WO2013100108A1 - 太陽電池用保護材 - Google Patents
太陽電池用保護材 Download PDFInfo
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- WO2013100108A1 WO2013100108A1 PCT/JP2012/083997 JP2012083997W WO2013100108A1 WO 2013100108 A1 WO2013100108 A1 WO 2013100108A1 JP 2012083997 W JP2012083997 W JP 2012083997W WO 2013100108 A1 WO2013100108 A1 WO 2013100108A1
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- WIPO (PCT)
- Prior art keywords
- protective material
- film
- solar cell
- moisture
- adhesive layer
- Prior art date
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Images
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Definitions
- the present invention relates to a protective material used for solar cells and the like, and more particularly, to a protective material for solar cells capable of maintaining moisture resistance and preventing the occurrence of delamination.
- a solar cell is made of an ethylene-vinyl acetate copolymer, polyethylene, polypropylene film or the like between a front protective sheet (hereinafter sometimes referred to as a front sheet) and a back protective sheet (hereinafter sometimes referred to as a back sheet). It is set as the structure which sealed the cell for solar cells with the sealing film.
- a solar cell is usually manufactured by laminating a front protective film, a sealing material, a power generation element, a sealing material, and a back protective film in this order, and bonding and integrating them by heating and melting.
- a solar cell protective material that is a front surface protection sheet or a back surface protection sheet of a solar cell, it is required to have excellent durability against ultraviolet rays. In addition, rusting of internal conductors and electrodes due to permeation of moisture and the like is required. In order to prevent this, it is extremely important to have excellent moisture resistance. Furthermore, it is desired to develop an excellent protective material that causes little deterioration in moisture resistance under long-term use or high-temperature conditions.
- a polyester adhesive is used for a moisture-proof film having a water vapor transmission rate of 0.22 g / m 2 / day based on a biaxially stretched polyester film, and a weather-resistant polyester film on the inorganic vapor deposition surface side.
- a protective material for a solar cell is prepared by pasting a polypropylene film on the back surface, and the moisture resistance after a 1000 hour test is evaluated at 85 ° C. and 85% humidity, and a proposal for preventing the moisture resistance from being lowered is made.
- a polyurethane adhesive layer is provided on both sides of a moisture-proof film having a water vapor transmission rate of 1 to 2 g / m 2 / day based on a biaxially stretched polyester film, and weather resistance is provided on both sides.
- a protective polyester film is manufactured by laminating a conductive polyester film, and the barrier performance and interlayer strength after a 1000 hour accelerated test at 85 ° C. and 85% humidity are evaluated, and a proposal for preventing deterioration of both characteristics is made.
- Patent Document 3 after a PVF film is bonded to a moisture-proof film having a water vapor transmission rate of 0.5 g / m 2 / day based on a biaxially stretched polyester film, using a two-component curable polyurethane adhesive.
- the moisture resistance and interlayer strength before and after the pressure cooker test (PCT) severe environmental test by high temperature and pressure, 105 ° C., 92 hours) are evaluated, and a proposal for preventing deterioration of the characteristics is made.
- PCT pressure cooker test
- each of the techniques disclosed in Patent Documents 1 to 3 relates to a laminate having a moisture-proof film having a water vapor transmission rate of 0.1 g / m 2 / day or more, and requires higher moisture resistance.
- a solar cell protective material such as a compound-based power generation element solar cell module
- long-term moisture-proofing properties in harsh environments that are replaced by accelerated durability tests such as the pressure cooker test (PCT) Maintenance and prevention of delamination at the edge of the protective material could not be sufficiently performed.
- PCT pressure cooker test
- a protective material for solar cells a material that is excellent in moisture proofing and prevention of delamination and that can maintain the moisture proof and prevention of delamination over a long period of time is desired.
- the problem of the present invention is that, with respect to the protective material for solar cells including a moisture-proof film having a water vapor transmission rate of less than 0.1 g / m 2 / day, the moisture-proof property does not deteriorate for a long time, and the occurrence of delamination is prevented.
- An object of the present invention is to provide a solar cell protective material that realizes a solar cell protective material excellent in flexibility and moisture resistance, prevents the performance of the solar cell from being lowered, and is effective in improving the durability of the solar cell.
- the present inventors have at least a fluorine resin film, an adhesive layer, and an inorganic layer on at least one surface of the base material, and a water vapor transmission rate of 0.1 g / m 2 / day.
- a protective material for a solar cell obtained by laminating a moisture-proof film of less than the protective material constituting layer P, and the protective material constituting layer P other than the fluorine-based resin film with respect to the width (W A ) of the fluorine-based resin film.
- the present invention [1] Protective material structure comprising at least a fluorine resin film, an adhesive layer, and a moisture-proof film having an inorganic layer on at least one surface of the substrate and having a water vapor transmission rate of less than 0.1 g / m 2 / day A solar cell protective material formed as a layer P, which is a ratio of the maximum width W P of the protective material constituting layer P other than the fluororesin film to the width W A of the fluororesin film (W P / W A ) a solar cell protective material with a value less than 1. [2] The solar cell protective material according to [1], wherein the W P / W A is 0.7 to 0.98.
- the adhesive layer has a tensile storage modulus of 5.0 ⁇ 10 4 to 5.0 ⁇ 10 5 Pa at 100 ° C., a frequency of 10 Hz, and a strain of 0.1%, and a thickness of 13 ⁇ m or more.
- a method for producing a solar cell protective material comprising sequentially performing the following steps (1) to (3): (1) Step of producing laminate X having an adhesive layer on moisture-proof film (2) Step of slitting both ends in width direction of laminate X to form laminate X ′ (3) On the adhesive layer the fluororesin film having a width W a than 'the width W X of the' stack X, a fluorine-based process both ends of the resin film bonded so as to protrude from both ends of the pressure-sensitive adhesive layer [13] the step ( In 1), a laminate X having a release sheet 1 on the pressure-sensitive adhesive layer is prepared, and after the step (2), before the fluororesin film is bonded, the release sheet The method for producing a protective material for a solar cell according to [12], which undergoes a step of peeling 1; [14] In the step (1), after the pressure-sensitive adhesive layer composition is applied on the release sheet 1 and dried to form a pressure-sensitive adhesive layer, a laminate X is formed by attaching
- the present invention there is no decrease in moisture resistance or occurrence of delamination even when used at high temperature and high humidity over a long period of time, excellent flexibility and moisture resistance, preventing a decrease in the performance of solar cells, and It is possible to provide a protective material for a highly moisture-proof solar cell that is effective for improving the durability of the solar cell.
- the solar cell protective material of the present invention is excellent in flexibility and moisture resistance, in which moisture resistance and interlaminar strength do not decrease even after heat treatment in a high heat environment, that is, heat lamination conditions.
- Sectional drawing which shows one Embodiment of the protective material for solar cells of this invention
- Sectional drawing which shows one use example of the protective material for solar cells of this invention
- the figure explaining the evaluation method of bending length The figure explaining the evaluation method of load bearing dent
- Sectional drawing which shows an example of the protective material for solar cells obtained by the manufacturing method of the conventional protective material for solar cells
- the protective material for solar cells can prevent moisture from entering from the exposed surface of the film by being laminated with a moisture-proof film, but it can be used for a long time as an alternative to accelerated testing in a high-temperature, high-humidity environment.
- the present inventors have configured the solar cell protective material to have at least a fluorine-based resin film, an adhesive layer, and an inorganic layer on at least one surface of the substrate, and a water vapor transmission rate of 0.1 g.
- the laminate is formed by laminating a moisture-proof film of less than / m 2 / day as a protective material constituting layer P, and the width of the protective material constituting layer P including the moisture-proof film other than the fluorine-based resin film is By making the configuration shorter than the width, as illustrated in FIG. 2, the width of the sealing agent (20) on the solar cell (30) is shorter than the width of the fluororesin film (1) during vacuum lamination. Realize both the prevention of moisture-proof deterioration and the prevention of delamination from the end by the effect of wrapping around the end face of the pressure-sensitive adhesive layer (21) and moisture-proof film (3) and sealing the end face. To find It was.
- the present invention has at least a fluorine resin film (1), an adhesive layer (21), and an inorganic layer on at least one surface of a substrate, and has a water vapor transmission rate. a 0. 1g / m 2 / day less than the moisture-proof film (3) and the protective material constituting layer P formed by laminating a solar cell protective member (10), to the width W a of the fluorine resin film,
- the present invention relates to a solar cell protective material in which the ratio (W P / W A ) of the maximum width W P of the protective material constituent layer P other than the fluorine resin film is smaller than 1.
- the solar cell protective material of the present invention has hydrolysis resistance and weather resistance, and has a fluororesin film in order to impart long-term durability.
- the fluororesin film preferably has weather resistance.
- fluororesin examples include polytetrafluoroethylene (PTFE), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene / hexa Fluoropropylene copolymer (FEP), tetrafluoroethylene / ethylene copolymer (ETFE), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF) and the like are preferably used.
- PTFE polytetrafluoroethylene
- PFA perfluoroalkyl vinyl ether copolymer
- FEP tetrafluoroethylene / hexa Fluoropropylene copolymer
- ETFE tetrafluoroethylene / ethylene copolymer
- PCTFE polychlorotrifluoroethylene
- PVDF polyvinylidene fluoride
- PVF polyviny
- tetrafluoroethylene / ethylene copolymer (ETFE) and tetrafluoroethylene / hexafluoropropylene copolymer (FEP) are more preferably used as the resin.
- the fluorine resin film preferably has a small characteristic change during vacuum lamination, temperature change or humidity change. Therefore, in the case of a fluorine-based film having a large shrinkage rate, a film having a low shrinkage rate by prior heat treatment is preferable.
- W P / W A is preferably 0.7 to 0.98, more preferably 0.75 to 0.95 for more stable delamination prevention, and 0.8 to 0.92 is more preferable.
- the “film width” means the length in the lateral direction with respect to the length direction of the film unwound from the roll when the protective material is provided in a roll, and is provided in a single sheet. The short side of the four sides.
- additives can be added to the fluororesin film as necessary.
- the additive include, but are not limited to, an ultraviolet absorber, a weather resistance stabilizer, an antioxidant, an antistatic agent, and an antiblocking agent.
- the thickness of the fluororesin film is generally about 20 to 200 ⁇ m, preferably 20 to 100 ⁇ m, more preferably 20 to 60 ⁇ m from the viewpoint of film handling and cost.
- the moisture-proof film has at least an inorganic layer formed on at least one surface of the substrate and the water vapor transmission rate thereof is less than 0.1 g / m 2 / day. Since the protective material for solar cells of the present invention is desired to maintain high moisture resistance for a long period of time, the initial moisture resistance needs to be a certain level or more. Accordingly, in the present invention, the moisture-proof film is less than the water vapor transmission rate of 0.1g / m 2 / day, preferably not more than 0.05g / m 2 / day, more preferably, 0.03 g / m 2 / Day or less.
- the moisture-proof film is preferably transparent when the solar cell protective material is used as a front sheet used on the light-receiving surface side.
- the thickness of the moisture-proof film is generally 5 to 300 ⁇ m, and preferably 25 to 250 ⁇ m, more preferably 38 from the viewpoints of curling suppression, voltage resistance, cushioning, productivity, and handleability of the solar cell protective material. It is ⁇ 200 ⁇ m, more preferably 50 to 180 ⁇ m.
- a resin film is preferable, and any material can be used without particular limitation as long as it is a resin that can be used for an ordinary solar cell material.
- polyolefins such as homopolymers or copolymers such as ethylene, propylene and butene; amorphous polyolefins such as cyclic polyolefins; polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); nylon 6 , Polyamides such as nylon 66, nylon 12 and copolymer nylon; ethylene-vinyl acetate copolymer partial hydrolyzate (EVOH), polyimide, polyetherimide, polysulfone, polyethersulfone, polyetheretherketone, polycarbonate, polyvinyl Examples include butyral, polyarylate, fluororesin, acrylic resin, biodegradable resin, and the like, and among them, a thermoplastic resin is preferable.
- polyesters, polyamides, and polyolefins are preferable from the viewpoints of film properties and costs
- polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) are particularly preferable from the viewpoints of surface smoothness, film strength, heat resistance, and the like.
- additives can be added to the substrate as necessary.
- the additive include, but are not limited to, an antistatic agent, an ultraviolet absorber, a plasticizer, a lubricant, a filler, a colorant, a weathering stabilizer, an antiblocking agent, and an antioxidant.
- ultraviolet absorbers examples include various types such as benzophenone-based, benzotriazole-based, triazine-based, salicylic acid ester-based, and various commercially available products can be applied.
- benzophenone ultraviolet absorbers examples include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-n.
- benzotriazole ultraviolet absorber examples include hydroxyphenyl-substituted benzotriazole compounds such as 2- (2-hydroxy-5-methylphenyl) benzotriazole and 2- (2-hydroxy-5-tert-butylphenyl).
- Benzotriazole 2- (2-hydroxy-3,5-dimethylphenyl) benzotriazole, 2- (2-methyl-4-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-3-methyl-5-t- Butylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-t-amylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-t-butylphenyl) benzotriazole, etc. be able to.
- triazine ultraviolet absorbers examples include 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2- ( Examples include 4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyloxy) phenol.
- salicylic acid esters include phenyl salicylate and p-octylphenyl salicylate.
- the content of the ultraviolet absorber in the substrate is usually about 0.01 to 2.0% by mass, preferably 0.05 to 0.5% by mass.
- Hindered amine light stabilizers can be used as a weather stabilizer that imparts weather resistance in addition to the above ultraviolet absorbers.
- a hindered amine light stabilizer does not absorb ultraviolet rays like an ultraviolet absorber, but exhibits a remarkable synergistic effect when used together with an ultraviolet absorber.
- hindered amine light stabilizers include dimethyl-1- (2-hydroxyethyl) succinate-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly [ ⁇ 6- (1,1 , 3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl ⁇ ⁇ (2,2,6,6-tetramethyl-4-piperidyl) imino ⁇ hexamethylene ⁇ (2, 2,6,6-tetramethyl-4-piperidyl) imino ⁇ ], N, N′-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2, 6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2- (3 , 5-Di-tert-4 Hydroxybenzyl) -2
- antioxidant various commercial products can be used, and various types such as monophenol type, bisphenol type, polymer type phenol type, sulfur type and phosphite type can be exemplified.
