JP2001144309A - Rear-surface protection sheet for solar cell module and solar cell module using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To stably provide a low-cost and safe rear-surface protection sheet together with a solar cell module using it, which is rigid, and superior in weather resistance, heat resistance, waterproofness, insulation resistance, wind- pressure resistance, dew-condensation resistance, chemical resistance, moisture resistance, contamination resistance, light reflectivity, light diffusion characteristics, design, etc., with the moisture resistance for preventing infiltration of moisture and oxygen, etc., significantly improved, while the long-term performance degradation is suppressed to a minimum for high durability and protective capability. SOLUTION: On one surface of a weather-resistant base material, a vapor deposited film of inorganic oxide is provided, on which a print layer is provided for this solar cell module.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a solar cell module.
More specifically, the present invention relates to a solar cell module using the same, and more specifically, has excellent strength, weather resistance, heat resistance, water resistance, light resistance, wind pressure resistance, and hail resistance. , Chemical resistance, moisture resistance, stain resistance, light reflection,
A backside protection sheet for a solar cell module which is excellent in various properties such as light diffusion property, design property, etc., extremely durable and excellent in protection ability, and a solar cell module using the same.
It is about the file.

[0002]

2. Description of the Related Art In recent years, attention has been paid to solar cells as a clean energy source due to increasing awareness of environmental issues. At present, solar cell modules of various forms have been developed and proposed. . In general, the above solar cell module produces, for example, a crystalline silicon solar cell element or an amorphous silicon solar cell element, and uses such a solar cell element to form a surface protective sheet layer, a filler layer, It is manufactured by laminating a solar cell element as a photovoltaic element, a filler layer, a backside protective sheet layer, and the like in that order, vacuum-sucking, and heat-compressing, for example, using a lamination method. Thus, the above-mentioned solar cell module is first applied to calculators and thereafter applied to various electronic devices and the like, and its application range is rapidly expanding for consumer use. Furthermore, it is said that the most important issue in the future is to realize large-scale centralized solar cell power generation. By the way, as a back surface protective sheet layer constituting the above-mentioned solar cell module, a plastic substrate or the like having excellent strength is most commonly used at present, and a metal plate or the like is also used. . Thus, in general, the backside protective sheet layer constituting the solar cell module has, for example, excellent strength, weather resistance, heat resistance, water resistance, light resistance, wind pressure resistance, hail resistance, Excellent in various fastnesses such as chemical resistance, light reflectivity, light diffusion, design, etc., in particular, excellent in moisture proofness to prevent the invasion of moisture, oxygen, etc., and also high in surface hardness and surface dirt It is required to satisfy conditions such as excellent antifouling property for preventing accumulation of dust and the like, extremely high durability, high protection ability, and others.

[0003]

However, for example, a plastic substrate having excellent strength, which is most commonly used at present, is used as a back surface protective sheet layer constituting a solar cell module. In the case, it is rich in plasticity, light weight, workability, workability, cost reduction, etc., but strength, weather resistance, heat resistance, water resistance, light resistance, chemical resistance, impact resistance, light reflection Inferior in various fastnesses, such as properties, light diffusion properties, etc., and in particular, lacks moisture resistance, stain resistance, and design. Further, when a metal plate or the like is used as the back surface protective sheet layer constituting the solar cell module, it is excellent in strength, and has weather resistance, heat resistance, water resistance, light resistance, chemical resistance, Excellent in stab resistance, impact resistance, and other robustness, and also excellent in moisture resistance, etc. In addition, the surface hardness is hard and the antifouling property to prevent the accumulation of surface dirt and dust etc. It has the advantages of excellent and extremely high protection ability, but lacks plasticity, lightness, light reflection, light diffusion, design, etc., and further has poor workability, workability, etc., and low There is a problem that the cost is low. Therefore, the present invention is excellent in strength, and weather resistance, heat resistance, water resistance, light resistance, wind pressure resistance, hail resistance, chemical resistance, moisture resistance,
Excellent in various properties such as antifouling property, light reflection property, light diffusing property, design property, etc., and in particular, significantly improves moisture resistance to prevent moisture and oxygen from entering, and minimizes long-term performance deterioration. The backside protection sheet which constitutes a solar cell module which is extremely durable, has excellent protection ability, is lower in cost and is safer, and a solar cell module using the same is stable. It is to provide.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted various studies on the backside protective sheet layer constituting the solar cell module in order to solve the above-mentioned problems. On one side of the material, silicon oxide, or a transparent glassy material such as aluminum oxide, and provided with a vapor-deposited film of an inorganic oxide excellent in water vapor barrier properties, oxygen barrier properties, and the like. A solar cell module is formed by providing a printing layer of an ink composition obtained by adding a coloring agent such as a dye and a pigment, and the like to a main component of a vehicle for an ink, and kneading the mixture on the evaporation film as a main component. Back protection sheet for the solar cell module.
For example, a surface protection sheet for a normal solar cell module made of a glass plate or the like, a filler layer, a solar cell element as a photovoltaic element, a filler layer, and the above solar cell A back surface protection sheet for a module is sequentially laminated with the printed layers facing each other, and then a solar cell is applied by using a lamination method or the like in which these are integrally vacuum-sucked and heated and pressed. When the module is manufactured, it has excellent strength,
Furthermore, it has excellent properties such as weather resistance, heat resistance, water resistance, light resistance, wind pressure resistance, hail resistance, chemical resistance, antifouling property, etc.,
In particular, it has excellent moisture-proof properties to prevent intrusion of moisture, oxygen, etc., and also has remarkably improved light reflectivity, light diffusivity, design, etc., minimizes long-term performance deterioration, and is extremely durable. SUMMARY OF THE INVENTION The present invention has been completed by finding that a solar cell module which is rich in heat resistance, has excellent protection ability, can be manufactured at low cost and is safe can be stably manufactured.

