Patent Application
20140130851
1. Field of Invention
The present invention relates to a tacky sheet for protecting a back face of a solar battery module, and a solar battery module using the same.
2. Description of the Related Art
In recent years, solar photovoltaic power generation as a clean energy source has attracted attention owing to increasing awareness of environmental issues such as global warming, thereby leading to development of solar batteries having a variety of configurations. This solar battery is constructed with a plurality of solar battery modules produced by packaging and unitizing a plurality of solar battery cells generally wired in series or in parallel.
For the aforementioned solar battery modules, sufficient durability, weather resistance and the like for permitting use outdoors for a long period of time are needed. As shown in
In the solar battery module, detachment and discoloration of the filler layers 103 and 105, corrosion of the wiring, deterioration of functions of the solar battery cell 104 may be caused when water vapor, oxygen gas or the like infiltrates inside. Therefore, according to the back sheet 106 for the solar battery module described above, gas barrier properties against water vapor, oxygen gas and the like are needed in addition to basic performances such as strength, weather resistance, heat resistance and the like. In the conventional back sheet 106 for a solar battery module, a multilayered structure etc., has been employed in which a pair of synthetic resin layers are laminated on both two faces of a gas barrier layer, for example. Specific examples of conventionally developed back sheet 106 for solar a battery module include (a) those having a structure in which a pair of polyvinyl fluoride films are laminated on both two faces of an aluminum foil (see, Japanese Unexamined Patent Application Publication No. Hei 6-177412 and the like); (b) those having a structure in which a polyethylene terephthalate film is each laminated on both two faces of a resin film on which a metal oxide is vapor deposited (Japanese Unexamined Patent Application Publication No. 2002-100788); and the like.
However, according to the conventional back sheet 106 for a solar battery module, and the solar battery module 101 provided with the same, it is difficult to prevent damage from physical impact caused in installation and the like of solar battery panels. Such damage from physical impact, and physical defects 109 such as cracks generated by use for a long period of time, and the like deteriorate durability, insulation properties, water vapor barrier property etc., of the back sheet 106, and in turn cause deterioration of filler layers 103 and 105, thereby leading to impairment of functions of the solar battery cell 104 itself consequently. Accordingly, there exist disadvantages of failure of possible use of the solar battery module itself for a long period of time when physical defects such as cracks are caused in the back sheet 106, even though main body and the like of the solar battery cell 104 can be still used satisfactorily.
The present invention was made taking into account these disadvantages, and an object of the present invention is to provide a tacky sheet for protecting a back face of a solar battery module and a solar battery module using the same, the tacky sheet capable of inhibiting evolution of physical defects such as scratches and cracks generated in a back sheet by a physical impact on the solar battery module or use for a long period of time, and also preventing deterioration of a filler layer and solar battery cells which may occur due to penetration of water vapor, and the like from the physical defect sites thereof, whereby extension of useful life of the solar battery module is achieved.
An aspect of the present invention made for solving the aforementioned problems is directed to a tacky sheet for protecting a back face of a solar battery module,
the tacky sheet including: a synthetic resin substrate layer; and a tacky material layer laminated on one face side of the synthetic resin substrate layer,
the tacky material layer having an average thickness of 0.01 mm or greater and 1 mm or less, and
the tacky sheet being to be attached to a back face of a back sheet of a solar battery module via the tacky material layer.
According to the tacky sheet for protecting a back face of a solar battery module, by laminating the tacky sheet on a back face of a back sheet of a back face of a solar battery module in which physical defects such as damaging and cracks are caused, penetration of water vapor and the like from the physical defect sites can be prevented, and the expansion of the defect sites can be inhibited. In addition, according to the tacky sheet for protecting a back face of a solar battery module, since the tacky material layer has an average thickness of 0.01 mm or greater and 1 mm or less, expansion of defects such as scratches and cracks can be inhibited, and penetration of water vapor and the like from outside to inside the solar battery module can be certainly prevented by embedding the tacky material layer into the deepest portion of the physical defect sites which can usually occur on the back sheet. In other words, according to the tacky sheet for protecting a back face of a solar battery module, extension of useful life of the solar battery module can be achieved by providing to attach the tacky material layer on a back face of the back sheet.
In addition, due to including a tacky material layer laminated on one face side of the synthetic resin substrate layer, the tacky sheet for protecting a back face of a solar battery module can be attached to a back face of a back sheet of a conventional solar battery module via the tacky material layer, thereby allowing extension of useful life of the conventional solar battery module to be realized. In addition, since the tacky sheet for protecting a back face of a solar battery module can be replaced with new one either at regular intervals, or upon occurrence of physical defects, the solar battery module can be consistently maintained in a state free from physical defects on its back face, whereby extension of useful life of the solar battery module is enabled.
As a tacky material that constitutes the tacky material layer, an acrylic tacky material is preferably used. According to the tacky sheet for protecting a back face of a solar battery module, an acrylic tacky material having a strong tacky adhesive force, and superior durability and weather resistance is used as the tacky material, whereby functions of inhibiting expansion of the physical defects, and preventing penetration of water vapor and the like can be certainly improved, and the functions can be sustained for a long period of time.
As the tacky material that constitutes the tacky material layer, a butyl rubber-based tacky material may be used. According to the tacky sheet for protecting a back face of a solar battery module, use as the tacky material, of a butyl rubber-based tacky material having favorable weather resistance, cold resistance and following capability to irregularity enables the functions of inhibiting expansion of the physical defects and preventing penetration of water vapor and the like to be certainly improved, and the functions can be sustained for a long period of time.
It is preferred to include a barrier layer laminated on another face side of the synthetic resin substrate layer (i.e., a face side other than the one face side of the synthetic resin substrate layer), between the synthetic resin substrate layer and the tacky material layer, or both on another face side of the synthetic resin substrate layer and between the synthetic resin substrate layer and the tacky material layer. When the tacky sheet for protecting a back face of a solar battery module thus includes the barrier layer, superior gas barrier properties against water vapor and the like can be achieved.
The barrier layer preferably contains an inorganic substance. When the tacky sheet for protecting a back face of a solar battery module thus has a barrier layer containing an inorganic substance, still superior gas barrier properties against water vapor and the like are provided, and also mechanical strength can be improved.
The inorganic substance is preferably an inorganic oxide or aluminum. According to the tacky sheet for protecting a back face of a solar battery module, gas barrier properties and mechanical strength can be further improved by containing the inorganic oxide or aluminum in the barrier layer, and due to superior thermal conductive property of an inorganic oxide or aluminum, a heat dissipation property can be improved by allowing locally generated heat to be diffused to the entire face of the sheet. Thus, prolongation of the duration of use of the solar battery module can be further promoted. Moreover, according to the tacky sheet for protecting a back face of a solar battery module, the rigidity is enhanced due to thus having a layer that contains a metal layer, whereby handleability of the sheet, and workability in attaching the sheet are improved.
The tacky sheet for protecting a back face of a solar battery module preferably has a plurality of the barrier layer. By the plurality of barrier layers thus laminated in the tacky sheet for protecting a back face of a solar battery module, the gas barrier properties and mechanical strength can be significantly improved.
One face of the tacky material layer is preferably covered with a release sheet. Since the tacky sheet for protecting a back face of a solar battery module can prevent the tacky material layer from being in contact with others due to the covering of one face with a release sheet, superior workability is maintained until just before the operation of attaching, and the tacky adhesion function of the tacky sheet in attaching can be improved.
The barrier layer is preferably laminated on an outermost surface on another face side of the synthetic resin substrate layer. By thus including two layers of the synthetic resin substrate layer and the barrier layer, use of, for example, a material having a superior water vapor barrier property, etc., for the synthetic resin substrate layer or the barrier layer is enabled, and thus the tacky sheet for protecting a back face of a solar battery module can have still superior functional properties. In addition, by providing the barrier layer separately on the outermost surface, easy formation of the tacky sheet for protecting a back face of a solar battery module is enabled, and formation of the barrier layer meeting a desired heat dissipation property can be readily carried out.
It is preferred that the barrier layer has a fine bumpy shape on an entire surface on the opposite side to the synthetic resin substrate layer. Due to having a fine bumpy shape on the entire surface on the opposite side to the synthetic resin substrate layer, the surface area of the face on the opposite side to the synthetic resin substrate layer significantly increases in the tacky sheet for protecting a back face of a solar battery module, thereby enabling improvement of the heat dissipation function.
The barrier layer may include fine particles, and a binder for the fine particles. According to the tacky sheet for protecting a back face of a solar battery module, the fine particles enable a fine bumpy shape to be formed easily on an entire surface of a front face (another face of the heat dissipation film) such that a desired shape is provided, and thus the heat dissipation property can be improved certainly.
The fine particles may be at least one type of beads selected from metal beads and inorganic oxide beads. According to the tacky sheet for protecting a back face of a solar battery module, by using beads as the fine particles, a fine bumpy shape can be certainly provided on the entire surface of the front face (a face on the opposite side to the synthetic resin substrate layer of the barrier layer). In addition, since the metal and the inorganic oxide have a high thermal conductivity, the heat dissipation property can be further improved by allowing the heat locally generated to be diffused over the entire face of the sheet.
The barrier layer is also preferably a metal foil. According to the tacky sheet for protecting a back face of a solar battery module, the heat dissipation property can be improved by diffusing the heat locally generated to the entire surface of the sheet due to an extremely high thermal conductivity of the metal foil. In addition, since the barrier layer that is a metal foil has a superior water vapor barrier function, improvement of resistance to hydrolysis is enabled.
Therefore, according to a solar battery module including a translucent substrate, a first filler layer, solar battery cells as a photovoltaic device, a second filler layer, a back sheet, and the tacky sheet for protecting a back face of a solar battery module laminated in this order from a front face side, the solar battery module being characterized in that the tacky sheet for protecting a back face of a solar battery module is provided to attach via the tacky material layer thereof on a back face of the back sheet, even in the case in which physical defects such as scratches and cracks are generated in the back face of the back sheet, expansion of the physical defects can be inhibited, and permeation of water vapor and the like from the physical defect sites can be prevented by the tacky sheet for protecting a back face of a solar battery module, whereby extension of useful life of the solar battery module can be promoted. Moreover, according to the solar battery module, suppress of occurrence per se of the physical defects of the back face of the back sheet is enabled.
The term “front face side” of the solar battery module herein means a light-receiving face side of the solar battery module. The term “back face side” means a face on an opposite side to the front face side, i.e., the aforementioned light-receiving face side.
As described in the foregoing, according to the tacky sheet for protecting a back face of a solar battery module of the present invention, when physical defects such as scratches and cracks occur in a back face of a back sheet of a solar battery module, the tacky sheet provided via the tacky material layer leads to filling of the defect sites by the tacky material layer, whereby expansion of the defect sites can be suppressed, and prevention of penetration of water vapor and the like from the defect sites enables prevention of deterioration of the solar battery module, and extension of useful life can be achieved. Therefore, the solar battery module provided with the tacky sheet for protecting a back face of a solar battery module of the present invention can inhibit deterioration of the filler layer and solar battery cells, and enables use for a long period of time. In addition, according to the tacky sheet for protecting a back face of a solar battery module of the present invention, by attaching on a back face of a solar battery module via the tacky material layer, the heat dissipation property of the solar battery module can be improved. As a result, efficiency of electric power generation of the solar battery module can be enhanced, and extension of useful life of the solar battery module can be achieved.
Hereinafter, the tacky sheet for protecting a back face of a solar battery module of the present invention, and a solar battery module using the same are explained in detail with appropriate references to the drawings.
The tacky sheet 1 for protecting a back face of a solar battery module according to a first embodiment shown in
The substrate layer 2 is formed using a synthetic resin as a principal component. A synthetic resin included in the substrate layer 2 as a principal component is not particularly limited, and examples thereof include e.g., a polyolefin-derived resin, a fluorine-containing resin, a poly(meth)acrylic resin, a polycarbonate-based resin, a polyester-based resin, a polyamide-based resin, a polyimide-based resin, a polyamideimide-based resin, a polyarylphthalate-based resin, a silicone-based resin, a polysulfone-based resin, a polyphenylenesulfide-based resin, a polyether sulfone-based resin, a polyurethane-based resin, an acetal-based resin, a cellulose-based resin, an acrylonitrile-styrene copolymer (AS resin), an acrylonitrile-butadiene-styrene copolymer (ABS resin), a polyvinyl chloride-based resin, and the like. Among the resins described above, a polyolefin-derived resin, a polyester-based resin, a fluorine-containing resin which have high heat resistance, physical strength, weather resistance and durability, and gas barrier properties against water vapor and the like, and the like are preferred.
Examples of the polyolefin-derived resin include polyethylene (e.g., high density polyethylene, low density polyethylene and the like), polypropylene, copolymers of ethylene with an unsaturated carboxylate ester (e.g., ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate copolymer and the like), copolymers of ethylene and unsaturated carboxylic acid (e.g., ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer and the like), ionomer resins, and the like. Among these, polyethylene that exhibits favorable balance of costs and various functions such as resistance to hydrolysis, heat resistance, weather resistance and the like, as well as cyclic polyolefin-based resins that are excellent in functional properties such as heat resistance, strength, weather resistance, durability and gas barrier properties.
Examples of the cyclic polyolefin-based resin include e.g., a) polymers obtained by polymerization of a cyclic diene such as cyclopentadiene (and a derivative thereof), dicyclopentadiene (and a derivative thereof), cyclohexadiene (and a derivative thereof), norbornadiene (and a derivative thereof) or the like, b) copolymers obtained by copolymerization of one, or two or more of the olefin-based monomers such as ethylene, propylene, 4-methyl-1-pentene, styrene, butadiene and isoprene with the cyclic diene, and the like. Among these cyclic polyolefin-based resins, polymers of a cyclic diene such as cyclopentadiene (and a derivative thereof), dicyclopentadiene (and a derivative thereof) or norbornadiene (and a derivative thereof) that are excellent in the strength, heat resistance, weather resistance and the like are particularly preferred.
As the polyester-based resin, for example, polyethylene terephthalate, polyethylene naphthalate, and the like are exemplified. Among these polyester-based resins, polyethylene terephthalate having favorable balance of costs and various functions such as heat resistance, weather resistance etc., is particularly preferred.
As the fluorine-containing resin, for example, polytetrafluoroethylene (PTFE), a perfluoroalkoxy resin (PFA) constituted with a copolymer of tetrafluoroethylene with perfluoroalkylvinyl ether, a copolymer (FEP) of tetrafluoroethylene with hexafluoropropylene, a copolymer (EPE) of tetrafluoroethylene, perfluoroalkylvinyl ether and hexafluoropropylene, a copolymer (ETFE) of tecrafluoroethylene with ethylene or propylene, a polychlorotrifluoroethylene resin (PCTFE), a copolymer (ECTFE) of ethylene with chlorotrifluoroethylene, a vinylidene fluoride-based resin (PVDF), a vinyl fluoride-based resin (PVF), and the like may be exemplified. Among these fluorine-containing resins, a polyvinyl fluoride-based resin (PVF), and a copolymer (ETFE) of tetrafluoroethylene with ethylene or propylene that are superior in strength, heat resistance, weather resistance and the like are particularly preferred.
