロゲンランプ 12V4A、0°~-45°後分光方式)を用いて反射法により太陽電池バックシート用フィルム、太陽電池バックシートの色調(b値)をn=3で測定し、その平均値として求めた。 (5) UV resistance (color change during UV treatment test)
(5-1) Color tone (b value) measurement Based on JIS-Z-8722 (2000), a spectroscopic color difference meter SE-2000 (manufactured by Nippon Denshoku Industries Co., Ltd., light source halogen lamp 12V4A, 0 ° to −45 °) The color tone (b value) of the film for solar battery backsheet and the solar battery backsheet was measured at n = 3 by a reflection method using a post-spectral method, and the average value was obtained.
本発明の太陽電池バックシート用フィルム、太陽電池バックシートにアイスーパー紫外線テスターS-W151(岩崎電気(株)製)にて、温度60℃、相対湿度60%、照度100mW/cm2(光源:メタルハライドランプ、波長範囲:295~450nm、ピーク波長:365nm)の条件下で48時間照射した前後の色調(b値)を前記(5-1)項に従い測定し、次の(α)式より紫外線照射後の色調変化(Δb)を算出した。尚、本発明の太陽電池バックシート用フィルムが片面にP2層を有する構成の場合、P2層側の表面に紫外線試験光が当たるように試験を行った。また、太陽電池バックシートの場合、実施例32から37、45から46、50から53においては機能層Bを有する面の反対面に、実施例38から44、47から49においては機能層Bを有する表面に、54から56においては機能層B’を有する表面に紫外線試験光が当たるように試験を行った。
紫外線照射後の色調変化(Δb)=b1―b0 (α)
b0:紫外線照射前の色調(b値)
b1:紫外線照射後の色調(b値)
得られた紫外線処理試験前後の色調変化(Δb)から、耐紫外線性を以下のように判定した。
紫外線照射処理試験前後の色調変化(Δb)が3未満の場合:A
紫外線照射処理試験前後の色調変化(Δb)が3以上6未満の場合:B
紫外線照射処理試験前後の色調変化(Δb)が6以上10未満の場合:C
紫外線照射処理試験前後の色調変化(Δb)が10以上20未満の場合:D
紫外線照射処理試験前後の色調変化(Δb)が20以上の場合:E
耐紫外線性はA~Dが良好であり、その中で最もAが優れている。 (5-2) Color tone change Δb
The film for solar cell backsheet of the present invention, the solar cell backsheet, and eye super ultraviolet tester S-W151 (manufactured by Iwasaki Electric Co., Ltd.), temperature 60 ° C., relative humidity 60%, illuminance 100 mW / cm 2 (light source: The color tone (b value) before and after irradiation for 48 hours under the conditions of a metal halide lamp (wavelength range: 295 to 450 nm, peak wavelength: 365 nm) was measured according to the above item (5-1), and ultraviolet rays were obtained from the following formula (α). The change in color tone (Δb) after irradiation was calculated. In addition, when the film for solar cell backsheets of this invention was the structure which has P2 layer on the single side | surface, the test was done so that an ultraviolet test light might hit the surface of the P2 layer side. Further, in the case of the solar battery back sheet, in Examples 32 to 37, 45 to 46, and 50 to 53, the functional layer B is provided on the surface opposite to the surface having the functional layer B, and in Examples 38 to 44 and 47 to 49, The test was conducted so that the ultraviolet test light hits the surface having the functional layer B ′ in 54 to 56.
Color tone change after UV irradiation (Δb) = b1−b0 (α)
b0: Color tone before UV irradiation (b value)
b1: Color tone after UV irradiation (b value)
From the color tone change (Δb) before and after the obtained ultraviolet treatment test, ultraviolet resistance was determined as follows.
When the color change (Δb) before and after the ultraviolet irradiation treatment test is less than 3: A
When the color tone change (Δb) before and after the ultraviolet irradiation treatment test is 3 or more and less than 6: B
When the color change (Δb) before and after the ultraviolet irradiation treatment test is 6 or more and less than 10: C
When the color tone change (Δb) before and after the ultraviolet irradiation treatment test is 10 or more and less than 20: D
When the color change (Δb) before and after the ultraviolet irradiation treatment test is 20 or more: E
As for UV resistance, A to D are good, and A is the best among them.
本発明の太陽電池バックシート用フィルムの熱伝導率評価として、ATSM E 1530に基づき試験を行った。下部ヒーターを30℃、上部ヒーターを80℃に設定とし、n=3で測定し、その平均値を熱伝導率とし、得られた熱伝導率から以下のように判定した。
熱伝導率が0.08W/m・K以下:A
熱伝導率が0.08W/m・Kを超えて、0.12W/m・K以下:B
熱伝導率が0.12W/m・Kを超えて、0.14W/m・K以下:C
熱伝導率が0.14W/m・Kを超える:D
熱伝導率はA~Bが良好で有り、その中で最もAが優れている。 (6) Thermal conductivity evaluation As a thermal conductivity evaluation of the film for solar cell backsheet of the present invention, a test was performed based on ATSM E 1530. The lower heater was set to 30 ° C. and the upper heater was set to 80 ° C., and measurement was carried out at n = 3. The average value was defined as the thermal conductivity, and the obtained thermal conductivity was determined as follows.
Thermal conductivity is 0.08 W / m · K or less: A
Thermal conductivity is over 0.08 W / m · K and 0.12 W / m · K or less: B
Thermal conductivity exceeds 0.12 W / m · K and 0.14 W / m · K or less: C
Thermal conductivity exceeds 0.14 W / m · K: D
The thermal conductivity is good from A to B, and A is the best among them.
(7-1)太陽電池の出力向上性評価
多結晶シリコン型太陽電池セル「ジンテック社製G156M3」の表面と裏面の銀電極部分に、フラックス「HOZAN社製H722」をディスペンサーで塗布し、表面と裏面の銀電極の上に、155mmの長さに切断した配線材「日立電線社製銅箔SSA-SPS0.2×1.5(20)」を、表面側のセルの片端から10mm離れたところが配線材の端に、そして裏面側は表面側と対称になるように乗せ、半田ごてを用いて、セル裏面側から半田ごてを接触させて表面と裏面を同時に半田溶着し、1セルストリングスを作製した。
次に、作製した1セルストリングスのセルから飛び出している前記の配線材の長手方向と、180mmに切断した取り出し電極「日立電線社製銅箔A-SPS0.23×6.0」の長手方向が垂直になるよう置き、前記の配線材と取り出し電極が重なる部分に前記のフラックスを塗布して半田溶着を行い、取り出し電極付きストリングスを作製した。この時点において、JIS C8914:2005の基準状態に準じて短絡電流の測定を実施し、セル単体の発電性能とした。 (7) Solar cell characteristic evaluation (7-1) Solar cell output improvement evaluation The flux “HOZAN H722” is applied to the front and back silver electrode portions of the polycrystalline silicon solar cell “Gintech G156M3”. A wiring material “copper foil SSA-SPS0.2 × 1.5 (20) manufactured by Hitachi Cable, Ltd.” cut into a length of 155 mm on the front and back silver electrodes was applied with a dispenser, and the cell on the front side Place the wire 10 mm away from one end of the wire on the end of the wiring material and the back side to be symmetrical with the front side, and use the soldering iron to bring the soldering iron into contact from the back side of the cell so that the front and back sides are simultaneously Solder welding was performed to produce 1 cell strings.
Next, the longitudinal direction of the wiring material protruding from the cell of the produced 1 cell string and the longitudinal direction of the extraction electrode “copper foil A-SPS0.23 × 6.0 manufactured by Hitachi Cable, Ltd.” cut into 180 mm are shown. Placed vertically, the flux was applied to the portion where the wiring material and the extraction electrode overlapped, and solder welding was performed, thereby producing strings with extraction electrodes. At this time, the short-circuit current was measured according to the standard state of JIS C8914: 2005, and the power generation performance of the cell alone was obtained.