That is, the present invention is characterized in that a weather-resistant base material is provided with an inorganic oxide vapor-deposited film on one surface thereof, and a printed layer is further provided on the inorganic oxide vapor-deposited film. The present invention relates to a back protection sheet for a battery module and a solar cell module using the same.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The above-mentioned present invention will be described below in more detail with reference to the drawings and the like. In the present invention, a sheet means any of a sheet-like material and a film-like material.
This means any of a film-like material and a sheet-like material. Solar cell module according to the present invention
The backside protective sheet for solar cells and the solar cell module using the same will be described in more detail with reference to the drawings and the like. FIGS. 1 and 2 show solar cell modules according to the present invention. FIGS. 3 and 4 are schematic cross-sectional views illustrating one example of the layer configuration of the back surface protection sheet for use.
Is a back surface protection sheet for a solar cell module according to the present invention.
FIG. 5 is a schematic cross-sectional view illustrating another example of the layer structure of the deposited film of the inorganic oxide constituting the solar cell module. FIG.
FIG. 4 is a schematic cross-sectional view illustrating an example of a layer configuration of a solar cell module manufactured using a solar cell module.

First, as shown in FIG. 1, a backside protection sheet A for a solar cell module according to the present invention is provided with a vapor-deposited inorganic oxide film 2 on one surface of a weather-resistant substrate 1. On the inorganic oxide deposited film 2, a printing layer 3 made of an ink composition comprising an ink vehicle as a main component, a coloring agent such as a dye and a pigment, and the like added thereto and sufficiently kneaded. Is provided as a basic structure.
As a specific example of the back surface protection sheet for a solar cell module according to the present invention, as shown in FIG. 2, a vapor-deposited film 2 of an inorganic oxide is provided on one surface of a weather-resistant substrate 1,
The ink vehicle is mainly provided on the inorganic oxide vapor-deposited film 2 via a primer layer 4 made of a primer composition for improving the tight adhesion between the inorganic oxide vapor-deposited film 2 and the printed layer 3. and component, to which a dye, a colorant such as a pigment, added other like, a solar cell module consisting sufficiently kneaded print layer 3 formed configuration by the ink composition which - for the backside Le protective sheet - DOO a ₁ Can be exemplified. The above-mentioned examples are only examples of the back surface protection sheet for a solar cell module according to the present invention, and the present invention is, of course, not limited thereto. For example, in the back surface protection sheet for a solar cell module shown in FIGS. 1 and 2 above, as a vapor deposition film of an inorganic oxide, as shown in FIGS. Or more than two layers of inorganic oxide deposited film by chemical vapor deposition,
A multilayer film 2a (FIG. 3) in which two or more layers of inorganic oxide vapor-deposited films 2 and 2 are stacked, or an inorganic oxide vapor-deposited film 2b formed by a physical vapor deposition method described later and an inorganic oxide vapor-deposited film 2b formed by a chemical vapor deposition method. An inorganic oxide deposited film 2 different from the oxide deposited film 2c
b, 2c (FIG. 4) or the like.