- monophenols include 2,6-di-tert-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-tert-butyl-4-ethylphenol, and the like.
- Bisphenols include 2,2′-methylene-bis- (4-methyl-6-tert-butylphenol), 2,2′-methylene-bis- (4-ethyl-6-tert-butylphenol), 4,4 '-Thiobis- (3-methyl-6-tert-butylphenol), 4,4'-butylidene-bis- (3-methyl-6-tert-butylphenol), 3,9-bis [ ⁇ 1,1-dimethyl- 2- ⁇ - (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ⁇ ethyl ⁇ 2,4,9,10-tetraoxaspiro] 5,5-undecane.
- Examples of the high molecular phenolic group include 1,1,3-tris- (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3 , 5-di-tert-butyl-4-bidoxybenzyl) benzene, tetrakis- ⁇ methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate ⁇ methane, bis ⁇ (3,3′-bis-4′-hydroxy-3′-tert-butylphenyl) butyric acid ⁇ glycol ester, 1,3,5-tris (3 ′, 5′-di-tert-butyl-4 Examples include '-hydroxybenzyl) -s-triazine-2,4,6- (1H, 3H, 5H) trione, triphenol (vitamin E), and the like.
- sulfur-based compounds include dilauryl thiodipropionate, dimyr
- phosphites include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, 4,4′-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl) phosphite, Crick neopentanetetrayl bis (octadecyl phosphite), tris (mono and / or di) phenyl phosphite, diisodecyl pentaerythritol diphosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- Oxide, 10- (3,5-di-tert-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10 pho
- phenol-based and phosphite-based antioxidants are preferably used in view of the effect of the antioxidant, thermal stability, economy, etc., and it is more preferable to use a combination of both.
- the addition amount of the antioxidant is usually about 0.1 to 1% by mass in the base material, and 0.2 to 0.5% by mass is preferably added.
- the resin film as the substrate is formed by using the above raw materials, but may be unstretched or stretched. Further, it may be either a single layer or a multilayer.
- a substrate can be produced by a conventionally known method. For example, the raw material is melted by an extruder, extruded by an annular die or a T die, and rapidly cooled to be substantially amorphous and not oriented. A stretched film can be produced. Further, by using a multilayer die, it is possible to produce a single layer film made of one kind of resin, a multilayer film made of one kind of resin, a multilayer film made of various kinds of resins, and the like.
- the unstretched film is subjected to a known method such as uniaxial stretching, tenter sequential biaxial stretching, tenter simultaneous biaxial stretching, tubular simultaneous biaxial stretching, or the like.
- a film stretched in a uniaxial direction or a biaxial direction can be produced by stretching in a direction (horizontal axis) perpendicular thereto.
- the draw ratio can be arbitrarily set, the 150 ° C. heat shrinkage ratio is preferably 0.01 to 5%, more preferably 0.01 to 2%.
- a biaxially stretched polyethylene terephthalate film a biaxially stretched polyethylene naphthalate film, a polyethylene terephthalate and / or a coextruded biaxially stretched film of polyethylene naphthalate and another resin is preferable.
- the thickness of the base material of the moisture-proof film is generally 5 to 300 ⁇ m, and preferably 25 to 250 ⁇ m from the viewpoint of curling suppression, voltage resistance, cushioning, and productivity and handleability of the solar cell protective material. More preferably, it is 38 to 200 ⁇ m, and still more preferably 50 to 180 ⁇ m.
- the thickness of the base material constituting the moisture-proof film is 25 ⁇ m or more, the solar cell protective material is excellent in curling suppression effect and excellent in voltage resistance, impact resistance, and cushioning properties.
- the thickness of the said base material exceeds 300 micrometers, it is unpreferable at the point of productivity or handleability.
- the thickness of the base material of the moisture-proof film is equal to or greater than the thickness of the fluororesin film from the viewpoint of curling suppression.
- the ratio T A ′ / T B ′ of the thickness T A ′ of the fluororesin film to the thickness T B ′ of the base material of the moisture-proof film is preferably 1.0 or less. From the viewpoint of curling generation suppression, T A ′ / T B ′ is more preferably 0.07 to 0.8, and still more preferably 0.2 to 0.7.
- the anchor coat layer includes a solvent-based or water-based polyester resin; an alcoholic hydroxyl group-containing resin such as an isocyanate resin, a urethane resin, an acrylic resin, a modified vinyl resin, or a vinyl alcohol resin; a vinyl butyral resin, a nitrocellulose resin, or an oxazoline group Resins, carbodiimide group-containing resins, melamine group-containing resins, epoxy group-containing resins, modified styrene resins, modified silicone resins and the like can be used alone or in combination of two or more.
- an alcoholic hydroxyl group-containing resin such as an isocyanate resin, a urethane resin, an acrylic resin, a modified vinyl resin, or a vinyl alcohol resin
- a vinyl butyral resin a nitrocellulose resin, or an oxazoline group
- an alkyl titanate, a silane coupling agent, a titanium coupling agent, an ultraviolet absorber, a weathering stabilizer, a lubricant, an anti-blocking agent, an antioxidant and the like can be added to the anchor coat layer as necessary.
- the ultraviolet absorber, weather stabilizer and antioxidant the same ones as those used for the aforementioned substrate can be used, and the weather stabilizer and / or ultraviolet absorber is copolymerized with the resin described above.
- the polymer type can also be used.
- the thickness of the anchor coat layer is preferably 10 to 200 nm, and more preferably 10 to 100 nm, from the viewpoint of improving the adhesion with the inorganic layer.
- a known coating method is appropriately adopted as the formation method.
- a reverse roll coater, a gravure coater, a rod coater, an air doctor coater, or a coating method using a spray can be used.
- the substrate may be immersed in a resin solution.
- the solvent can be evaporated using a known drying method such as hot air drying at a temperature of about 80 to 200 ° C., heat drying such as hot roll drying, or infrared drying.
- the crosslinking process by electron beam irradiation can also be performed.
- the formation of the anchor coat layer may be a method performed in the middle of the substrate production line (inline) or a method performed after the substrate production (offline).
- inorganic layer examples of the inorganic substance constituting the inorganic layer include silicon, aluminum, magnesium, zinc, tin, nickel, titanium and the like; or their oxides, carbides, nitrides; or a mixture thereof.
- silicon oxide, silicon nitride, silicon oxynitride, aluminum oxide, and diamond-like carbon are preferable because they are transparent.
- silicon oxide, silicon nitride, silicon oxynitride, and aluminum oxide are preferable because high gas barrier properties can be stably maintained.
- any method such as a vapor deposition method and a coating method can be used, but the vapor deposition method is preferable in that a uniform thin film having a high gas barrier property can be obtained.
- This vapor deposition method includes any method such as physical vapor deposition (PVD) or chemical vapor deposition (CVD). Examples of physical vapor deposition include vacuum vapor deposition, ion plating, and sputtering, and chemical vapor deposition includes plasma CVD using plasma and a catalyst that thermally decomposes a material gas using a heated catalyst body. Examples include chemical vapor deposition (Cat-CVD).
- the inorganic layer may be a single layer or a multilayer. In the case of multiple layers, the same film formation method may be used, or a different film formation method may be used for each layer. From the viewpoint of sex.
- the multilayer structure includes an inorganic layer formed by a vacuum deposition method, an inorganic layer formed by a chemical vapor deposition method, and an inorganic layer formed by a vacuum deposition method in this order. Is preferred.
- each layer may consist of the same inorganic substance, or may consist of a different inorganic substance.
- the thickness of the inorganic layer is preferably 10 to 1000 nm, more preferably 20 to 800 nm, and still more preferably 20 to 600 nm, from the viewpoint of stable moisture resistance.
- a pressure-sensitive adhesive diluted with a solvent is formed on the resin film or the like to a predetermined thickness.
- the solvent is evaporated by applying and drying usually in the range of 70 ° C. to 140 ° C. to form an adhesive layer on a resin film or the like.
- another resin film or the like is bonded to the pressure-sensitive adhesive layer side.
- it is prepared through curing at a predetermined temperature. Curing is performed, for example, in the range of 30 ° C. to 80 ° C. for 1 day to 1 week.
- the degree of softness and thickness is reduced to some extent from the viewpoint of reducing the stress due to shrinkage of the resin film resulting from residual strain from being transmitted to the inorganic layer, protecting the inorganic layer and preventing deterioration of moisture resistance.
- the adhesive layer preferably has a tensile storage modulus of 5.0 ⁇ 10 4 to 5.0 ⁇ 10 5 Pa at 100 ° C., a frequency of 10 Hz, and a strain of 0.1%. That is, when the tensile storage elastic modulus at 100 ° C.
- the tensile storage modulus of the pressure-sensitive adhesive layer at 100 ° C., frequency 10 Hz, and strain 0.1% is preferably 7.0 ⁇ 10 4 Pa to 5.0 ⁇ 10 5 Pa, and 1.0 ⁇ 10 5 Pa. More preferably, it is ⁇ 5.0 ⁇ 10 5 Pa.
- the pressure-sensitive adhesive layer has a tensile storage modulus of 1.0 ⁇ 10 6 Pa or more at 20 ° C., a frequency of 10 Hz, and a strain of 0.1% from the viewpoint of maintaining adhesive strength at normal temperature (20 ° C.). preferable.
- a cause of inferior moisture resistance of the protective material for solar cells inferior in moisture resistance of the adhesive itself. For this, it is effective to select an adhesive that is difficult to hydrolyze.
- the pressure-sensitive adhesive used in the pressure-sensitive adhesive layer preferably includes an acrylic pressure-sensitive adhesive, and more preferably includes an acrylic pressure-sensitive adhesive as a main component.
- the term “main component” is intended to allow other components to be included within a range that does not hinder the effects of the present invention.
- the specific content is not limited, the main component is generally 50 parts by mass or more, preferably 65 parts by mass or more, more preferably 100 parts by mass as a whole of the constituent components of the pressure-sensitive adhesive layer. Is 80 parts by mass or more and 100 parts by mass or less.
- acrylic pressure-sensitive adhesive examples include a main monomer component having a low glass transition point (Tg) that imparts tackiness, a comonomer component having a high Tg that imparts adhesiveness and cohesive force, and a functional group-containing monomer for improving crosslinking and adhesion.
- Tg glass transition point
- comonomer component having a high Tg that imparts adhesiveness and cohesive force
- a functional group-containing monomer for improving crosslinking and adhesion examples of the acrylic (co) polymer.
- acrylic acid esters such as ethyl acrylate, butyl acrylate, amyl acrylate, 2-ethylhexyl acrylate, and octyl acrylate. These may be used alone or in combination of two or more.
- comonomer component of the acrylic (co) polymer methyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, vinyl acetate, styrene, acrylonitrile Etc. These may be used alone or in combination of two or more.
- Examples of the functional group-containing monomer component of the acrylic (co) polymer include, for example, carboxyl group-containing monomers such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxy Examples thereof include hydroxyl group-containing monomers such as propyl (meth) acrylate and N-methylolacrylamide, acrylamide, methacrylamide and glycidyl methacrylate. These may be used alone or in combination of two or more.
- the initiator used for polymerization of the monomer component of the acrylic (co) polymer examples include azobisisobutylnitrile, benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide, and the like.
- the copolymerization form of the acrylic (co) polymer used as the main component of the said acrylic adhesive Any of a random, a block, and a graft copolymer may be sufficient.
- the molecular weight when the acrylic pressure-sensitive adhesive is the above-mentioned acrylic (co) polymer is preferably 300,000 to 1,500,000 in terms of mass average molecular weight, and more preferably 400,000 to 1,000,000. preferable. By setting the mass average molecular weight within the above range, adhesion to the adherend and adhesion durability can be secured, and floating and peeling can be suppressed.
- the content of the functional group-containing monomer component unit is preferably in the range of 1 to 25% by mass.
- the adhesion to the adherend and the degree of crosslinking are ensured, and the tensile storage modulus of the pressure-sensitive adhesive layer is 5.degree. At 100.degree. C., frequency 10 Hz, and strain 0.1%.
- the value can be in the range of 0 ⁇ 10 4 to 5.0 ⁇ 10 5 Pa.
- a strong chemical bond is formed between the pressure-sensitive adhesive layer and the inorganic layer, a large stress is applied to the inorganic layer due to a change in the viscoelasticity of the pressure-sensitive adhesive layer or decomposition or shrinkage of the pressure-sensitive adhesive layer coating film.
- a factor for forming the bond is considered to be due to a reaction between a defective portion of an inorganic layer such as a SiO x layer and a hydroxyl group in the pressure-sensitive adhesive layer.
- the number of reactive functional groups in the pressure-sensitive adhesive may be reduced, and it is preferable to reduce the number of unreacted functional groups after application and curing of the pressure-sensitive adhesive layer.
- the pressure-sensitive adhesive layer in the present invention preferably contains an ultraviolet absorber.
- an ultraviolet absorber the same thing as what is used for the above-mentioned base material can be used.
- the pressure-sensitive adhesive layer may be formed by directly applying to a fluororesin film or a moisture-proof film, or the pressure-sensitive adhesive may be applied to a release-treated surface of a release sheet that has been subjected to a release treatment. Can also be formed by bonding to a moisture-proof film.
- the pressure-sensitive adhesive to be coated (hereinafter referred to as coating liquid) includes an organic solvent system, an emulsion system, and a solvent-free system, but an organic solvent system is desirable for uses such as solar cell members that are required to have water resistance.
- organic solvent used in the organic solvent-based coating liquid examples include toluene, xylene, methanol, ethanol, isobutanol, n-butanol, acetone, methyl ethyl ketone, ethyl acetate, and tetrahydrofuran. These may be used alone or in combination of two or more.
- the coating liquid is preferably prepared using these organic solvents so that the solid content concentration is in the range of 10 to 50% by mass.
- Coating of the coating liquid is, for example, conventionally known coating methods such as bar coating, roll coating, knife coating, roll knife coating, die coating, gravure coating, air doctor coating, doctor blade coating, etc. It can be done by a method.
- the pressure-sensitive adhesive layer is formed by drying treatment usually at a temperature of 70 to 110 ° C. for about 1 to 5 minutes.
- the thickness of the pressure-sensitive adhesive layer is preferably 13 ⁇ m or more, more preferably 15 ⁇ m or more, still more preferably 18 ⁇ m or more, and most preferably 20 ⁇ m or more from the viewpoint of obtaining sufficient adhesive strength. Further, from the viewpoint of providing a coatable thickness, the thickness is preferably 100 ⁇ m or less, and more preferably 50 ⁇ m or less.