得られた太陽電池モジュールを、JIS C8914:2005の基準状態に準じて測定した短絡電流の測定を実施し、本発明の太陽電池バックシートを搭載した太陽電池の発電性能とした。
このようにして得られたセル単体の発電性能と本発明の太陽電池バックシートを搭載した太陽電池の発電性能から、次の(β)式に従い、本発明の太陽電池バックシートを搭載した太陽電池の発電向上率を算出した。
モジュール化による発電向上率(%)=(モジュール化後の発電性能/セル単体の発電性能-1)×100(%) (β)
得られた発電向上率から、出力向上性を以下のように判定した。
発電向上率が8.0%以上の場合:A
発電向上率が7.5%以上、8.0%未満の場合:B
発電向上率が7.0%以上、7.5%未満の場合:C
発電向上率が6.5%以上、7.0%未満の場合:D
発電向上率が6.5%未満の場合:E
太陽電池の出力向上性はA~Dが良好であり、その中でもAが最も優れている。
(7-2)太陽電池の密着性評価
(7-1)項で作製した太陽電池を10個準備し、85℃85%RHに調整した恒温恒湿槽(エスペック(株)製)で4000hr処理した後、ラミネートした太陽電池バックシート用フィルムに剥離が発生していないかを目視で確認を行った。太陽電池の密着性は10個の太陽電池のうち、目視でシートが剥離しているものが何個あるかについて確認し、以下のように判定を行った。
全ての太陽電池で剥離が発生していない場合:A
作製した太陽電池のうち1個以上4個未満の太陽電池からシートが剥離していた場合:B
作製した太陽電池のうち4個以上8個未満の太陽電池からシートが剥離していた場合:C
作製した太陽電池のうち8個以上シートが太陽電池から剥離していた場合:D
全ての太陽電池で剥離が発生している場合:E
太陽電池の密着性はA~Dが良好であり、その中でもAが最も優れている。 Next, 190 mm × 190 mm glass (3.2 mm thick white plate heat-treated glass for solar cells manufactured by Asahi Glass Co., Ltd.) as a cover material, and 190 mm × 190 mm ethylene vinyl acetate (Sanvik sealing material 0.5 mm as a front side sealing material) Thickness), strings with extraction electrodes that have been evaluated for power generation performance of a single cell, 190 mm x 190 mm ethylene vinyl acetate (0.5 mm thick sealant manufactured by Sunvic) as the back side sealing material, and 190 mm x 190 mm The film for solar cell backsheet of the present invention was stacked and fixed in order, and the glass was set so as to be in contact with the hot plate of the vacuum laminator, the hot plate temperature was 145 ° C., the vacuum was drawn for 4 minutes, the press was 1 minute, and the holding time. Under the condition of 10 minutes, vacuum lamination was performed to produce a solar cell for evaluation. At this time, the strings with extraction electrodes were set so that the glass surface was on the cell surface side. In addition, when the film for solar battery backsheets of this invention was a structure which has P2 layer on the single side | surface, it installed so that the P2 layer side might face the electric power generation cell side.
The obtained solar cell module was subjected to measurement of a short-circuit current measured according to the standard state of JIS C8914: 2005, and the power generation performance of the solar cell equipped with the solar cell backsheet of the present invention was obtained.
From the power generation performance of the single cell thus obtained and the power generation performance of the solar cell on which the solar cell backsheet of the present invention is mounted, the solar cell on which the solar cell backsheet of the present invention is mounted according to the following equation (β) The power generation improvement rate was calculated.
Power generation improvement rate by modularization (%) = (Power generation performance after modularization / Power generation performance of single cell-1) x 100 (%) (β)
From the power generation improvement rate obtained, the output improvement was determined as follows.
When the power generation improvement rate is 8.0% or more: A
When the power generation improvement rate is 7.5% or more and less than 8.0%: B
When the power generation improvement rate is 7.0% or more and less than 7.5%: C
When the power generation improvement rate is 6.5% or more and less than 7.0%: D
When the power generation improvement rate is less than 6.5%: E
The output improvement of the solar cell is good from A to D, and among them, A is the best.
(7-2) Evaluation of Adhesiveness of Solar Cell Ten solar cells prepared in item (7-1) were prepared and treated for 4000 hr in a constant temperature and humidity chamber (manufactured by Espec Corp.) adjusted to 85 ° C. and 85% RH. Then, it was visually confirmed whether or not peeling occurred on the laminated film for solar battery backsheet. The adhesion of the solar cells was determined as follows by checking how many of the ten solar cells had the sheet peeled off visually.
When peeling does not occur in all solar cells: A
When the sheet is peeled from one or more than four solar cells among the produced solar cells: B
When sheets are peeled from 4 or more and less than 8 solar cells among the produced solar cells: C
When 8 or more sheets of the produced solar cells are peeled from the solar cells: D
When peeling occurs in all solar cells: E
Adhesiveness of the solar cell is good from A to D, and among them, A is the best.
太陽電池バックシート用フィルム、太陽電池バックシートのヤング率をASTM-D882(1997)に基づいて測定した。なお、測定はチャック間50mm、引っ張り速度300mm/min、測定回数n=5とし、また、シートの長手方向、幅方向のそれぞれについて測定した後、その平均値をヤング率とした。得られたヤング率から、以下のように判定した。
ヤング率が、2.0GPa以下の場合:A
ヤング率が、2.0GPaを超えて、3.0GPa以下の場合:B
ヤング率が、3.0GPaを超えて、4.0GPa以下の場合:C
ヤング率が、4.0GPaを超える場合:D
ヤング率はA~Cが良好であり、その中で最もAが優れている。 (8) Evaluation of Young's Modulus The Young's modulus of the solar cell backsheet film and solar cell backsheet was measured based on ASTM-D882 (1997). The measurement was performed with the chuck spacing of 50 mm, the pulling speed of 300 mm / min, and the number of measurements n = 5. After measuring in the longitudinal direction and the width direction of the sheet, the average value was defined as the Young's modulus. From the obtained Young's modulus, it was determined as follows.
When Young's modulus is 2.0 GPa or less: A
When Young's modulus exceeds 2.0 GPa and is 3.0 GPa or less: B
When Young's modulus is more than 3.0 GPa and 4.0 GPa or less: C
When Young's modulus exceeds 4.0 GPa: D
The Young's modulus is good from A to C, and A is the best among them.
太陽電池バックシートの評価として以下の手順でカール高さ(カール性)の評価を行った。
1.外径84.2mmの紙管に、200mm×200mmにカットした太陽電池バックシートを巻いて固定し、40℃50%RHにおいて1週間保管し、得られたフィルムを紙管から外しカール高さ評価用シートを得る。
2.得られたカール高さ評価用シートを、25℃の環境下で、平らな板の上に、カール高さ評価用シートの中央部が板に接触する向きに置く。
3.カール高さ評価用シートの4箇所の角の板からの距離(カール高さ)をノギスで測定する。
4.3.で得られた4箇所のカール高さの平均値を取り、得られたカール高さの平均値からカール高さ評価は以下のように判定した。
カール高さの平均値が5mm未満:A
カール高さの平均値が5mm以上、10mm未満:B
カール高さの平均値が10mm以上、15mm未満:C
カール高さの平均値が15mm以上:D
カール高さはA~Cが良好で有り、その中で最もAが優れている。 (9) Evaluation of curl height As an evaluation of the solar cell backsheet, the curl height (curling property) was evaluated by the following procedure.
1. A solar battery backsheet cut to 200 mm × 200 mm is wrapped around a paper tube having an outer diameter of 84.2 mm, fixed, stored at 40 ° C. and 50% RH for one week, and the resulting film is removed from the paper tube and evaluated for curl height. Get a sheet for.
2. The obtained curl height evaluation sheet is placed on a flat plate in an environment at 25 ° C. so that the central portion of the curl height evaluation sheet contacts the plate.
3. The distance (curl height) from the four corner plates of the curl height evaluation sheet is measured with a caliper.
4.3. The average value of the four curl heights obtained in
The average curl height is less than 5 mm: A
Average value of curl height is 5 mm or more and less than 10 mm: B
The average curl height is 10 mm or more and less than 15 mm: C
The average curl height is 15 mm or more: D
The curl height is good in A to C, and A is the best among them.
太陽電池バックシートの水蒸気バリア性の評価として、JIS K7129(2008)の赤外線センサ法に準じて、測定面積50cm2、40℃90%RH環境下における水蒸気透過率を測定した。得られた値から、水蒸気バリア性は以下のように判定した。
水蒸気透過率が0.5g/m2/day未満:A
水蒸気透過率が0.5g/m2/day以上、1.0g/m2/day未満:B
水蒸気透過率が1.0g/m2/day以上、2.0g/m2/day未満:C
水蒸気透過率が2.0g/m2/day以上、3.0g/m2/day未満:D
水蒸気透過率が3.0g/m2/day以上:E
水蒸気バリア性はA~Dが良好で有り、その中で最もAが優れている。 (10) Evaluation of water vapor barrier property As an evaluation of the water vapor barrier property of the solar battery back sheet, the water vapor transmission rate in a measurement area of 50 cm 2 and 40 ° C. and 90% RH is measured according to the infrared sensor method of JIS K7129 (2008). did. From the obtained value, the water vapor barrier property was determined as follows.
Water vapor transmission rate is less than 0.5 g / m 2 / day: A
Water vapor transmission rate is 0.5 g / m 2 / day or more and less than 1.0 g / m 2 / day: B
Water vapor transmission rate is 1.0 g / m 2 / day or more and less than 2.0 g / m 2 / day: C
Water vapor transmission rate is 2.0 g / m 2 / day or more and less than 3.0 g / m 2 / day: D
Water vapor transmission rate is 3.0 g / m 2 / day or more: E
The water vapor barrier properties A to D are good, and A is the best among them.