Next, in the present invention, an example of a solar cell module manufactured by using the above-described back surface protection sheet for a solar cell module according to the present invention will be described with reference to FIG. The solar cell module according to the present invention shown
FIG. 5 shows an example in which the back surface protection sheet A for
As shown in FIG. 1, first, a normal surface protection sheet 11 for a solar cell module, a filler layer 12, a solar cell element 13 as a photovoltaic element, a filler layer 14, and the above-described solar cell module. A back protection sheet 15 (A) for the metal layer is sequentially laminated with the surface of the printed layer 3 facing the same, and then these are integrally formed, followed by vacuum suction and heat compression bonding, such as a lamination method. By using the molding method described above, the solar cell module T can be manufactured by using each of the above-mentioned layers as an integrally molded body. The above example is a solar cell module manufactured using the back surface protection sheet for a solar cell module according to the present invention.
However, the present invention is not limited thereto. For example, although not shown, solar cell modules having various forms can be manufactured in the same manner as described above using the solar cell module back surface protection sheet shown in FIG. In addition, in the above-mentioned solar cell module, solar light absorption,
For the purpose of reinforcement, etc., other layers can be arbitrarily added and laminated.

Next, in the present invention, the material constituting the back surface protection sheet for a solar cell module according to the present invention, the solar cell module using the same, the manufacturing method, and the like will be described in more detail. First, the weather-resistant base material constituting the solar cell module back protective sheet, solar cell module, etc. according to the present invention is excellent in mechanical or chemical or physical strength, and specifically, Excellent in various robustness such as weather resistance, heat resistance, water resistance, light resistance, wind pressure resistance, hail resistance, chemical resistance, etc.In particular, it is excellent in weather resistance and moisture proof to prevent moisture, oxygen etc. from entering. It has excellent properties such as high surface hardness, high surface hardness, and excellent antifouling property to prevent accumulation of dirt and dust on the surface, extremely high durability, and high protection ability. It is desirable. Furthermore, as the weather-resistant substrate, it can withstand vapor deposition conditions and the like for forming a vapor-deposited film of an inorganic oxide described below, and can be favorably retained without impairing the properties of the vapor-deposited film of the inorganic oxide and the like. Substrates are desirable.

In the present invention, concrete examples of the weather-resistant substrate as described above include polyethylene resin,
Polypropylene resin, cyclic polyolefin resin, fluorine resin, polystyrene resin, acrylonitrile
Styrene copolymer (AS resin), acrylonitrile-
Butadiene-styrene copolymer (ABS resin), polyvinyl chloride resin, fluorine resin, poly (meth) acrylic resin, polycarbonate resin, polyethylene terephthalate, polyethylene naphthalate, etc. Polyester resins, polyamide resins such as nylon, polyimide resins, polyamide imide resins, polyaryl phthalate resins, silicone resins, polysulfone resins, polyphenylene sulfide resins, polyether sulfone resins And films or sheets of various resins such as polyurethane resins, acetal resins, cellulose resins, and others. In the present invention, among the above resin films or sheets, particularly, a fluorine resin, a cyclic polyolefin resin, a polyester resin, a polyamide resin, a polycarbonate resin, or a poly (meth) resin It is preferable to use an acrylic resin film or sheet. Thus, in the present invention, a film or sheet of the above-mentioned fluorine resin, cyclic polyolefin resin, polyester resin, polyamide resin, polycarbonate resin, or poly (meth) acrylic resin. -Excellent mechanical properties, chemical properties, physical properties, etc., specifically, weather resistance, heat resistance, water resistance, light resistance, moisture resistance, stain resistance, chemical resistance, etc. It has excellent robustness, is useful as a backside protection sheet that composes solar cells, has excellent durability, protective functionality, etc., and also has flexibility, mechanical properties, chemical properties, etc. It has advantages such as light weight, excellent workability, etc., and easy handling.

In the present invention, among the various resin films or sheets described above, particularly, for example,
Polytetrafluoroethylene (PTFE), a perfluoroalkoxy resin (PF) comprising a copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether
A), tetrafluoroethylene and hexafluoropropylene copolymer (FEP), tetrafluoroethylene and perfluoroalkylvinyl ether and hexafluoropropylene copolymer (EPE), copolymer of tetrafluoroethylene and ethylene or propylene (ET
FE), polychlorotrifluoroethylene resin (PCT)
FE), a copolymer of ethylene and chlorotrifluoroethylene (ECTFE), a vinylidene fluoride resin (P
It is preferable to use a fluororesin sheet made of one or more fluororesins such as VDF) or a vinyl fluoride resin (PVF). In addition,
In the present invention, among the above-mentioned fluorine-based resin sheets, in particular, a polyvinyl fluoride-based resin (PVF) or a fluorine-based resin sheet comprising a copolymer of tetrafluoroethylene and ethylene or propylene (ETFE) Are preferred.