As the material for forming the substrate layer 2, the aforementioned synthetic resin can be used alone, or as a mixture of two or more thereof. Moreover, a variety of additives can be blended in the material for forming the substrate layer 2 for the purpose of improving and/or modifying the processability, heat resistance, weather resistance, mechanical properties, dimension accuracy and the like. Examples of the additive include e.g., lubricants, crosslinking agents, antioxidants, ultraviolet ray-absorbing agents, light stabilizers, fillers, reinforcing fibers, strengthening agents, antistatic agents, fire retardants, flame retardants, foaming agents, fungicides, pigment, and the like. The method of molding the substrate layer 2 is not particularly limited, but for example, a known method such as an extrusion method, a cast molding method, a T-die method, a cutting method, an inflation method or the like may be employed. The substrate layer 2 may have either a monolayer structure, or a multilayer structure including two or more layers.
The lower limit of the average thickness of the substrate layer 2 is preferably 0.3 mm, and particularly preferably 0.5 mm. In contrast, the upper limit of the average thickness of the substrate layer 2 is preferably 5 mm, and particularly preferably 3 mm.
The substrate layer 2 having an average thickness of less than the aforementioned lower limit causes disadvantages such as bringing difficulty in handling of the tacky sheet 1 for protecting a back face of a solar battery module, and insufficient functional properties such as barrier properties against water vapor. In particular, the tacky sheet for protecting a back face of a solar battery module is cut to fit the size of a preexisting solar battery module and to fit the position and the size of a junction box of the solar battery module, and thereafter attached to a back face of a solar battery module. Therefore, when the average thickness is less than the aforementioned lower limit, workability in cutting and attaching may be deteriorated and thus attaching to meet each solar battery module size may be difficult, or stickiness with a back sheet may be lowered due to attachment shifted, and may lead to failure in sufficiently exerting the function of preventing expansion of defects and the barrier function against water vapor and the like.
To the contrary, when the substrate layer 2 has an average thickness exceeding the upper limit, demands for reduction in thickness and weight saving of the solar battery module may not be satisfied. Further, when the average thickness of the substrate layer 2 exceeds the above-described upper limit, the weight of the tacky sheet 1 for protecting a back face of a solar battery module increases, whereby workability in attaching on the back face may be similarly deteriorated and thus attaching to meet each solar battery module size may be difficult, or stickiness with the back sheet may be lowered due to attachment shifted, and may lead to failure in sufficiently exerting the function of preventing expansion of defects and the barrier function against water vapor and the like.
The substrate layer 2 may include a pigment dispersed therein. By thus including a pigment dispersed in the substrate layer 2, various characteristics such as heat resistance, weather resistance, durability, thermal dimensional stability, strength and the like of the substrate layer 2 and, in turn, of the tacky sheet 1 for protecting a back face of a solar battery module can be improved. Further, by including a white pigment dispersed in the substrate layer 2, a function of allowing the rays of light transmitted through the solar battery cell to be reflected is added, whereby the power generation efficiency can be further improved. Moreover, design of the solar battery module can be improved by including a black pigment dispersed in the substrate layer 2 to provide a variously colored substrate layer 2.
The white pigment is not particularly limited, but for example, calcium carbonate, titanium oxide, zinc oxide, lead carbonate, barium sulfate or the like can be used. Among them, calcium carbonate is preferred which is excellent in dispersibility in the resin material that forms the substrate layer 2, and which exhibits a comparatively great effect of improving the durability, heat resistance, strength and the like of the substrate layer 2. The calcium carbonate can have a crystal form such as calcite, aragonite, vaterite and the like, and any crystal form is acceptable for use. This calcium carbonate may be subjected to a surface finishing treatment with stearic acid, sodium dodecylbenzenesulfonate, a silane coupling agent, a titanium coupling agent or the like, and impurities such as magnesium oxide, aluminum oxide, silicon dioxide, titanium dioxide and the like may be also included in an amount of approximately 10% or less. Examples of other pigments include black pigments such as carbon black, blue pigments such as ultramarine and prussian blue, red pigments such as blood red (iron oxide red), cadmium red and molybdenum orange, metal powder pigments that impart metallic luster, and the like, which can be responsible for improvement of the solar battery module design.
The average particle size of the pigment is preferably 100 nm or greater and 30 μm or less, and particularly preferably 300 nm or greater and 3 μm or less. It should be noted that the average particle size referred to herein means an average of particle size of thirty particles randomly extracted from particles observed on an electron microscope at 1,000-fold magnification. In addition, the particle size is defined by means of a Feret diameter (interval determined when the profile view is sandwiched with parallel lines along a certain direction).
When the average particle size of the pigment is below the above range, uniform dispersion in the substrate layer 2 may be difficult due to the aggregation or the like. In contrast, when the average particle size of the pigment exceeds the above range, the effect of improving various characteristics such as heat resistance for the substrate layer 2 may be decreased.
The content of the pigment is preferably 8% by mass or greater and 30% by mass or less. When the content of the pigment is smaller than the aforementioned lower limit, the effect of improving the durability, heat resistance, strength and the like of the substrate layer 2 may be decreased. In contrast, when the content of the pigment is greater than the aforementioned upper limit, dispersibility of the pigment in the substrate layer 2 may be deteriorated, whereby reduction in strength of the substrate layer 2 may be caused.
Moreover, a face other than the one face (face on the side to be contact with the external air) of the substrate layer 2 may be subjected to a top coating treatment. By thus subjecting another face of the substrate layer 2 to a top coating treatment, the substrate layer 2 can be sealed and protected. As a result, handleability of the tacky sheet 1 is improved, and deterioration of the strength, weather resistance and the like is suppressed, even if the substrate layer 2 has defects such as scratches and recessed parts, whereby aged deterioration of the substrate layer 2 can be inhibited.
Examples of top coating agent used for the top coating treatment include e.g., polyester-based top coating agents, polyamide-based top coating agents, polyurethane-based top coating agents, epoxy-based top coating agents, phenol-based top coating agents, (meth)acrylic top coating agents, polyvinyl acetate-based top coating agents, polyolefin-based top coating agents such as polyethylene or polypropylene, cellulose-based top coating agent, and the like. Among such top coating agents, polyester-based top coating agents that exhibit superior adhesion strength with the substrate layer 2, and are responsible for surface protection and the like of the substrate layer 2 are particularly preferred.
The lower limit of the amount of coating of the top coating agent (on the solid content basis) is preferably 1 g/m2, and particularly preferably 3 g/m2. On the other hand, the upper limit of the amount of coating of the top coating agent is preferably 10 g/m2, and particularly preferably 7 g/m2. When the amount of coating of the top coating agent is less than the lower limit described above, the effect of protecting the substrate layer 2 may be inferior. On the other hand, even if the amount of coating of the top coating agent exceeds the upper limit, the effect of protecting the substrate layer 2 is less likely to be enhanced, and rather leads to an increase in thickness of the tacky sheet 1, whereby results contrary to demands for reduction in thickness and weight saving may be produced.
It is to be noted that various types of additives such as a silane coupling agent for improving contact adhesion properties, an ultraviolet ray absorbing agent for improving weather resistance etc., an inorganic filler for improving heat resistance etc., may be mixed ad libitum in the top coating agent. The amount of such additives mixed is preferably 0.1% by mass or greater and 10% by mass or less in light of the balance between development of effects of the additive, and inhibition of functions of the top coating agent.
The ultraviolet ray absorbing agent which may be included in the top coating agent is not particularly limited as long as it: absorbs ultraviolet rays; can efficiently convert ultraviolet rays into a thermal energy; and is a compound stable to light, and any well-known agent may be used. In particular, salicylic acid-based ultraviolet ray absorbing agents, benzophenone-based ultraviolet ray absorbing agents, benzotriazole-based ultraviolet ray absorbing agents and cyanoacrylate-based ultraviolet ray absorbing agents that have superior function of absorbing ultraviolet rays and have favorable miscibility with the top coating agent, which are present stably are preferred. One, or at least to selected from the group of these agents may be used. Moreover, a polymer having an ultraviolet ray-absorbing group in the molecular chain (for example, “UW UV” series available from Nippon Shokubai Co., Ltd., etc.) may be also used suitably as the ultraviolet ray absorbing agent. By using such a polymer having an ultraviolet ray-absorbing group in the molecular chain, high miscibility with the top coating agent is achieved, and deterioration of the function to absorb ultraviolet rays due to bleeding out of the ultraviolet ray absorbing agent can be prevented.
The tacky material layer 3 is a layer formed from a tacky material, and may be also referred to as a “sticky material layer”. The “tacky material” as referred to means a substance that exerts a resistance force against detachment without need of a hardening process. The tacky material is typically a viscoelastic substance that has a high viscosity and a low modulus of elasticity and has tackiness, and achieves an adhesive force at a normal temperature which can be perceived upon pressurization, whereas it maintains tacky adhesiveness even after the tacky adhesion without a substantial change of the molecular structure of the material. In addition, according to the tacky material layer 3, repeatedly attachable/detachable joining is enabled, thereby allowing for temporary adhesion.
The tacky material layer 3 is formed by coating the tacky material on one face of the substrate layer 2. The lower limit of the average thickness of the tacky material layer 3 is 0.01 mm, preferably 0.015 mm, and particularly preferably 0.02 mm. In addition, the upper limit of the average thickness of the tacky material layer 3 is 1 mm, preferably 0.1 mm, and particularly preferably 0.05 mm. According to the tacky sheet 1 for protecting a back face of a solar battery module including the tacky material layer 3 having the average thickness described above, by laminating the tacky sheet 1 on a back sheet surface of a back face of a solar battery module on which physical defects such as scratches and cracks occurred, penetration of water vapor from the physical defect sites can be prevented, and expansion of the physical defects can be suppressed. In addition, since the average thickness of the tacky material layer 3 falls within the above range according to the tacky sheet 1 for protecting a back face of a solar battery module, the tacky material layer 3 can be embedded into the deepest portion of physical defects which can usually occur, and expansion of the physical defects such as scratches and cracks can be inhibited, and penetration of water vapor and the like from the outside can be prevented certainly.
When the average thickness of the tacky material layer 3 is less than the lower limit described above, the tacky material cannot fill in the physical defects such as scratches and cracks having the depth that may usually occur, leading to generation of gaps. Accordingly, evolution of the expansion of the defects is accelerated, and penetration of water vapor and the like from the gap results in deterioration of barrier properties against water vapor and the like. To the contrary, when the average thickness of the tacky material layer 3 exceeds the upper limit described above, workability may be deteriorated such as, for example, interference of operation of cutting to make the tacky sheet have a desired shape due to the thickness of the tacky material layer 3.
The lower limit of Young's modulus of the tacky material layer 3 is preferably 10−3 MPa, and more preferably 10−2 M Pa. On the other hand, the upper limit of Young's modulus of the tacky material layer 3 is preferably 2 MPa, and more preferably 1 MPa. When the Young's modulus of the tacky material layer 3 is less than the lower limit, the tacky sheet for protecting a back face of a solar battery module attached to a back face of a back sheet may be less likely to be peeled off. Also, when the Young's modulus of the tacky material layer 3 is beyond the upper limit, the tacky material layer may fail to enter into the deepest portion of physical defects generated on the surface of the back sheet.
The lower limit of dynamic viscoelasticity (tan δ) of the tacky material layer 3 at 120° C. is preferably 0.15, and more preferably 0.20. On the other hand, the upper limit of the dynamic viscoelasticity of the tacky material layer 3 at 120° C. is preferably 0.60, and more preferably 0.55. When the dynamic viscoelasticity of the tacky material layer 3 at 120° C. is less than the lower limit, fluidity of the tacky material becomes so high leading to a difficulty in following deformation of the back sheet at a high temperature, and the tacky adhesive force may be reduced. In addition, when the dynamic viscoelasticity of the tacky material layer 3 at 120° C. exceeds the upper limit, fluidity at a high temperature of the tacky material becomes so low that stress applied upon deformation of the back sheet cannot be relaxed, whereby the durability is likely to be deteriorated.
In addition, a temperature at which a maximum dynamic viscoelasticity (tan δ) of the tacky material layer 3 is attained is preferably no greater than −10° C., and more preferably no greater than −20° C. When the temperature at which a maximum dynamic viscoelasticity of the tacky material layer 3 is attained is greater than the lower limit, the tacky adhesive force at a low temperature may be reduced.
Moreover, a glass transition temperature (Tg) of the tacky material layer 3 is preferably no greater than −10° C., and more preferably no greater than −20° C. When the glass transition temperature of the tacky material layer 3 is greater than the lower limit, the tacky adhesive force at a low temperature may be reduced.
Although the tacky material which may be used in the tacky material layer 3 is not particularly limited, for example, acrylic tacky materials, acrylic rubber-based tacky materials, natural rubber-based tacky materials, synthetic rubber-based tacky materials such as butyl rubber-based tacky materials, silicone-based tacky materials, polyurethane-based tacky materials, epoxy-based tacky materials, polyethylene-based tacky materials, polyester-based tacky materials, and the like are exemplified. Of these, acrylic tacky materials because of well harmonized tacky adhesive force, retentive force and tackiness, as well as favorable durability and weather resistance, and availability at low costs, alternatively, butyl rubber-based tacky materials that are favorable in weather resistance, low-temperature resistance and following capability to irregularity are particularly preferred.
Although the monomer for forming the acrylic tacky material is not particularly limited, examples thereof include: acrylic acid alkyl esters and methacrylic acid alkyl esters (wherein, alkyl group having 1 to 20 carbon atoms, for example) such as methyl acrylate, ethyl acrylate, n-butyl acrylate, methyl methacrylate, isobutyl acrylate, t-butyl acrylate, n-octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, isononyl acrylate, ethyl methacrylate, n-butyl acrylate, isobutyl methacrylate, and 2-ethylhexyl methacrylate; acrylic acid hydroxyalkyl esters and methacrylic acid hydroxyalkyl esters (wherein, hydroxyalkyl group having 1 to 20 carbon atoms, for example) such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and 4-hydroxybutyl methacrylate; unsaturated aliphatic carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, and itaconic acid; vinyl acetate; and combinations thereof, and the like. Of these, use of n-butyl acrylate or 2-ethylhexyl acrylate as a monomer is particularly preferred due to favorable tacky adhesion characteristics such as tacky adhesive force, retentive force and tackiness. The aforementioned acrylic tacky material is produced by allowing such a monomer to be polymerized in the presence of a polymerization initiator by solution polymerization, bulk[0] polymerization, emulsion polymerization, suspension polymerization or the like with a common method. Particularly, emulsified acrylic tacky materials obtained by emulsion polymerization are preferred in attempts to reduce burden to the global environment and in light of safety in producing the tacky sheet 1, since water is used as a main polymerization solvent.
Since the acrylic tacky material is superior in compatibility with polycarbonates, an effect of preventing deterioration of the substrate layer 2 is significantly achieved when the acrylic tacky material is used as the tacky material layer 3 and the polycarbonate-based resin is used as the substrate layer 2, whereby durability of the tacky sheet 1 for protecting a back face of a solar battery module can be improved.
The butyl rubber-based tacky material usually contains a butyl rubber, a softening agent and a tackifier resin.