- the solar cell protective material of the present invention preferably has at least the fluorine-based resin film, the pressure-sensitive adhesive layer, and the moisture-proof film in this order, and when used for a front sheet, has a fluorine-based resin film on the exposed side. It is preferable.
- the solar cell protective material when laminating a fluororesin film and a moisture-proof film through an adhesive layer, when the laminate is made with the inorganic layer side of the moisture-proof film facing the fluororesin film side, the solar cell protective material is stored and used. It is preferable because damage to the inorganic layer can be reduced.
- the solar cell protective material of the present invention is intended to further improve physical properties (flexibility, heat resistance, transparency, adhesiveness, etc.), molding processability, economic efficiency, etc.
- any layer that can be used for the solar cell protective material can be usually used.
- a sealing material, a light collecting material, a conductive material, Layers such as a heat transfer material and a moisture adsorbing material can be laminated.
- Various additives can be added to these other layers as necessary. Examples of the additive include, but are not limited to, an antistatic agent, an ultraviolet absorber, a plasticizer, a lubricant, a filler, a colorant, a weathering stabilizer, an antiblocking agent, and an antioxidant.
- the ultraviolet absorber, the weather resistance stabilizer and the antioxidant the same materials as those used for the above-mentioned substrate can be used.
- the thickness of the solar cell protective material of the present invention is not particularly limited, but is preferably 60 to 600 ⁇ m, more preferably 75 to 350 ⁇ m, from the viewpoint of curling suppression and voltage resistance.
- the thickness is preferably 90 to 300 ⁇ m.
- the solar cell protective material of the present invention uses a moisture-proof film having an inorganic layer as a base material and a moisture permeability of less than 0.1 g / m 2 / day. preferably not more than 0.1g / m 2 / day, more preferably, to not more than 0.05g / m 2 / day.
- the solar cell protective material of the present invention is excellent in initial moisture resistance, and also excellent in moisture resistance and prevention of delamination even when stored in a high temperature and high humidity environment.
- the moisture-proof property is determined by the degree of decrease in moisture-proof property due to the continuous high-temperature and high-humidity environment by the vacuum lamination and the pressure coker test according to JIS C 60068-2-66, that is,
- the water vapor transmission rate after the high temperature and high humidity environment / initial water vapor transmission rate) can be usually 25 or less, preferably 15 or less, more preferably 10 or less, and even more preferably 2 or less.
- the “initial moisture resistance” of the protective material for solar cells in the present invention refers to moisture resistance before the member receives a history of heat, etc. in a high temperature and high humidity environment such as vacuum lameet conditions. It means the value before sex degradation occurs.
- Each moisture-proof property in the present invention can be evaluated according to various conditions of JISJZ0222 “moisture-proof packaging container moisture permeability test method” and JIS Z0208 “moisture-proof packaging material moisture permeability test method (cup method)”.
- the occurrence of curling is suppressed by the thickness of the base material of the moisture-proof film being 25 to 250 ⁇ m.
- the thickness of the protective material for solar cells is 90 ⁇ m or more, the voltage resistance and cushioning properties are also excellent.
- the withstand voltage can be evaluated, for example, by measuring a partial discharge voltage. Specifically, it can be evaluated by the method described in the examples.
- the protective material for solar cells of the present invention preferably has a partial discharge voltage measured in accordance with IEC60664-1: 2007 Clause 6.1.3.5 of 400 V or more, more preferably 600 V or more. More preferably, it is 800 V or more.
- the encapsulating material-integrated protective material of the present invention is obtained by further laminating an encapsulating material layer on the moisture-proof film side of the solar cell protective material of the present invention described above.
- a sealing material integrated protective material in which a sealing material layer is laminated in advance, each of the front sheet, the sealing material, the power generating element, the sealing material, and the back sheet in the vacuum laminating process in the solar cell module manufacturing described later. Can be reduced, and the efficiency of solar cell module manufacturing can be improved.
- examples of the sealing material constituting the sealing material layer include a silicone resin-based sealing material, an ethylene-vinyl acetate copolymer, and ethylene and ⁇ -olefin.
- a random copolymer etc. are mentioned.
- examples of the ⁇ -olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 3-methyl-butene-1, 4-methyl -Pentene-1 and the like.
- the width W D of the encapsulating material layer is smaller than the width W A of the fluororesin film, and the maximum width W P of the protective material constituting layer other than the fluororesin film. Larger is preferred. Thereby, at the time of vacuum lamination, the end surface of the protective material constituting layer other than the fluorine-based resin film can be sealed with the sealing material, and the moisture-proof deterioration and delamination of the protective material can be prevented.
- the thickness of the laminated sealing material layer is preferably 200 to 750 ⁇ m, more preferably 300 to 600 ⁇ m from the viewpoint of protecting the solar cell element.
- the method for laminating the sealing material layer on the solar cell protective material of the present invention a known method can be used. For example, what is necessary is just to laminate
- the same adhesive as described above, or a known adhesive such as a solution-type adhesive, a thermosetting adhesive, or a hot-melt adhesive can be used.
- the adhesive preferably includes a polyurethane adhesive, and more preferably includes a polyurethane adhesive as a main component.
- the roll-like material of the present invention is formed by winding the above-described protective material for solar cell or the protective material integrated protective material of the present invention. By making it into a roll-like product, the subsequent processability, transportability, and productivity can be improved, and the appearance can be easily protected.
- the winding length is preferably 50 m or more, and more preferably 100 m or more.
- the roll-like product with a cover sheet of the present invention is a roll-shaped product obtained by winding the solar cell protective material or the sealing material-integrated protective material of the present invention described above, of the surfaces of the roll-shaped product. And covering at least a part of the portion corresponding to the portion from which the fluororesin film protrudes with a cover sheet having a bending length of 70 mm or less measured under the following conditions and a load-bearing dent of 0.1 or less. It will be.
- the bending length is an index indicating how easily the cover sheet or the like is bent.
- the temperature condition of a measurement is about 23 degreeC.
- a plate having a bottom surface of 20 mm ⁇ 20 mm is first placed on the portion of the sample table, and then a 5 kg weight is placed on the plate.
- the height of the plate is about 5 to 15 mm, and the material is not particularly limited, and examples thereof include a glass plate and an iron plate.
- [Load dent] (1) Collect a 100 mm square sample. (2) A sample is placed on a glass plate having a thickness of 20 mm, a steel ball having a diameter of 5 mm and a weight of 0.5 g is placed on the center of the sample, and a load of 2 kg is further applied on the steel ball. (3) The dent “d” (unit: ⁇ m) of the sample is measured, and the ratio “d / t” to the thickness “t” (unit: ⁇ m) of the sample is defined as a load-bearing dent.
- the load bearing dent is an index indicating the difficulty of the dent of the cover sheet or the like.
- the depth “d” of the sample measures the depth of the deepest recess.
- the protective material for a solar cell or the sealing material-integrated protective material of the present invention described above has a wide width of the fluororesin film, the film has a protruding portion that protrudes from the other protective material constituting layers. Therefore, the roll-shaped object which wound up the protective material for solar cells of this invention mentioned above or the sealing material integrated protective material also has such a protrusion part. And the roll-shaped thing which has such a protrusion may bend a protrusion part at the time of transportation, etc., or a wrinkle may arise.
- the roll-like product with a cover sheet of the present invention has a protruding portion at the time of transportation or the like by covering at least a part of the surface of the roll-like product with a cover sheet corresponding to the location where the fluororesin film protrudes. This prevents bending and wrinkling.
- the cover sheet may cover at least a portion corresponding to the portion where the fluororesin film protrudes, but it is preferable to cover 50% or more of the portion, and it is more preferable to cover the entire portion. Moreover, a still more preferable aspect is to cover the entire surface of the roll-shaped material.
- the ratio ([W K ] / [W A ]) between the width W k of the cover sheet and the width W A of the fluororesin film is preferably 1 or more, more preferably 1.05 or more. More preferably, it is 15 or more. Further, from the viewpoint of handling properties, [W K ] / [W A ] is preferably 1.5 or less, and more preferably 1.3 or less.
- the object of the present invention can be achieved by covering the surface of the roll-shaped object with the cover sheet. Furthermore, in consideration of the load from the left-right direction of the roll-shaped object, the side surface of the roll-shaped object may be covered with a cover sheet.
- the bending length is preferably 60 mm or less, more preferably 50 mm or less, and further preferably 40 mm or less.
- the load bearing dent is preferably 0.05 or less, and more preferably 0.03 or less.
- the bending length is 5 mm or more, and the load dent is 0.01 or more. It is preferable that the bending length is 10 mm or more, and the load bearing dent is more preferably 0.02 or more.
- Cover sheets include polyolefins such as homopolymers or copolymers of ethylene, propylene, butene, etc .; amorphous polyolefins such as cyclic polyolefin (Cyclo-Olefin-Polymer: COP); polyethylene terephthalate (PET), polyethylene naphthalate Polyester such as (PEN); polyamide such as nylon 6, nylon 66, nylon 12, copolymer nylon; polyimide, triacetyl cellulose (TAC), cellulose diacetate, cellulose acetate butyrate, polyether sulfone, polysulfone, polymethyl Use plastic sheets such as pentene, polyvinyl chloride, polyvinyl acetal, polyether ketone, polymethyl methacrylate, polycarbonate, polyurethane, etc. It can be.
- the thickness of the cover sheet is preferably 50 ⁇ m to 2 mm, more preferably 100 ⁇ m to 1 mm.
- the cover sheet may cause blocking with the roll.
- the cover sheet positioned below the roll-shaped object is likely to cause blocking between the roll-shaped object and the cover sheet due to the weight of the roll-shaped object.
- the cover sheet preferably has a predetermined surface roughness, and specifically, a cover sheet having an arithmetic average roughness Ra of JIS B 0601 of 50 nm or more is suitable.
- the cover sheet preferably has a cushioning property while having a predetermined strength.
- the foamed plastic film based on the plastic sheet illustrated above is suitable.
- a foamed plastic film is opaque, it is suitable also in the point which is easy to distinguish when the transparency of a laminated body is high, the point which is excellent in blocking prevention property, and the point which is excellent also in handling property since it is lightweight.
- the cover sheet only needs to be configured to cover the surface of the roll-shaped object, but the cover sheet and the roll-shaped object are used with a tape or an adhesive so that the state does not collapse during transportation. It is preferable to partially stick together. Moreover, when the cover sheet covers the entire surface of the roll-shaped object, it is preferable to fix both ends of the cover sheet in the length direction with a tape or an adhesive.
- the cover sheet and the fluororesin film preferably satisfy the following conditions (a ′) and / or (b ′).
- a ′) [Bend length of cover sheet] / [Bend length of fluorine resin film] is 2 or less
- (b ′) [Load dent of cover sheet] / [Load dent of fluorine resin film] 2 or less By satisfying the condition (a ′) or (b ′), it is possible to easily prevent the protrusion from being bent or wrinkled. By satisfying the conditions (a ′) and (b ′), This makes it easier to prevent bending and wrinkles.
- (a ′) [the bending length of the cover sheet] / [the bending length of the fluororesin film] is preferably 1 or less, and more preferably 0.1 to 0.6.
- (b ′) [Load dent of cover sheet] / [Load dent of fluorine resin film] is more preferably 1 or less, further preferably 0.5 or less, and 0.01 to More preferably, it is 0.2.
- the method for producing a protective material for solar cell of the present invention sequentially performs the following steps (1) to (3).
- Step of producing laminate X having an adhesive layer on moisture-proof film (2) Step of slitting both ends in width direction of laminate X to form laminate X ′ (3)
- the fluororesin film having a width W a than 'the width W X of the' stack X both ends of the fluororesin film is bonded so as to protrude from both ends of the pressure-sensitive adhesive layer step
- a laminate X having an adhesive layer on a moisture-proof film is produced.
- the laminated body X should just have an adhesive layer (21) on a moisture-proof film (3), as shown in FIG.
- the laminated body X may have another adhesive layer, another functional layer, etc. in the surface on the opposite side of a moisture-proof film (3).
- the laminate X can be produced by applying an adhesive layer composition on a moisture-proof film and drying to form an adhesive layer. Moreover, an adhesive layer can also be formed by transferring the adhesive layer formed on another base material to a moisture-proof film.
- the laminated body X when the laminated body X has a release sheet, the laminated body X can also be produced by bonding the release sheet after forming the pressure-sensitive adhesive layer on the moisture-proof film, but on the release sheet.
- the adhesive layer composition is preferably applied and dried to form an adhesive layer, and then a moisture-proof film is bonded to the adhesive layer.
- a laminate X having an adhesive layer on the moisture-proof film can be easily produced by using a material having excellent heat resistance as the release sheet. This is preferable in terms of points.
- the conveyance speed of the moisture-proof film or release sheet is preferably 5 to 15 m / min.
- the conveyance speed of the moisture-proof film or release sheet is preferably 5 to 15 m / min.
- Step (2) both ends in the width direction of the stacked body X are slit to form a stacked body X ′.
- the width of the pressure-sensitive adhesive layer (21) is narrower than the width of the moisture-proof film (3) and the release sheet. There is a difference in level. This is because when the pressure-sensitive adhesive layer composition is applied so that the width of the pressure-sensitive adhesive layer matches the width of the base material, the pressure-sensitive adhesive layer composition wraps around the back side of the base material, resulting in a manufacturing failure. This is unavoidable for manufacturing reasons.
- the position of the slit is preferably a position where all of the materials constituting the laminate X (moisture-proof film, pressure-sensitive adhesive layer, release sheet) can be slit.
- the slit method is not particularly limited and can be performed using a known slitter.
- the laminated body X has a release sheet
- Step (3) a fluorine-based resin film having a width W A wider than the width W X ′ of the laminate X ′ is placed on the pressure-sensitive adhesive layer, and both ends of the fluorine-based resin film protrude from both ends of the pressure-sensitive adhesive layer. Paste together.
- the fluororesin film (1) protrudes from both ends of the pressure-sensitive adhesive layer (21) and the moisture-proof film (3) in the width direction. It is a laminate having a portion 11.
- the laminate X ′ and the fluororesin film can be bonded using a known laminating apparatus or the like.