In the present invention, among the above-mentioned various resin films or sheets, in addition to the above-mentioned fluororesin sheets, particularly, for example, cyclopentadiene and its derivatives, dicyclopentadiene And its derivatives, cyclohexadiene and its derivatives, norbornadiene and its derivatives, polymers obtained by polymerizing cyclic diene such as others, or the cyclic diene and ethylene, propylene, 4-methyl-1-pentene,
It is preferable to use a transparent cyclic polyolefin resin sheet made of a copolymer obtained by copolymerizing one or more olefin monomers such as styrene, butadiene, isoprene and others. In the present invention, among the above-mentioned transparent cyclic polyolefin-based resin sheets, in particular, cyclopentadiene and derivatives thereof, dicyclopentadiene and derivatives thereof, or cyclic diene polymers such as norbornadiene and derivatives thereof may be used. A cyclic polyolefin resin sheet made of a copolymer is preferred. Thus, in the present invention, by using the above-mentioned fluorine-based resin sheet or cyclic polyolefin-based resin sheet, the fluorine-based resin sheet or the cyclic polyolefin-based resin sheet has Excellent properties such as mechanical properties, chemical properties, physical properties, etc., specifically, weather resistance, heat resistance, water resistance, light resistance, moisture resistance, stain resistance, chemical resistance,
A backside protection sheet for forming a solar cell by utilizing various other properties, thereby having durability, protection functionality, etc., and its flexibility, mechanical properties, and chemical properties. It has advantages such as lightness in terms of mechanical properties, excellent workability, etc., and easy handling.

In the present invention, as the film or sheet of the above-mentioned various resins, for example, one or more of the above-mentioned various resins are used, and the extrusion method, the cast molding method, the T-die method, and the cutting method are used. A method of forming the above various resins alone using a film forming method such as an inflation method, an inflation method, etc., or a multi-layer coextrusion film forming using two or more kinds of various resins. A film or sheet of various resins is manufactured by a method of forming two or more resins, and a method of mixing and forming a film before forming a film. For example, various resin films or sheets stretched in a uniaxial or biaxial direction using a tenter method or a tuber method can be used. In the present invention, the film thickness of various resin films or sheets is 6 to 300 μm.
And more preferably about 9 to 150 μm.

When one or more of the above various resins are used and the film is formed, for example, the processability, heat resistance, weather resistance, mechanical properties, dimensional stability,
For the purpose of improving or modifying the antioxidant properties, slip properties, mold release properties, flame retardancy, anti-mold properties, electrical properties, strength, etc., various plastic additives and additives can be added. Can,
The addition amount can be arbitrarily added from a very small amount to several tens% depending on the purpose. In the above, as a general additive, for example, a lubricant, a crosslinking agent,
Antioxidants, ultraviolet absorbers, light stabilizers, fillers, reinforcing fibers, reinforcing agents, antistatic agents, flame retardants, flame retardants, foaming agents, fungicides, pigments, etc. can be used. May use a modifying resin or the like.

In the present invention, among the above additives, one or more of an ultraviolet absorber, an antioxidant, and a reinforcing fiber are preferably used in order to improve weather resistance, piercing resistance and the like. It is preferable to use various resin films or sheets obtained by kneading two or more kinds. The above-mentioned ultraviolet absorber absorbs harmful ultraviolet rays in sunlight and produces harmless heat energy in the molecule.
To prevent excitation of the active species that initiates photodegradation in the polymer, for example, benzophenone, benzotriazole, saltyl, acrylonitrile, metal complex salts, One or more inorganic UV absorbers such as hindered amine-based, ultra-fine titanium oxide (particle size, 0.01 to 0.06 μm) or ultra-fine zinc oxide (0.01 to 0.04 μm) Can be used. Further, as the above antioxidant, it is one that prevents light deterioration or heat deterioration of the polymer,
For example, phenol-based, amine-based, sulfur-based, phosphoric-based, and other antioxidants can be used. Further, as the above-mentioned ultraviolet absorber or antioxidant, for example, the above-mentioned benzophenone-based ultraviolet absorber or the above-mentioned phenol
A polymer-type ultraviolet absorber or an antioxidant obtained by chemically bonding an antioxidant such as toluene or the like can also be used. Further, as the reinforcing fibers, for example, glass fibers, carbon fibers, aramid fibers, polyamide fibers, polyester fibers, polypropylene fibers, polyacrylonitrile fibers, natural fibers, and the like can be used,
They can be used as long or short fibrous materials, or woven or non-woven materials, and the like. The content of the above ultraviolet absorber, antioxidant, reinforcing fiber, etc., varies depending on the particle shape, density, etc.,
About 0.1 to 10% by weight is preferred.