The butyl rubber is obtained by copolymerization using isobutylene as a principal component, with isoprene in an amount of 1 to 2% by mass for permitting crosslinking. Butyl rubbers are characterized by extremely low gas permeability. The butyl rubber is preferably crosslinked for improving the balance of the tacky adhesive force and the cohesive force, which may be carried out by vulcanization with a polyalkyl phenol resin, electron beam crosslinking, ultraviolet crosslinking carried out by adding a photoinitiator, a photopolymerizable mutilfunctional monomer (for example, trimethylolpropane triacrylate, etc.), or the like. Of these, vulcanization with a polyalkyl phenol resin is preferred because a vulcanization catalyst required for other rubber-based tacky materials is not necessary, and favorable heat resistance and anti-staining properties are exhibited.
The softening agent is added for the purpose of lowering the glass transition temperature of the butyl rubber to improve initial adhesion properties during a low temperature stage, whereby maintaining superior balance of the cohesive force and the tacky adhesive force. Examples of the softening agent include e.g., petroleum-based agents such as process oils and extender oils; liquid rubbers such as liquid polyisobutylene, liquid polybutene and liquid polyisoprene; dibasic acid ester-based plasticizers such as dibutyl phthalate and dioctyl phthalate.
The tackifier resin is added for the purpose of improving initial adhesion properties, and examples thereof include e.g., rosin-based resins such as rosins, modified rosins and rosin esters; terpene-based resins such as terpene resins, aromatic modified terpene resins, hydrogenated terpene resins and terpene phenols; petroleum resins such as aliphatic-based (C5-based) petroleum resins, aromatic (C9-based) petroleum resins, C5/C9-based copolymerized petroleum resins, alicyclic petroleum resins, coumarone indene resins and styrene-based petroleum resins; phenol-based resins such as alkylphenol resins and rosin modified phenol resins; all common tackifier resins such as xylene resins. In light of favorable weather resistance, petroleum resins are preferred.
To the butyl rubber-based tacky material may be added, for example, a filler, an anti-aging agent and the like ad libitum within the range to avoid deterioration of tacky adhesion physical properties and the like thereof.
Examples of the filler include e.g., calcium carbonate; magnesium carbonate; calcium such as dolomite; magnesium carbonate; silicic acid salts such as kaolin, calcined clay, pyrophyllite, bentonite, sericite, zeolite, nepheline syenite, talc, attapulgite and wollastonite; silicic acid such as diatomaceous earth and silica flour; aluminum hydroxide; barium sulfate such as pallite and precipitated barium sulfate; calcium sulfate such as gypsum; calcium sulfite; carbon black; zinc oxide; titanium dioxide; and the like.
Examples of the anti-aging agent include e.g., phenol-based anti-aging agents, amine-based anti-aging agents, imidazole-based anti-aging agents, dithiocarbamic acid salt-based anti-aging agents, phosphorus-based anti-aging agents, sulfur ester-based anti-aging agents, and the like.
As the tacky material which may be used in the tacky material layer 3, an ultraviolet curable tacky material may be also used in place of the noncurable tacky material described above. The ultraviolet curable tacky material serves as the present tacky material through coating an uncured liquid basic ingredient for the tacky material on one face of the substrate layer 2, and thereafter irradiating an ultraviolet ray to permit crosslinking, etc., thereby causing tackiness. Thus, the drying step required in the case of use of the solvent type tacky material or the emulsion type tacky material described above can be omitted. Therefore, the coating can be completed at a higher speed, leading to a possible improvement of productivity.
As a basic ingredient for the tacky material of the ultraviolet curable tacky material, any one containing an ultraviolet curable component may be used in addition to the tacky polymer component described above, or any one containing an ultraviolet curable polymer having a form in which an unsaturated double bond is added to the side chain of the tacky polymer may be also used.
As the ultraviolet curable component, any component which causes a reaction by the ultraviolet curable component (for example, a reaction among ultraviolet curable components, a reaction between the ultraviolet curable component and other component in the tacky material layer (for example, an acrylic polymer, etc.) or the like) upon ultraviolet irradiation may be used. Specifically, as the ultraviolet curable component, a compound such as a monomer, an oligomer or a polymer, having at least one group containing an unsaturated double bond in the molecule (unsaturated double bond-containing group) may be used, and a non volatile compound is particularly suited. The ultraviolet curable component may be used alone, or two or more thereof may be used in combination.
The unsaturated double bond-containing group in the ultraviolet curable component is particularly preferably a group containing a carbon-carbon double bond (carbon-carbon double bond-containing group), and examples of the carbon-carbon double bond-containing group, include e.g., ethylenic unsaturated bond-containing groups such as a vinyl group, allyl groups, and (meth)acryloyl groups, and the like. The unsaturated double bond-containing group may be used alone, or two or more thereof may be used in combination. One molecule of the ultraviolet curable component preferably has the unsaturated double bond-containing group in the number of at least two. When the ultraviolet curable component has at least two unsaturated double bond-containing groups in one molecule, the same unsaturated double bond-containing group may be used in multiple number, or at least two kinds of unsaturated double bond-containing groups may be used.
As the ultraviolet curable component, for example, esterified products of (meth)acrylate and a polyhydric alcohol, ester acrylic compounds, urethane acrylic compounds, cyanurate-based compounds having an unsaturated double bond-containing group, as well as isocyanurate-based compounds having an unsaturated double bond-containing group, and the like may be exemplified.
More specifically, the ultraviolet curable component may be exemplified by, for example, di(meth)acrylates of an alkylene glycol (e.g., (meth)acrylic acid di(alkylene glycol) esters; for example, di(meth)acrylates of a C1-9 alkylene glycol or a poly(C1-9 alkylene glycol) such as di(meth)acrylate of tetraethylene glycol, di(meth)acrylate of polyethylene glycol, di(meth)acrylate of propylene glycol, di(meth)acrylate of polypropylene glycol, di(meth)acrylate of 1,4-butylene glycol, di(meth)acrylate of 1,6-hexanediol, di(meth)acrylate of neopentyl glycol, etc.),
2-propenyl-di-3-butenyl cyanurate, di(meth)acrylate of tris(2-hydroxyethyl)isocyanurate, di(meth)acrylates of diols obtained by addition of 4 mol or more ethylene oxide or propylene oxide based on 1 mol of neopentyl glycol, di(meth)acrylates of bisphenol A or a modified product thereof, di(meth)acrylates of trimethylolpropane or a modified product thereof, tri(meth)acrylates of trimethylolpropane or a modified product thereof, tetramethylolmethane tetra(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, poly(meth)acrylates of dipentaerythritol, caprolactone-modified tris[(meth)acryloxyethyl]isocyanurate, poly(meth)acrylates of caprolactone-modified dipentaerythritol, neopentyl glycol adipate-modified di(meth)acrylate, neopentyl glycol hydroxypivalate di(meth)acrylate, hydroxypivalic acid ester-modified neopentyl glycol di(meth)acrylate, caprolactone-modified neopentyl glycol hydroxypivalate di(meth)acrylate, dioxane-modified di(meth)acrylate, cyclopentanyl di(meth)acrylate, ethylene oxide-modified phosphoric acid di(meth)acrylate, ethylene oxide-modified alkylated phosphoric acid di(meth)acrylate, poly(meth)acrylates of alkyl-modified dipentaerythritol, and the like.
Although the rate of the ultraviolet curable component contained is not particularly limited, for example, it is about 5 to 500 parts by mass, and preferably 10 to 200 parts by mass based on 100 parts by mass of the tacky polymer component such as an acrylic resin.
It is to be noted that the basic ingredient for the tacky material of the ultraviolet curable tacky material may be blended with additives such as a photopolymerization initiator and a crosslinking agent as needed in addition to the tacky polymer component and the ultraviolet curable component.
The photopolymerization initiator is not particularly limited as long as it is a photopolymerization initiator which can be activated by an ultraviolet ray, and can cause a reaction of the ultraviolet curable component. Specific examples of the photopolymerization initiator which may be used include e.g., acetophenone-based photopolymerization initiators, benzoin-based photopolymerization initiators, benzyl-based photopolymerization initiators, benzoinalkyl ether-based photopolymerization initiators, benzophenone-based photopolymerization initiators, ketal-based photopolymerization initiators, thioxanthone-based photopolymerization initiators, α-ketol-based photopolymerization initiators, aromatic sulfonyl chloride-based photopolymerization initiators, photoactive oxime-based
photopolymerization initiators, and the like. The photopolymerization initiator may be used alone, or two or more thereof may be used in combination.
As the photopolymerization initiator, an acetophenone-based photopolymerization initiator, or a benzoin-based photopolymerization initiator is suitable. Examples of the acetophenone-based photopolymerization initiator include e.g., 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-phenyl-2-hydroxy-2-methylpropane-1-one, 1-[4-(2-hydroxyethyl)-phenyl]-2-hydroxy-2-methylpropane-1-one, 1-hydroxycyclohexyl phenyl ketone, and the like. As the benzoin-based photopolymerization initiator, for example, benzoin and the like may be exemplified.
In addition, the benzyl-based photopolymerization initiator includes, for example, benzyl and the like. Examples of the benzoinalkyl ether-based photopolymerization initiator include e.g., benzoinmethyl ether, benzoinethyl ether, benzoinpropyl ether, benzoinisopropyl ether, benzoinisobutyl ether, and the like. Examples of the benzophenone-based photopolymerization initiator include e.g., benzophenone, benzoylbenzoic acid, 3,3-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, α-hydroxycyclohexylphenyl ketone, and the like. Examples of the ketal-based photopolymerization initiator include e.g., benzyldimethyl ketal, and the like. Examples of the thioxanthone-based photopolymerization initiator include e.g., thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone, and the like.
Moreover, as the crosslinking agent, for example, a polyisocyanate-based crosslinking agent, a melamine resin, a urea resin, an aziridine-based compound, an epoxy-based crosslinking agent such as an epoxy resin, a low-molecular compound having multiple carboxyl groups, or an anhydride thereof, a polyamine, a polymer having multiple carboxyl groups, or the like may be used.
Alternatively, as the tacky material which may be used in the tacky material layer 3, a hot melt type tacky material may be also used. The hot melt type tacky material is a tacky mixture containing as a base a thermoplastic polymer having a solid content of 100% at room temperature, and is coated on one face of the substrate layer 2 by heat melting at 100° C. to 180° C. to impart fluidity, without need of a solvent or water. After the coating, the fluidity disappears by cooling to give the tacky material layer 3 having tackiness.
According to the tacky sheet 1 for protecting a back face of a solar battery module, by providing to attach the tacky sheet 1 via the tacky material layer 3 on a back face of a back sheet of a back face of a solar battery module in which physical defects such as damaging and cracks are caused, penetration of water vapor and the like from the physical defect sites can be prevented, and the expansion of the defect sites can be inhibited. In addition, according to the tacky sheet for protecting a back face of a solar battery module, since the tacky material layer 3 has a given thickness, expansion of defects such as scratches and cracks can be inhibited, and penetration of water vapor and the like from outside to inside the solar battery module can be certainly prevented by embedding the tacky material layer into the deepest portion of the physical defect which can usually occur on the back sheet.
The tacky sheet 11 for protecting a back face of a solar battery module shown in
The barrier layer 4 contains an inorganic substance. Although the inorganic substance is not particularly limited as long as it has gas barrier properties, it is preferably an inorganic oxide. The barrier layer 4 containing an inorganic oxide enables superior gas barrier properties against water vapor and the like to be exerted, and due to having an insulation property, portions having electric conductivity such as solar battery cells and wirings can be protected even in the cases in which physical defects such as cracks are significantly generated in the back sheet.
The barrier layer 4 including the inorganic oxide may be formed by vapor deposition of an inorganic oxide on one face of the substrate layer 2. The means for the vapor deposition is not particularly limited as long as vapor deposition of the inorganic oxide is executed without causing deterioration of the synthetic resin substrate layer 2 such as contraction. Examples of the applicable means include (a) physical vapor deposition (PVD) such as vacuum evaporation, sputtering, ion plating, ion cluster beam methods and the like, and (b) chemical vapor deposition (CVD) such as plasma chemical vapor deposition, thermal chemical vapor deposition, photochemical vapor deposition and the like. Among these vapor deposition, vacuum evaporation and ion plating are preferred which enable formation of the barrier layer 4 having high quality with high productivity.
The inorganic oxide that constitutes the barrier layer 4 is not particularly limited as long as it has gas barrier properties, and for example, aluminum oxide, silica oxide, titanium oxide, zirconium oxide, zinc oxide, tin oxide, magnesium oxide or the like may be used. Of these, aluminum oxide or silica oxide is particularly preferred because of favorable balance of costs and gas barrier properties.
When the barrier layer 4 is formed by vapor deposition of the inorganic oxide, the lower limit of the average thickness of the barrier layer 4 is preferably 3 Å, and particularly preferably 400 Å. In contrast, when the barrier layer 4 is formed by vapor deposition of the inorganic oxide, the upper limit of the average thickness of the barrier layer 4 is preferably 3000 Å, and particularly preferably 800 Å. When the average thickness of the barrier layer 4 is less than the aforementioned lower limit, gas barrier properties are likely to be deteriorated. To the contrary, the average thickness of the barrier layer 4 is greater than the aforementioned upper limit, less flexibility of the barrier layer 4 is achieved, whereby defects such as cracking are likely to occur.
In addition, the barrier layer 4 may include aluminum as an inorganic substance, and may be formed by vapor deposition of aluminum. When the barrier layer 4 is formed by vapor deposition of aluminum, gas barrier properties are particularly improved according to the tacky sheet 1, and rays of light passed through the solar battery cell are reflected and subjected to recycling due to the aluminum vapor deposition surface having metal gloss, whereby efficiency of electric power generation can be promoted.
As the method for forming the barrier layer 4 by vapor deposition of aluminum, a method similar to the vapor deposition method of the inorganic oxide described above may be used. When the barrier layer 4 is formed by vapor deposition of aluminum, the lower limit of the average thickness of the barrier layer 4 is preferably 10 nm, and particularly preferably 20 nm. On the other hand, the upper limit of the thickness of the barrier layer 4 formed by aluminum vapor deposition is preferably 200 nm, and particularly preferably 100 nm. When the thickness of the barrier layer 4 is less than the aforementioned lower limit, the gas barrier properties may be deteriorated. To the contrary, when the barrier layer 4 has a thickness exceeding the aforementioned upper limit, defects such as cracks are more likely to be generated in the barrier layer 4.
The barrier layer 4 may have either a monolayer structure, or a multilayer structure including two or more layers. By the formation of the barrier layer 4 having a multilayer structure, deterioration of the substrate layer 2 can be minimized through reduction of thermal burden applied during the vapor deposition, and further, adhesiveness between the substrate layer 2 and the barrier layer 4 can be improved. In addition, conditions of the vapor deposition employed in the aforementioned physical vapor deposition and chemical vapor deposition may be arbitrarily determined depending on the resin type of the substrate layer 2, thickness of the barrier layer 4, and the like.
in addition, the barrier layer 4 may be formed by a sol-gel method using a composition containing a metal alkoxide and/or a hydrolysate thereof. By forming the barrier layer 4 with such a sol-gel method, adhesiveness with the substrate layer 2 is enhanced, whereby superior gas barrier properties can be exerted. In addition, the barrier layer 4 can be formed at a comparatively low temperature by employing the sol-gel method in which the temperature is not elevated so high as in accordance with vapor deposition. Therefore, since a burden is less likely to be imposed to the substrate layer 2 which is not comparatively resistant to high temperatures, barrier layer 4 having multi layers can be easily formed.