1.PET原料A(PET-a)
テレフタル酸ジメチル100質量部、エチレングリコール57.5質量部、酢酸マンガン4水和物0.03質量部、三酸化アンチモン0.03質量部を150℃、窒素雰囲気下で溶融した。この溶融物を撹拌しながら230℃まで3時間かけて昇温し、メタノールを留出させ、エステル交換反応を終了した。エステル交換反応終了後、リン酸0.005質量部とリン酸二水素ナトリウム2水和物0.021質量部をエチレングリコール0.5質量部に溶解したエチレングリコール溶液(pH5.0)を添加した。このときのポリエステル組成物の固有粘度は0.2未満であった。この後、重合反応を最終到達温度285℃、真空度0.1Torrで行い、固有粘度0.52、末端カルボキシル基量が15当量/トンのポリエチレンテレフタレートを得た。得られたポリエチレンテレフタレートを160℃で6時間乾燥、結晶化させた。その後、220℃、真空度0.3Torr、8時間の固相重合を行い、固有粘度0.82、末端カルボキシル基量が10当量/トンのポリエチレンテレフタレート(PET-a)を得た。得られたポリエチレンテレフタレート組成物のガラス転移温度は82℃、融点は255℃であった。 (Polyester resin material used for P1 layer)
1. PET raw material A (PET-a)
100 parts by mass of dimethyl terephthalate, 57.5 parts by mass of ethylene glycol, 0.03 parts by mass of manganese acetate tetrahydrate and 0.03 parts by mass of antimony trioxide were melted at 150 ° C. in a nitrogen atmosphere. While stirring this melt, the temperature was raised to 230 ° C. over 3 hours to distill methanol, and the transesterification reaction was completed. After the transesterification reaction, an ethylene glycol solution (pH 5.0) in which 0.005 parts by mass of phosphoric acid and 0.021 parts by mass of sodium dihydrogen phosphate dihydrate were dissolved in 0.5 parts by mass of ethylene glycol was added. . The intrinsic viscosity of the polyester composition at this time was less than 0.2. Thereafter, the polymerization reaction was performed at a final temperature of 285 ° C. and a degree of vacuum of 0.1 Torr to obtain polyethylene terephthalate having an intrinsic viscosity of 0.52 and a terminal carboxyl group amount of 15 equivalents / ton. The obtained polyethylene terephthalate was dried and crystallized at 160 ° C. for 6 hours. Thereafter, solid-state polymerization was performed at 220 ° C. and a vacuum degree of 0.3 Torr for 8 hours to obtain polyethylene terephthalate (PET-a) having an intrinsic viscosity of 0.82 and a terminal carboxyl group amount of 10 equivalents / ton. The obtained polyethylene terephthalate composition had a glass transition temperature of 82 ° C. and a melting point of 255 ° C.
固相重合の時間を10時間とした以外はPET原料Aと同様に行い、固有粘度0.85、末端カルボキシル基量が6当量/トンのポリエチレンテレフタレート(PET-b)を得た。 2. PET raw material B (PET-b)
A polyethylene terephthalate (PET-b) having an intrinsic viscosity of 0.85 and a terminal carboxyl group amount of 6 equivalents / ton was obtained except that the solid phase polymerization time was 10 hours.
重合反応の最終到達温度290℃とした以外はPET原料Aと同様に行い、固有粘度0.79、末端カルボキシル基量が15当量/トンのポリエチレンテレフタレート(PET-c)を得た。 3. PET raw material C (PET-c)
A polyethylene terephthalate (PET-c) having an intrinsic viscosity of 0.79 and a terminal carboxyl group content of 15 equivalents / ton was obtained except that the final temperature of the polymerization reaction was 290 ° C.
重合反応の最終到達温度295℃とした以外はPET原料Aと同様に行い、固有粘度0.77、末端カルボキシル基量が20当量/トンのポリエチレンテレフタレート(PET-d)を得た。 4). PET raw material D (PET-d)
Except that the final temperature of the polymerization reaction was 295 ° C., the same procedure as in PET raw material A was performed to obtain polyethylene terephthalate (PET-d) having an intrinsic viscosity of 0.77 and a terminal carboxyl group amount of 20 equivalents / ton.
重合反応の最終到達温度300℃とした以外はPET原料Aと同様に行い、固有粘度0.75、末端カルボキシル基量が28当量/トンのポリエチレンテレフタレート(PET-e)を得た。 5. PET raw material E (PET-e)
A polyethylene terephthalate (PET-e) having an intrinsic viscosity of 0.75 and a terminal carboxyl group content of 28 equivalents / ton was obtained except that the final temperature of the polymerization reaction was 300 ° C.
反応触媒として酢酸マンガンの代わりに酢酸マグネシウム2水和物0.03質量部、エステル交換反応終了後、リン酸0.005質量部のみを添加した以外はPET原料Aと同様に行い、固有粘度0.80、末端カルボキシル基量が10当量/トンのポリエチレンテレフタレート(PET-f)を得た。 6). PET raw material F (PET-f)
As the reaction catalyst, 0.03 parts by mass of magnesium acetate dihydrate instead of manganese acetate, and after completion of the transesterification reaction, the same procedure as in PET raw material A was performed except that only 0.005 parts by mass of phosphoric acid was added. Polyethylene terephthalate (PET-f) having a terminal carboxyl group amount of 10 equivalents / ton was obtained.
重合反応の最終到達温度297℃とした以外はPET原料Aと同様に行い、固有粘度0.76、末端カルボキシル基量が24当量/トンのポリエチレンテレフタレート(PET-g)を得た。 7). PET raw material G (PET-g)
A polyethylene terephthalate (PET-g) having an intrinsic viscosity of 0.76 and a terminal carboxyl group content of 24 equivalents / ton was obtained except that the final temperature of the polymerization reaction was 297 ° C.
重合反応の最終到達温度305℃とした以外はPET原料Aと同様に行い、固有粘度0.65、末端カルボキシル基量が34当量/トンのポリエチレンテレフタレート(PET-h)を得た。 8). PET raw material H (PET-h)
A polyethylene terephthalate (PET-h) having an intrinsic viscosity of 0.65 and a terminal carboxyl group amount of 34 equivalents / ton was obtained except that the final temperature of the polymerization reaction was 305 ° C.
上記1.項によって得られたPET樹脂A(PET-a)42質量部と、ポリプラスチックス株式会社製シクロオレフィンコポリマー(COC)“TOPAS”(登録商標)6018(ビカット軟化点=188℃)、40質量部、東レデュポン株式会社製ポリエステル系エラストマー(TPE)“ハイトレル”(登録商標)7247 18質量部を、ベントした290℃の押出機内で溶融混練し、空洞核剤マスターペレットAを作製した。 9. Hollow core master pellet A
Above 1. 42 parts by mass of PET resin A (PET-a) obtained by the above section, cycloolefin copolymer (COC) “TOPAS” (registered trademark) 6018 (Vicat softening point = 188 ° C.) manufactured by Polyplastics Co., Ltd., 40 parts by mass Then, 18 parts by mass of polyester elastomer (TPE) “Hytrel” (registered trademark) 7247 manufactured by Toray DuPont Co., Ltd. was melt-kneaded in a vented extruder at 290 ° C. to prepare a hollow core agent master pellet A.
PET樹脂Aの代わりに上記2.項によって得られたPET樹脂Bを用いた以外は、7.項の空洞核剤マスターペレットAと同様の組成、及び方法で空洞核剤マスターペレットBを作製した。 10. Hollow nucleant master pellet B
In place of PET resin A, 2. 6. Except for using the PET resin B obtained in the above section. The hollow nucleating agent master pellet B was produced by the same composition and method as the hollow nucleating agent master pellet A of the item.
PET樹脂Aの代わりに上記3.項によって得られたPET樹脂Cを用いた以外は、7.項の空洞核剤マスターペレットAと同様の組成、及び方法で空洞核剤マスターペレットCを作製した。 11. Hollow nucleant master pellet C
In place of PET resin A, the above 3. 6. Except for using the PET resin C obtained in the above section. The hollow nucleating agent master pellet C was produced by the same composition and method as the hollow nucleating agent master pellet A of the item.
PET樹脂Aの代わりに上記4.項によって得られたPET樹脂Dを用いた以外は、7.項の空洞核剤マスターペレットAと同様の組成、及び方法で空洞核剤マスターペレットDを作製した。 12 Hollow core master pellet D
In place of PET resin A, the above 4. 6. Except for using the PET resin D obtained in the above section. The hollow nucleating agent master pellet D was produced by the same composition and method as the hollow nucleating agent master pellet A of the item.
PET樹脂Aの代わりに上記5.項によって得られたPET樹脂Fを用いた以外は、7.項の空洞核剤マスターペレットAと同様の組成、及び方法で空洞核剤マスターペレットFを作製した。 13 Hollow core master pellet F
In place of PET resin A, 5. 6. Except for using the PET resin F obtained in the above section. The hollow nucleating agent master pellet F was produced by the same composition and method as the hollow nucleating agent master pellet A.
上記1.項によって得られたPET樹脂A(PET-a)26.3質量部と、ポリプラスチックス株式会社製シクロオレフィンコポリマー“TOPAS”(登録商標)6018(ビカット軟化点=188℃)、40質量部、東レデュポン株式会社製ポリエステル系エラストマー(TPE)“ハイトレル”(登録商標)7247 18質量部、イーストマンケミカル社製非晶性PET樹脂(PET-G)Copolyester GN071 15.3質量部をベントした290℃の押出機内で溶融混練し、空洞核剤マスターペレットGを作製した。 14 Hollow core master pellet G
Above 1. 26.3 parts by mass of the PET resin A (PET-a) obtained according to the item, cycloolefin copolymer “TOPAS” (registered trademark) 6018 (Vicat softening point = 188 ° C.), 40 parts by mass, manufactured by Polyplastics Co., Ltd. Polyester elastomer (TPE) “Hytrel” (registered trademark) 7247 18 parts by mass produced by Toray DuPont Co., Ltd., 290 ° C. vented with 15.3 parts by mass of amorphous PET resin (PET-G) Copolyester GN071 produced by Eastman Chemical Co., Ltd. The mixture was melt-kneaded in an extruder of No. 1 to produce a hollow nucleating agent master pellet G.