In the present invention, the surface of the film or sheet of various resins may be optionally used in order to improve the tight adhesion with an inorganic oxide vapor-deposited film described later.
A desired surface treatment layer can be provided in advance. In the present invention, as the surface treatment layer, for example, corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment,
Pretreatment such as oxidation treatment using a chemical agent or the like is optionally performed, and for example, a corona treatment layer, an ozone treatment layer, a plasma treatment layer, an oxidation treatment layer, or the like can be formed and provided. The above-mentioned surface pretreatment is carried out as a method for improving the tight adhesion between various resin films or sheets and a later-described inorganic oxide vapor-deposited film. In addition, as a method of improving, for example, a primer coat agent layer, an undercoat agent layer, an anchor coat agent layer, and an adhesive agent may be previously formed on the surface of various resin films or sheets. An agent layer, a vapor-deposited anchor coat agent layer, or the like may be arbitrarily formed to form a surface treatment layer. As the coating agent layer of the above pretreatment,
For example, polyester resin, polyamide resin, polyurethane resin, epoxy resin, phenol resin,
A resin composition containing a (meth) acrylic resin, a polyvinyl acetate resin, a polyolefin resin such as polyethylene aliha polypropylene or a copolymer or modified resin thereof, a cellulose resin, or the like as a main component of a vehicle. Can be used.

Incidentally, in order to improve weather resistance and the like, for example, an ultraviolet absorber and / or an antioxidant can be added to the above resin composition. As the above-mentioned ultraviolet absorber, one or more of the above-mentioned ultraviolet absorbers can be similarly used. Further, as the above-mentioned antioxidant, the above-mentioned antioxidant can be similarly used. As described above, the content of the ultraviolet absorber and / or antioxidant varies depending on the particle shape, density and the like, but is preferably about 0.1 to 10% by weight. In the above, as a method of forming the coating agent layer, for example, a coating agent such as a solvent type, an aqueous type, or an emulsion type is used, and a roll coating method, a gravure roll coating is used. The coating can be performed by using a coating method such as a coating method, a kiss coating method, or the like. The coating may be performed after forming a resin film or sheet or by biaxial stretching. As a post-process after processing, or film formation,
Alternatively, it can be carried out by in-line processing of biaxial stretching processing or the like.

Next, in the present invention, the back surface protection sheet for a solar cell module and the solar cell module according to the present invention.
Explained about the deposited film of the inorganic oxide constituting the metal and the like, as the deposited film of the inorganic oxide, for example, a physical vapor deposition method, or a chemical vapor deposition method, or a combination thereof, It can be manufactured by forming a single layer film composed of one layer of an inorganic oxide vapor-deposited film or a multilayer film or composite film composed of two or more layers.

The inorganic oxide vapor-deposited film formed by the physical vapor deposition method will be described in more detail. Examples of the inorganic oxide vapor-deposited film formed by the physical vapor deposition method include vacuum vapor deposition, sputtering, and ion plating. Physical vapor deposition methods (P
physical Vapor Deposition
, PVD method) can be used to form a deposited film of an inorganic oxide. In the present invention, specifically, a metal oxide is used as a raw material, which is heated and vaporized, and this is vapor-deposited on one of the weather-resistant substrates, or a metal or metal as a raw material. Using an oxide, oxidizing by introducing oxygen, oxidizing and depositing on one of the weather-resistant substrates, using a plasma-assisted oxidation-reactive deposition method that further assists the oxidation reaction with plasma. A deposition film can be formed. In the above, as a heating method of the evaporation material, for example, a resistance heating method, a high-frequency induction heating method, an electron beam heating method (EB), or the like can be used.