The metal included in the metal alkoxide is exemplified by trivalent or higher valent metals such as e.g., transition metals, rare-earth metals, metals in Groups 3 to 5 in the periodic table, and metals belonging to Group 3B or Group 4 in the periodic table are preferred. The metals belonging to Group 3B in the periodic table include, for example, Al and the like. The metals belonging to Group 4 in the periodic table include, for example, Ti and Zr belonging to Group 4A, as well as Si belonging to Group 4B, and the like. Among these metals, because a film can be easily formed with a sol-gel method and a superior planarizing function of boundary surfaces is exhibited, Al and Si are preferred and Si is particularly preferred.
Examples of the alkoxy group included in the metal alkoxide include e.g., a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a pentyloxy group, a hexyloxy group, and the like. Of these, lower alkoxy groups having 1 to 4 carbon atoms that are superior in hydrolytic polymerizability are preferred, and a methoxy group, an ethoxy group, and a propoxy group are particularly preferred. In addition, for the purpose of promoting hydrolytic polymerizability, a metal alkoxide having at least two alkoxy groups is preferred.
The metal alkoxide may have a hydrocarbon group. Examples of the hydrocarbon group include e.g., alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, and a hexyl group; cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group; aryl groups such as a phenyl group, and a naphthyl group; aralkyl groups such as a benzyl group, and a 2-phenylethyl group, and the like. Among these hydrocarbon groups, alkyl groups and aryl groups are preferred. Of these alkyl groups, lower alkyl groups having 1 to 4 carbon atoms are preferred, and a methyl group, an ethyl group and a propyl group are particularly preferred. In addition, of the aryl groups, a phenyl group is preferred. The number of hydrocarbon groups in the metal alkoxide may be selected appropriately depending on the number of the alkoxy groups, and is, in general, about 0 to 2 in one molecule.
Specifically, the metal alkoxide is preferably one represented by the following formula (1):
(R1)mM(OR2)x-m (1)
in the above formula (1): R1 represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, which may have a substituent; R2 represents a lower alkyl group; R1 and R2 may be different depending on “m”; M represents a trivalent or higher valent metal; X represents the valence of the metal M; m represents an integer of 0 to 2; and the difference (X−m) is no less than 2.
In particular, the metal alkoxide in which the metal is Si is preferably represented by the following formula (2):
(R1)nSi(OR2)4-n (2)
in the above formula (2): R1 represents an alkyl group or an aryl group, which may have a substituent; R2 represents a lower alkyl group; R1 and R2 may be different depending on “n”; and n represents an integer of 0 to 2.
Specific examples of the metal alkoxide in which the metal is Al include trimethoxyaluminate, triethoxyaluminate, ethyldiethoxyaluminate, tripropoxyaluminate, and the like.
Specific examples of the metal (Si) alkoxide represented by the above formula (2) include tetramethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, tetraethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyitriethoxysilane, butyltriethoxysilane, tetrapropoxysilane, methyltripropoxysilane, ethyltripropoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dipropyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-mercaptopropyltrimethoxysiiane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and the like.
Among the metal (Si) alkoxide represented by the above formula (2), compounds having 0 to 2 alkyl group(s) or aryl group(s) having about 1 to 4 carbon atoms, and 2 to 4 alkoxy groups having about 1 to 3 carbon atoms, for example, tetramethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, tetraethoxysilane, ethyltriethoxysilane, diethyldiethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and the like are particularly preferred.
In the aforementioned composition, the same type or different type of the metal alkoxide may be used alone or as a mixture of two or more thereof. Moreover, in the composition, monoalkoxysilane in which n is 3 may be added for adjusting hardness and flexibility of the composition, and the like. Furthermore, a compound of a Group 5B element such as, for example, a phosphorus-based compound such as a methyl phosphonous dimethyl ester, ethyl phosphonous dimethyl ester, trichloromethyl phosphonous diethyl ester, methyl phosphonous diethyl ester, methyl phosphonic dimethyl ester, phenyl phosphonic dimethyl ester, or phosphoric acid trialkyl ester, or a boron compound such as boric acid trialkyl ester may be added to the composition described above. Moreover, an alkaline earth metal compound having at least one hydrolyzable organic group may be added as needed to the composition described above. This alkaline earth metal compound may have both the hydrocarbon group and the hydrolyzable organic group.
In the aforementioned composition, a metal alkoxide (A) having a functional group containing at least one of nitrogen, oxygen, sulfur and halogen may be contained. By applying and curing such a composition containing the metal alkoxide (A) having a functional group containing at least one of nitrogen, oxygen, sulfur and halogen, a specific polysiloxane structure is exhibited in the barrier layer 4, and the film physical properties and in turn, gas barrier properties of the barrier layer 4 can be improved. Still more, the temperature dependency of the gas barrier properties of the barrier layer 4 can be reduced.
As the functional group containing at least one of nitrogen, oxygen, sulfur and halogen, for example, an amino group, a chlorine atom, a mercapto group, a glycidoxy group and the like may be exemplified. Examples of the metal alkoxide (A) having the functional group containing at least one of nitrogen, oxygen, sulfur and halogen include e.g., γ-chloropropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyitrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-ureidepropyltriethoxysilane, bis(β-hydroxyethyl)-γ-aminopropyltriethoxysilane, γ-aminopropylsilicone, and the like, and either one, or at least two of these metal alkoxides may be used.
The content of the metal alkoxide (A), i.e., the content in the composition based on the entire metal alkoxide is preferably 1% by mass or greater and 50% by mass or less, and particularly preferably 3% by mass or greater and 30% by mass or less. When the content of the metal alkoxide (A) falls within the above range, a polysiloxane structure that is responsible for gas barrier properties can be provided on the barrier layer 4.
In the aforementioned composition, a solvent-soluble polymer may be contained. By forming the barrier layer 4 according to the sol-gel method using a composition containing such a solvent-soluble polymer and the metal alkoxide, film physical properties of the barrier layer 4 are improved, and the gas barrier properties (particularly, gas barrier properties in conditions with high temperatures) of the barrier layer 4 can be further enhanced.
As the aforementioned solvent-soluble polymer, polymers having any of a variety of functional groups or functional binding groups (for example, a hydroxyl group, a carboxyl group, an ester bond, an ether bond, a carbonate bond, an amide group, an amide bond, etc.), polymers having a glycidyl group, halogen-containing polymers, and derivatives from these polymers, and the like are exemplified. These functional groups or functional binding groups may be present either in the main chain or the side chain of the polymer. The solvent-soluble polymer may be either a thermoplastic resin or a thermosetting resin, which may be used either alone or as a mixture of two or more thereof. In addition, although the solvent-soluble polymer may be either inert or active for the reaction with the metal alkoxide, a nonreactive polymer is generally employed. The term “amide bond” herein referred to is not limited to “—NHC(O)—”, but falls under a concept including a >NC(O)— bond unit.
Examples of the aforementioned polymer having a hydroxyl group and a derivatives thereof include e.g., polyvinyl alcohols, polyvinyl acetals, ethylene-vinyl alcohol copolymers, phenol resins, methylolmelamine and the like, and derivatives thereof (for example, acetalized products, hexamethoxymethylmelamine, etc.). Examples of the aforementioned polymer having carboxyl and derivatives thereof include e.g., homopolymers or copolymers including polymerizable unsaturated acid units such as poly(meth)acrylic acid, maleic anhydride and itaconic acid, and esterified products of these polymers. Examples of the aforementioned polymer having an ester bond include e.g., homopolymers or copolymers including units of a vinyl ester such as vinyl acetate, a (meth)acrylic ester such as methyl methacrylate (for example, polyvinyl acetate, ethylene-vinyl acetate copolymers, (meth)acrylic resins, etc.), saturated polyesters, unsaturated polyesters, vinyl ester resins, diallyl phthalate resins, cellulose esters, and the like. Examples of the polymer having an ether bond include e.g., polyalkylene oxides, polyoxyalkylene glycols, polyvinyl ethers, silicon resins, and the like. Examples of the aforementioned polymer having a carbonate bond include polycarbonates such as bisphenol A type polycarbonates.
Examples of the aforementioned polymer having an amide bond include e.g., N-acylated products such as polyoxazoline having a >N(COR)— bond, and polyalkyleneimine; polyvinylpyrrolidone having a >NC(O)— bond and derivatives thereof; polyurethane having a urethane bond —HNC(O)O—; polymers having a urea bond —HNC(O)NH—; polymers having an amide bond —C(O)NH—; polymer having a biuret linkage; polymer having an allophanate linkage; and the like. In the above formula representing the binding, R represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.
In the case of polyoxazoline having a >N(COR)— bond, the alkyl group represented by R may include, for example, an alkyl group having about 1 to 10 carbon atoms, preferably a lower alkyl group having 1 to 4 carbon atoms, and particularly, a methyl group, an ethyl group, a propyl group, an isopropyl group, or the like. The substituent of the alkyl group includes, for example, a halogen atom such as fluorine, chlorine or bromine, a hydroxyl group, an alkoxy group having about 1 to 4 carbon atoms, a carboxyl group, an alkoxycarbonyl group with an alkyl moiety having about 1 to 4 carbon atoms, and the like. Examples of the aryl group include e.g., phenyl, naphthyl groups, and the like. Examples of the substituent of the aryl group include e.g., the aforementioned halogen atoms, alkyl groups having about 1 to 4 carbon atoms, a hydroxyl group, alkoxy groups having about 1 to 4 carbon atoms, a carboxyl group, alkoxycarbonyl groups with an alkyl moiety having about 1 to 4 carbon atoms, and the like.
Examples of the oxazoline include e.g., 2-oxazoline, 2-methyl-2-oxazoline, 2-ethyl-2-oxazoline, 2-propyl-2-oxazoline, 2-isopropyl-2-oxazoline, 2-butyl-2-oxazoline, 2-dichloromethyl-2-oxazoline, 2-trichloromethyl-2-oxazoline, 2-pentafluoroethyl-2-oxazoline, 2-phenyl-2-oxazoline, 2-methoxycarbonylethyl-2-oxazoline, 2-(4-methylphenyl)-2-oxazoline, 2-(4-chlorophenyl)-2-oxazoline, and the like. In particular, 2-oxazoline, 2-methyl-2-oxazoline, 2-ethyl-2-oxazoline and the like are preferred. Polymers of such oxazoline may be used either alone, or as a mixture of two or more thereof. The polyoxazoline may be either a homopolymer or a copolymer. In addition, the polyoxazoline may be a copolymer in which a polyoxazoline segment is grafted to a polymer.
The polyoxazoline is obtained by ring-opening polymerization of oxazoline which may have a substituent in the presence of a catalyst. As the catalyst, for example, a sulfuric acid ester or a sulfonic acid ester such as dimethyl sulfate, or p-toluenesulfonate alkyl ester; a halogenated alkyl such as alkyl iodide (for example, methyl iodide); metal fluoride among Friedel-Crafts catalysts; an acid such as sulfuric acid, hydrogen iodide or p-toluenesulfonic acid, or an oxazolinium salt which is a salt formed with such an acid and oxazoline, or the like may be used.
Examples of the acylated product of polyalkyleneimine include polymers corresponding to the aforementioned polyoxazoline such as e.g., polymers having an N-acylamino group such as N-acetylamino or N-propionylamino. The polyvinylpyrrolidone and derivatives thereof include polymers of vinylpyrrolidone which may have a substituent, for example, polyvinylpyrrolidone, and the like. Examples of the polyurethane having a urethane bond include e.g., polyurethanes produced by a reaction of a polyisocyanate (tolylenediisocyanate, hexamethylenediisocyanate, etc.) with a polyol (a polyhydric alcohol such as ethylene glycol, propylene glycol, tetramethylene glycol or glycerin; a polyether polyol such as diethylene glycol, polyethylene glycol, dipropylene glycol, or polypropylene glycol; a polyester polyol, or the like). Examples of the polymer having a urea bond include e.g., polymers produced by a reaction of polyurea, polyisocyanate and polyamine (for example, a diamine such as ethylene diamine, diethylene triamine).
Examples of the polymer having an amide bond include polyamide, poly(meth)acrylamide, polyamino acid, and the like. The polymer having an amide bond is preferably a polymer of oxazoline which may have a substituent, an N-acylated product of polyalkyleneimine, polyvinylpyrrolidone, polyurethane, polyamide, poly(meth)acrylamide, and the like. Examples of the polymer having a biuret linkage include polymers produced by a reaction of the polyisocyanate with a compound having a urethane bond. Examples of the polymer having an allophanate linkage include polymers produced by a reaction of the polyisocyanate with a compound having a urea bond, and the like. Examples of the polymer having a glycidyl group include e.g., epoxy resins, homopolymers or copolymers of glycidyl (meth)acrylate, and the like. Examples of the halogen-containing polymer include e.g., polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, vinylidene chloride-based polymers having a vinylidene chloride unit, chlorinated polypropylene, and the like.
The solvent-soluble polymer is, in general, soluble in water; alcohols such as methanol, ethanol, propanol, isopropanol, butanol and cyclohexanol; aliphatic hydrocarbons such as hexane and octane; alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as methyl chloride, methylene chloride, chloroform and trichloroethylene; esters such as methyl acetate, ethyl acetate and butyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether, dioxane, dimethoxyethane and tetrahydrofuran; nitrogen-containing solvents (for example, N-methylpyrrolidone, nitriles such as acetonitrile, amides such as dimethylformamide and dimethylacetamide, etc.) as well as aprotic polar solvents such as sulfoxides (for example, dimethyl sulfoxide, etc.); or mixed solvents of the same.
As the solvent-soluble polymer, those having a group capable of forming a hydrogen bond such as e.g., a hydroxyl group, a carboxyl group, an amide group, an amide bond, a nitrogen atom or the like are preferred. When such a solvent-soluble polymer having a group capable of forming a hydrogen bond is used, the solvent for the metal alkoxide and/or a hydrolysate thereof may often be one that is in common, and it is believed that the hydroxyl group of the organic metal polymer produced by hydrolytic polymerization of the metal alkoxide forms a hydrogen bond with a functional group and/or a binding group of the solvent-soluble polymer, and consequently forms a uniform organic-inorganic hybrid thereby enabling a transparent coating film which is uniform at the micro level to be formed.
In addition, as the solvent-soluble polymer, an alcohol-soluble polymer is preferred since a solvent common with that for the metal alkoxide can be used. The alcohol-soluble polymer is preferably a water-soluble polymer such as a polymer having a hydroxyl group, and particularly preferably a polymer having a nitrogen atom (for example, the polymer having an amide bond described above).
The content of the solvent-soluble polymer based on 100 parts by mass of the metal alkoxide (including a hydrolysate thereof) is preferably 40% by mass or greater and 90% by mass or less, and particularly preferably 50% by mass or greater and 80% by mass or less. When the content of the solvent-soluble polymer is below the above range, the effect of improving the gas barrier properties is deteriorated, and formation of a uniform a coating film with a complex of the inorganic polymer and the organic polymer may be difficult. On the other hand, when the content of the solvent-soluble polymer is beyond the above range, the film formability and the uniformity are likely to be improved, whereas the gas barrier properties may be deteriorated.