- an EPC (edge position control) device is used to laminate the laminate X ′ and the fluorine-based film. It is preferable to adjust the position of the width with the resin film.
- step (3) it is preferable that the transport speed of the laminate X ′ and the fluororesin film is 20 to 30 m / min.
- the transport speed of the laminate X ′ and the fluororesin film is 20 to 30 m / min.
- 20 m / min or more production efficiency can be increased, and by setting it to 30 m / min or less, it is easy to perform width adjustment by an EPC apparatus.
- the solar cell protective material of the present invention can be used as a solar cell surface protective material as it is, or further bonded to a glass plate or the like.
- a solar cell module can be manufactured by using the solar cell protective material of the present invention in a layer structure of a surface protective material such as a front sheet and a back sheet, and fixing the solar cell element.
- a solar cell module various types can be exemplified.
- the solar cell protective material of the present invention is used as a front sheet
- a solar cell module produced using a sealing material, a solar cell element, and a back sheet can be mentioned.
- front sheet protection material for solar cell of the present invention
- sealing material sealing resin layer
- solar cell element sealing material (sealing resin layer)
- back sheet A structure in which a sealing material and a front sheet (protective material for solar cell of the present invention) are formed on a solar cell element formed on the inner peripheral surface of the sheet
- front sheet protection for solar cell of the present invention
- a sealing material and a back sheet are formed on a solar cell element formed on the inner peripheral surface of the material), for example, an amorphous solar cell element produced by sputtering on a fluororesin-based transparent protective material. The thing etc. can be mentioned.
- Examples of solar cell elements include single crystal silicon type, polycrystalline silicon type, amorphous silicon type, gallium-arsenic, copper-indium-selenium, copper-indium-gallium-selenium, cadmium-tellurium, III-V group and II -VI group compound semiconductor type, dye sensitized type, organic thin film type, and the like.
- the moisture-proof property is less than 0.1 g / m 2 / day in terms of water vapor transmission rate depending on the type of the solar cell power generation element.
- the other members constituting the solar cell module manufactured using the solar cell protective material of the present invention are not particularly limited.
- the solar cell protective material of the present invention may be used for both the front sheet and the back sheet, but on the other hand, a single layer or a multilayer such as a sheet made of an inorganic material such as metal or glass or various thermoplastic resin films These sheets may be used.
- the metal include tin, aluminum, and stainless steel
- examples of the thermoplastic resin film include single-layer or multilayer sheets of polyester, fluorine-containing resin, polyolefin, and the like.
- the surface of the front sheet and / or the back sheet can be subjected to a known surface treatment such as a primer treatment or a corona treatment in order to improve the adhesion with a sealing material or other members.
- the solar cell module produced using the solar cell protective material of the present invention is a front sheet (solar cell protective material of the present invention) / sealing material / solar cell element / sealing material / back sheet as described above.
- the configuration will be described as an example.
- the solar cell protective material, sealing material, solar cell element, sealing material, and back sheet are laminated in order from the solar light receiving side, and a junction box (from the solar cell element) is further formed on the lower surface of the back sheet.
- a terminal box for connecting wiring for taking out the generated electricity to the outside is bonded.
- the solar cell elements are connected by wiring in order to conduct the generated current to the outside. The wiring is taken out through a through hole provided in the backsheet and connected to the junction box.
- a known manufacturing method can be applied, and it is not particularly limited, but in general, the solar cell protective material, sealing material, solar cell element, sealing of the present invention.
- the step of vacuum suction and thermocompression bonding is, for example, a vacuum laminator, the temperature is preferably 130 to 180 ° C., more preferably 130 to 150 ° C., the degassing time is 2 to 15 minutes, and the press pressure is 0.05 to 0. .1 MPa, pressing time is preferably 8 to 45 minutes, more preferably 10 to 40 minutes.
- batch type manufacturing equipment, roll-to-roll type manufacturing equipment, and the like can be applied.
- the solar cell module produced using the solar cell protective material of the present invention is installed on a small solar cell represented by a mobile device, a roof or a roof, regardless of the type and module shape of the applied solar cell. It can be applied to various uses such as large solar cells, both indoors and outdoors. In particular, among electronic devices, it is suitably used as a protective material for solar cells for flexible solar cell modules such as compound-based power generation element solar cell modules and amorphous silicon.
- Tensile storage modulus of pressure-sensitive adhesive layer A pressure-sensitive adhesive was applied on a silicone release PET film so as to be 25 g / m 2 . This was cured at 40 ° C. for 4 days, and then maintained at 150 ° C. for 30 minutes to form an adhesive layer. Thereafter, only the pressure-sensitive adhesive layer is taken out, a predetermined number of sheets are stacked so that the thickness becomes 200 ⁇ m, a sample (4 mm long, 60 mm wide, 200 ⁇ m thick) is prepared, and the obtained sample is manufactured by IT Measurement Co., Ltd.
- Viscoelastic Spectrometer DVA-200 vibration frequency is 10 Hz, strain is 0.1%, heating rate is 3 ° C./min. The stress against the strain applied to the sample up to 180 ° C. was measured, and the tensile storage modulus (MPa) at 100 ° C., frequency 10 Hz, and strain 0.1% was determined from the obtained data.
- MPa tensile storage modulus
- the water vapor transmission rate of the moisture-proof film was measured by the following method as the water vapor transmission rate after storage at 40 ° C for one week after the moisture-proof film was produced.
- the measured value after curing is the initial water vapor transmission rate, and after the curing, glass, solar cell protective material (fluorine resin film is exposed side) ), Heat treatment is performed at 150 ° C. for 30 minutes, and the measured value of each solar cell protective material after the pressure cooker test is performed under the condition (3) above is the water vapor permeation after the pressure cooker test.
- the rate value was used.
- JIS Z 0222 “moisture-proof packaging container moisture permeability test method” and JIS Z 0208 “moisture-proof packaging material moisture permeability test method (cup method) the following methods were used for evaluation.
- a bag with about 20 g of anhydrous calcium chloride added as a hygroscopic agent and sealed on all sides was produced, and the bag was heated to 40 ° C relative humidity Place in a 90% thermo-hygrostat and measure the mass until about 200 days at intervals of 72 hours or more. From the slope of the regression line between the elapsed time after the fourth day and the bag weight, the water vapor transmission rate g / m 2 / The day was calculated. The degree of decrease in moisture resistance was calculated by [water vapor permeability after pressure cooker test (PC48) / initial water vapor permeability].
- ⁇ Structure film> (Fluorine resin film)
- a tetrafluoroethylene / ethylene copolymer (ETFE) film manufactured by Asahi Glass Co., Ltd., trade name: Aflex 50 MW1250 DCS, thickness 50 ⁇ m
- A-1 Fluorine-based resin film was cut to a width of 200 mm and used
- A-2 Fluorine-based resin film was cut to a width of 230 mm and used.
- A-3 A fluororesin film was cut into a width of 180 mm and used.
- Adhesive 1 Using a reactor equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen gas inlet tube, a mixed solution of 90 parts by mass of butyl acrylate, 10 parts by mass of acrylic acid, 75 parts by mass of ethyl acetate, and 75 parts by mass of toluene, 0.3 parts by mass of azobisisobutyronitrile was added, and polymerization was performed at 80 ° C. for 8 hours in a nitrogen gas atmosphere. After completion of the reaction, the solid content was adjusted to 30% by mass with toluene to obtain a resin having a mass average molecular weight of 500,000.
- Adhesive 2 Using a reactor equipped with a thermometer, stirrer, reflux condenser, and nitrogen gas inlet tube, 40 parts by mass of butyl acrylate, 10 parts by mass of isobutyl acrylate, 40 parts by mass of methyl acrylate, 10 parts by mass of acrylic acid, acetic acid 0.3 parts by mass of azobisisobutyronitrile was added to a mixed solution of 75 parts by mass of ethyl and 75 parts by mass of toluene, and polymerization was performed at 80 ° C. for 8 hours in a nitrogen gas atmosphere. After completion of the reaction, the solid content was adjusted to 30% by mass with toluene to obtain a resin having a mass average molecular weight of 500,000.
- a biaxially stretched polyethylene naphthalate film (made by Teijin DuPont, “Q51C12”) having a thickness of 12 ⁇ m is used, and the following coating solution is applied and dried on the corona-treated surface, thereby anchor coating having a thickness of 0.1 ⁇ m A layer was formed.
- a moisture-proof film having a thin film was obtained, cut into a width of 180 mm and used.
- the produced moisture-proof film B-1 had a water vapor transmission rate of 0.01 g / m 2 / day.
- Coating solution “GOHSENOL” manufactured by Nippon Gosei Co., Ltd. (degree of saponification: 97.0 to 98.8 mol%, degree of polymerization: 2400) was added to 2810 g of ion-exchanged water and added to an aqueous solution obtained by heating and dissolving. 645 g of 35 mol% hydrochloric acid was added with stirring at ° C. Subsequently, 3.6 g of butyraldehyde was added with stirring at 10 ° C., and after 5 minutes, 143 g of acetaldehyde was added dropwise with stirring to precipitate resin fine particles.
- Adhesive and adhesive coating solution HD1013 manufactured by Rock Paint Co., Ltd. is used as the main component containing the polyurethane polyol component, and H62 manufactured by Rock Paint Co., Ltd. is used as the curing agent containing the aliphatic hexamethylene diisocyanate component, resulting in a weight ratio of 10: 1.
- H62 manufactured by Rock Paint Co., Ltd. is used as the curing agent containing the aliphatic hexamethylene diisocyanate component, resulting in a weight ratio of 10: 1.
- Glass A cover glass TCB09331 (3.2 mm thickness) manufactured by AGC Fabritech Co., Ltd. was used and cut into glass of the same size as the fluororesin film used in each of the examples and comparative examples.
- Example 1 Adhesive 1 was applied to a 38 ⁇ m-thick silicone release PET film (Nakamoto Pax, NS-38 + A, melting point 262 ° C., width 180 mm) to a thickness of 20 ⁇ m and dried to form an adhesive layer.
- Thickness The protective material E-1 for solar cells of 82 micrometers was produced.
- the length of a fluorine resin film, a moisture-proof film, and an adhesive layer is substantially the same.
- Example 2 A protective material E-2 having a thickness of 82 ⁇ m was prepared in the same manner as in Example 1 except that A-2 was used as the fluorine resin film. Thereafter, in the same manner as in Example 1, the end face sealing state, the water vapor transmission rate, and the delamination generation time were evaluated. The results are shown in Table 1.
- Example 3 Adhesive 1 was applied to a thickness of 20 ⁇ m on a 38 ⁇ m-thick silicone release PET film (Nakamoto Pax, NS-38 + A, melting point 262 ° C., width 180 mm), and dried to form an adhesive layer.
- the SiO X surface of the moisture-proof film was bonded to the formed adhesive surface, then the silicone release PET film was peeled off, and the fluorine resin film A-1 was bonded to the other adhesive surface.
- an adhesive coating liquid was applied to a polyethylene terephthalate film having a thickness of 188 ⁇ m so as to have a thickness of 7 ⁇ m and dried to form an adhesive surface.
- the moisture-proof film surface of the laminate prepared above was bonded to the adhesive surface and cured at 40 ° C. for 4 days to prepare a solar cell protective material E-3 having a thickness of 287 ⁇ m. Thereafter, in the same manner as in Example 1, the end face sealing state, the water vapor transmission rate, and the delamination generation time were evaluated. The results are shown in Table 1.
- Example 4 A solar cell protective material E-4 having a thickness of 82 ⁇ m was produced in the same manner as in Example 1 except that the adhesive 1 of Example 1 was changed to the adhesive 2. Thereafter, in the same manner as in Example 1, the end face sealing state, the water vapor transmission rate, and the delamination generation time were evaluated. The results are shown in Table 1.
- Comparative Example 1 A solar cell protective material E-5 having a thickness of 82 ⁇ m was produced in the same manner as in Example 1 except that the fluororesin film A-1 in Example 1 was changed to A-3. Thereafter, in the same manner as in Example 1, the end face sealing state, the water vapor transmission rate, and the delamination generation time were evaluated. The results are shown in Table 1.
- each of Examples 1 to 4 within the scope of the present invention is excellent in moisture resistance and prevention of delamination, while the width of each layer forming the protective material for solar cells.
- Comparative Example 1 which is not within the specified range of the present invention was inferior in delamination prevention performance.
- Example 5 The pressure-sensitive adhesive 1 was applied to the moisture-proof film side surface of the solar cell protective material E-1 produced in Example 1 so as to have a thickness of 5 ⁇ m, and dried to form an adhesive layer 1 made of the pressure-sensitive adhesive 1. .
- a sealing material D-1 having a width of 190 mm was laminated on the adhesive surface of the formed layer and cured at 40 ° C. for 4 days to produce a sealing material integrated protective material F-1 having a thickness of 700 ⁇ m.
- the obtained sealing material-integrated protective material F-1 had good adhesion between the solar cell protective material E-1 and the sealing material layer. Further, when the sealing material integrated protective material F-1 was evaluated for the PC delamination time and the end surface sealing state, the same evaluation as in Example 1 was obtained while being superior in workability to Example 1. It was.
- the moisture-proof film B-2 is the same as the moisture-proof film B-1, except that the base material of the moisture-proof film B-1 is changed to a biaxially stretched polyethylene naphthalate film (Mitsubishi Resin, T100) with a thickness of 125 ⁇ m. Produced. The produced moisture-proof film B-2 had a water vapor transmission rate of 0.01 g / m 2 / day.
- the moisture-proof film B-3 is the same as the moisture-proof film B-1, except that the base material of the moisture-proof film B-1 is changed to a biaxially stretched polyethylene naphthalate film (manufactured by Mitsubishi Plastics, T100) with a thickness of 100 ⁇ m.
- the produced moisture-proof film B-3 had a water vapor transmission rate of 0.01 g / m 2 / day.
- the moisture-proof film B-4 is the same as the moisture-proof film B-1, except that the base material of the moisture-proof film B-1 is changed to a biaxially stretched polyethylene naphthalate film (Mitsubishi Resin, T100) with a thickness of 50 ⁇ m.
- the produced moisture-proof film B-3 had a water vapor transmission rate of 0.01 g / m 2 / day.
- Partial discharge voltage The partial discharge voltage of the solar cell protective materials E6 to E8 was measured according to IEC60664-1: 2007 Clause 6.1.3.5. The measurement was performed in a measurement room in which the environment was controlled at a temperature of 23 ⁇ 5 ° C. and a relative humidity of 40 ⁇ 10%.