上記1.項によって得られたPET樹脂A(PET-a)60質量部と、ポリプラスチックス株式会社製シクロオレフィンコポリマー“TOPAS”(登録商標)6018(ビカット軟化点=188℃)、40質量部をベントした290℃の押出機内で溶融混練し、空洞核剤マスターペレットHを作製した。 15. Hollow nucleant master pellet H
Above 1. 60 parts by mass of PET resin A (PET-a) obtained by the above section and 40 parts by mass of cycloolefin copolymer “TOPAS” (registered trademark) 6018 (Vicat softening point = 188 ° C.) manufactured by Polyplastics Co., Ltd. were vented. Cavity nucleating agent master pellets H were prepared by melt-kneading in an extruder at 290 ° C.
上記1.項によって得られたPET樹脂A(PET-a)42質量部と、三井化学株式会社製ポリメチルペンテン(PMP)“TPX”(登録商標)DX820(ビカット軟化点=172℃)、40質量部、東レデュポン株式会社製ポリエステル系エラストマー(TPE)“ハイトレル”(登録商標)7247 18質量部を、ベントした290℃の押出機内で溶融混練し、空洞核剤マスターペレットIを作製した。 16. Hollow nucleant master pellet I
Above 1. 42 parts by mass of the PET resin A (PET-a) obtained by the above section, polymethylpentene (PMP) “TPX” (registered trademark) DX820 (Vicat softening point = 172 ° C.), 40 parts by mass, 18 parts by mass of a polyester-based elastomer (TPE) “Hytrel” (registered trademark) 7247 manufactured by Toray DuPont Co., Ltd. was melt-kneaded in a vented 290 ° C. extruder to prepare a hollow nucleating agent master pellet I.
上記1.項によって得られたPET樹脂A(PET-a)56質量部と、住友化学株式会社製ポリプロピレン(PP)“ノーブレン”(登録商標)FLX80E4(ビカット軟化点=135℃)、40質量部、三洋化成工業株式会社製酸変性ポリプロピレン(酸変性PP)“ユーメックス”(登録商標)PP1010 4質量部を、ベントした290℃の押出機内で溶融混練し、空洞核剤マスターペレットJを作製した。 17. Hollow core master pellet J
Above 1. 56 parts by mass of PET resin A (PET-a) obtained according to the above, polypropylene (PP) “Noblen” (registered trademark) FLX80E4 (Vicat softening point = 135 ° C.), 40 parts by mass,
上記1.項によって得られたPET樹脂A(PET-a)100質量部と、平均粒子径210nmのルチル型酸化チタン粒子(TiO2)100質量部を、ベントした290℃の押出機内で溶融混練し、酸化チタンマスターペレットを作製した。 18. Titanium oxide master pellet 100 parts by mass of PET resin A (PET-a) obtained according to the above and 100 parts by mass of rutile-type titanium oxide particles (TiO 2 ) having an average particle diameter of 210 nm are melt-kneaded in a vented 290 ° C. extruder, and oxidized. A titanium master pellet was prepared.
上記1.項によって得られたPET樹脂A(PET-a)100質量部と、平均粒子径1.5μmの硫酸バリウム粒子(BaSO4)100質量部を、ベントした290℃の押出機内で溶融混練し、硫酸バリウムマスターペレットを作製した。 19. Barium sulfate master pellet 100 parts by mass of PET resin A (PET-a) obtained according to the above and 100 parts by mass of barium sulfate particles (BaSO 4 ) having an average particle size of 1.5 μm were melt-kneaded in a vented 290 ° C. extruder, and sulfuric acid was added. Barium master pellets were prepared.
20.ポリエチレンフィルム
東レフィルム加工(株)製白色ポリエチレンフィルム“4807W”を使用した。 (Film and coating agent used for functional layer B)
20. Polyethylene film A white polyethylene film “4807W” manufactured by Toray Film Processing Co., Ltd. was used.
ポリエチレンビニルアセテート(ビニルアセテート含有量5質量%)のチップ50質量部と、無機粒子として、数平均二次粒径0.25μmの二酸化チタン30質量%を分散させたポリエチレンマスターチップ(マスターチップ総量に対して二酸化チタン30質量%含有)50質量部とを、190℃の温度に加熱された押出機に供給し、Tダイから押し出されたポリエチレンビニルアセテートフィルムを使用した。 21. Polyethylene vinyl acetate copolymer film Polyethylene in which 50 parts by mass of polyethylene vinyl acetate (vinyl acetate content 5% by mass) and 30% by mass of titanium dioxide having a number average secondary particle size of 0.25 μm are dispersed as inorganic particles. 50 parts by mass of master chips (containing 30% by mass of titanium dioxide with respect to the total amount of master chips) were supplied to an extruder heated to a temperature of 190 ° C., and a polyethylene vinyl acetate film extruded from a T die was used.
東レフィルム加工(株)製白色ポリプロピレンフィルム“B011W”を使用した。 22. Polypropylene film White polypropylene film “B011W” manufactured by Toray Film Processing Co., Ltd. was used.
デュポン社製“テドラー”(登録商標)を使用した。
24.PVDFフィルム
アルケマ社製“カイナー”(登録商標)を使用した
25.ETFEフィルム
ダイキン工業(株)製“ネオフロン”(登録商標)EFシリーズを使用した。 23. PVF film “Tedlar” (registered trademark) manufactured by DuPont was used.
24. PVDF film Arkema “Kyner” (registered trademark) was used. ETFE Film Daikin Industries, Ltd. “Neofluon” (registered trademark) EF series was used.
塗剤aの調合として、表9の主剤の欄に示される配合によって、(株)日本触媒製のアクリル系コーティング剤である“ハルスハイブリット”(登録商標)ポリマー UV-G301(固形分濃度:40質量%)に、着色顔料のテイカ(株)製酸化チタン粒子JR-709、および溶剤を一括混合し、ビーズミル機を用いてこれらの混合物を分散させた。その後、可塑剤としてDIC(株)製ポリエステル系可塑剤“ポリサイザー”(登録商標)W-220ELを添加して、固形分濃度が51質量%である樹脂層形成用の塗剤aの主剤を得た。 26. Urethane coating agent (coating agent a, coating agent b)
As a preparation of coating agent a, “Halshybrit” (registered trademark) polymer UV-G301 (solid content concentration: 40), which is an acrylic coating agent manufactured by Nippon Shokubai Co., Ltd., is prepared according to the formulation shown in the main agent column of Table 9. (Mass%) were mixed together with colored pigment Titanium Co., Ltd. titanium oxide particles JR-709 and a solvent, and the mixture was dispersed using a bead mill. Thereafter, a polyester plasticizer “Polysizer” (registered trademark) W-220EL manufactured by DIC Corporation is added as a plasticizer to obtain a main component of coating agent a for resin layer formation having a solid content concentration of 51 mass%. It was.
三菱化学(株)製“テックバリア”(登録商標)LXを使用した。 27. An inorganic compound film “Tech Barrier” (registered trademark) LX manufactured by Mitsubishi Chemical Corporation was used.
ポリエステルフィルムとして東レ(株)製“ルミラー”(登録商標)MX11を使用した。 28. Polyester film “Lumirror” (registered trademark) MX11 manufactured by Toray Industries, Inc. was used as a polyester film.
積層用接着剤として、DIC(株)製ドライラミネート剤“ディックドライ”(登録商標)TAF-300を36質量部、硬化剤としてヘキサメチレンジイソシアネート系樹脂を主成分とするDIC(株)製TAFハードナーAH-3を3質量部、および酢酸エチルを30質量部量りとり、15分間攪拌することにより固形分濃度30質量%の積層用接着剤である塗剤cを得た。 29. Laminating adhesive (Coating c)
As a laminating adhesive, 36 parts by mass of a dry laminating agent “Dick Dry” (registered trademark) TAF-300 manufactured by DIC Corporation, and a TAF hardener manufactured by DIC Corporation containing hexamethylene diisocyanate resin as a main component as a curing agent. 3 parts by weight of AH-3 and 30 parts by weight of ethyl acetate were weighed and stirred for 15 minutes to obtain a coating agent c as a laminating adhesive having a solid content concentration of 30% by weight.