In the composition described above, an organic solvent is generally blended. As the organic solvent, an inert appropriate solvent for the polymerization reaction depending on the type of the metal alkoxide, such as for example, an alcohol, an aromatic hydrocarbon, an ether, a nitrogen-containing solvent, a sulfoxide, or a mixed solvent thereof, or the like may be used. Alternatively, the aforementioned solvent-soluble polymer may be also used as the organic solvent. This organic solvent is preferably a solvent that is miscible with the solvent for the metal alkoxide, and is particularly preferably a good solvent that is common for both the solvent-soluble polymer and the metal alkoxide.
In addition, the composition may contain a curing catalyst, and hydrolytic polymerization of the metal alkoxide may be carried out in the presence of the curing catalyst. As the curing catalyst, a tertiary amine which is substantially insoluble in water and soluble in an organic solvent, an acid catalyst or the like is used. Examples of the tertiary amine include e.g., N,N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine, and the like. Examples of the acid catalyst include inorganic acids such as e.g., hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid; organic acids such as e.g., carboxylic acids such as formic acid, acetic acid, trichloroacetic acid, trifluoroacetic acid and propionic acid, sulfonic acids such as methanesulfonic acid, ethanesulfonic acid and p-toluenesulfonic acid, and the like.
In the composition for forming the barrier layer 4 by a sol-gel method may be blended as needed a variety of additives such as a plasticizer, an antioxidant, an ultraviolet ray absorbing agent, a fire retardant, an antistatic agent, a surfactant, a filler, a colorant, and the like ad libitum.
Next, a method for forming the barrier layer 4 by a sol-gel method is explained. The composition is prepared by adding a solvent-soluble polymer, a curing catalyst, an organic solvent and the like to a metal alkoxide and/or a hydrolysate thereof ad libitum, and sufficiently kneading. This composition is coated on the surface of the substrate layer 2 by a common coating method, and then dried by heating. The composition is further subjected to an aging treatment or the like to form the barrier layer 4 as a coated and cured film. This heating temperature is appropriately selected depending on the hydrolyzability of the metal alkoxide, and the heat resistance of the substrate layer 2, which temperature is preferably 50° C. or higher and 120° C. or lower. The polymerization reaction may be carried out in the presence of an inert gas, or under a reduced pressure. Moreover, the polymerization may be allowed while removing alcohols produced as the hydrolytic polymerization proceeds.
In the method for forming the barrier layer 4 by a sol-gel method, it is preferred to subject the composition to ultraviolet irradiation in the heating step. By thus subjecting the composition to ultraviolet irradiation in the heating step of the sol-gel method, the composition is cured at a lower temperature (no higher than 100° C.), and defects of the barrier layer 4 are significantly reduced with superior film physical properties and improved adhesiveness between the barrier layer 4 and the substrate layer 2. Thus, the gas barrier properties of the barrier layer 4 can be further enhanced.
Moreover, for improving the contact adhesion properties and the like between the substrate layer 2 and the barrier layer 4, one face of the substrate layer 2 may be subjected to a surface finishing treatment. Examples of such a surface finishing treatment for improving the adhesiveness include e.g., (a) a corona discharge treatment, an ozone treatment, low-temperature plasma treatment using an oxygen gas, a nitrogen gas or the like, a glow discharge treatment, oxidizing treatments using a chemical or the like, (b) a primer coating treatment, an undercoating treatment, an anchor coating treatment, a vapor deposition anchor coating treatment, and the like. Among these surface finishing treatments, the corona discharge treatment and the anchor coating treatment are preferred which achieve enhancement of the adhesive strength to the barrier layer 4, and are responsible for formation of compact and uniform barrier layer 4.
Examples of the anchor coating agent which may be used in the aforementioned anchor coating treatment include e.g., polyester-based anchor coating agents, polyamide-based anchor coating agents, polyurethane-based anchor coating agents, epoxy-based anchor coating agents, phenol-based anchor coating agents, (meth)acrylic anchor coating agents, polyvinyl acetate-based anchor coating agents, polyolefin-based anchor coating agents such as those including polyethylene or polypropylene as the base, cellulose-based anchor coating agents, and the like. Among these anchor coating agents, polyester-based anchor coating agents which can further enhance the adhesive strength between the substrate layer 2 and the barrier layer 4 are particularly preferred.
The lower limit of the amount of coating of the aforementioned anchor coating agent (calculated based on the solid content) is preferably 0.1 g/m2, and particularly preferably 1 g/m2. In contrast, the upper limit of the amount of coating of the anchor coating agent is preferably 5 g/m2, and particularly preferably 3 g/m2. When the amount of coating of the anchor coating agent is less than the aforementioned lower limit, the effect of improving the adhesiveness between the substrate layer 2 and the barrier layer 4 may be decreased. To the contrary, when the amount of coating of the anchor coating agent is greater than the aforementioned upper limit, strength, durability and the like of the tacky sheet 1 for protecting a back face of a solar battery module may be deteriorated.
In the anchor coating agent described above, can be blended a variety of additives such as a silane coupling agent for improving contact adhesion properties, an antiblocking agent for preventing blocking with the substrate layer 2, an ultraviolet ray-absorbing agent for improving weather resistance, and the like. The amount of blending of such additives is preferably 0.1% by mass or more and 10% by mass or less in light of the balance of the effect exhibited by the additive, and possible inhibition of the function to be performed by the anchor coating agent.
Furthermore, one face (the external side face not brought into contact with the substrate layer 2) of the barrier layer 4 is preferably subjected to a top coating treatment. By thus subjecting the external face of the barrier layer 4 to a top coating treatment, the barrier layer 4 is sealed and protected, and consequently, handleability of the tacky sheet 11 is improved. In addition, even if there are defects such as scratches and recessed parts in the barrier layer 4, deterioration of the gas barrier properties can be suppressed, and further aged deterioration of the barrier layer 4 can be inhibited. As the top coating agent for use in the top coating treatment described above, one similar to the agent for use in the substrate layer 2 may be used.
The lower limit of the amount of coating of the top coating agent (calculated based on the solid content) is preferably 1 g/m2, and particularly preferably 3 g/m2. On the other hand, the upper limit of the amount of coating of the top coating agent is preferably 10 g/m2, and particularly preferably 7 g/m2. When the amount of coating of the top coating agent is less than the lower limit described above, the effect of sealing and protecting the barrier layer 4 may be inferior. On the other hand, even if the amount of coating of the top coating agent exceeds the upper limit described above, the effect of sealing and protecting the barrier layer 4 is less likely to be enhanced, and rather leads to an increase in the thickness of the tacky sheet 11, whereby results contrary to demands for reduction in thickness and weight saving may be produced.
It is to be noted that various types of additives such as a silane coupling agent for improving contact adhesion properties, an ultraviolet ray absorbing agent for improving weather resistance etc., an inorganic filler for improving heat resistance etc., may be mixed ad libitum in the top coating agent. The amount of mixing of such additives is preferably 0.1% by mass or greater and 10% by mass or less in light of the balance between development of effects of the additive, and inhibition of functions of the top coating agent.
Since the tacky sheet 11 for protecting a back face of a solar battery module thus has the barrier layer 4 laminated on another face side of the substrate layer 2, superior gas barrier properties are provided, and the mechanical strength can be improved. Moreover, in the case in which the tacky sheet 11 for protecting a back face of a solar battery module has the barrier layer 4 including an inorganic oxide, and due to having a superior insulation property, portions having electric conductivity such as solar battery cells and wirings can be protected even in the cases in which deep physical defects are generated in the back sheet.
The tacky sheet 21 for protecting a back face of a solar battery module shown in
An aluminum foil is used for the barrier layer 5. The material entity of the aluminum foil may include aluminum or an aluminum alloy, and is preferably an aluminum-iron-based alloy (soft material). The iron content in the aluminum-iron-based alloy is preferably no less than 0.3% and no greater than 9.0%, and particularly preferably no less than 0.7% and no greater than 2.0%. When the iron content is less than the lower limit described above, an effect of preventing generation of pinholes may be insufficient. To the contrary, when the iron content exceeds the upper limit described above, the flexibility is inhibited, and the processability may be deteriorated. Furthermore, as the material of the aluminum foil, soft aluminum subjected to an annealing treatment is preferred in light of prevention of the pinhole generation.
The lower limit of the thickness (average thickness) of the aluminum foil is preferably 6 μm, and particularly preferably 1.5 μm. On the other hand, the upper limit of the thickness of the aluminum foil is preferably 30 μm, and particularly preferably 20 μm. When the thickness of the aluminum foil is less than the lower limit described above, breaking of the aluminum foil is likely to occur during the processing, and the gas barrier properties may be deteriorated resulting from the pinhole and the like. On the other hand, when the thickness of the aluminum foil is greater than the upper limit described above, cracks and the like may be generated during the processing, and the thickness and the weight of the tacky sheet 21 for protecting a back face of a solar battery module increase, whereby results contrary to social demands for reduction in thickness and weight saving may be produced.
In light of prevention of dissolution and corrosion, the surface of the aluminum foil may be subjected to a surface treatment such as, for example, a chromate treatment, a phosphate treatment, or a lubricating resin-coating treatment. Moreover, in light of acceleration of the adhesion properties, the surface of the aluminum foil may be subjected to a coupling treatment and the like. Additionally, the aluminum foil may have an increased surface area by forming fine irregularities by means of emboss processing etc., in order to allow a superior heat dissipation function to be exerted from the surface.
In addition, one face (the face on the side not brought into contact with the adhesive layer 6) of the aluminum foil that is provided as the barrier layer 5 is preferably subjected to a top coating treatment similarly to the barrier layer 4 of the tacky sheet 11 for protecting a back face of a solar battery module. By thus subjecting the external face of the barrier layer 5 to a top coating treatment, the barrier layer 5 is sealed and protected, and consequently, handleability of the tacky sheet 21 is improved. In addition, even if there are defects such as scratches and recessed parts in the barrier layer 5, deterioration of the gas barrier properties can be suppressed, and further aged deterioration of the barrier layer 5 can be inhibited.
Although the adhesive that constitutes the adhesive layer 6 is not particularly limited, an adhesive for lamination or a melt-extruded resin is suitably used. Examples of the adhesive for lamination include e.g., adhesives for dry lamination, adhesives for wet lamination, adhesives for hot melt lamination, adhesives for nonsolvent lamination, and the like. Among these adhesives for lamination, adhesives for dry lamination are particularly preferred which are excellent in the adhesive strength, durability, weather resistance and the like, and have the sealing and protecting functions to compensate for defects (for example, scratch, pinhole, recessed part and the like) of the surface of the substrate layer 2.
Examples of the adhesive for dry lamination include e.g., polyvinyl acetate-based adhesives, polyacrylic ester-based adhesives consisting of a homopolymer of an ethyl, butyl, 2-ethylhexyl ester or the like of acrylic acid, or a copolymer of the acrylic acids and methyl methacrylate, acrylonitrile, styrene or the like, cyano acrylate-based adhesives, ethylene copolymer-based adhesives consisting of a copolymer of ethylene and a monomer such as vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid or the like, cellulose-based adhesives, polyester-based adhesives, polyamide-based adhesives, polyimide-based adhesives, amino resin-based adhesives consisting of an urea resin, a melamine resin or the like, phenol resin-based adhesives, epoxy-based adhesives, polyurethane-based adhesives, reactive (meth)acrylic adhesives, rubber-based adhesives consisting of a chloroprene rubber, a nitrile rubber, a styrene-butadiene rubber or the like, silicone-based adhesives, inorganic adhesives consisting of alkali metal silicates, low-melting point glass or the like. Among these adhesives for dry lamination, polyurethane-based adhesives, particularly polyester urethane-based adhesives are preferred which prevent the tacky sheet 21 for protecting a back face of a solar battery module from decrease in the adhesive strength and from delamination caused by the long-term use out of doors, and which suppress deterioration such as yellowing and the like of the tacky material layer 6. Meanwhile, an aliphatic polyisocyanate accompanied by less thermal yellowing is preferred as a curing agent.
As the melt extruded resin one or two or more thermoplastic resin(s) such as, for example, polyethylene-based resins, polypropylene-based resins, acid modified polyethylene-based resins, acid modified polypropylene-based resins, ethylene-acrylic acid or methacrylic acid copolymers, SURLYN-based resins, ethylene-vinyl acetate copolymers, polyvinyl acetate-based resins, ethylene-acrylic ester or methacrylic ester copolymers, polystyrene-based resins, polyvinyl chloride-based resins and the like can be used. When the extrusion lamination method is employed in which the melt extruded resin is used, it is desired that the opposing face to the lamination of each film described above is subjected to the aforementioned surface finishing treatment such as anchor coating treatment or the like for achieving more rigid adhesion strength.
The lower limit of the amount of lamination (calculated based on the solid content) of the adhesive layer 6 is preferably 1 g/m2, and particularly preferably 3 g/m. In contrast, the upper limit of the amount of lamination of the adhesive layer 6 is preferably 10 g/m2, and particularly preferably 7 g/m2. When the amount of lamination of the adhesive layer 6 is smaller than the aforementioned lower limit, adhesion strength and the sealing function to compensate for the defects of the barrier layer 4 may not be attained. To the contrary, when the amount of lamination of the adhesive layer 6 is greater than the aforementioned upper limit, strength and durability of the laminated layer may be deteriorated.
In the adhesive for lamination or the melt extruded resin for forming the adhesive layer 6 may be blended a variety of additives ad libitum such as e.g., a solvent, a lubricant, a crosslinking agent, an antioxidant, an ultraviolet ray-absorbing agent, a light stabilizer, a filler, a reinforcing fiber, a strengthening agent, an antistatic agent, a fire retardant, a flame retardant, a foaming agent, an fungicide, a pigment and the like for the purpose of improving and modifying the handleability, heat resistance, weather resistance, mechanical properties and the like.
When an aluminum foil is used for the barrier layer 5 in the tacky sheet 21 for protecting a back face of a solar battery module, gas barrier properties against water vapor and the like and mechanical strength are further improved. Additionally, due to high thermal conductivity of aluminum, superior heat dissipation effect is achieved, and thus elevation of the temperature of the solar battery cells can be inhibited, whereby prolongation of the duration of use of the solar battery module can be further promoted.
The tacky sheet 31 for protecting a back face of a solar battery module shown in
Since the tacky sheet 31 for protecting a back face of a solar battery module has thus two barrier layers 4 and 5 via the adhesive layer 6, extremely superior water vapor-barrier function and mechanical strength are provided. In addition, even if the adhesive layer 6 has defects such as pinholes, crystalline interfaces, and cracks being present on the surface of the inside barrier layer 4, the tacky sheet 31 achieves significantly improved gas barrier properties against water vapor and the like due to coverage of such surface defects.
The tacky sheet 41 for protecting a back face of a solar battery module shown in
According to the tacky sheet 41 for protecting a back face of a solar battery module, due to having a barrier layer 4 similarly to the tacky sheet 11 for protecting a back face of a solar battery module shown in
In these tacky sheets 1, 11, 21, 31 and 41 for protecting a back face of a solar battery module, one face (the face on the side not brought into contact with the substrate layer 2, and in the tacky sheet 41, the face on the side not brought into contact with the barrier layer 4) of the tacky material layer 3 is preferably covered with a release sheet. Since the tacky sheet for protecting a back face of a solar battery module is covered with the release sheet on one face, the tacky material layer can be prevented from contact with other substance until immediately before the operation of attachment, and thus the workability is improved, and the tacky adhesion function of the tacky sheet in attaching can be enhanced.