In the present invention, a specific example of a method for forming a thin film of an inorganic oxide by physical vapor deposition is shown in FIG. It is. As shown in FIG. 6, the weather-resistant base material 1 unwound from the unwinding roll 23 in the vacuum chamber 22 of the take-up type vacuum evaporation apparatus 21 was cooled through the guide rolls 24 and 25. It is guided to the coating drum 26. Thus, the evaporation source 28 heated by the crucible 27, for example, metal aluminum or aluminum oxide is evaporated on the weather-resistant substrate 1 guided on the cooled coating drum 26. Further, if necessary, an oxygen gas or the like is ejected from the oxygen gas outlet 29, and while supplying the same, a deposited film of an inorganic oxide such as aluminum oxide is formed through the masks 30 and 30 to form a film. Then, in the above, for example, the weather-resistant base material 1 on which a deposited film of an inorganic oxide such as aluminum oxide is formed is sent out through guide rolls 25 'and 24'.
By winding the film on the winding roll 31, a deposited film of an inorganic oxide can be formed by the physical vapor deposition method according to the present invention. In the present invention, first, a first-layer inorganic oxide vapor-deposited film is formed using the above-mentioned winding vacuum vapor deposition apparatus, and then, similarly, the inorganic oxide vapor-deposited film is formed. On top of this, an inorganic oxide vapor deposition film is further formed, or by using a roll-up vacuum vapor deposition device as described above, this is connected in series, and the inorganic oxide vapor deposition is continuously performed. By forming the film, an inorganic oxide vapor-deposited film including a multilayer film of two or more layers can be formed.

In the above description, the inorganic oxide deposited film can be basically used as long as it is a thin film on which a metal oxide is deposited. For example, silicon (Si), aluminum (Al), magnesium (Mg) , Calcium (C
a), potassium (K), tin (Sn), sodium (N
a), a vapor-deposited film of an oxide of a metal such as boron (B), titanium (Ti), lead (Pb), zirconium (Zr), and yttrium (Y) can be used. Thus, preferred are silicon (Si), aluminum (A
1) and the like.
Thus, the above-mentioned vapor-deposited film of a metal oxide can be referred to as a metal oxide, such as silicon oxide, aluminum oxide, and magnesium oxide. The notation is, for example, SiO _x , AlO _x MO such as MgO _X
X (wherein, M represents a metal element, and the value of X is
The range differs depending on the metal element. ). The range of the value of X is silicon (S
i) is 0-2, and aluminum (Al) is 0-1.
5. Magnesium (Mg) is 0-1, calcium (C
a) is 0-1, potassium (K) is 0-0.5, tin (Sn) is 0-2, and sodium (Na) is 0-0.
5, boron (B) is 0-1,5, titanium (Ti) is
0-2, lead (Pb): 0-1, zirconium (Zr)
Can have a value in the range of 0 to 2 and yttrium (Y) can have a value in the range of 0 to 1.5. In the above, when X = 0,
It is a perfect metal, is not transparent and cannot be used at all, and the upper end of the range of X is a fully oxidized value. In the present invention, generally, except for silicon (Si) and aluminum (Al), examples used are scarce. Silicon (Si) is 1.0 to 2.0, aluminum (A)
For l), a value in the range of 0.5 to 1.5 can be used. In the present invention, the thickness of the above-mentioned inorganic oxide vapor-deposited film varies depending on the type of the metal used or the metal oxide.
It is desirable to arbitrarily select and form it within the range of about 00 °, preferably about 100 to 1000 °. Further, in the present invention, as the deposited metal film of the inorganic oxide, the metal to be used, or as the oxide of the metal, used in one kind or a mixture of two or more kinds, and the inorganic oxide mixed with different materials is used. A vapor deposition film can also be formed.

Next, in the present invention, the vapor-deposited inorganic oxide film formed by the above-described chemical vapor deposition method will be further described. Chemical vapor deposition (Ch) such as vapor deposition, thermochemical vapor deposition, photochemical vapor deposition, etc.
electrical Vapor Deposition method,
A deposited film of an inorganic oxide can be formed by using a CVD method or the like. In the present invention, specifically, on one surface of the weather-resistant substrate, a monomer gas for vapor deposition such as an organic silicon compound is used as a raw material, and an argon gas is used as a carrier gas.
Using an inert gas such as helium gas, and further using an oxygen gas as an oxygen supply gas, and using a low-temperature plasma chemical vapor deposition method using a low-temperature plasma generator or the like, an inorganic oxide such as silicon oxide Can be formed. In the above, as the low-temperature plasma generator, for example, a high-frequency plasma, a pulse wave plasma, a microwave plasma or the like generator may be used.
In the present invention, in order to obtain highly active and stable plasma, it is desirable to use a generator using a high-frequency plasma method.