- Example 6 A protective material E-6 for a solar cell with a thickness of 195 ⁇ m was prepared in the same manner as in Example 1 except that B-2 was used as the moisture-proof film.
- Example 7 A protective material E-7 for solar cells having a thickness of 170 ⁇ m was prepared in the same manner as in Example 1 except that B-3 was used as the moisture-proof film.
- Example 8 A protective material E-8 for solar cells having a thickness of 120 ⁇ m was prepared in the same manner as in Example 1 except that B-4 was used as the moisture-proof film.
- the solar cell protective materials of Examples 6 to 8 were excellent in curling suppression effect and withstand voltage.
- the solar cell protective materials of Examples 6 to 8 when the end face sealing state, the water vapor transmission rate, and the delamination generation time were evaluated in the same manner as in Example 1, the same results as in Example 1 were obtained. It was.
- K-1 Foamed polyethylene sheet (made by Pollen Chemical Industry Co., Ltd., Polene sheet, thickness 700 ⁇ m, width 250 mm)
- K-2 Polypropylene film (manufactured by KOKUGO, polypropylene sheet (product code: 07-175-02), thickness 500 ⁇ m, width 250 mm)
- K-3 Transparent polyester film (Mitsubishi Resin, Diafoil T100, thickness 380 ⁇ m, width 250 mm)
- K-4 Polyethylene film (manufactured by TGK, product code: 125-18-18-01, thickness 30 ⁇ m, width 250 mm)
- the cover sheet and the fluororesin film A-1 are cut into strips having a width of 20 mm and a length of 120 mm, and a measurement sample S of the cover sheet and the fluororesin film is obtained. Produced. Next, the sample S is placed on a table 71 having a height of 100 mm or more so that a portion of the sample S having a width of 20 mm ⁇ a length of 100 mm protrudes from the table, and the bottom surface of the sample S is 20 mm ⁇ 20 mm. Then, an iron plate having a height of 10 mm was placed thereon, and a weight 72 having a weight of 5 kg was placed thereon.
- Example 9 Adhesive 1 was applied to a thickness of 20 ⁇ m on a 38 ⁇ m-thick silicone release PET film (Nakamoto Pax, NS-38 + A, melting point 262 ° C., width 180 mm), and dried to form an adhesive layer.
- the formed adhesive surface adhered to SiO X surface of the moisture-proof film, then peeling off the silicone release PET film, laminating the fluorine-based resin film A-1 to the other adhesive face, a fluorine resin film A-1 / A laminate (protective material for solar cell) having the configuration of pressure-sensitive adhesive layer / moisture-proof sheet B-1 was obtained.
- the laminate was wound into a core having an outer diameter of 172.4 mm to obtain a 200 m roll.
- Example 10 A roll-like product with a cover sheet of Example 10 was obtained in the same manner as Example 9, except that K-2 was used as the cover sheet.
- Example 11 A roll with a cover sheet of Example 11 was obtained in the same manner as in Example 9 except that K-3 was used as the cover sheet.
- Reference example 1 A roll-like product with a cover sheet of Reference Example 1 was obtained in the same manner as in Example 9 except that K-4 was used as the cover sheet.
- Example 3 the rolls with cover sheets of Examples 9 to 11 were excellent in bending resistance and handling properties.
- the laminates (protective materials for solar cells) constituting the roll sheets with cover sheets of Examples 9 to 11 the end face sealing state, water vapor transmission rate, and delamination occurrence time were evaluated in the same manner as in Example 1. As a result, the same result as in Example 1 was obtained.
- Example 12 A pressure-sensitive adhesive 1 was applied to a 38 ⁇ m-thick silicone release PET film (Nakamoto Pax, NS-38 + A, melting point 262 ° C., width 200 mm) to a thickness of 20 ⁇ m, and dried to form a pressure-sensitive adhesive layer. An adhesive sheet was prepared. An adhesive sheet was bonded to the surface of the moisture-proof film B-1 on the SiO x side to obtain a laminate X. Subsequently, both ends in the width direction of the laminate X were slit by 10 mm to obtain a laminate X ′ (width W X ′ : 180 mm).
- the fluororesin film (A-1) the adhesive layer—the moisture-proof film
- a solar cell protective material (E-12) of Example 12 having the structure of (B-1) was obtained.
- Example 13 A solar cell protective material (E-13) of Example 13 was obtained in the same manner as in Example 12 except that A-2 was used as the fluorine resin film.
- the solar cell protective materials of Examples 12 and 13 were capable of preventing foaming.
- the same results as in Example 1 were obtained. It was.
- Fluorine-based resin film 21 Adhesive layer 3: Moisture-proof film 51, 52: Release sheet 6: Slitter 10: Protective material 11 for solar cell 11: Protruding part 20: Sealing material 30: Solar cell
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Abstract
Description
このような太陽電池は、通常、前面保護フィルム、封止材 、発電素子、封止材及び裏面保護フィルムをこの順で積層し、加熱溶融させることにより接着一体化することで製造される。太陽電池の前面保護シート又は裏面保護シートである太陽電池用保護材としては、紫外線に対する耐久性に優れることが要求されるが、加えて、湿気等の透過による内部の導線や電極の発錆を防止するために、防湿性に優れることが極めて重要な要件となる。さらには長期使用や高温条件下における防湿性の低下が少ない優れた保護材の開発が望まれている。
また、特許文献2の実施例では、二軸延伸ポリエステルフィルムを基材とする水蒸気透過率が1~2g/m2/dayの防湿フィルムの両側にポリウレタン系接着剤層を設け、その両側に耐候性ポリエステルフィルムを積層し太陽電池用保護材を製作し、85℃、85%湿度下で1000時間加速試験後のバリア性能と層間強度を評価し、両特性の低下防止の提案を行なっている。
特許文献3では、同じく二軸延伸ポリエステルフィルムを基材とする水蒸気透過率が0.5g/m2/dayの防湿フィルムに二液硬化型ポリウレタン系接着剤を用いてPVFフィルムを貼り合わせた後、プレッシャークッカーテスト(PCT)(高温高圧による過酷環境試験、105℃ 92時間)前後の防湿性と層間強度を評価して、特性の低下防止の提案を行なっている。
太陽電池用保護材としては、防湿性及びデラミネーションの発生防止に優れるものであって、さらに該防湿性やデラミネーションの発生防止が長期に維持されるものが望まれるが、これまで、水蒸気透過率が0.1g/m2/day未満の高い防湿性を有するフィルムを用いた場合、防湿性及びデラミネーションの発生防止を長期に可能とする具体的な提案はなされていないのが実情であった。
[1]少なくとも、フッ素系樹脂フィルムと、粘着剤層と、基材の少なくとも一方の面に無機層を有し水蒸気透過率が0.1g/m2/day未満の防湿フィルムとを保護材構成層Pとして積層してなる太陽電池用保護材であって、前記フッ素系樹脂フィルムの幅WAに対する、フッ素系樹脂フィルム以外の保護材構成層Pの最大幅WPの比(WP/WA)が1より小さい太陽電池用保護材、
[2]前記WP/WAが、0.7~0.98である、前記[1]に記載の太陽電池用保護材、
[3]前記フッ素系樹脂フィルム以外の保護材構成層Pの最大幅を有する層が防湿フィルムである、前記[1]又は[2]に記載の太陽電池用保護材、
[4]前記粘着剤層の100℃、周波数10Hz、歪0.1%における引張貯蔵弾性率が5.0×104~5.0×105Paであり、その厚みが13μm以上である、前記[1]~[3]のいずれかに記載の太陽電池用保護材、
[6]前記防湿フィルムを、前記無機層側の面を前記フッ素系樹脂フィルム側にして積層してなる、前記[1]~[5]のいずれかに記載の太陽電池用保護材、
[7]前記[1]~[6]のいずれかに記載の太陽電池用保護材の前記防湿フィルム側に、さらに封止材層が積層されてなる、封止材一体型保護材、
[8]前記封止材層の幅WDが、前記フッ素系樹脂フィルムの幅WAより小さく、かつ前記フッ素系樹脂フィルム以外の保護材構成層Pの最大幅WPより大きい、前記[7]に記載の封止材一体型保護材、
[10]前記[9]に記載のロール状物の表面のうち、フッ素系樹脂フィルムが突出する箇所に対応する箇所の少なくとも一部を、以下の条件により測定される撓み長さが70mm以下であり、かつ耐荷重凹みが0.1以下であるカバーシートで覆ってなる、カバーシート付きロール状物、
[撓み長さ]
(1)幅20mm、長さ120mmのサンプルを採取する。
(2)サンプルを台上に、サンプルのうち長さ100mmの部分が台から突出するようにして配置し、サンプルの台上の部分に、重さ5kgの重りを乗せてサンプルを固定する。
(3)サンプルの台から突出する部分の端部が、台から垂れ下がる長さ「x」(単位:mm)を測定し、この値を撓み長さとする。
[耐荷重凹み]
(1)100mm四方のサンプルを採取する。
(2)サンプルを厚さ20mmのガラス板上に設置し、サンプルの中央部に直径5mmで重さ0.5gの鋼球を載せ、さらに鋼球上から2kgの荷重をかける。
(3)サンプルの凹み「d」(単位:μm)を測定し、サンプルの厚み「t」(単位:μm)との比「d/t」を耐荷重凹みとする。
[11]以下(a’)及び/又は(b’)の条件を満たす、前記[10]に記載のカバーシート付きロール状物。
(a’)[カバーシートの撓み長さ]/[フッ素系樹脂フィルムの撓み長さ]が2以下
(b’)[カバーシートの耐荷重凹み]/[フッ素系樹脂フィルムの耐荷重凹み]が2以下
(1)防湿フィルム上に粘着剤層を有する積層体Xを作製する工程
(2)積層体Xの幅方向の両端をスリットし、積層体X’とする工程