表1に示す組成となるように、P1層を構成する原料として180℃で2時間真空乾燥したPET原料A(PET-a)を77.5質量部と空洞核剤マスターペレットAを22.5質量部とを混合し、一方でP2層を構成する原料として180℃で2時間真空乾燥したPET原料A(PET-a)を72質量部と酸化チタンマスターペレットを28質量部とを混合し、それぞれを異なる2台の280℃に昇温した押出機内で溶融させて吐出し、フィードブロックにてP2/P1/P2と積層するように合流させた後、Tダイから共押出した。次いで共押出した溶融シートを表面温度50℃に保たれたドラム上に静電印加法で密着冷却固化させて、未延伸シートを得た。続いて、該未延伸シートを80℃の温度に加熱したロール群で予熱した後、88℃の温度に加熱したロールと25℃の温度に調整したロール間で3倍の速度差をつけることで長手方向(縦方向)に3倍に延伸した後、25℃の温度のロール群で冷却して一軸延伸シートを得た。次いで、得られた一軸延伸シートの両端をクリップで把持しながらテンター内の80℃の温度の予熱ゾーンに導き、引き続き連続的に90℃に保たれた加熱ゾーンで長手方向に直角な方向(幅方向)に3.5倍に延伸した。更に引き続いて、テンター内の熱処理ゾーンにて220℃で20秒間の熱処理を施し、さらに4%幅方向に弛緩処理を行いながら均一に徐冷し、ポリエステルフィルムを製膜した。 (Example 1)
In order to obtain the composition shown in Table 1, 77.5 parts by mass of PET raw material A (PET-a) vacuum-dried at 180 ° C. for 2 hours as a raw material constituting the P1 layer and 22.5 parts of the hollow nucleating agent master pellet A were obtained. On the other hand, 72 parts by mass of PET raw material A (PET-a) vacuum-dried at 180 ° C. for 2 hours as a raw material constituting the P2 layer and 28 parts by mass of titanium oxide master pellets were mixed, Each was melted and discharged in two different extruders heated to 280 ° C., merged so as to be laminated with P2 / P1 / P2 in a feed block, and then co-extruded from a T die. Next, the co-extruded molten sheet was closely cooled and solidified by an electrostatic application method on a drum maintained at a surface temperature of 50 ° C. to obtain an unstretched sheet. Subsequently, after preheating the unstretched sheet with a roll group heated to a temperature of 80 ° C., a three-fold speed difference is created between the roll heated to a temperature of 88 ° C. and the roll adjusted to a temperature of 25 ° C. After stretching 3 times in the longitudinal direction (longitudinal direction), it was cooled with a roll group at a temperature of 25 ° C. to obtain a uniaxially stretched sheet. Next, while holding both ends of the obtained uniaxially stretched sheet with clips, the tenter is guided to a preheating zone at a temperature of 80 ° C. in the tenter, and subsequently in a heating zone maintained at 90 ° C. in a direction perpendicular to the longitudinal direction (width) Direction). Subsequently, heat treatment was carried out at 220 ° C. for 20 seconds in a heat treatment zone in the tenter, and further uniformly cooled while performing relaxation treatment in the 4% width direction to form a polyester film.
空洞核剤マスターペレット量、及び空洞核剤マスターペレットG~Iを使用、またはP1層にP2層で使用した酸化チタンマスターペレットを混合して、P1層の組成を表1の通りに変更した以外は、実施例1と同様に太陽電池バックシート用フィルムを得た。 (Examples 2 to 11)
Except for changing the composition of the P1 layer as shown in Table 1, using the amount of the hollow nucleating agent master pellet and the hollow nucleating agent master pellets G to I, or mixing the titanium oxide master pellet used in the P2 layer with the P1 layer. Obtained the film for solar cell backsheets similarly to Example 1.
更に太陽電池特性評価を行った結果、実施例1に比べて空洞面積比の増加に伴い出力向上性が低下するものの、密着性とともに良好な範囲であることがわかった。 About the obtained film for solar cell backsheets, as a result of performing solar cell backsheet characteristic evaluation, as shown in Table 2, it is a good range although it is partially inferior to Example 1 and inferior in thermal conductivity. I understood it.
Furthermore, as a result of evaluating the solar cell characteristics, it was found that although the output improvement was reduced as the cavity area ratio was increased as compared with Example 1, it was within a good range together with the adhesion.
P1層及びP2層の主成分であるPET樹脂を表3に示す通り、PET-b~fに変更した以外は実施例1と同様に太陽電池バックシート用フィルムを得た。 (Examples 12 to 16)
As shown in Table 3, a solar cell backsheet film was obtained in the same manner as in Example 1 except that the PET resin as the main component of the P1 layer and the P2 layer was changed to PET-b to f as shown in Table 3.
更に太陽電池特性評価を行った結果、実施例1に比べてと末端カルボキシル基量の増加に伴い出力向上性が低下するものの、密着性ともに良好な範囲であることがわかった。また実施例16は実施例1と固有粘度や末端カルボキシル基量と同様にも関わらず、太陽電池バックシートの密着性や太陽電池の出力向上性、密着性を劣るものの、良好な範囲であることがわかった。 As a result of evaluating the solar battery back sheet characteristics of the obtained film for solar battery back sheet, as shown in Table 4, Examples 12 to 15 are in a good range although the adhesion is inferior to that of Example 1. I understood it. The heat and humidity resistance decreased with a decrease in intrinsic viscosity IV and an increase in the amount of terminal carboxyl groups. It was also found that the thermal conductivity was excellent as in Example 1.
Furthermore, as a result of evaluating the characteristics of the solar cell, it was found that although the output improvement was reduced with the increase in the amount of terminal carboxyl groups as compared with Example 1, the adhesion was in a good range. Moreover, although Example 16 is inferior to Example 1 in terms of the intrinsic viscosity and the amount of terminal carboxyl groups, the adhesion of the solar battery backsheet, the output improvement of the solar battery, and the adhesion are inferior, but it is in a good range. I understood.
太陽電池バックシートの積層比やフィルム構成、P2層の無機粒子量、キャスト温度を表3に示す通り変更した以外は実施例1と同様に太陽電池バックシート用フィルムを得た。 (Examples 17 to 25)
A solar battery backsheet film was obtained in the same manner as in Example 1 except that the lamination ratio and film configuration of the solar battery backsheet, the amount of inorganic particles in the P2 layer, and the casting temperature were changed as shown in Table 3.
表3に示す通り、P1層単膜のフィルム構成でP1層中に無機粒子を高濃度添加した以外は実施例1と同様に太陽電池バックシート用フィルムを得た。 (Example 26)
As shown in Table 3, a solar cell backsheet film was obtained in the same manner as in Example 1 except that a high concentration of inorganic particles was added to the P1 layer in the P1 layer single film configuration.
P2層の無機粒子として硫酸バリウム粒子を用いるため硫酸バリウムマスターペレットを用い、ポリエステルフィルムの積層比(P2:P1:P2)が1:1:1となるように押出機の吐出量を調整した以外は実施例3と同様に太陽電池バックシート用フィルムを得た。得られた太陽電池バックシート用フィルムの空洞面積比を確認したところ、表4に示す通り、(Sc/Scs)、(Sc/Scs’)ともに実施例3よりも小さくなった。
得られた太陽電池バックシート用フィルムについて、太陽電池バックシート特性評価を行った結果、実施例3に比べて劣るものの良好な密着性を有することがわかった。熱伝導率は実施例1と同様に優れたものであるものだった。更に太陽電池特性評価を行った結果、実施例3に比べて劣るものの良好な密着性を有し、出力向上性については問題ない範囲であることがわかった。 (Example 27)
Since barium sulfate particles are used as the inorganic particles of the P2 layer, barium sulfate master pellets are used, and the discharge rate of the extruder is adjusted so that the lamination ratio (P2: P1: P2) of the polyester film is 1: 1: 1. Obtained the film for solar cell backsheets similarly to Example 3. When the cavity area ratio of the obtained solar cell backsheet film was confirmed, as shown in Table 4, both (Sc / Scs) and (Sc / Scs') were smaller than Example 3.
About the obtained solar cell backsheet film, as a result of evaluating the solar cell backsheet characteristics, it was found that the film for the solar cell backsheet had good adhesion although it was inferior to Example 3. The thermal conductivity was excellent as in Example 1. Furthermore, as a result of evaluating the solar cell characteristics, it was found that the solar cell characteristics were inferior to those of Example 3 but had good adhesiveness, and there was no problem in terms of output improvement.
P1層及びP2層の主成分であるPET樹脂を表3の通り、PET-gに変更した以外は実施例1と同様に太陽電池バックシート用フィルムを得た。 (Example 28)
As shown in Table 3, a solar cell backsheet film was obtained in the same manner as in Example 1 except that the PET resin as the main component of the P1 layer and the P2 layer was changed to PET-g as shown in Table 3.
更に太陽電池特性評価を行った結果、表に示す通り、実施例1に比べてと末端カルボキシル基量の増加に伴い出力向上性がやや低下するものの、密着性ともに良好な範囲であることがわかった。 About the obtained film for solar cell back sheets, as a result of performing characteristic evaluation, it turned out that adhesiveness is favorable as shown in a table | surface. Moreover, although the heat-and-moisture resistance slightly decreased with a decrease in intrinsic viscosity IV and an increase in the amount of terminal carboxyl groups, it was in a range where there was no problem. It was also found that the thermal conductivity was excellent as in Example 1.
Furthermore, as a result of evaluating the solar cell characteristics, as shown in the table, it was found that although the output improvement was slightly reduced with the increase in the amount of terminal carboxyl groups as compared with Example 1, the adhesion was in a good range. It was.
製膜時にライン速度を変更し、フィルムの全体厚みを表3の通り、変更した以外は実施例1と同様に太陽電池バックシート用フィルムを得た。 (Examples 29 to 31)
A film for a solar battery back sheet was obtained in the same manner as in Example 1 except that the line speed was changed during film formation and the total thickness of the film was changed as shown in Table 3.
得られた太陽電池バックシート用フィルムについて、太陽電池バックシート特性評価を行った結果、表4に示す通り、フィルム厚みの薄いフィルムでは、密着性がやや低下することがわかった。また熱伝導率も実施例1に比べてやや低下するが良好な範囲であることがわかった。
更に太陽電池特性評価を行った結果、表に示す通り、フィルム厚みの低下に伴い、太陽電池の密着性がやや低下することがわかった。また、出力向上性も実施例1に比べてやや低下するが、良好な範囲であることがわかった。 When the cavity area ratio of the obtained solar cell backsheet film was confirmed, both (Sc / Scs) and (Sc / Scs ′) were similar to those in Example 1.