More specifically, an example of a method of forming a deposited film of an inorganic oxide by the low-temperature plasma chemical vapor deposition method will be described. FIG. FIG. 1 is a schematic configuration diagram of a low-temperature plasma chemical vapor deposition apparatus showing an outline of a method of forming an oxide deposition film. As shown in FIG. 7 described above, in the present invention, the vacuum chamber of the plasma enhanced chemical vapor deposition apparatus 41 is used.
The weather-resistant base material 1 is unwound from the unwinding roll 43 disposed in the inside 42, and the weather-resistant base material 1 is further fed to the auxiliary roll 4
4 and is conveyed onto the peripheral surface of the cooling / electrode drum 45 at a predetermined speed. Thus, in the present invention, the gas supply device 4
Oxygen gas, an inert gas, a monomer gas for vapor deposition of an organic silicon compound, etc., and the like are supplied from the raw material volatilization supply device 48 and the like, and a mixed gas composition for vapor deposition composed of them is adjusted. Introducing the mixed gas composition for vapor deposition into the vacuum chamber 42 through the raw material supply nozzle 49;
Then, a plasma is generated by the glow discharge plasma 50 on the weather-resistant substrate 1 conveyed on the peripheral surface of the cooling / electrode drum 45, and the plasma is emitted to irradiate the plasma with the inorganic oxide such as silicon oxide. A deposition film is formed and a film is formed. In the present invention, at this time, a predetermined power is applied to the cooling / electrode drum 45 from a power source 51 disposed outside the chamber. The generation of plasma is promoted by arranging the magnet 52, and then the weather-resistant base material 1 on which the deposited film of the inorganic oxide such as silicon oxide is formed is wound up through the auxiliary roll 53. It is possible to produce an inorganic oxide vapor-deposited film by the plasma enhanced chemical vapor deposition method according to the present invention. In the figure, 55 represents a vacuum pump. The above exemplification is merely an example, and it goes without saying that the present invention is not limited thereby. Although not shown, in the present invention, the inorganic oxide deposited film is not limited to one layer of the inorganic oxide deposited film, but may be a multilayer film in which two or more layers are stacked. The materials may be used alone or as a mixture of two or more types, and a vapor-deposited film of an inorganic oxide mixed with different materials may be used. In the present invention, a first layer of an inorganic oxide vapor-deposited film is first formed using the low-temperature plasma-enhanced chemical vapor deposition apparatus as described above, and then the inorganic oxide vapor-deposited film is similarly formed. On the film, further, a deposited film of an inorganic oxide is formed, or by using a low-temperature plasma-enhanced chemical vapor deposition apparatus as described above, this is connected in series, and continuously,
By forming a deposited film of an inorganic oxide, a deposited film of an inorganic oxide including two or more multilayer films can be formed.

In the above description, as a monomer gas for vapor deposition of an organic silicon compound or the like for forming a vapor deposition film of an inorganic oxide such as silicon oxide, for example, 1.1.3.3-tetramethyldisiloxane, hexamethyldisiloxane Siloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane,
Phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, and the like can be used. In the present invention, among the organic silicon compounds as described above, the use of 1.1.3.3-tetramethyldisiloxane or hexamethyldisiloxane as a raw material is advantageous in terms of handleability and formed deposited film. It is a particularly preferable raw material in view of its properties and the like. In the above, for example, an argon gas, a helium gas, or the like can be used as the inert gas.

In the present invention, the vapor-deposited silicon oxide film formed above reacts chemically with a monomer gas such as an organic silicon compound and oxygen gas, and the reaction product is formed on one surface of the weather-resistant substrate. closely wear, dense, it is possible to form a thin film rich in flexibility or the like, usually, the general formula SiO _X (provided that, X
Represents a number from 0 to 2). In view of transparency, barrier properties, and the like, the silicon oxide vapor-deposited film has the general formula S
iO _X (where, X represents the number of 1.3 to 1.9.)
It is preferable that the thin film is mainly composed of a silicon oxide vapor deposition film represented by the following formula. In the above, the value of X is the molar ratio of the monomer gas to the oxygen gas, the energy of the plasma.
Generally, as the value of X decreases, the gas permeability decreases, but the film itself becomes yellowish and the transparency deteriorates. Further, the above-described deposited film of silicon oxide has silicon (Si) and oxygen (O) as essential constituent elements, and furthermore, one of carbon (C) and hydrogen (H), or
It consists of a deposited film of silicon oxide containing both elements as trace constituent elements, and has a thickness of 50 ° to 500 °.
And the composition ratio between the essential constituent elements and the trace constituent elements continuously changes in the film thickness direction. Further, when the silicon oxide vapor-deposited film contains a compound composed of carbon, the content of carbon is reduced in the depth direction of the film thickness. Thus, in the present invention, for the above-mentioned deposited film of silicon oxide, for example, an X-ray photoelectron spectrometer (Xray Photoelectron Spect)
ROSCOPY, XPS), secondary ion mass spectrometer (Secondary Ion Mass Spect)
roscopy, SIMS), etc.
The physical properties as described above can be confirmed by performing elemental analysis of the deposited silicon oxide film using a method of performing analysis by ion etching in the depth direction or the like. Also,
In the present invention, the thickness of the deposited silicon oxide film is desirably about 50 to 4000 °,
Specifically, the film thickness is desirably about 100 to 1000 °, and in the above, if the thickness is more than 1000 °, or even 4000 °, cracks and the like are easily generated in the film, which is not preferable. , 100 °, or even less than 50 °, it is not preferable because it becomes difficult to exhibit the barrier effect. In the above, the film thickness can be measured using, for example, a fluorescent X-ray analyzer (model name: RIX2000 type) manufactured by Rigaku Corporation.
It can be measured by the fundamental parameter method. Further, in the above, as a means for changing the thickness of the deposited film of silicon oxide, increasing the volume velocity of the deposited film, that is, a method of increasing the amount of the monomer gas and the oxygen gas or the rate of the deposition. It can be performed by a method of slowing down.