(3)粘着剤層上に、積層体X’の幅WX'よりも広い幅WAを有するフッ素系樹脂フィルムを、フッ素系樹脂フィルムの両端が粘着剤層の両端から突出するようにして貼り合わせる工程
[13]前記工程(1)において、積層体Xとして、粘着剤層上にさらに離型シート1を有するものを作製し、前記工程(2)の後であって、フッ素系樹脂フィルムを貼り合わせる前に、離型シート1を剥離する工程を経る、前記[12]に記載の太陽電池用保護材の製造方法、
[14]前記工程(1)において、離型シート1上に粘着剤層組成物を塗布、乾燥して粘着剤層を形成した後、粘着剤層に防湿フィルムを貼り合わせることにより積層体Xを作製する、前記[13]に記載の太陽電池用保護材の製造方法、及び
[15]前記[1]~[6]のいずれかに記載の太陽電池用保護材又は前記[7]及び[8]のいずれかに記載の封止材一体型保護材を用いて作製された太陽電池モジュール、
に存する。
太陽電池用保護材は防湿フィルムが積層されていることによりフィルムの暴露面からの水分の浸入を防止することが可能であるが,高温高湿環境下での加速試験に代替される長期の使用においては太陽電池用保護材の端面からの水分の浸入により、各フィルムの積層に使用している接着剤や防湿フィルムの基材が徐々に劣化し、端部からのデラミネーションの発生や防湿性能低下が起こることがある。
特に、0.1g/m2/day未満程度の高い防湿性をもった防湿フィルムの場合、フィルムの収縮による防湿性の低下や端部からの水分侵入による影響は著しい。これは防湿フィルムの無機層内部及び基材と無機層との界面でのわずかな欠陥や基材の加水分解等による劣化が防湿性に対して重大な影響を与えるからである。
[フッ素系樹脂フィルム]
本発明の太陽電池用保護材は、耐加水分解性や耐候性を備え、長期の耐久性を付与するために、フッ素系樹脂フィルムを有する。
フッ素系樹脂フィルムは、耐候性を有するものが好ましく、フッ素系樹脂としては、例えば、ポリテトラフルオロエチレン(PTFE)、テトラフルオロエチレン・パーフルオロアルキルビニルエーテル共重合体(PFA)、テトラフルオロエチレン・ヘキサフルオロプロピレン共重合体(FEP)、テトラフルオロエチレン・エチレン共重合体(ETFE)、ポリクロロトリフルオロエチレン(PCTFE)、ポリビニリデンフルオライド(PVDF)、ポリビニルフルオライド(PVF)等が好ましく用いられる。
フッ素系樹脂フィルムとしては、真空ラミネーションの際や、温度変化や湿度変化の際においての特性変化が小さいことが好適である。したがって、収縮率が大きいフッ素系フィルムの場合は、事前の熱処理により低収縮率化したものが好適である。
本発明において、防湿フィルムは、基材及び基材の少なくとも一方の面に形成される無機層を少なくとも有するものであり、その水蒸気透過率は0.1g/m2/day未満である。本発明の太陽電池用保護材は、長期に高い防湿性を保持することが望まれるため、初期の防湿性も一定以上のものである必要がある。したがって、本発明において、上記防湿フィルムは水蒸気透過率が0.1g/m2/day未満であり、好ましくは0.05g/m2/day以下であり、より好ましくは、0.03g/m2/day以下である。また、該防湿フィルムは、太陽電池用保護材が、受光面側に用いられるフロントシートとして使用される場合には、透明であることが好ましい。
防湿フィルムの厚みは、一般に5~300μmであり、太陽電池用保護材のカール抑制、耐電圧性、クッション性、及び生産性や取り扱い性の点からは、好ましくは25~250μm、より好ましくは38~200μm、さらに好ましくは50~180μmである。
上記防湿フィルムの基材としては、樹脂フィルムが好ましく、その材料としては、通常の太陽電池用材料に使用しうる樹脂であれば特に制限なく用いることができる。
具体的には、エチレン、プロピレン、ブテン等の単独重合体又は共重合体等のポリオレフィン;環状ポリオレフィン等の非晶質ポリオレフィン;ポリエチレンテレフタレート(PET)、ポリエチレンナフタレート(PEN)等のポリエステル;ナイロン6、ナイロン66、ナイロン12、共重合ナイロン等のポリアミド;エチレン-酢酸ビニル共重合体部分加水分解物(EVOH)、ポリイミド、ポリエーテルイミド、ポリサルホン、ポリエーテルサルホン、ポリエーテルエーテルケトン、ポリカーボネート、ポリビニルブチラール、ポリアリレート、フッ素樹脂、アクリル系樹脂、生分解性樹脂等が挙げられ、中でも熱可塑性樹脂が好ましい。さらにフィルム物性、コスト等の点から、ポリエステル、ポリアミド、ポリオレフィンが好まく、表面平滑性、フィルム強度、耐熱性等の点から、ポリエチレンテレフタレート(PET)、ポリエチレンナフタレート(PEN)が特に好ましい。
ベンゾフェノン系紫外線吸収剤としては、例えば、2-ヒドロキシ-4-メトキシベンゾフェノン、2-ヒドロキシ-4-メトキシ-2’-カルボキシベンゾフェノン、2-ヒドロキシ-4-オクトキシベンゾフェノン、2-ヒドロキシ-4-n-ドデシルオキシベンゾフェノン、2-ヒドロキシ-4-n-オクタデシルオキシベンゾフェノン、2-ヒドロキシ-4-ベンジルオキシベンゾフェノン、2-ヒドロキシ-4-メトキシ-5-スルホベンゾフェノン、2-ヒドロキシ-5-クロロベンゾフェノン、2,4-ジヒドロキシベンゾフェノン、2,2’-ジヒドロキシ-4-メトキシベンゾフェノン、2,2’-ジヒドロキシ-4,4’-ジメトキシベンゾフェノン、2,2’,4,4’-テトラヒドロキシベンゾフェノン等を挙げることができる。
サリチル酸エステル系としては、フェニルサリチレート、p-オクチルフェニルサリチレート等を挙げることができる。
基材中の紫外線吸収剤の含有量は、通常0.01~2.0質量%程度であり、好ましくは0.05~0.5質量%である。
モノフェノール系としては、例えば、2,6-ジ-tert-ブチル-p-クレゾール、ブチル化ヒドロキシアニゾール、2,6-ジ-tert-ブチル-4-エチルフェノール等を挙げることができる。ビスフェノール系としては、2,2’-メチレン-ビス-(4-メチル-6-tert-ブチルフェノール)、2,2’-メチレン-ビス-(4-エチル-6-tert-ブチルフェノール)、4,4’-チオビス-(3-メチル-6-tert-ブチルフェノール)、4,4’-ブチリデン-ビス-(3-メチル-6-tert-ブチルフェノール)、3,9-ビス〔{1,1-ジメチル-2-{β-(3-tert-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオニルオキシ}エチル}2,4,9,10-テトラオキサスピロ〕5,5-ウンデカン等を挙げることができる。
硫黄系としては、ジラウリルチオジプロピオネート、ジミリスチルチオジプロピオネート、ジステアリルチオプロピオネート等を挙げることができる。
かかる基材は、従来公知の方法により製造することができ、例えば、原料を押出機により溶融し、環状ダイやTダイにより押出して、急冷することにより実質的に無定型で配向していない未延伸フィルムを製造することができる。また、多層ダイを用いることにより、1種の樹脂からなる単層フィルム、1種の樹脂からなる多層フィルム、多種の樹脂からなる多層フィルム等を製造することができる。
防湿フィルムを構成する上記基材の厚みが25μm以上であると、太陽電池用保護材のカール発生の抑制効果に優れ、耐電圧性、耐衝撃性、及びクッション性にも優れる。また、上記基材の厚みが300μmを超えると、生産性や取り扱い性の点で好ましくない。
無機層を構成する無機物質としては、珪素、アルミニウム、マグネシウム、亜鉛、錫、ニッケル、チタン等;又はこれらの酸化物、炭化物、窒化物;あるいはこれらの混合物が挙げられる。これらの無機物質の中でも、透明であることから酸化珪素、窒化珪素、酸化窒化珪素、酸化アルミニウム、ダイアモンドライクカーボンが好ましい。特に、酸化珪素、窒化珪素、酸化窒化珪素、酸化アルミニウムは、高いガスバリア性が安定に維持できるため好ましい。
また、特に、真空蒸着法により形成した無機層、化学蒸着法により形成した無機層及び真空蒸着法により形成した無機層をこの順で形成した層構成が、多層構成の中に含まれていることが好ましい。
なお、無機層が多層の場合、各層は同じ無機物質からなっていても、異なる無機物質からなっていてもよい。
太陽電池用保護材の製造においては、例えば、太陽電池用保護材を構成する樹脂フィルム等の構成部材を積層する際に、溶剤を用いて希釈した粘着剤を樹脂フィルム等上に所定の厚みに塗布し、通常70℃~140℃の範囲での乾燥により溶剤を蒸発させ樹脂フィルム等上に粘着剤層を形成する。その後、他の樹脂フィルム等を粘着剤層側に向けて貼り合わせる。最後に所定の温度での養生を経て作製する。養生は例えば30℃~80℃の範囲で1日から1週間行なわれる。
さらに、太陽電池用保護材の防湿性の劣下の原因として、粘着剤自身の防湿性の劣下が挙げられる。これについては加水分解しにくい粘着剤を選択することが有効である。
前記アクリル系(共)重合体の主モノマー成分としては、例えば、アクリル酸エチル、アクリル酸ブチル、アクリル酸アミル、アクリル酸2-エチルヘキシル、アクリル酸オクチル等のアクリル酸エステル等が挙げられる。これらは単独で用いてもよいし、2種以上組み合わせて用いてもよい。
前記アクリル系(共)重合体の官能基含有モノマー成分としては、例えば、アクリル酸、メタクリル酸、マレイン酸、イタコン酸等のカルボキシル基含有モノマーや、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、N-メチロールアクリルアミド等のヒドロキシル基含有モノマー、アクリルアミド、メタクリルアミド、グリシジルメタクリレート等が挙げられる。これらは単独で用いてもよいし、2種以上組み合わせて用いてもよい。
また、前記アクリル系粘着剤が上述のアクリル系(共)重合体である場合の分子量としては、質量平均分子量で30万~150万であるものが好ましく、40万~100万であることがさらに好ましい。質量平均分子量を上記範囲にすることによって被着体に対する密着性や接着耐久性を確保し、浮きや剥がれ等を抑制することができる。
粘着剤層と無機層が強い化学結合を形成すると、粘着剤層の粘弾性の変化や粘着剤層塗膜の分解、収縮によって無機層に大きな応力がかかるが、無機層と粘着剤層が化学結合を形成する要因は、例えばSiOx層等の無機層の欠陥部分と粘着剤層中の水酸基等が反応することによると考えられる。これを抑制するためには、粘着剤中の反応性官能基の数を減らせばよく、粘着剤層の塗布、硬化後の未反応官能基の数を少なくすることが好ましい。
塗工する前記粘着剤(以下、塗工液という)には、有機溶剤系、エマルション系、無溶剤系があるが、耐水性が問われる太陽電池部材等の用途には有機溶剤系が望ましい。
有機溶剤系の塗工液に用いられる有機溶剤としては、例えば、トルエン、キシレン、メタノール、エタノール、イソブタノール、n-ブタノール、アセトン、メチルエチルケトン、酢酸エチル、テトラヒドロフラン等が挙げられる。これらは1種を単独で用いてもよく、2種以上組み合わせて用いてもよい。
塗工液の塗工は、例えば、バーコート法、ロールコート法、ナイフコート法、ロールナイフコート法、ダイコート法、グラビアコート法、エアドクターコート法、ドクターブレードコート法等、従来公知の塗工方法により行うことができる。
塗工後、通常70~110℃の温度で1~5分程度乾燥処理することにより、粘着剤層が形成される。
本発明の太陽電池用保護材には、本発明の主旨を逸脱しない範囲で、諸物性(柔軟性、耐熱性、透明性、接着性等)や成形加工性あるいは経済性等をさらに向上させる目的で、その他の層を積層させてもよい。
本発明の太陽電池用保護材において積層しうるその他の層としては、通常、太陽電池用保護材に使用しうるいかなる層も使用可能であるが、例えば封止材、集光材、導電材、伝熱材、水分吸着材等の層を積層することができる。
これらのその他の層には、必要に応じて、種々の添加剤を添加することができる。該添加剤としては、例えば、帯電防止剤、紫外線吸収剤、可塑剤、滑剤、フィラー、着色剤、耐候安定剤、ブロッキング防止剤、酸化防止剤等が挙げられるが、これらに限られない。紫外線吸収剤、耐候安定剤及び酸化防止剤としては、前述の基材に用いるものと同様のものを使用することができる。
本発明の太陽電池用保護材は、上述の通り、基材に無機層を有する水蒸気透過率0.1g/m2/day未満の防湿フィルムを用いることにより、初期防湿性が、水蒸気透過率で好ましくは0.1g/m2/day以下であり、より好ましくは0.05g/m2/day以下であるものとすることができる。
本発明の太陽電池用保護材は、初期防湿性に優れ、且つ、高温高湿環境下での保存においても防湿性やデラミネーション防止にも優れる。
なお、本発明における太陽電池用保護材の「初期防湿性」とは、部材が真空ラミート条件等の高温高湿環境下での熱等の履歴を受ける前の防湿性をいい、熱等による防湿性劣化が起こる前の値を意味する。よって、製造直後から高温高湿処理前までの経時的な変化を含むものである。例えば、100℃前後の高温高湿環境、130~180℃で10分~40分行われる熱ラミネーション処理等の熱処理が行われていない状態での防湿性の値を意味する。「初期水蒸気透過率」も同様である。
本発明の封止材一体型保護材は、前述した本発明の太陽電池用保護材の前記防湿フィルム側に、さらに封止材層が積層されてなるものである。予め封止材層を積層した封止材一体型の保護材とすることにより、後述する太陽電池モジュール製造において、真空ラミネート工程におけるフロントシート、封止材、発電素子、封止材、バックシートそれぞれを個々に積層する作業を低減でき、太陽電池モジュール製造の効率化を図ることができる。
本発明のロール状物は、上述した本発明の太陽電池用保護材又は封止材一体型保護材が巻き取られてなるものである。ロール状物とすることにより、その後の加工性、運搬性、生産性を良好にすることができ、外観の保護を図りやすくできる。
巻取りの長さは、50m以上とすることが好ましく、100m以上とすることがより好ましい。
本発明のカバーシート付きロール状物は、上述した本発明の太陽電池用保護材又は封止材一体型保護材が巻き取られてなるロール状物であって、前記ロール状物の表面のうち、フッ素系樹脂フィルムが突出する箇所に対応する箇所の少なくとも一部を、以下の条件により測定される撓み長さが70mm以下であり、かつ耐荷重凹みが0.1以下であるカバーシートで覆ってなるものである。
(1)幅20mm、長さ120mmのサンプルを採取する。
(2)サンプルを台上に、サンプルのうち長さ100mmの部分が台から突出するようにして配置し、サンプルの台上の部分に、重さ5kgの重りを乗せてサンプルを固定する。
(3)サンプルの台から突出する部分の端部が、台から垂れ下がる長さ「x」(単位:mm)を測定し、この値を撓み長さとする。
なお、撓み長さは、数値が安定した状態で測定することが好ましく、通常、サンプルを固定して5分経過後に測定を行う。また、測定の温度条件は23℃程度であることが好適である。
また、サンプルの台上の部分には、まず底面が20mm×20mmの板を乗せ、次いで該板の上に5kgの重りを乗せることが好ましい。板の高さは5~15mm程度で、材質は特に問わず、ガラス板、鉄板等が挙げられる。
(1)100mm四方のサンプルを採取する。
(2)サンプルを厚さ20mmのガラス板上に設置し、サンプルの中央部に直径5mmで重さ0.5gの鋼球を載せ、さらに鋼球上から2kgの荷重をかける。
(3)サンプルの凹み「d」(単位:μm)を測定し、サンプルの厚み「t」(単位:μm)との比「d/t」を耐荷重凹みとする。
なお、サンプルの凹み「d」は、一番深い凹み箇所の深さを測定するものとする。
また、耐荷重凹みは、数値が安定した状態で測定することが好ましく、通常、サンプルに鋼球を載せ、さらに鋼球上から荷重をかけてから23℃で24時間経過後に測定を行う。