As a result of performing solar cell back sheet characteristic evaluation about the obtained film for solar cell back sheets, as shown in Table 4, it was found that the adhesiveness of the film having a small film thickness was slightly lowered. Further, it was found that the thermal conductivity is in a good range although it is slightly lower than that in Example 1.
Furthermore, as a result of performing solar cell characteristic evaluation, as shown in the table, it was found that the adhesiveness of the solar cell slightly decreased as the film thickness decreased. Moreover, although the output improvement property also fell a little compared with Example 1, it turned out that it is a favorable range.
実施例1で得られた太陽電池バックシート用フィルムのP2層の一方の面に、積層用接着剤として準備した塗料cを用いて、ワイヤーバーを用いて塗布し、80℃の温度で45秒間乾燥し、乾燥後の塗膜厚みが5.0μmとなるように積層用接着剤層を形成した。
次に、表5に示す機能層Bを接着剤層上に積層し、40℃の温度で3日間エージングし太陽電池バックシートとした。得られた太陽電池バックシートは、密着性、耐湿熱性、耐紫外線性は良好であり、少なくともヤング率、カール高さ、水蒸気バリア性のいずれかが優れていた。また、太陽電池特性に優れていた。 (Examples 32 to 44)
Using the coating material c prepared as the laminating adhesive on one surface of the P2 layer of the film for solar battery backsheet obtained in Example 1, it was applied using a wire bar and at a temperature of 80 ° C. for 45 seconds. The dried adhesive layer was formed so that the thickness of the coating film after drying was 5.0 μm.
Next, the functional layer B shown in Table 5 was laminated | stacked on the adhesive bond layer, and it aged for 3 days at the temperature of 40 degreeC, and was set as the solar cell backsheet. The obtained solar cell backsheet had good adhesion, heat and humidity resistance, and ultraviolet resistance, and at least one of Young's modulus, curl height, and water vapor barrier property was excellent. Moreover, it was excellent in the solar cell characteristic.
実施例32~44と同様にして、表6に示す機能層Bを接着剤層上に積層し、40℃の温度で3日間エージングし太陽電池バックシートとした。得られた実施例45~49に示す太陽電池バックシートは、密着性、耐湿熱性、耐紫外線性は良好であり、ヤング率、カール高さは大きくなっているが、水蒸気バリア性が優れていた。また、太陽電池特性に優れていた。 (Examples 45 to 49)
In the same manner as in Examples 32 to 44, the functional layer B shown in Table 6 was laminated on the adhesive layer and aged at a temperature of 40 ° C. for 3 days to obtain a solar cell backsheet. The solar cell backsheets shown in Examples 45 to 49 had good adhesion, moist heat resistance, and ultraviolet resistance, and had a large Young's modulus and curl height, but had excellent water vapor barrier properties. . Moreover, it was excellent in the solar cell characteristic.
実施例1で得られた太陽電池バックシート用フィルムのP2層の一方の面に、乾燥後の機能層Bの厚みが表6に示す厚みとなるよう、表6に従いワイヤーバーを用いて塗料a、塗料bをそれぞれ塗布し、100℃の温度で60秒間乾燥して太陽電池バックシート用フィルムを作製した(なお、実施例50~53では、空隙率や(Sc/Scs)、(Sc/Scs’)は、機能層Bを含めた積層フィルムをもとに求めた)。得られた太陽電池バックシート用フィルムを、太陽電池バックシートとして用いて評価を実施したところ、バックシート特性、太陽電池特性ともに優れていた。 (Examples 50 to 53)
Using one of the P2 layers of the solar cell backsheet film obtained in Example 1, the thickness of the functional layer B after drying becomes the thickness shown in Table 6, using a wire bar according to Table 6, and paint a The coating material b was applied and dried at a temperature of 100 ° C. for 60 seconds to produce solar cell backsheet films (in Examples 50 to 53, porosity, (Sc / Scs), (Sc / Scs) ') Was determined based on a laminated film including the functional layer B). When the obtained solar cell backsheet film was evaluated as a solar cell backsheet, both the backsheet characteristics and the solar cell characteristics were excellent.
実施例1で得られた太陽電池バックシート用フィルムのP2層の一方の面に、積層用接着剤として準備した塗料cを用いて、ワイヤーバーを用いて塗布し、80℃の温度で45秒間乾燥し、乾燥後の塗膜厚みが5.0μmとなるように積層用接着剤層を形成した。
次に、表6に示す機能層B’を接着剤層上に積層し、40℃の温度で3日間エージングした。更に、機能層B’を積層していないもう一方のP2層に積層用接着剤として準備した塗料cを用いて、ワイヤーバーを用いて塗布し、80℃の温度で45秒間乾燥し、乾燥後の塗膜厚みが5.0μmとなるように積層用接着剤層を形成した。積層用接着剤層上に、表6に示す機能層Bを積層し、40℃の温度で3日間エージングし太陽電池バックシートとした。得られた実施例54、55に示す太陽電池バックシートは、密着性、耐湿熱性、耐紫外線性は良好であり、ヤング率、カール高さ、水蒸気バリア性に優れていた。また、太陽電池特性に優れていた。 (Examples 54 and 55)
Using the coating material c prepared as the laminating adhesive on one surface of the P2 layer of the film for solar battery backsheet obtained in Example 1, it was applied using a wire bar and at a temperature of 80 ° C. for 45 seconds. The dried adhesive layer was formed so that the thickness of the coating film after drying was 5.0 μm.
Next, the functional layer B ′ shown in Table 6 was laminated on the adhesive layer and aged at a temperature of 40 ° C. for 3 days. Furthermore, using the coating material c prepared as a laminating adhesive on the other P2 layer on which the functional layer B ′ is not laminated, it is applied using a wire bar, dried at a temperature of 80 ° C. for 45 seconds, and after drying The adhesive layer for lamination was formed so that the thickness of the coating film was 5.0 μm. The functional layer B shown in Table 6 was laminated on the laminating adhesive layer and aged at a temperature of 40 ° C. for 3 days to obtain a solar cell backsheet. The obtained solar cell backsheets shown in Examples 54 and 55 had good adhesion, wet heat resistance, and ultraviolet resistance, and were excellent in Young's modulus, curl height, and water vapor barrier properties. Moreover, it was excellent in the solar cell characteristic.
実施例1で得られた太陽電池バックシート用フィルムのP2層の一方の面に、乾燥後の機能層Bの厚みが表6に示す厚みとなるよう、表6に従いワイヤーバーを用いて塗料aを塗布し、100℃の温度で60秒間乾燥して機能層Bを有する太陽電池バックシート用フィルムを得た。更に、機能層Bを積層していない片方のP2層に積層用接着剤として準備した塗料cを用いて、ワイヤーバーを用いて塗布し、80℃の温度で45秒間乾燥し、乾燥後の塗膜厚みが5.0μmとなるように積層用接着剤層を形成した。積層用接着剤層上に、表6に示す機能層B’を積層し、40℃の温度で3日間エージングし太陽電池バックシートとした。得られた実施例56に示す太陽電池バックシートは、ヤング率、カール高さは大きくなっているが、水蒸バリア性に優れていた。また、太陽電池特性も優れていた。 (Example 56)
Using one of the P2 layers of the solar cell backsheet film obtained in Example 1, the thickness of the functional layer B after drying becomes the thickness shown in Table 6, using a wire bar according to Table 6, and paint a Was applied and dried at a temperature of 100 ° C. for 60 seconds to obtain a solar battery backsheet film having a functional layer B. Further, using a coating c prepared as a laminating adhesive on one P2 layer on which the functional layer B is not laminated, it is applied using a wire bar, dried at a temperature of 80 ° C. for 45 seconds, and dried. The adhesive layer for lamination was formed so that the film thickness was 5.0 μm. A functional layer B ′ shown in Table 6 was laminated on the laminating adhesive layer and aged at a temperature of 40 ° C. for 3 days to obtain a solar cell backsheet. The solar cell back sheet shown in Example 56 was excellent in water vapor barrier property, although Young's modulus and curl height were large. Moreover, the solar cell characteristics were also excellent.
P1層の空洞核剤量を3質量%とした以外は実施例1と同様に太陽電池バックシート用フィルムを得た。
得られた太陽電池バックシート用フィルムの空隙率を確認したところ、フィルム全体の空隙率が9%と本発明の範囲から外れることがわかった。
更に比較例1で得られた太陽電池バックシート用フィルムは密着性、熱伝導率が劣る太陽電池バックシートであることがわかった。また太陽電池特性についても出力向上性、及び密着性に劣る太陽電池であることがわかった。 (Comparative Example 1)
A solar cell backsheet film was obtained in the same manner as in Example 1 except that the amount of the hollow nucleating agent in the P1 layer was 3% by mass.
When the porosity of the obtained film for solar battery back sheets was confirmed, it was found that the porosity of the entire film was 9%, which was out of the scope of the present invention.
Furthermore, it turned out that the film for solar cell backsheets obtained by the comparative example 1 is a solar cell backsheet inferior in adhesiveness and heat conductivity. Moreover, it turned out that it is a solar cell inferior to an output improvement property and adhesiveness also about a solar cell characteristic.