Although the release sheet is not particularly limited, an appropriate film material constituted with a film of a synthetic resin such as polyethylene, polypropylene, an ethylene-vinyl acetate copolymer, an ethylene-vinyl alcohol copolymer or polyethylene terephthalate, a rubber sheet, paper, a cloth, a nonwoven fabric, a net, an expanded sheet, a metal foil or a laminate thereof, or the like may be used. The surface of the release sheet is preferably subjected to a releasability-imparting treatment such as a silicone treatment, a long-chain alkyl treatment or a fluorine treatment as needed in order to improve release characteristics from the tacky material layer 3. The release characteristics of the release sheet can be controlled by regulating the type and/or the amount of coating etc., of the reagent used for the releasability-imparting treatment.
The solar battery module 51 shown in
The translucent substrate 52 is to be laminated on the frontmost face, and is required: a) to have transmittivity of sunlight, and electrical insulation properties; b) to be excellent in mechanical, chemical and physical strength, specifically, in weather resistance, heat resistance, durability, water resistance, gas barrier properties against water vapor and the like, wind blast resistance, chemical resistance, and toughness; and c) to have high surface hardness, and to be excellent in antifouling properties to prevent the surface from fouling, accumulation of dirt and the like.
As the material for forming the translucent substrate 52, glass or a synthetic resin may be used. Examples of the synthetic resin used in the translucent substrate 52 include e.g., polyethylene-based resins, polypropylene-based resins, cyclic polyolefin-based resins, fluorine-based resins, polystyrene-based resins, acrylonitrile-styrene copolymers (AS resins), acrylonitrile-butadiene-styrene copolymers (ABS resins), polyvinyl chloride-based resins, fluorine-based resins, poly(meth)acrylic resins, polycarbonate-based resins, polyester-based resins such as polyethylene terephthalate and polyethylene naphthalate, polyamide-based resins such as a variety of nylon, polyimide-based resins, polyamideimide-based resins, polyaryl phthalate-based resins, silicone-based resins, polyphenylene sulfide-based resins, polysulfone-based resins, acetal-based resins, polyether sulfone-based resins, polyurethane-based resins, cellulose-based resins, and the like. Among these resins, fluorine-based resins, cyclic polyolefin-based resins, polycarbonate-based resins, poly(meth)acrylic resins and polyester-based resins are particularly preferred.
In the case of the translucent substrate 52 made of a synthetic resin, (a) lamination of a transparent vapor deposition film of an inorganic oxide such as silicon oxide, aluminum oxide or the like on one face thereof by the PVD or CVD method as described above for the purpose of improving the gas barrier properties and the like; and (b) blending a variety of additives such as e.g., a lubricant, a crosslinking agent, an antioxidant, an ultraviolet ray-absorbing agent, an antistatic agent, a light stabilizer, a filler, a reinforcing fiber, a strengthening agent, a fire retardant, a flame retardant, a foaming agent, an fungicide, a pigment and the like for the purpose of improving and modifying the processability, heat resistance, weather resistance, mechanical properties, dimension accuracy and the like are also acceptable.
The thickness (average thickness) of the translucent substrate 52 is not particularly limited, and may be determined ad libitum such that necessary strength, gas barrier properties and the like are provided depending on the material used. The thickness of the translucent substrate 52 made of the synthetic resin is preferably 6 μm or greater and 300 μm or less, and particularly preferably 9 μm or greater and 150 μm or less. Moreover, the thickness of the translucent substrate 32 made of glass is generally about 3 mm.
The filler layer 53 and the filler layer 55 are filled around the solar battery cell 54 between the translucent substrate 52 and the back sheet 56, and has (a) adhesion properties between the translucent substrate 52 and the back sheet 56; and scratch resistance, shock absorbing properties and the like for protecting the solar battery cell 54. The filler layer 53 laminated on the surface of the solar battery cell 54 has transparency that permits transmission of the sunlight, in addition to the various functions as described above.
Examples of the material for forming the filler layer 53 and the filler layer 55 include e.g., fluorine-based resins, ethylene-vinyl acetate copolymers, ionomer resins, ethylene-acrylic acid or methacrylic acid copolymers, acid-modified polyolefin-based resins prepared by modification of a polyolefin-based resin such as a polyethylene resin, a polypropylene resin or polyethylene with an unsaturated carboxylic acid such as acrylic acid, polyvinyl butyral resins, silicone-based resins, epoxy-based resins, (meth)acrylic resins and the like. Among these synthetic resins, fluorine-based resins, silicone-based resins or ethylene-vinyl acetate-based resins that are excellent in the weather resistance, heat resistance, gas barrier properties and the like are preferred.
Moreover, the material which can be used for forming the filler layer 53 and the filler layer 55 includes heat reversible crosslinkable olefin-based polymer compositions described in Japanese Unexamined Patent Application Publication No. 2000-34376. More specifically the composition includes (a) a modified olefin-based polymer prepared by modification with an unsaturated carboxylic anhydride and an unsaturated carboxylate ester, with the average biding number of the carboxylic anhydride group per molecule being one or more, and with the ratio of the number of the carboxylate ester groups to the number of the carboxylic anhydride groups in the modified olefin-based polymer being 0.5 to 20, and (b) a hydroxyl group-containing polymer having an average number of the bound hydroxyl groups per molecule being one or more, in which the ratio of the number of the hydroxyl groups in the component (b) to the number of the carboxylic anhydride groups in the component (a) is 0.1 to 5, and the like.
In the material for forming the filler layer 53 and the filler layer 55 may be blended a variety of additives ad libitum such as e.g., a crosslinking agent, a thermal antioxidant, a light stabilizer, an ultraviolet ray-absorbing agent, a photooxidation inhibitor and the like for the purpose of improving weather resistance, heat resistance, gas barrier properties and the like. Moreover, the thickness of the filler layer 53 and the filler layer 55 is not particularly limited, but is preferably 200 μm or greater and 1000 μm or less, and particularly preferably 350 μm or greater and 600 μm or less.
The aforementioned solar battery cell 54 is a photovoltaic device that converts light energy into electrical energy, and is provided between the filler layer 53 and the filler layer 55. A plurality of the solar battery cells 54 are laid on a substantially identical plane, which are wired in series or in parallel. As the solar battery cell 54, for example, crystalline silicon solar battery elements such as single crystalline silicon type solar battery elements, polycrystalline silicon type solar battery elements and the like, amorphous silicon solar battery elements of single joint type, tandem structure type and the like, semiconductor solar battery elements with compounds of groups 3 to 5 such as gallium arsenic (GaAs), indium phosphorus (InP) and the like, compound semiconductor solar battery elements with compounds of groups 2 to 6 such as cadmium tellurium (CdTe), copper indium selenide (CuInSe2) and the like can be used, and the hybrid element of the same can be also used. The filler layer 53 or the filler layer 55 is also filled among a plurality of the solar battery cells 54 without any gap.
The back sheet 56 protects the solar battery cell 54, and the filler layers 53 and 55 from the back face, and has gas barrier properties against water vapor, oxygen gas etc., in addition to basic performances such as strength, weather resistance and heat resistance. Well-known sheets may be used as the back sheet 56. The back sheet 56 has a multilayer structure in which a pair of synthetic resin layers are each laminated on a front face and a back face of the gas barrier layer.
The tacky sheet 1 for protecting a back face of a solar battery module is provided to attach on a back face of the back sheet 56 via the tacky material layer 3. The tacky sheet 1 for protecting a back face of a solar battery module is cut into a shape in which a portion corresponding to the junction box 58 is excluded.
The method for production of the solar battery module 51 is not particularly limited, but in general, includes (1) a step of superposing the translucent substrate 52, the filler layer 53, a plurality of the solar battery cells 54, the filler layer 55 and the back sheet 56 in this order, (2) a step of laminating to perfect integral molding by a vacuum heat lamination method or the like in which they are integrated by vacuum aspiration and heat pressure joining, (3) a step of providing the junction box 58 on the back face of the back sheet 56, and (4) a step of laminating the tacky sheet 1 for protecting a back face of a solar battery module on the back face of the back sheet 56 at a site except for the portion on which the junction box 58 was provided. In the method for production of the solar battery module 51, (a) coating of a heat melt adhesive, a solvent type adhesive, a photocurable adhesive or the like, (b) to the opposing face to the lamination an ozone treatment, a corona discharge treatment, a low-temperature plasma treatment, a glow discharge treatment, an oxidizing treatment, an under coating treatment, a primer coating treatment, an anchor coating treatment or the like can be carried out for the purpose of achieving the adhesiveness between each layer.
It should be noted that the tacky sheet 1 for protecting a back face of a solar battery module may be laminated on the back face of a solar battery module already put into practical use, which includes a translucent substrate 52, a filler layer 53, multiple solar battery cells 54, a filler layer 55, and a back sheet 56 laminated in this order, and which is provided with junction box 58 having two terminals of a wiring 57 that connects each solar battery cell 54 on the back face of the back sheet 56, or may be laminated in production of the solar battery module.
Since the solar battery module 51 has the tacky sheet 1 for protecting a back face of a solar battery module as described above, even in the case in which physical defects 59 such as scratches and cracks had been already generated on the surface of the back sheet 56 resulting from use for a long period of time and the like, the physical defects 59 are filled with the tacky material layer 3 of the tacky sheet 1 for protecting a back face of a solar battery module, whereby expansion of the physical defects 59 is suppressed, and permeabilization of water vapor and the like from the physical defect 59 sites can be prevented. Accordingly, extension of useful life of the solar battery module can be promoted. Also, in the case of a solar battery module in which no physical defect such as a crack is generated on the back face of the back sheet 56, extension of useful life of the tacky sheet 1 solar battery module is enabled since the solar battery module 51 can be maintained in the state not having a physical defect on the back face by replacing the tacky sheet 1 periodically or when a physical defect is generated.
Furthermore, since the tacky sheet 1 for protecting a back face of a solar battery module is attached to the back face of the back sheet of the solar battery module via the tacky material layer having repetitive attachability/detachability, even when the position is shifted when attached to the back face of the back sheet, easy replacement can be executed without damaging the back sheet. Furthermore, when the tacky sheet 1 for protecting a back face of a solar battery module is attached during transportation of the solar battery module, deformation or damage of the back sheet from a physical impact resulting from an operation error can be prevented. Accordingly, occurrence of defects of the solar battery module during transportation can be reduced.
It should be noted that the tacky sheet for protecting a back face of a solar battery module of the present invention and a solar battery module using the same are not limited to the foregoing embodiments. For example, the solar battery module may have any of the tacky sheets 11, 21, 31, 41 for protecting a back face of a solar battery module and other tacky sheet for protecting a back face of a solar battery module laminated, other than the tacky sheet 1 for protecting a back face of a solar battery module.
Alternatively, the barrier layer formed by vapor deposition may be also laminated to provide multiple layers via other layer. According to such a tacky sheet for protecting a back face of a solar battery module, the barrier layer provided in plural number can result in not only just improvement of the water vapor barrier property, but also an increase of compactness of the barrier layer of the external side as a consequence of coverage of the physical surface defects in the surface of the inner barrier layer between layers of the barrier layer, and enhancement of the smoothness of the interface on which the barrier layer of the external side is laminated. Therefore, defects such as pinholes, crystalline interfaces and cracks in the barrier layer of the second or subsequent layers are reduced according to the tacky sheet, and thus gas barrier properties against water vapor and the like are improved. The layer provided between the barrier layers laminated by vapor deposition may be a layer formed by the sol-gel method described above.
Moreover, the barrier layer may be provided on both two face sides with respect to the substrate layer. The barrier layer may be laminated by vapor deposition of aluminum, an inorganic oxide of a metal or the like, or an aluminum foil may be laminated as the barrier layer. By thus laminating the barrier layer on two face sides with respect to the substrate layer, gas barrier properties, physical durability and the like of the tacky sheet for protecting a back face of a solar battery module can be further improved.
In the second embodiment, with an attention to a heat dissipation effect of the barrier layer of the tacky sheet for protecting a back face of a solar battery module, a tacky sheet for protecting a back face of a solar battery module will be explained having a configuration that enables improvement of a heat dissipation property of the solar battery module, and realizes extension of useful life while preventing deterioration of the solar battery module.
The tacky sheet 61 for protecting a back face of a solar battery module according to the second embodiment shown in
The substrate layer 64 is formed using a synthetic resin as a principal component, and one similar to the substrate layer 2 shown in
The lower limit of the substrate layer 64 is preferably 1.2 μm, and particularly preferably 25 μm. On the other hand, the upper limit of the thickness of the substrate layer 64 is preferably 1 mm, and particularly preferably 500 μm.
The substrate layer 64 having a thickness of less than the aforementioned lower limit causes disadvantages such as bringing difficulty in handling of the tacky sheet 61 for protecting a back face of a solar battery module, and an insufficient barrier property against water vapor. In particular, the tacky sheet 61 for protecting a back face of a solar battery module is cut to fit the size of a preexisting solar battery module and to fit the position and the size of junction box of the solar battery module, and thereafter attached to a back face of a solar battery module. Therefore, when the thickness is less than the aforementioned lower limit, workability in cutting and attaching may be deteriorated and thus attaching to meet each solar battery module size may be difficult, or stickiness with a back sheet may be lowered due to attachment shifted, which may consequently lead to failure in sufficiently exerting the heat dissipation function as the thermal conductivity is lowered.
To the contrary, when the substrate layer 64 has a thickness exceeding the upper limit, demands for reduction in thickness and weight saving of the solar battery module may not be satisfied. In addition, when the thickness of the substrate layer 64 exceeds the above upper limit, the thermal conductivity is lowered because of the thick substrate layer 64, and heat capacity of the substrate layer 64 and the tacky sheet 61, in turn increases, whereby the heat dissipation efficiency is deteriorated. Further, when the thickness of the substrate layer 64 exceeds the above-described upper limit, the weight of the tacky sheet 61 for protecting a back face of a solar battery module increases, whereby workability in attaching on the back face may be similarly deteriorated and thus attaching to meet each solar battery module size may be difficult, or stickiness with the back sheet may be lowered due to attachment shifted, which may consequently lead to failure in sufficiently exerting the heat dissipation function as the thermal conductivity is lowered.
The barrier layer 65 includes fine particles 66, and a binder 67 for the fine particles 66. By thus containing fine particles 66 in the barrier layer 65, a fine bumpy shape 68 can be formed uniformly and easily on an entire front face of the barrier layer 65 (another face of the heat dissipation film 62). Thus the fine bumpy shape 68 thus provided on an entire surface of the front face (another face of the heat dissipation film 62) of the barrier layer 65 leads to enlargement of the surface area, whereby heat dissipation function from the front face (another face of the heat dissipation film 62) is dramatically enhanced. It should be noted that the average thickness of the barrier layer 65 is not particularly limited, and may be for example, about 5 μm or greater and 1 mm or less.