本発明のカバーシート付きロール状物は、ロール状物の表面のうち、フッ素系樹脂フィルムが突出する箇所に対応する箇所の少なくとも一部をカバーシートで覆うことにより、輸送時等に突出部が折れ曲がったり、シワが生じることを防止したものである。
カバーシートの幅Wkとフッ素系樹脂フィルムの幅WAとの比([WK]/[WA])は1以上であることが好ましく、1.05以上であることがより好ましく、1.15以上であることがさらに好ましい。また、ハンドリング性の観点から、[WK]/[WA]は1.5以下であることが好ましく、1.3以下であることがより好ましい。
なお、突出部の折れ曲がりやシワは、主としてロール状物の上下方向からの負荷であるため、ロール状物の表面をカバーシート覆えば本発明の目的を達成することができる。さらに、ロール状物の左右方向からの負荷を考慮して、ロール状物の側面もカバーシートで覆ってもよい。
また、カバーシートでロール状物の表面を覆う際のハンドリング性や、カバーシートの長さ方向端部の固定を維持する観点から、撓み長さが5mm以上、耐荷重凹みが0.01以上であることが好ましく、撓み長さが10mm以上、耐荷重凹みが0.02以上であることがより好ましい。
カバーシートの厚みは、50μm~2mmが好ましく、100μm~1mmがより好ましい。
なお、発泡プラスチックフィルムは、不透明であるため積層体の透明性が高い場合に区別しやすい点、ブロッキング防止性に優れる点、及び軽量であるためハンドリング性にも優れる点でも好適である。
(a’)[カバーシートの撓み長さ]/[フッ素系樹脂フィルムの撓み長さ]が2以下
(b’)[カバーシートの耐荷重凹み]/[フッ素系樹脂フィルムの耐荷重凹み]が2以下
上記(a’)又は(b’)の条件を満たすことにより、突出部の折れ曲がりやシワを防止しやすくでき、上記(a’)及び(b’)の条件を満たすことにより突出部の折れ曲がりやシワをさらに防止しやすくできる。
本発明の太陽電池用保護材の製造方法は、以下の(1)~(3)の工程を順に行うものである。
(1)防湿フィルム上に粘着剤層を有する積層体Xを作製する工程
(2)積層体Xの幅方向の両端をスリットし、積層体X’とする工程
(3)粘着剤層上に、積層体X’の幅WX'よりも広い幅WAを有するフッ素系樹脂フィルムを、フッ素系樹脂フィルムの両端が粘着剤層の両端から突出するようにして貼り合わせる工程
工程(1)では、防湿フィルム上に粘着剤層を有する積層体Xを作製する。
積層体Xは、図5に示すように、防湿フィルム(3)上に粘着剤層(21)を有していればよい。なお、図示しないが、積層体Xは、防湿フィルム(3)の反対側の面に、別の粘着剤層や他の機能層等を有していても良い。
また、工程(2)でのスリット作業性や、ハンドリング性を向上させるために、粘着剤層上には図示しない離型シートを有することが好ましい。
後者の手法によれば、防湿フィルムが耐熱性に劣る材料である場合、離型シートとして耐熱性に優れる材料を用いることにより、防湿フィルム上に粘着剤層を有する積層体Xを容易に作製できる点で好適である。
工程(2)では、積層体Xの幅方向の両端をスリットし、積層体X’とする。
図5に示すように、工程(1)が完了した段階では、防湿フィルム(3)及び離型シートの幅よりも、粘着剤層(21)の幅が狭くなっており、積層体Xの側面に段差が生じている。これは、基材幅に粘着剤層の幅を一致させるようにして粘着剤層組成物を塗布しようとすると、粘着剤層組成物が基材の裏側に回りこみ、製造不良となってしまうため、製造の都合上やむをえないことである。
そして、積層体の側面に段差を有したままフッ素系樹脂フィルム(1)を貼り合わせると、図6のように、突出部を有する積層体の側面に狭い凹部が形成されてしまう。そして、該積層体を封止材を用いて真空ラミネートする際、この狭い凹部に空気が残存しやすく、発泡の原因となりやすい。
一方、本発明のように工程(2)のスリット工程を経ることにより、積層体X’の側面は段差がなくなり、フッ素系樹脂フィルムを貼り合わせても突出部を有する積層体の側面に狭い凹部が形成されることを防止でき、封止材を用いた真空ラミネート時の発泡を防止することができる。
スリットの方式は特に制限されることなく、公知のスリッターを用いて行うことができる。
工程(3)では、粘着剤層上に、積層体X’の幅WX'よりも広い幅WAを有するフッ素系樹脂フィルムを、フッ素系樹脂フィルムの両端が粘着剤層の両端から突出するようにして貼り合わせる。
工程(3)で得られた積層体は、図5に示すように、フッ素系樹脂フィルム(1)は幅方向において粘着剤層(21)及び防湿フィルム(3)の両端から突出しており、突出部11を有する積層体となっている。
本発明の太陽電池用保護材は、そのまま、あるいはさらにガラス板等と貼り合わせて太陽電池用表面保護材として用いることができる。
本発明の太陽電池用保護材をフロントシート、バックシート等の表面保護材の層構成に使用し、太陽電池素子を固定することにより太陽電池モジュールを製作することができる。
本発明における太陽電池用保護材を用いて、太陽電池モジュールを形成する場合、前記太陽電池発電素子の種類により防湿性が、水蒸気透過率で0.1g/m2/day未満程度の低防湿フィルムから0.01g/m2/day未満程度の高防湿フィルムまで素子のタイプに応じて適宜選択し、適当な引張貯蔵弾性率と厚みを有する粘着剤を使用し積層して形成する。
また、バッチ式の製造設備やロール・ツー・ロール式の製造設備等も適用することができる。
(1) 粘着剤層の引張貯蔵弾性率
シリコーン離型PETフィルム上に粘着剤を、25g/m2となるよう塗布した。これを40℃で4日間養生し、さらにその後150℃、30分保持し粘着剤層を形成した。その後当該粘着剤層のみを取り出し、厚みが200μmになるように所定の枚数を重ね、試料(縦4mm、横60mm、厚み200μm)を調製し、得られた試料について、アイティ計測(株)製の粘弾性測定装置、商品名「粘弾性スペクトロメーターDVA-200」を用いて、振動周波数10Hz、歪0.1%、昇温速度3℃/分、チャック間25mmで横方向について、-100℃から180℃までサンプルに印加される歪に対する応力を測定し、得られたデータから100℃、周波数10Hz、歪0.1%における引張貯蔵弾性率(MPa)を求めた。
ガラス、封止材と各太陽電池用保護材E-1~E-6を、フッ素系樹脂フィルムが暴露側になるように順に積層し、150℃×15分の条件で真空ラミネーションを行い、状態を観察し、下記の基準で評価した。
(○)封止材がフッ素系樹脂フィルム幅端面まで到達し、極端な薄肉化が起きていない。
(×)封止材がフッ素系樹脂フィルム幅端面まで回りこんでいない、もしくは到達している封止材の厚みが少なく、端部で薄肉化が起こっている。
太陽電池用保護材(E-1~E-6)を上記の方法で真空ラミネーションを行った後、トミー精工社製プレッシャークッカー試験LSK-500を用い、105℃、湿度100%、48時間の試験(PC48)条件でプレッシャークッカー試験を行った後、水蒸気透過率を測定した。
養生後の太陽電池用保護材(E-1~E-6)を上記の方法で真空ラミネーションを行った後、トミー精工社製プレッシャークッカー試験LSK-500を用い、105℃、湿度100%の試験条件で、太陽電池用保護材の端面部においてデラミネーションの発生を目視で確認できるまでの試験時間を測定した。90時間にてデラミネーションが発生を確認できないものは90時間超(>90)とした。
防湿フィルムの水蒸気透過率は、防湿フィルム作製後,一週間40℃保管後の時点における水蒸気透過率として、下記の手法で測定した。
また、太陽電池用保護材(E-1~E-6)については、養生後の測定値を初期水蒸気透過率とし、当該養生後に、ガラス、太陽電池用保護材(フッ素系樹脂フィルムが暴露側)を積層し、150℃で30分の条件での熱処理を行い、上記(3)の条件でプレッシャークッカー試験を行った後の各太陽電池用保護材の測定値をプレッシャークッカー試験後の水蒸気透過率の値とした。
具体的には、JIS Z 0222「防湿包装容器の透湿度試験方法」、JIS Z 0208「防湿包装材料の透湿度試験方法(カップ法)」の諸条件に順じ、次の手法で評価した。
(フッ素系樹脂フィルム)
フッ素系樹脂フィルムとして、テトラフルオロエチレン・エチレン共重合体(ETFE)フィルム(旭硝子(株)製、商品名:アフレックス50 MW1250DCS、厚み50μm)で下記サイズのものを使用した。
A-1 フッ素系樹脂フィルムを幅200mmに裁断し使用した
A-2 フッ素系樹脂フィルムを幅230mmに裁断し使用した。
A-3 フッ素系樹脂フィルムを幅180mmに裁断し使用した。
温度計、撹拌機、還流冷却管、窒素ガス導入管を備えた反応装置を用い、アクリル酸ブチル90質量部、アクリル酸10質量部、酢酸エチル75質量部、トルエン75質量部の混合溶液に、アゾビスイソブチロニトリル0.3質量部を加え、窒素ガス雰囲気下、80℃で8時間重合した。反応終了後、トルエンにて固形分30質量%に調製し、質量平均分子量50万である樹脂を得た。得られた樹脂100質量部に対して、イソシアナート系架橋剤としてコロネートL(商品名:日本ポリウレタン工業社製、固形分75質量%)1質量部を添加して、粘着剤1を調製した。100℃における引張貯蔵弾性率を測定した結果を表1に示す。
温度計、撹拌機、還流冷却管、窒素ガス導入管を備えた反応装置を用い、アクリル酸ブチル40質量部、アクリル酸イソブチル10質量部、アクリル酸メチル40質量部、アクリル酸10質量部、酢酸エチル75質量部、トルエン75質量部の混合溶液に、アゾビスイソブチロニトリル0.3質量部を加え、窒素ガス雰囲気下、80℃で8時間重合した。反応終了後、トルエンにて固形分30質量%に調製し、質量平均分子量50万である樹脂を得た。得られた樹脂100質量部に対して、イソシアナート系架橋剤としてコロネートL(商品名:日本ポリウレタン工業社製、固形分75質量%)1質量部を添加して、粘着剤2を調製した。100℃における引張貯蔵弾性率を測定した結果を表1に示す。
基材として、厚さ12μmの二軸延伸ポリエチレンナフタレートフィルム(帝人デュポン製、「Q51C12」)を用い、そのコロナ処理面に、下記のコート液を塗布乾燥して厚さ0.1μmのアンカーコート層を形成した。
次いで、真空蒸着装置を使用して1.33×10-3Pa(1×10-5Torr)の真空下でSiOを加熱蒸発させ、アンカーコート層上に厚さ50nmのSiOx(x=1.5)薄膜を有する防湿フィルムを得て、幅180mmに裁断し使用した。作製した防湿フィルムB-1の水蒸気透過率は0.01g/m2/dayであった。
日本合成(株)製「ゴーセノール」(ケン化度:97.0~98.8mol%、重合度:2400)のポリビニルアルコール樹脂220gをイオン交換水2810gに加え加温溶解した水溶液に、20℃で攪拌しながら35mol%塩酸645gを加えた。次いで、10℃でブチルアルデヒド3.6gを攪拌しながら添加し、5分後に、アセトアルデヒド143gを攪拌しながら滴下し、樹脂微粒子を析出させた。次いで、60℃で2時間保持した後、液を冷却し、炭酸水素ナトリウムで中和し、水洗、乾燥し、ポリビニルアセトアセタール樹脂粉末(アセタール化度75mol%)を得た。
また、架橋剤としてイソシアネート樹脂(住友バイエルウレタン(株)製「スミジュールN-3200」)を用い、水酸基に対するイソシアネート基の当量比が1:2になるように混合した。
ポリウレタンポリオール成分を含む主剤としてロックペイント株式会社製HD1013を使用し、脂肪族系のヘキサメチレンジイソシアナート成分を含む硬化剤としてロックペイント株式会社製H62を使用し、重量比で10:1となるように混合し、固形分濃度が30%となるように酢酸エチルで希釈して接着剤塗液を調製した。
ブリヂストン社製、封止材 商品名:EVASKY S11(厚み500μm融点69.6℃)を使用した。
AGCファブリテック社製太陽電池専用カバーガラス TCB09331(3.2mm厚)を使用し、実施例、比較例それぞれで使用するフッ素系樹脂フィルムと同じサイズのガラスに切削加工し使用した。
厚み38μmのシリコーン離型PETフィルム(中本パックス社製、NS-38+A、融点262℃、幅180mm)に粘着剤1を厚み20μmとなるよう塗布し、乾燥して粘着剤層を形成した。形成した粘着面に防湿フィルムのSiOX面を貼り合せ、その後シリコーン離型PETフィルムを剥離し、もう一方の粘着面にフッ素系樹脂フィルムA-1を貼合し40℃で4日間養生し厚み82μmの太陽電池用保護材E-1を作製した。なお、フッ素系樹脂フィルム、防湿フィルム及び粘着剤層の長さは略同一である。
ガラス、封止材、太陽電池用保護材E-1(フッ素系樹脂フィルムが暴露側)の順になるように積層し、150℃×15分の条件で真空ラミネートを行い、端面封止状態を評価し、その後プレッシャークッカー試験、プレッシャークッカーデラミネーション試験を実施し、水蒸気透過率とデラミネーション発生時間を測定した。結果を表1に示す。
フッ素系樹脂フィルムとしてA-2を使用した以外は実施例1同様に厚み82μm太陽電池用保護材E-2を作製した。その後、実施例1と同様に、端面封止状態、水蒸気透過率、デラミネーション発生時間を評価した。結果を表1に示す。
厚み38μmのシリコーン離型PETフィルム(中本パックス社製、NS-38+A、融点262℃、幅180mm)に粘着剤1を厚みが20μmとなるよう塗布し、乾燥して粘着剤層を形成した。形成した粘着面に防湿フィルムのSiOX面を貼り合せ、その後シリコーン離型PETフィルムを剥離し、もう一方の粘着面にフッ素系樹脂フィルムA-1を貼合した。
次に厚み188μmのポリエチレンテレフタレートフィルムに接着剤塗液を厚み7μmとなるよう塗工、乾燥して接着面を形成した。先に作製した積層体の防湿フィルム面を該接着面と貼り合せ40℃で4日間養生し厚み287μmの太陽電池用保護材E-3を作製した。その後、実施例1と同様に、端面封止状態、水蒸気透過率、デラミネーション発生時間を評価した。結果を表1に示す。
実施例1の粘着剤1を粘着剤2としたこと以外は実施例1と同様に厚み82μmの太陽電池用保護材E-4を作製した。その後、実施例1と同様に、端面封止状態、水蒸気透過率、デラミネーション発生時間を評価した。結果を表1に示す。
実施例1のフッ素系樹脂フィルムA-1をA-3としたこと以外は実施例1と同様に厚み82μmの太陽電池用保護材E-5を作製した。その後、実施例1と同様に、端面封止状態、水蒸気透過率、デラミネーション発生時間を評価した。結果を表1に示す。
実施例1で作製した太陽電池用保護材E-1の防湿フィルム側の面に、粘着剤1を厚み5μmとなるように塗布し、乾燥して粘着剤1からなる接着剤層1を形成した。形成した層の粘着面に、幅190mmの封止材D-1を積層し、40℃で4日間養生し、厚み700μmの封止材一体型保護材F-1を作製した。
得られた封止材一体型保護材F-1は、太陽電池用保護材E-1と封止材層との間の接着性が良好であった。また、封止材一体型保護材F-1について、PCデラミネーション時間及び端面封止状態の評価を行ったところ、実施例1よりも作業性に優れながら、実施例1と同様の評価が得られた。
防湿フィルムB-1の基材を、厚さ125μmの二軸延伸ポリエチレンナフタレートフィルム(三菱樹脂社製、T100)に変更した以外は、防湿フィルムB-1と同様に、防湿フィルムB-2を作製した。作製した防湿フィルムB-2の水蒸気透過率は0.01g/m2/dayであった。
防湿フィルムB-1の基材を、厚さ100μmの二軸延伸ポリエチレンナフタレートフィルム(三菱樹脂社製、T100)に変更した以外は、防湿フィルムB-1と同様に、防湿フィルムB-3を作製した。作製した防湿フィルムB-3の水蒸気透過率は0.01g/m2/dayであった。
防湿フィルムB-1の基材を、厚さ50μmの二軸延伸ポリエチレンナフタレートフィルム(三菱樹脂社製、T100)に変更した以外は、防湿フィルムB-1と同様に、防湿フィルムB-4を作製した。作製した防湿フィルムB-3の水蒸気透過率は0.01g/m2/dayであった。