P1層の組成を表の通りとするために、空洞核剤マスターペレット量、及び空洞核剤マスターペレットG~Jを使用、またはP1層に空洞核剤として硫酸バリウム粒子を用いるため硫酸バリウムマスターペレットを用いた以外は、実施例1と同様に太陽電池バックシート用フィルムを得た。 (Comparative Examples 2 to 6)
In order to make the composition of the P1 layer as shown in the table, the amount of the hollow nucleating agent master pellets and the hollow nucleating agent master pellets G to J are used, or the barium sulfate master pellets are used in the P1 layer for using barium sulfate particles as the hollow nucleating agent. A film for a solar battery back sheet was obtained in the same manner as in Example 1 except that was used.
ポリエステルフィルムの積層比(P2:P1:P2)が1:1:1となるように押出機の吐出量を調整した以外は実施例1と同様に太陽電池バックシート用フィルムを得た。 (Comparative Example 7)
A film for a solar battery back sheet was obtained in the same manner as in Example 1 except that the discharge rate of the extruder was adjusted so that the lamination ratio (P2: P1: P2) of the polyester film was 1: 1: 1.
P1層及びP2層の主成分であるPET樹脂をPET-hに変更した以外は実施例1と同様に太陽電池バックシート用フィルムを得た。 (Comparative Example 8)
A solar cell backsheet film was obtained in the same manner as in Example 1 except that the PET resin, which is the main component of the P1 layer and P2 layer, was changed to PET-h.
更に比較例8で得られた太陽電池バックシート用フィルムは密着性と耐湿熱性が劣る太陽電池バックシートであることがわかった。また太陽電池特性についても出力向上性、及び密着性の両方が劣る太陽電池であることがわかった。 When the cavity area ratio of the obtained solar cell backsheet film was confirmed, both (Sc / Scs) and (Sc / Scs') were the same as in Example 1, but the polymer properties were measured to determine the amount of terminal carboxyl groups. Decreased to 40 equivalents / ton.
Furthermore, it turned out that the film for solar cell backsheets obtained by the comparative example 8 is a solar cell backsheet inferior in adhesiveness and heat-and-moisture resistance. Moreover, it turned out that it is a solar cell in which both an output improvement property and adhesiveness are inferior also about the solar cell characteristic.
製膜時にP1層の単膜構成でTダイから押出、冷却を行い得られた未延伸シートを70℃の温度に加熱したロール群で予熱した後、シートの両表面から15mm離れた位置に設置した赤外線ヒーターにて、50W/cmの出力で0.72秒間加熱して長手方向(縦方向)に3倍に延伸した以外は比較例2と同様に太陽電池バックシート用フィルムを得た。
得られた太陽電池バックシート用フィルムの空洞面積比を確認したところ、比較例2とは異なり、厚み方向の空洞面積に偏りが見られた。しかしながら、フィルム表面から深さ10μmまでの範囲では空洞1個あたりの平均面積は小さくなるのみで、フィルム全体厚みに対して25~75%の深さにおいては、空洞1個あたりの平均面積に差は無く、(Sc/Scs)、(Sc/Scs’)は1.0であった。
比較例9で得られた太陽電池バックシート用フィルムは比較例2と同様に、密着性が劣る太陽電池バックシートであることがわかった。また太陽電池特性についても出力向上性、及び密着性の両方が劣る太陽電池であることがわかった。 (Comparative Example 9)
Pre-heated unstretched sheet obtained by extruding and cooling from a T-die with a P1 layer single-layer structure during film formation with a roll group heated to a temperature of 70 ° C, and then placed at a
When the cavity area ratio of the obtained solar cell backsheet film was confirmed, unlike Comparative Example 2, the cavity area in the thickness direction was biased. However, in the range from the film surface to a depth of 10 μm, the average area per cavity is only small, and at a depth of 25 to 75% of the total film thickness, there is a difference in the average area per cavity. (Sc / Scs) and (Sc / Scs ′) were 1.0.
As in Comparative Example 2, the film for solar battery back sheet obtained in Comparative Example 9 was found to be a solar battery back sheet having poor adhesion. Moreover, it turned out that it is a solar cell in which both an output improvement property and adhesiveness are inferior also about the solar cell characteristic.
太陽電池バックシート用フィルムを比較例6のフィルムを使用した以外は実施例32と同様にして、表9に示す機能層Bを積層し、40℃の温度で3日間エージングし太陽電池バックシートとした。得られた太陽電池バックシートは、ヤング率、カール高さは劣るものであった。また、太陽電池特性について、密着性は比較例6から改善されるが、出力向上性は劣る太陽電池であった。 (Comparative Example 10)
A solar battery back sheet was laminated in the same manner as in Example 32 except that the film for Comparative Example 6 was used, and the functional layer B shown in Table 9 was laminated and aged at a temperature of 40 ° C. for 3 days. did. The obtained solar cell back sheet was inferior in Young's modulus and curl height. Moreover, about the solar cell characteristic, although adhesiveness was improved from the comparative example 6, it was a solar cell with inferior output improvement.
太陽電池バックシート用フィルムを比較例6のフィルムを使用した以外は実施例42と同様にして、表9に示す機能層Bを積層し、40℃の温度で3日間エージングし太陽電池バックシートとした。得られた太陽電池バックシートは、ヤング率、カール高さは劣るものであった。また、太陽電池特性について、密着性、及び出力向上性が劣る太陽電池であった。 (Comparative Example 11)
A solar battery back sheet was laminated in the same manner as in Example 42 except that the film of Comparative Example 6 was used, and the functional layer B shown in Table 9 was laminated and aged at a temperature of 40 ° C. for 3 days. did. The obtained solar cell back sheet was inferior in Young's modulus and curl height. Moreover, it was a solar cell inferior to adhesiveness and output improvement about a solar cell characteristic.
2:封止材
3:発電素子
4:透明基板
5:太陽電池バックシートの封止材2側の面
6:太陽電池バックシートの封止材2と反対側の面
7:フィルムの厚み方向
8:フィルムの面方向
9:フィルム厚み方向中心点とフィルム表面との中間点(C2-1点)
10:フィルム厚み方向中心点(C1点)
11:フィルム厚み方向中心点とフィルム表面との中間点(C2-2点)
12:C2-1点を通る分割水平線
13:C1点を通る分割水平線
14:C2-2点を通る分割水平線
15:空洞
16:機能層B
17:太陽電池バックシート用フィルム
18:機能層B’
19:接着層
1: Solar cell back sheet 2: Sealing material 3: Power generation element 4: Transparent substrate 5: Surface on the sealing material 2 side of the solar cell back sheet 6:
10: Film thickness direction center point (point C1)
11: Intermediate point between the film thickness direction center point and the film surface (point C2-2)
12: Split horizontal line passing through point C2-1 13: Split horizontal line passing through point C1 14: Split horizontal line passing through point C2-2 15: Cavity 16: Functional layer B
17: Film for solar cell backsheet 18: Functional layer B ′
19: Adhesive layer
Claims (14)
- 空洞含有ポリエステルフィルムであって、
フィルム全体の空隙率が10%以上であり、
該ポリエステルフィルムの厚み方向断面において、
フィルムの一方の表面からもう一方の表面に面方向に垂直な線を引き、該一方の表面からもう一方の表面をつなぐ線を厚み方向に4等分する3点(フィルム厚み方向中心点(C1点)、フィルム厚み方向中心点とフィルム表面との中間点(C2-1点)、(C2-2点))のそれぞれを通るフィルムの面方向に平行な線(分割水平線)のそれぞれにおいて、
C1点を通る分割水平線上に存在する空洞1個当たりの平均面積をSc(μm2)、
C2-1点を通る分割水平線上に存在する空洞1個当たりの平均面積をScs(μm2)、
C2-2点を通る分割水平線上に存在する空洞1個当たりの平均面積をScs’(μm2)としたとき、(Sc/Scs)、(Sc/Scs’)のうち少なくとも一方が1.1以上35以下であり、ポリエステルフィルムを構成するポリエステル樹脂の末端カルボキシル基量が35当量/トン以下である太陽電池バックシート用フィルム。
(なお、(Sc/Scs)、(Sc/Scs’)は、ポリエステルフィルムの任意の5箇所にける、フィルムの長手方向に平行にフィルムを切断したフィルムの厚み方向断面、フィルムの幅方向に平行にフィルムを切断したフィルムの厚み方向断面から得られる値の平均値として求める。) A void-containing polyester film,
The porosity of the entire film is 10% or more,
In the thickness direction cross section of the polyester film,
A line perpendicular to the surface direction is drawn from one surface of the film to the other surface, and a line connecting the one surface to the other surface is divided into four equal parts in the thickness direction (film thickness direction center point (C1 In each of the lines parallel to the surface direction of the film (divided horizontal lines) passing through each of the intermediate points between the film thickness direction center point and the film surface (point C2-1, point C2-2)),
Sc (μm 2 ), the average area per cavity existing on the dividing horizontal line passing through the C1 point,
Scs (μm 2 ), the average area per cavity existing on the dividing horizontal line passing through the C2-1 point,
When the average area per cavity existing on the divided horizontal line passing through the point C2-2 is Scs ′ (μm 2 ), at least one of (Sc / Scs) and (Sc / Scs ′) is 1.1. The film for solar battery back sheets which is 35 or less and the amount of terminal carboxyl groups of the polyester resin constituting the polyester film is 35 equivalents / ton or less.
(Note that (Sc / Scs) and (Sc / Scs ′) are parallel to the film thickness direction cross section and the film width direction at any five locations of the polyester film, the film being cut in parallel to the film longitudinal direction. The average value of the values obtained from the cross-section in the thickness direction of the film obtained by cutting the film. - ポリエステルフィルムの全体厚みが45μm以上であることを特徴とする請求項1に記載の太陽電池バックシート用フィルム。 The film for solar battery backsheet according to claim 1, wherein the total thickness of the polyester film is 45 µm or more.