The fine particles 66 can be generally classified into inorganic particles and organic particles. Specific examples of the inorganic particles which may be used include metal particles of aluminum, iron, an alloy, etc., inorganic oxide such as silicon dioxide, aluminum oxide, zinc oxide and zirconium dioxide, as well as aluminum hydroxide, barium sulfide, magnesium silicate, boron nitride, silicon carbide, silicon nitride, aluminum nitride, zircon silicate and the like, and mixtures thereof. Examples of the specific material which may be used for the organic particles include acrylic resins, acrylonitrile resins, polyurethane, polyvinyl chloride, polystyrene, polyacrylonitrile, polyamide and the like. Among these, metal particles or inorganic oxide particles having a high thermal conductivity are preferred, metals or metal oxides are particularly preferred, and silicon dioxide and aluminum oxide are still particularly preferred. When the fine particles 66 are metal particles or inorganic oxide particles, the heat generated from solar battery cells transmitted from the side of the substrate layer 64 can be quickly transmitted to the front face (another face of the heat dissipation film 62) side. Therefore, as the heat dissipation property improves, diffusion of locally generated heat over the entire surface of the sheet is enabled, and thus the heat dissipation property can be improved also in this regard.
As the fine particles 66, particles having a comparatively high thermal conductivity and a high electric resistance value are also preferred. When the fine particles 66 are such a type of the particles, the heat dissipation property of the sheet can be improved, whereas the electric conductivity can be minimized at a low level; therefore, the voltage endurance can be improved. Such particles may include inorganic nitride such as boron nitride and silicon nitride, and the like.
The shape of the fine particles 66 is not particularly limited, and examples thereof include e.g., spherical, cubic, needle-like, rod-like, spindle, platy, squamous, fibrous and the like. Of these, a spherical shape, i.e., beads shape is preferred which can certainly form a fine bumpy shape easily to give a desired size on the front face (another face of the heat dissipation film 62).
It is preferred that the lower limit of the amount of the light fine particles 66 (incorporated amount per 100 parts of the substrate polymer in the polymer composition being the material for forming the binder 67, which is calculated on the basis of the solid content) be 10 parts, particularly 20 parts, and still more 50 parts, and that the upper limit of the incorporated amount be 500 parts, particularly 300 parts, and still more 200 parts. When the amount of the incorporated fine particles 66 is less than the lower limit described above, formation of the fine bumpy shape 68 on a front face (another face of the heat dissipation film 62) may be insufficient, and the surface area is not enlarged enough, leading to failure in exhibiting prominent heat dissipation effect. Also, since the intervals among fine particles are large (not being adjacent), heat conduction among the fine particles 66 is impaired, leading to reduction of the heat diffusion speed, and as a result, the heat dissipation property may be deteriorated. On the other hand, when the amount of the incorporated fine particles 66 exceeds the upper limit described above, the thermal conductivity and the heat dissipation property may be enhanced, but an effect of fixing the fine particles 66 may be impaired.
The lower limit of the average particle size of the fine particles 66 is preferably 100 nm, particularly preferably 3 μm, and still more preferably 10 μm, whereas the upper limit of the average particle size of the fine particles 66 is preferably 1 mm, particularly preferably 400 μm, and still more preferably 100 μm. When the average particle size of the fine particles 66 is less than the lower limit described above, satisfactory formation of the bumpy shape 68 on the front face (another face of the heat dissipation film 62) may be difficult, leading to failure in enlargement of the surface area, and thus the heat dissipation function is not sufficiently exerted. To the contrary, when the average particle size of the fine particles 66 exceeds the upper limit described above, the thickness of the barrier layer 65 increases, contrary to demands for reduction in thickness and weight saving of solar battery modules.
The binder 67 contains a substrate polymer as a principal component. The aforementioned substrate polymer is not particularly limited, and examples thereof include e.g., acrylic resins, polyurethanes, polyesters, fluorine-based resins, silicone-based resins, polyamide imides, epoxy resins, ultraviolet-curable resins and the like. One or two or more of these polymers may be used as a mixture. Particularly, a highly processable polyol that can be readily formed into the barrier layer 65 by a means such as coating or the like is preferred as the substrate polymer.
Examples of the polyol include e.g., polyols obtained by polymerizing a monomer component including a hydroxyl group-containing unsaturated monomer, polyester polyols obtained under a condition with excess hydroxyl groups present, and the like. These may be used alone or two or more of them may be used as a mixture.
Examples of the hydroxyl group-containing unsaturated monomer include (a) hydroxyl group-containing unsaturated monomers such as e.g., 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, allyl alcohol, homoallyl alcohol, cinnamic alcohol, and crotonyl alcohol, and (b) hydroxyl group-containing unsaturated monomers obtained by a reaction of a dihydric alcohol or an epoxy compound such as e.g., ethylene glycol, ethylene oxide, propylene glycol, propylene oxide, butylene glycol, butylene oxide, 1,4-bis(hydroxymethyl)cyclohexane, phenyl glycidyl ether, glycidyl decanoate or PRACCEL FM-1 (manufactured by Daicel Chemical Industries, Ltd.), with an unsaturated carboxylic acid such as e.g., acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid or itaconic acid. The polyol can be manufactured by polymerizing one or two or more selected from these hydroxyl group-containing unsaturated monomers.
Moreover, the polyol can be also manufactured by polymerizing one or two or more ethylenic unsaturated monomers selected from ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, tert-butyl acrylate, ethylhexyl acrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, ethylhexyl methacrylate, glycidyl methacrylate, cyclohexyl methacrylate, styrene, vinyltoluene, acrylic acid, methacrylic acid, acrylonitrile, vinyl acetate, vinyl propionate, vinyl stearate, allyl acetate, diallyl adipate, diallyl itaconate, diethyl maleate, 1-methylstyrene, vinyl chloride, vinylidene chloride, acrylamide, N-methylolacrylamide, N-butoxymethylacrylamide, diacetone acrylamide, ethylene, propylene, isoprene and the like, with the hydroxyl group-containing unsaturated monomer selected from those in the above (a) and (b).
The polyol obtained by polymerizing the monomer component including the hydroxyl group-containing unsaturated monomer may have a number average molecular weight of 1,000 or greater and 500,000 or less, and preferably 5,000 or greater and 100,000 or less. Furthermore, the hydroxyl value of the polyol may be 5 or greater and 300 or less, preferably 10 or greater and 200 or less, and more preferably 20 or greater and 150 or less.
The polyester polyol obtained under a condition with excess hydroxyl groups being present can be manufactured by allowing a reaction of (c) a polyhydric alcohol such as e.g., ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, hexamethylene glycol, decamethylene glycol, 2,2,4-trimethyl-1,3-pentanediol, trimethylolpropane, hexanetriol, glycerin, pentaerythritol, cyclohexanediol, hydrogenated bisphenol A, bis(hydroxymethyl)cyclohexane, hydroquinone bis(hydroxyethyl ether), tris(hydroxyethyl)isocyanurate or xylylene glycol with (d) a polybasic acid such as e.g., maleic acid, fumaric acid, succinic acid, adipic acid, sebacic acid, azelaic acid, trimellitic acid, terephthalic acid, phthalic acid or isophthalic acid, under a condition in which number of the hydroxyl groups in the polyhydric alcohol such as propanediol, hexanediol, polyethylene glycol, trimethylolpropane or the like is greater than the number of the carboxy groups of the aforementioned polybasic acid.
The polestet polyol obtained under a condition with excess hydroxyl groups being present may have a number average molecular weight of 500 or greater and 300,000 or less, and preferably 2,000 or greater and 100,000 or less. Furthermore, the hydroxyl value of the polestet polyol may be 5 or greater and 300 or less, preferably 10 or greater and 200 or less, and more preferably 20 or greater and 150 or less.
The polyol for use as the substrate polymer of the polymer composition may be preferably an acryl polyol which is obtained by polymerizing the aforementioned polyester polyol, and a monomer component comprising the hydroxyl group-containing unsaturated monomer, and which has a (meth)acrylic unit or the like. The binder 67 including the polyester polyol or acryl polyol as the substrate polymer is highly weather-resistant, and impairment of stickiness of the fine particles 66 can be suppressed. Either one of this polyester polyol or the acryl polyol may be used, alternatively, both of them may be used.
The number of the hydroxyl groups in the polyester polyol and the acryl polyol is not particularly limited as long as it is two or more per molecule, however, when the hydroxyl value in the solid content is 10 or less, crosslinking points may be reduced and thus, film physical properties such as solvent resistance, water resistance, heat resistance, surface hardness and the like are likely to be decreased.
The tacky material layer 63 is formed by coating the tacky material on one face of the heat dissipation film 62. The tacky material layer 63 which can be used is similar to the tacky material layer 3 shown in
According to the tacky sheet 61 for protecting a back face of a solar battery module including the tacky material layer 63 having the thickness described above, even when the tacky sheet 61 is laminated on a back sheet surface of a back face of a solar battery module on which scratches and cracks occurred, the back sheet and the tacky sheet 61 can be fully stuck by filling the scratch and crack portions with the tacky material, thereby enabling an increase of the thermal conductivity. Moreover, according to the tacky sheet, penetration of water vapor and the like is prevented, and expansion of defects such as scratches and cracks can be suppressed. In addition, since the thickness of the tacky material layer falls within the above range according to the tacky sheet 61 for protecting a back face of a solar battery module, the tacky material layer 63 can be embedded into the deepest portion of the physical scratches and cracks which can usually occur, and expansion of the physical defects such as scratches and cracks can be inhibited, and penetration of water vapor and the like from the outside can be prevented certainly.
When the thickness of the tacky material layer 63 is less than the lower limit described above, the tacky material cannot fill in the defects such as scratches and cracks having the depth that may usually occur, leading to generation of gaps. Accordingly, evolution of the expansion of the defects is accelerated, and penetration of water vapor and the like from the gap results in deterioration of barrier properties against water vapor and the like. In addition, due to the presence of the gap, the thermal conductivity is lowered, and in turn the heat dissipation efficiency is lowered. To the contrary, when the thickness of the tacky material layer 63 exceeds the upper limit described above, workability may be deteriorated such as, for example, interference of operation of cutting to make the tacky sheet 61 have a desired shape because of the thickness of the tacky material layer 63. Additionally, since the thermal conductivity is lowered, the heat dissipation efficiency is impaired.
Since the tacky sheet 61 for protecting a back face of a solar battery module includes a tacky material layer 63 laminated on one face side thereof, it can be directly attached to a back face of a conventional solar battery module. Accordingly, it improves the heat dissipation property of conventional solar battery modules, and in turn can enhance the efficiency of electric power generation and extend useful life of the solar battery module thereof. In addition, since the tacky sheet 61 for protecting a back face of a solar battery module includes a tacky material layer 63 laminated on one face side thereof, even when another face of the tacky sheet is scratched, or the heat dissipation property is impaired due to aged deterioration, the tacky sheet 61 can be easily replaced with new one, whereby a superior heat dissipation property of the solar battery module can be constantly maintained. Moreover, when the tacky sheet 61 for protecting a back face of a solar battery module is attached to a back face of solar battery module in which defects such as cracks are generated, the defects can be filled with the tacky material layer 63; therefore, the water vapor barrier property of the back face can be improved. Additionally, because the sealing can further elevate the thermal conductivity, promotion of the heat dissipation property is enabled. Furthermore, since the tacky sheet 61 for protecting a back face of a solar battery module has a barrier layer 65 including fine particles 66 and a binder 67, the fine bumpy shape 68 on the front face (another face of the heat dissipation film 62) results in enlargement of the surface area, whereby the heat dissipation effect can be improved.
A tacky sheet 71 for protecting a back face of a solar battery module shown in
The heat dissipation film 72 includes a substrate layer 73 in which the tacky material layer 63 is laminated on one face side, and a barrier layer 74 laminated on an outermost surface on another face side of the substrate layer 73. It is to be noted that the barrier layer 74 corresponds to one examples of the barrier layer laminated on the outermost surface on another face side of the synthetic resin substrate layer of the present invention.
Although the material for formation, the average thickness and the like of the substrate layer 73 are similar to those of the substrate layer 64 in the tacky sheet 61 for protecting a back face of a solar battery module shown in
The lower limit of the surface roughness (Ra) of another face (the face on which the fine bumpy shape has been formed) of the substrate layer 73 is preferably 1 μm, and particularly preferably 10 μm. On the other hand, the upper limit of the surface roughness (Ra) of the face of the substrate layer 73 on which the fine bumpy shape has been formed is preferably 1 mm, and particularly preferably 100 μm. Note that “surface roughness (Ra)” herein means a value as measured in accordance with JIS-B0601-1994, with a cut-off value of 8 mm, and an evaluation length of 40 mm.
By providing the barrier layer 74 on another face (the face on which the fine bumpy shape has been formed) of the substrate layer 73 having such a surface roughness, the surface area of the barrier layer 74 is enlarged, leading to significant improvement of the heat dissipation effect. When the surface roughness of another face (the face on which the fine bumpy shape has been formed) of the substrate layer 73 is less than the lower limit described above, the fine bumpy shape of the surface is not sufficiently formed when the barrier layer 74 is provided, whereby the surface area cannot be enlarged satisfactorily. To the contrary, the surface roughness of the face of the substrate layer 73 on which the fine bumpy shape has been formed exceeding the upper limit described above results in a rough surface, whereby executing uniform vapor deposition may be difficult, and the surface becomes more likely to be scratched.
The method for molding the substrate layer 73 is not particularly limited as long as the substrate layer 73 having the aforementioned structure can be formed, and various methods may be employed. As the method for producing the substrate layer 73, a method in which a bumpy shape is formed on a surface of a molded sheet, and a method of integral molding with sheet formation and bumpy shape formation may be employed. Specific methods are as follows:
(a) a method of forming the substrate layer 73 including laminating a resin material for formation onto a sheet mold having a shape reversal to the bumpy shape of a front face of the substrate layer 73, and stripping the sheet mold;
(b) a method of injection molding including injecting a melted resin material for formation into a die having a shape reversal to the bumpy shape of the front face of the substrate layer 73;
(c) a method including reheating the resin material for formation which had been formed into a sheet, sandwiching between a metal plate and a die similar to one described above, and pressing to transcribe the shape;
(d) a method of extrusion molding of a sheet including allowing a resin material for formation in a molten state to pass through a nip between a roll mold having on the circumference a shape reversal to the bumpy shape of the front face of the substrate layer 73, and other roll to transcribe the shape; and
(e) a method of forming the substrate layer 73 including providing a bumpy shape on the front face by sand blasting on the sheet surface.
The barrier layer 74 includes a vapor-deposited inorganic oxide. Since the barrier layer 74 includes an inorganic oxide, the heat dissipation property can be improved by diffusing the heat locally generated from the solar battery cell, etc., to an entire surface of the sheet due to a high thermal conductivity of the inorganic oxide. In addition, since the barrier layer 74 including an inorganic oxide has a superior water vapor barrier function, improvement of resistance to hydrolysis is enabled.
Any one which can be suitably used as the barrier layer 4 of the tacky sheet 11 for protecting a back face of a solar battery module shown in
The lower limit of the surface roughness (Ra) of the barrier layer 74 is preferably 1 μm, and particularly preferably 10 μm. On the other hand, the upper limit of the surface roughness (Ra) of the barrier layer 74 is preferably 1 mm, and particularly preferably 100 μm. Although this surface roughness is similar to that of the substrate layer 73, the acceptable range is different as described above since the average thickness of the barrier layer 74 is negligibly thin with respect to the surface roughness of the substrate layer 73. By the barrier layer 74 having a surface roughness falling within the above range, the surface area increases, and thus the heat dissipation effect is significantly improved.