太陽電池用保護材E6~E8を、150℃に保持したオーブン内に平置きし、5分間静置させた。その後、保護材の四隅の高さをマイクロノギスによって測定し、四隅の測定値の平均値をカール値とした。標線は保護材をフッ素系樹脂フィルムが上向きになるように水平の台の上に置いた時、台と保護材とが接する面とした。
カール値測定の結果をもとにカール抑制効果を下記の基準で判断した。
〇:カール値が0~40mm
△:カール値が40mmより大きく80mm以下
×:カール値が80mmより大きい
太陽電池用保護材E6~E8の部分放電圧の測定は、IEC60664-1:2007 Clause6.1.3.5に準拠して実施した。なお、測定は、環境が温度23±5℃、相対湿度40±10%に制御されている測定室にて実施した。
防湿フィルムとしてB-2を使用した以外は実施例1同様に厚み195μm太陽電池用保護材E-6を作製した。
防湿フィルムとしてB-3を使用した以外は実施例1同様に厚み170μm太陽電池用保護材E-7を作製した。
防湿フィルムとしてB-4を使用した以外は実施例1同様に厚み120μm太陽電池用保護材E-8を作製した。
カバーシートとして、以下のものを準備した。
K-1:発泡ポリエチレンシート(ポーレン化学産業社製、ポーレンシート、厚み700μm、幅250mm)
K-2:ポリプロピレンフィルム(コクゴ社製、ポリプロピレンシート(商品コード:07-175-02)、厚み500μm、幅250mm)
K-3:透明ポリエステルフィルム(三菱樹脂社製、ダイヤホイル T100、厚み380μm、幅250mm)
K-4:ポリエチレンフィルム(TGK社製、商品コード:125-18-18-01、厚み30μm、幅250mm)
図3に示すように、カバーシート及びフッ素系樹脂フィルムA-1を、幅20mm、長さ120mmの短冊状にカットし、カバーシート及びフッ素系樹脂フィルムの測定サンプルSを作製した。次いで、サンプルSを高さ100mm以上の台71に、サンプルSのうち幅20mm×長さ100mmの部分が台から突出するようにして設置し、サンプルSの台上の部分に底面が20mm×20mmで高さ10mmの鉄板を載せ、その上に重量5kgの重り72を乗せた。サンプルSの台から突出する部分の端部が、台71から垂れ下がる長さ「x」(単位:mm)を測定し、この値を撓み長さとした。
なお、測定はサンプルを固定して5分経過後に行い、測定時の温度条件は23℃とした。結果を表3に示す。
図4に示すように、カバーシート及びフッ素系樹脂フィルムA-1を、100mm四方にカットし、カバーシート及びフッ素系樹脂フィルムの測定サンプルSを作製した。次いで、サンプルSを厚さ20mmのガラス板81上に設置し、サンプルの中央部に直径5mmで重さ0.5gの鋼球82を載せ、さらに鋼球82上から2kgの荷重をかけた。23℃で24時間経過後のサンプルSの凹みのうち、一番深い凹み箇所の深さ「d」(単位:μm)を測定し、サンプルSの厚み「t」(単位:μm)との比「d/t」を耐荷重凹みとした。結果を表3に示す。
実施例9~11及び参考例1で得られたカバーシート付きロール状物について、カバーシートの上から、突出箇所に対応する箇所に5kgの荷重を24時間かけ、フッ素系樹脂フィルムの状態を目視で観察し、以下の基準で評価した。結果を表3に示す。
(〇):フッ素系樹脂フィルムの防湿フィルムよりも突出している部分が折れ曲がっていないもの
(×):フッ素系樹脂フィルムの防湿フィルムよりも突出している部分が折れ曲がっているもの
実施例9~11及び参考例1で得られたカバーシート付きロール状物を以下の基準で評価した。結果を表3に示す。
(〇):カバーシートのテープでの固定が3日以上維持できたもの
(△):カバーシートのテープでの固定が3日間維持できなかったもの
厚み38μmのシリコーン離型PETフィルム(中本パックス社製、NS-38+A、融点262℃、幅180mm)に粘着剤1を厚みが20μmとなるよう塗布し、乾燥して粘着剤層を形成した。形成した粘着面に防湿フィルムのSiOX面を貼り合せ、その後シリコーン離型PETフィルムを剥離し、もう一方の粘着面にフッ素系樹脂フィルムA-1を貼り合わせ、フッ素系樹脂フィルムA-1/粘着剤層/防湿シートB-1の構成からなる積層体(太陽電池用保護材)を得た。
該積層体を外径172.4mmの芯に200m巻き取りロール状物を得た。次いで、40℃で4日間養生し、ロール状物の表面全部をカバーシートK-1で覆い、端部をテープ(ダイヤテックス社製パイオランテープを幅50mm×長さ100mmにカットしたもの)1枚で固定し、実施例9のカバーシート付きロール状物を得た。
カバーシートとしてK-2を使用した以外は実施例9同様に、実施例10のカバーシート付きロール状物を得た。
カバーシートとしてK-3を使用した以外は実施例9同様に、実施例11のカバーシート付きロール状物を得た。
カバーシートとしてK-4を使用した以外は実施例9同様に、参考例1のカバーシート付きロール状物を得た。
ガラス、封止材と、実施例12、13及び比較例1の太陽電池用保護材(E-12、E-13、E-6)を、フッ素系樹脂フィルムが暴露側になるように順に積層し、真空ラミネーター(エヌ・ピー・シー社製、LM30×30)を用いて、温度150℃、脱気時間5分、プレス圧力0.1MPa、プレス時間10分の条件で真空ラミネーションを行い、状態を観察し、下記の基準で評価した。
(○):気泡が全くない状態
(×):気泡が1個以上確認される状態
厚み38μmのシリコーン離型PETフィルム(中本パックス社製、NS-38+A、融点262℃、幅200mm)に粘着剤1を厚みが20μmとなるよう塗布し、乾燥して粘着剤層を形成し、粘着シートを作製した。防湿フィルムB-1のSiOx側の面に粘着シートを貼り合わせ、積層体Xを得た。
次いで、積層体Xの幅方向の両端を10mmずつスリットして、積層体X’(幅WX':180mm)を得た。
次いで、積層体X’の離型シートを剥離して、フッ素系樹脂フィルムA-1を貼り合わせ、40℃で4日間養生し、フッ素系樹脂フィルム(A-1)-粘着剤層-防湿フィルム(B-1)の構成からなる、実施例12の太陽電池用保護材(E-12)を得た。
フッ素系樹脂フィルムとしてA-2を使用した以外は実施例12同様に、実施例13の太陽電池用保護材(E-13)を得た。
21:粘着剤層
3:防湿フィルム
51、52:離型シート
6:スリッター
10:太陽電池用保護材
11:突出部
20:封止材
30:太陽電池
Claims (15)
- 少なくとも、フッ素系樹脂フィルムと、粘着剤層と、基材の少なくとも一方の面に無機層を有し水蒸気透過率が0.1g/m2/day未満の防湿フィルムとを保護材構成層Pとして積層してなる太陽電池用保護材であって、前記フッ素系樹脂フィルムの幅WAに対する、フッ素系樹脂フィルム以外の保護材構成層Pの最大幅WPの比(WP/WA)が1より小さい太陽電池用保護材。
- 前記WP/WAが、0.7~0.98である、請求項1に記載の太陽電池用保護材。
- 前記フッ素系樹脂フィルム以外の保護材構成層Pのうち最大幅を有する層が前記防湿フィルムである、請求項1又は2に記載の太陽電池用保護材。
- 前記粘着剤層の100℃、周波数10Hz、歪0.1%における引張貯蔵弾性率が5.0×104~5.0×105Paであり、その厚みが13μm以上である、請求項1~3のいずれかに記載の太陽電池用保護材。
- 前記基材の厚みが25~250μmである、請求項1~4のいずれかに記載の太陽電池用保護材。
- 前記防湿フィルムを、前記無機層側の面を前記フッ素系樹脂フィルム側にして積層してなる、請求項1~5のいずれかに記載の太陽電池用保護材。
- 請求項1~6のいずれかに記載の太陽電池用保護材の前記防湿フィルム側に、さらに封止材層が積層されてなる、封止材一体型保護材。
- 前記封止材層の幅WDが、前記フッ素系樹脂フィルムの幅WAより小さく、かつ前記フッ素系樹脂フィルム以外の保護材構成層Pの最大幅WPより大きい、請求項7に記載の封止材一体型保護材。
- 請求項1~6のいずれかに記載の太陽電池用保護材又は請求項7及び8のいずれかに記載の封止材一体型保護材が巻き取られてなる、ロール状物。
- 請求項9に記載のロール状物の表面のうち、フッ素系樹脂フィルムが突出する箇所に対応する箇所の少なくとも一部を、以下の条件により測定される撓み長さが70mm以下であり、かつ耐荷重凹みが0.1以下であるカバーシートで覆ってなる、カバーシート付きロール状物。
[撓み長さ]
(1)幅20mm、長さ120mmのサンプルを採取する。
(2)サンプルを台上に、サンプルのうち長さ100mmの部分が台から突出するようにして配置し、サンプルの台上の部分に、重さ5kgの重りを乗せてサンプルを固定する。
(3)サンプルの台から突出する部分の端部が、台から垂れ下がる長さ「x」(単位:mm)を測定し、この値を撓み長さとする。
[耐荷重凹み]
(1)100mm四方のサンプルを採取する。
(2)サンプルを厚さ20mmのガラス板上に設置し、サンプルの中央部に直径5mmで重さ0.5gの鋼球を載せ、さらに鋼球上から2kgの荷重をかける。
(3)サンプルの凹み「d」(単位:μm)を測定し、サンプルの厚み「t」(単位:μm)との比「d/t」を耐荷重凹みとする。 - 以下(a’)及び/又は(b’)の条件を満たす、請求項10に記載のカバーシート付きロール状物。
(a’)[カバーシートの撓み長さ]/[フッ素系樹脂フィルムの撓み長さ]が2以下
(b’)[カバーシートの耐荷重凹み]/[フッ素系樹脂フィルムの耐荷重凹み]が2以下 - 以下の(1)~(3)の工程を順に行う、太陽電池用保護材の製造方法。
(1)防湿フィルム上に粘着剤層を有する積層体Xを作製する工程
(2)積層体Xの幅方向の両端をスリットし、積層体X’とする工程
(3)粘着剤層上に、積層体X’の幅WX'よりも広い幅WAを有するフッ素系樹脂フィルムを、フッ素系樹脂フィルムの両端が粘着剤層の両端から突出するようにして貼り合わせる工程 - 前記工程(1)において、積層体Xとして、粘着剤層上にさらに離型シート1を有するものを作製し、前記工程(2)の後であって、フッ素系樹脂フィルムを貼り合わせる前に、離型シート1を剥離する工程を経る、請求項12に記載の太陽電池用保護材の製造方法。
- 前記工程(1)において、離型シート1上に粘着剤層組成物を塗布、乾燥して粘着剤層を形成した後、粘着剤層に防湿フィルムを貼り合わせることにより積層体Xを作製する、請求項13に記載の太陽電池用保護材の製造方法。
- 請求項1~6のいずれかに記載の太陽電池用保護材又は請求項7及び8のいずれかに記載の封止材一体型保護材を用いて作製された太陽電池モジュール。
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CN201280064712.9A CN104025313A (zh) | 2011-12-28 | 2012-12-27 | 太阳能电池用保护材料 |
EP12863019.1A EP2800149A4 (en) | 2011-12-28 | 2012-12-27 | PROTECTIVE MATERIAL FOR SOLAR CELLS |
US14/368,907 US20140360581A1 (en) | 2011-12-28 | 2012-12-27 | Protective material for solar cells |
KR1020147017648A KR20140117371A (ko) | 2011-12-28 | 2012-12-27 | 태양 전지용 보호재 |
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JP2011-290036 | 2011-12-28 | ||
JP2011290036A JP5449312B2 (ja) | 2011-12-28 | 2011-12-28 | 太陽電池用保護材 |
JP2012-272841 | 2012-12-13 | ||
JP2012272837A JP5400948B1 (ja) | 2012-12-13 | 2012-12-13 | カバーシート付きロール状物及びカバーシート付きロール状物の製造方法 |
JP2012-272839 | 2012-12-13 | ||
JP2012272841A JP5474171B1 (ja) | 2012-12-13 | 2012-12-13 | 太陽電池用保護材 |
JP2012272839A JP2014117831A (ja) | 2012-12-13 | 2012-12-13 | 積層体の製造方法 |
JP2012-272837 | 2012-12-13 |
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US (1) | US20140360581A1 (ja) |
EP (1) | EP2800149A4 (ja) |
KR (1) | KR20140117371A (ja) |
CN (1) | CN104025313A (ja) |
TW (1) | TW201334968A (ja) |
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WO2016095952A1 (en) * | 2014-12-15 | 2016-06-23 | Ven Van De Marcus Leonardus Gerardus Maria | Covering film for generating photovoltaic electrical energy |
CN106279904A (zh) * | 2016-08-18 | 2017-01-04 | 苏州度辰新材料有限公司 | 一种挤出型太阳能背板及其制备方法 |
WO2021007451A1 (en) * | 2019-07-10 | 2021-01-14 | Primary Arms, Llc | Solar powered cap assembly for optical sighting systems |
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- 2012-12-27 WO PCT/JP2012/083997 patent/WO2013100108A1/ja active Application Filing
- 2012-12-27 EP EP12863019.1A patent/EP2800149A4/en not_active Withdrawn
- 2012-12-27 CN CN201280064712.9A patent/CN104025313A/zh active Pending
- 2012-12-27 US US14/368,907 patent/US20140360581A1/en not_active Abandoned
- 2012-12-27 KR KR1020147017648A patent/KR20140117371A/ko not_active Application Discontinuation
- 2012-12-28 TW TW101151328A patent/TW201334968A/zh unknown
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EP2800149A4 (en) | 2015-10-21 |
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CN104025313A (zh) | 2014-09-03 |
TW201334968A (zh) | 2013-09-01 |
US20140360581A1 (en) | 2014-12-11 |
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