- 前記ポリエステルフィルムが、3層以上の積層構成を有しており、両表層(一方の表層をP2層、もう一方の表層をP2’層とする)を構成する樹脂組成物のうち少なくとも一方の樹脂組成物が無機粒子を含有しており、表層を有さない層(当該層をP1層とする)が空洞を含有する請求項1または2の太陽電池バックシート用フィルム。 The polyester film has a laminated structure of three or more layers, and at least one of the resin compositions constituting both surface layers (one surface layer is a P2 layer and the other surface layer is a P2 ′ layer). The film for solar battery backsheets according to claim 1 or 2, wherein the composition contains inorganic particles, and a layer having no surface layer (the layer is referred to as P1 layer) contains a cavity.
- P1層の厚みをT1(μm)、P2層の厚みをT2(μm)、P2’層の厚みをT2’(μm)、P2層を構成する樹脂組成物に含まれる無機粒子濃度をW2(質量%)、P2’層を構成する樹脂組成物に含まれる無機粒子濃度をW2’(質量%)としたとき、
(T1/T2)×W2、(T1/T2’)×W2’のうち少なくとも一方が0.35以上1.50以下であることを特徴とする請求項3に記載の太陽電池バックシート用フィルム。 The thickness of the P1 layer is T1 (μm), the thickness of the P2 layer is T2 (μm), the thickness of the P2 ′ layer is T2 ′ (μm), and the inorganic particle concentration contained in the resin composition constituting the P2 layer is W2 (mass) %), When the inorganic particle concentration contained in the resin composition constituting the P2 ′ layer is W2 ′ (mass%),
The film for solar battery backsheet according to claim 3, wherein at least one of (T1 / T2) x W2 and (T1 / T2 ') x W2' is 0.35 or more and 1.50 or less. - P1層の厚みをT1(μm)、P2層の厚みをT2(μm)、P2’層の厚みをT2’(μm)としたとき、T1/(T1+T2+T2’)が0.6以上0.99以下であり、T2/(T1+T2+T2’)およびT2’/(T1+T2+T2’)が0.01以上0.2以下である請求項3または4に記載の太陽電池バックシート用フィルム。 When the thickness of the P1 layer is T1 (μm), the thickness of the P2 layer is T2 (μm), and the thickness of the P2 ′ layer is T2 ′ (μm), T1 / (T1 + T2 + T2 ′) is 0.6 or more and 0.99 or less The film for solar cell backsheet according to claim 3 or 4, wherein T2 / (T1 + T2 + T2 ') and T2' / (T1 + T2 + T2 ') are 0.01 or more and 0.2 or less.
- P2層の空隙率(Ps)およびP2’層の空隙率(Ps’)が5.0%以下である請求項3~5のいずれかに記載の太陽電池バックシート用フィルム。 The film for solar battery backsheet according to any one of claims 3 to 5, wherein the porosity (Ps) of the P2 layer and the porosity (Ps ') of the P2' layer are 5.0% or less.
- 熱伝導率が0.9W/m・K以下である請求項1~6のいずれかに記載の太陽電池バックシート用フィルム。 The film for solar battery backsheet according to any one of claims 1 to 6, which has a thermal conductivity of 0.9 W / m · K or less.
- 請求項1~7のいずれかに記載の太陽電池バックシート用フィルムと少なくとも1層以上の機能層を有する太陽電池バックシートであって、前記太陽電池バックシート用フィルムのヤング率が4.0GPa以下、前記太陽電池バックシートのヤング率が4.0GPa以下である太陽電池バックシート。 A solar cell backsheet having the solar cell backsheet film according to any one of claims 1 to 7 and at least one functional layer, wherein the Young's modulus of the solar cell backsheet film is 4.0 GPa or less. The solar cell back sheet, wherein the solar cell back sheet has a Young's modulus of 4.0 GPa or less.
- 前記機能層が次の群1から少なくとも1つ、あるいは複数の組み合わせを含む請求項8に記載の太陽電池バックシート。
群1:ポリエチレン、ポリプロピレン、エチレンビニルアセテート共重合体 The solar cell backsheet according to claim 8, wherein the functional layer includes at least one of the following group 1 or a plurality of combinations.
Group 1: Polyethylene, polypropylene, ethylene vinyl acetate copolymer - 前記機能層が次の群2から少なくとも1つ、あるいは複数の組み合わせを含む請求項8に記載の太陽電池バックシート。
群2:ポリフッ化ビニル(PVF)、ポリフッ化ビニリデン(PVDF)、エチレン-テトラフルオロエチレン共重合体(ETFE)、四フッ化エチレン-六フッ化プロピレン共重合体(FEP) The solar cell backsheet according to claim 8, wherein the functional layer includes at least one of the following group 2 or a plurality of combinations.
Group 2: Polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), ethylene-tetrafluoroethylene copolymer (ETFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP) - 前記機能層がポリウレタンを含む請求項8に記載の太陽電池バックシート。 The solar cell backsheet according to claim 8, wherein the functional layer contains polyurethane.
- 前記機能層が無機化合物を含む請求項8に記載の太陽電池バックシート。 The solar cell backsheet according to claim 8, wherein the functional layer contains an inorganic compound.
- 前記機能層がポリエステルを含み、前記太陽電池バックシート用フィルムと前記機能層が接着層を介して積層される請求項8に記載の太陽電池バックシート。 The solar cell backsheet according to claim 8, wherein the functional layer contains polyester, and the film for solar cell backsheet and the functional layer are laminated via an adhesive layer.
- 請求項1~7のいずれかに記載の太陽電池バックシート用フィルムまたは、請求項8~13のいずれかに記載の太陽電池バックシートを使用した太陽電池。
A solar cell using the solar cell backsheet film according to any one of claims 1 to 7 or the solar cell backsheet according to any one of claims 8 to 13.
Priority Applications (3)
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KR1020177026257A KR20180013845A (en) | 2015-05-27 | 2016-05-16 | BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solar cell backsheet film, |
JP2016537583A JP6743698B2 (en) | 2015-05-27 | 2016-05-16 | Film for solar cell back sheet, solar cell back sheet using the same, and solar cell |
CN201680023781.3A CN107534067B (en) | 2015-05-27 | 2016-05-16 | Film for solar cell back sheet, and solar cell |
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JP2015107210 | 2015-05-27 | ||
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PCT/JP2016/064417 WO2016190146A1 (en) | 2015-05-27 | 2016-05-16 | Film for solar-cell back sheet, solar-cell back sheet including same, and solar cell |
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JP (1) | JP6743698B2 (en) |
KR (1) | KR20180013845A (en) |
CN (1) | CN107534067B (en) |
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WO (1) | WO2016190146A1 (en) |
Cited By (3)
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WO2017110618A1 (en) * | 2015-12-24 | 2017-06-29 | 株式会社村田製作所 | Resin sheet, method for manufacturing resin sheet, and method for manufacturing multilayer resin substrate |
CN107553999A (en) * | 2017-09-08 | 2018-01-09 | 乐凯胶片股份有限公司 | A kind of PET sheet and its application |
CN108732877A (en) * | 2017-04-18 | 2018-11-02 | 佳能株式会社 | Electrophotographic photosensitive element, handle box and electronic photographing device |
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WO2019244313A1 (en) * | 2018-06-21 | 2019-12-26 | 三菱電機株式会社 | Data processing device, data processing method, and method for manufacturing solar cell module |
CN110079223A (en) * | 2019-05-15 | 2019-08-02 | 王崧 | It is a kind of it is high adherency, low permeable photovoltaic cell component packaging EVA adhesive film |
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2016
- 2016-05-16 WO PCT/JP2016/064417 patent/WO2016190146A1/en active Application Filing
- 2016-05-16 CN CN201680023781.3A patent/CN107534067B/en active Active
- 2016-05-16 JP JP2016537583A patent/JP6743698B2/en active Active
- 2016-05-16 KR KR1020177026257A patent/KR20180013845A/en unknown
- 2016-05-25 TW TW105116258A patent/TW201705509A/en unknown
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JP2002100788A (en) * | 2000-09-20 | 2002-04-05 | Mitsubishi Alum Co Ltd | Back sheet for solar battery cover material, and solar battery module using the same |
JP2003139926A (en) * | 2001-10-31 | 2003-05-14 | Toray Ind Inc | Optical reflection film and backlight device for image display using the same |
JP2012253203A (en) * | 2011-06-03 | 2012-12-20 | Toray Advanced Film Co Ltd | Rear surface protective sheet for solar cell module and solar cell module using the same |
JP2013235219A (en) * | 2012-05-11 | 2013-11-21 | Toray Ind Inc | Laminated polyester film |
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CN107553999A (en) * | 2017-09-08 | 2018-01-09 | 乐凯胶片股份有限公司 | A kind of PET sheet and its application |
Also Published As
Publication number | Publication date |
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CN107534067B (en) | 2020-07-07 |
KR20180013845A (en) | 2018-02-07 |
CN107534067A (en) | 2018-01-02 |
TW201705509A (en) | 2017-02-01 |
JP6743698B2 (en) | 2020-08-19 |
JPWO2016190146A1 (en) | 2018-04-12 |
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