According to the tacky sheet 71 for protecting a back face of a solar battery module, since the barrier layer 74 is provided by vapor deposition of inorganic oxides or aluminum or a sol-gel method in this manner, the heat dissipation property can be improved by diffusing the heat locally generated from the solar battery cell, etc., to the entire surface of the sheet due to a high thermal conductivity of the inorganic oxide. In addition, since the barrier layer 74 including an inorganic substance has a superior water vapor barrier function, improvement of resistance to hydrolysis is enabled, and extension of useful life of the solar battery module can be achieved. Furthermore, the tacky sheet 71 for protecting a back face of a solar battery module has a large surface area due to having a fine bumpy shape on another face (a front face of the barrier layer 74) of the heat dissipation film 62, thereby capable of enhancing the heat dissipation efficiency. Moreover, when the barrier layer 74 in the tacky sheet 71 for protecting a back face of a solar battery module includes an inorganic oxide having insulation property, the insulation property of the solar battery module can be improved, and thus protection of portions having electric conductivity such as solar battery cells and wirings is enabled.
The tacky sheet 81 for protecting a back face of a solar battery module shown in
The heat dissipation film 82 includes a substrate layer 64 in which the tacky material layer 63 is laminated on one face side thereof, and a barrier layer 84 laminated on another face side of the substrate layer 64 via an adhesive layer 83. Since the substrate layer 64 is similar to that of the tacky sheet 61 for protecting a back face of a solar battery module shown in
Although the adhesive that constitutes the adhesive layer 83 is not particularly limited, an adhesive for lamination or a melt-extruded resin is suitably used. Examples of the adhesive for lamination include e.g., adhesives for dry lamination, adhesives for wet lamination, adhesives for hot melt lamination, adhesives for nonsolvent lamination, and the like. Among these adhesives for lamination, adhesives for dry lamination are particularly preferred which are excellent in the adhesive strength, durability, weather resistance and the like, and have the sealing and protecting functions to compensate for defects (for example, scratches, pinholes, recessed parts and the like) of the surface of the substrate layer 64.
Examples of the adhesive for dry lamination include e.g., polyvinyl acetate-based adhesives, polyacrylic ester-based adhesives consisting of a homopolymer of an ethyl, butyl, 2-ethylhexyl ester or the like of acrylic acid, or a copolymer of the homopolymer and methyl methacrylate, acrylonitrile, styrene or the like, cyanoacrylate-based adhesives, ethylene copolymer-based adhesives consisting of a copolymer of ethylene and a monomer such as vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid or the like, cellulose-based adhesives, polyester-based adhesives, polyamide-based adhesives, polyimide-based adhesives, amino resin-based adhesives consisting of an urea resin, a melamine resin or the like, phenol resin-based adhesives, epoxy-based adhesives, polyurethane-based adhesives, reactive (meth)acrylic adhesives, rubber-based adhesives consisting of a chloroprene rubber, a nitrile rubber, a styrene-butadiene rubber or the like, silicone-based adhesives, inorganic adhesives consisting of alkali metal silicate, low-melting point glass or the like. Among these adhesives for dry lamination, polyurethane-based adhesives, particularly polyester urethane-based adhesives are preferred which prevent the tacky sheet 81 for protecting a back face of a solar battery module from a decrease in the adhesive strength and from delamination caused by the long-term use out of doors, and which suppress deterioration such as yellowing and the like of the adhesive layer 83. Meanwhile, aliphatic polyisocyanate accompanied by less thermal yellowing is preferred as a curing agent.
As the melt extruded resin one or two or more thermoplastic resin(s) such as, for example, polyethylene-based resins, polypropylene-based resins, acid modified polyethylene-based resins, acid modified polypropylene-based resins, ethylene-acrylic acid or methacrylic acid copolymers, SURLYN-based resins, ethylene-vinyl acetate copolymers, polyvinyl acetate-based resins, ethylene-acrylic ester or methacrylic ester copolymers, polystyrene-based resins, polyvinyl chloride-based resins and the like can be used. When the extrusion lamination method is employed in which the melt extruded resin is used, it is desired that the opposing face to the lamination of each film described above is subjected to the aforementioned surface finishing treatment such as anchor coating treatment or the like for achieving more rigid adhesion strength.
The lower limit of the amount of lamination of the adhesive layer 83 (calculated based on the solid content) is preferably 1 g/m2, and particularly preferably 3 g/m2. On the other hand, the upper limit of the amount of lamination of the adhesive layer 83 is preferably 20 g/m2, and particularly preferably 10 g/m2. When the amount of lamination of the adhesive layer 83 is smaller than the aforementioned lower limit, adhesion strength may not be attained, and a gap is generated between the barrier layer 84 and the adhesive layer 83, and thus the thermal conductivity and heat dissipation effect may be deteriorated. To the contrary, when the amount of lamination of the adhesive layer 83 is greater than the aforementioned upper limit, strength and durability of the laminated layers may be deteriorated.
In the adhesive for lamination or the melt extruded resin for forming the adhesive layer 83 may be blended a variety of additives ad libitum such as e.g., a solvent, a lubricant, a crosslinking agent, an antioxidant, an ultraviolet ray-absorbing agent, a light stabilizer, a filler, a reinforcing fiber, a strengthening agent, an antistatic agent, a fire retardant, a flame retardant, a foaming agent, an fungicide, a pigment and the like for the purpose of improving and modifying the handleability, heat resistance, weather resistance, mechanical properties and the like.
A metal foil provided with a fine bumpy shape is used for the barrier layer 84. The material entity of the metal foil may include aluminum, an aluminum alloy, copper, steel, stainless steel, and the like, and is preferably aluminum or an aluminum alloy and particularly preferably an aluminum-iron-based alloy (soft material). The iron content in the aluminum-iron-based alloy is preferably no less than 0.3% and no greater than 9.0%, and particularly preferably no less than 0.7% and no greater than 2.0%. When the iron content is less than the lower limit described above, an effect of preventing generation of pinholes may be insufficient. To the contrary, when the iron content exceeds the upper limit described above, the flexibility is inhibited, and the processability may be deteriorated. Furthermore, as the material of the metal foil, soft aluminum subjected to an annealing treatment is also preferred in light of prevention of the pinhole generation.
The lower limit of the thickness (average thickness) of the metal foil is preferably 6 μm, and particularly preferably 15 μm. On the other hand, the upper limit of the thickness of the metal foil is preferably 50 μm, and particularly preferably 30 μm. When the thickness of the metal foil is less than the lower limit described above, breaking of the metal foil is likely to occur during the processing, and the gas barrier properties may be deteriorated resulting from the pinholes and the like. On the other hand, when the thickness of the metal foil is greater than the upper limit described above, cracks and the like may be generated during the processing, and the thickness and the weight of the tacky sheet 81 for protecting a back face of a solar battery module increase, whereby results contrary to social demands for reduction in thickness and weight saving may be produced.
In light of prevention of dissolution and corrosion, the surface of the metal foil may be subjected to a surface treatment such as, for example, a chromate treatment, a phosphate treatment, or a lubricating resin-coating treatment. Moreover, in light of acceleration of the adhesion properties, the surface of the metal foil may be subjected to a coupling treatment and the like.
The fine bumpy shape formed on the metal foil may be provided by emboss processing or the like after the metal foil was laminated on the surface of the adhesive layer 83, or a metal foil which had been provided with a fine bumpy shape may be laminated on the surface of the adhesive layer 83.
The lower limit of the surface roughness (Ra) of the barrier layer 84 is preferably 1 μm, and particularly preferably 10 μm. On the other hand, the upper limit of the surface roughness (Ra) of the barrier layer 84 is preferably 1 mm, and particularly preferably 100 μm. When the surface roughness of the barrier layer 84 is smaller than the lower limit described above, the surface area is enlarged insufficiently, and thus improvement of the heat dissipation function by providing a bumpy shape may not be satisfactorily achieved. To the contrary, when the surface roughness of the barrier layer 84 exceeds the upper limit described above, the appearance of glare is caused due to roughening of the surface, and the surface becomes more likely to be scratched.
In addition, a front face (a face on the side not brought into contact with the adhesive layer 83) of the metal foil that is provided as the barrier layer 84 is preferably subjected to a top coating treatment similarly to the barrier layer 74 of the tacky sheet 71 for protecting a back face of a solar battery module. By thus subjecting the front face of the barrier layer 84 to a top coating treatment, the barrier layer 84 is sealed and protected, and consequently, handleability of the tacky sheet 81 is improved. In addition, even if there are defects such as scratches and recessed parts in the barrier layer 84, deterioration of the gas barrier properties can be suppressed, and further aged deterioration of the barrier layer 84 can be inhibited.
According to the tacky sheet 81 for protecting a back face of a solar battery module, because the barrier layer 84 is a metal foil, the heat dissipation function can be enhanced by diffusing the heat locally generated from solar battery cells, etc., to the entire surface of the sheet by way of an extremely high thermal conductivity of the metal foil. In addition, since the barrier layer 84 composed of a metal foil has a superior water vapor barrier function, the hydrolysis resistance can be improved. Moreover, the tacky sheet 81 for protecting a back face of a solar battery module has a large surface area since a bumpy shape is provided on the front face, thereby capable of exerting an extremely superior heat dissipation function.
In these tacky sheets 61, 71 and 81 for protecting a back face of a solar battery module, one face (the face on the side not brought into contact with the substrate layer) of the tacky material layer 63 is preferably covered with a release sheet. The release sheet which may be suitably used is similar to the release sheet for use in the tacky sheets 1, 11, 21, 31 and 41 for protecting a back face of a solar battery module.
The solar battery module 91 shown in
The tacky sheet 61 for protecting a back face of a solar battery module is provided to attach on the back face of the back sheet 56 via the tacky material layer 63. The tacky sheet 61 for protecting a back face of a solar battery module is cut into a shape in which a portion corresponding to the junction box 58 is excluded.
The method for production of the solar battery module 91 is not particularly limited, but in general, includes (1) a step of superposing the translucent substrate 52, the first filler layer 53, a plurality of the solar battery cells 54, the second filler layer 55 and the back sheet 56 in this order, (2) a step of laminating to perfect integral molding by a vacuum heat lamination method or the like in which they are integrated by vacuum aspiration and heat pressure joining, (3) a step of providing the junction box 58 on a back face of the back sheet 56, and (4) a step of laminating the tacky sheet 61 for protecting a back face of a solar battery module on the back face of the back sheet 56 at a site except for the portion on which the junction box 58 was provided. In the method for production of the solar battery module 91, (a) coating of a heat melt adhesive, a solvent type adhesive, a photocurable adhesive or the like, (b) to the opposing face to the lamination a corona discharge treatment, an ozone treatment, a low-temperature plasma treatment, a glow discharge treatment, an oxidizing treatment, a primer coating treatment, an under coating treatment, an anchor coating treatment or the like can be carried out for the purpose of achieving the adhesiveness between each layer.
It should be noted that the tacky sheet 61 for protecting a back face of a solar battery module may be laminated on the back face (the face on the side of the back sheet 56) of a solar battery module already put into practical use, which includes a translucent substrate 52, a first filler layer 53, multiple solar battery cells 54, a second filler layer 55, and a back sheet 56 laminated in this order from the front face side, and which is provided with junction box 58 having two terminals of a wiring 57 that connects each solar battery cell 54 on the back face of the back sheet 56, or may be laminated in production of the solar battery module.
Since the solar battery module 91 includes the tacky sheet 61 for protecting a back face of a solar battery module as described above, the heat dissipation property of the solar battery module can be improved. As a result, improvement of the efficiency of electric power generation and extension of the useful life can be achieved. In addition, since the heat dissipation sheet 61 for a back face of a solar battery module is attached via the tacky material layer 63 in the solar battery module 91, for example, a superior heat dissipation function can be constantly exerted by replacing the tacky sheet 61 for protecting a back face of a solar battery module, even when the heat dissipation film 62 is damaged. Furthermore, lamination to a solar battery module already used (one including a translucent substrate 52, a first filler layer 53, multiple solar battery cells 54, a second filler layer 55, and a back sheet 56 laminated in this order from the front face side, a back face of the back sheet 56 being provided with a junction box 58 that has two terminals of wirings 57 for connecting each solar battery cell 54) can enhance the heat dissipation efficiency of the preexisting solar battery module, whereby the efficiency of electric power generation can be improved. In addition, even when physical defects such as scratches and cracks are generated in the back face of the back sheet 56, the tacky sheet 61 for protecting a back face of a solar battery module can suppress expansion of the physical defects by way of the tacky material layer 63, and penetration of water vapor, etc., from the physical defect portions can be prevented, thereby enabling extension of useful life of the solar battery module to be promoted.
It should be noted that the tacky sheet for protecting a back face of a solar battery module of the present invention and a solar battery module using the same are not limited to the foregoing embodiments. For example, the solar battery module may include any of the tacky sheets 71 and 81 for protecting a back face of a solar battery module, and other tacky sheets for protecting a back face of a solar battery module laminated, other than the tacky sheet 61 for protecting a back face of a solar battery module.
Also, in the tacky sheet for protecting a back face of a solar battery module in which the barrier layer is an inorganic oxide or aluminum, the front face may not be provided with the fine bumpy shape. Since an inorganic oxide or aluminum has a high thermal conductivity, a heat dissipation effect can be exerted even if the surface area is not enlarged by providing the bumpy shape on the front face, through diffusion of the heat locally generated to the entire surface of the sheet by way of the heat dissipation film.
Similarly, also in the tacky sheet for protecting a back face of a solar battery module in which the barrier layer includes fine particles, and a binder for the fine particles, the fine bumpy shape may not be provided on the front face. Also in such a tacky sheet for protecting a back face of a solar battery module, the heat dissipation effect can be exerted by diffusing the heat locally generated to the entire surface of the sheet when the fine particles have a high thermal conductivity, and are contained densely such that each fine particle is in contact one another.
Alternatively, the heat dissipation film may not have a two-layer structure including the substrate layer and the barrier layer, but have a monolayer structure. More specifically, for example, a structure without including the barrier layer 74 in the tacky sheet 71 for protecting a back face of a solar battery module shown in
As in the foregoing, the tacky sheet for protecting a back face of a solar battery module of the present invention is used as a tacky sheet that protects a back face of a solar battery module for the purpose of extension of useful life of the solar battery module. In particular, the present tacky sheet can be suitably used as a tacky sheet for protecting a solar battery module installed outdoors which can be used in situations accompanied by severe aged deterioration.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2009-252461 | Nov 2009 | JP | national |
| 2009-252472 | Nov 2009 | JP | national |
This application is a continuation-in-part of U.S. patent application Ser. No. 12/925,851, filed Nov. 1, 2010, which claims priority to Japanese Patent Application No. 2009-252461, filed Nov. 2, 2009. This application is also a continuation-in-part of U.S. patent application Ser. No. 12/925,870, filed Nov. 1, 2010, which claims priority to Japanese Patent Application No. 2009-252472, filed Nov. 2, 2009. All of the aforesaid contents of all of the aforesaid applications are incorporated herein by reference in their entirety.
| Number | Date | Country | |
|---|---|---|---|
| Parent | 12925851 | Nov 2010 | US |
| Child | 14157129 | US | |
| Parent | 12925870 | Nov 2010 | US |
| Child | 12925851 | US |