Incidentally, in the present invention, as a backside protective sheet for a solar cell module according to the present invention, as a deposited film of an inorganic oxide constituting a solar cell module or the like, for example, a physical vapor deposition method can be used. By using both of the chemical vapor deposition methods together, a composite film composed of two or more layers of different inorganic oxide vapor deposited films can be formed and used. Thus, as a composite film composed of two or more layers of the above-described vapor-deposited films of different kinds of inorganic oxides, first, on a weather-resistant substrate, dense and flexible by chemical vapor deposition, An inorganic oxide deposited film capable of relatively preventing the occurrence of cracks is provided, and then an inorganic oxide deposited film formed by physical vapor deposition is provided on the inorganic oxide deposited film to form two layers. It is desirable to form an inorganic oxide vapor-deposited film composed of the above composite film. Of course, in the present invention, contrary to the above, on the weather-resistant substrate, first, a deposited film of an inorganic oxide is provided by a physical vapor deposition method, and then, by a chemical vapor deposition method, An inorganic oxide vapor-deposited film that is dense, highly flexible, and can relatively prevent cracks can be provided to form an inorganic oxide vapor-deposited film composed of a composite film composed of two or more layers. It is.

In the present invention, the weather-resistant substrate is protected on one side of the above-mentioned weather-resistant substrate against vapor deposition conditions when an inorganic oxide vapor-deposited film is formed. In addition, it suppresses yellowing, deterioration or shrinkage, or cohesive failure in the surface layer or inner layer of the substrate, and furthermore, favorably forms a deposited film of an inorganic oxide on one surface of the weather-resistant substrate. And
In addition, in order to improve the tight adhesion between the weather-resistant substrate and the inorganic oxide vapor-deposited film and the like, a surface pretreatment layer is formed on one surface of the weather-resistant substrate in advance, for example, by the above-described plasma chemistry. Chemical vapor deposition methods (Chemical Vapor De) such as vapor phase epitaxy, thermochemical vapor phase epitaxy, and photochemical vapor phase epitaxy
position method, CVD method) or, for example,
Physical vapor deposition methods such as a vacuum deposition method, a sputtering method, and an ion plating method.
A deposition-resistant protective film can be provided by forming a vapor-deposited thin film of an inorganic oxide using a deposition method or a PVD method. Note that, in the present invention, the thickness of the deposition-resistant protective film made of silicon oxide or the like is a thin film, and further, a non-barrier film having no barrier property against water vapor gas, oxygen gas, or the like is sufficient. In particular,
It is desirable that the film thickness is less than 150 °, specifically,
The film thickness is about 10 to 100 °, preferably 2 to 100 °.
It is desirable that the angle is about 0 to 80 °, and more preferably about 30 to 60 °. In the above, when the thickness is 150 ° or more, specifically, 100 °, further 80 °, and more than 60 °, it is difficult to form a good deposition-resistant protective film. , And 20
If it is less than 30 °, it is not preferable because the function as a deposition-resistant protective layer is lost and it becomes difficult to exhibit its effect.

Next, in the present invention, the back surface protection sheet for a solar cell module and the solar cell module according to the present invention.
For example, the printing layer may include, for example, one or more known ink vehicles as a main component, and a coloring agent such as a dye or a pigment added thereto. And further, for example, plasticizers, waxes, greases, light stabilizers, ultraviolet absorbers, antioxidants, surfactants, reinforcing fibers, reinforcing agents, slip agents, fillers,
Various additives such as others are arbitrarily added and sufficiently kneaded with a solvent, a diluent or the like to prepare a desired ink composition such as a solution type, a dispersion type or the like. Next, in the present invention, the ink composition prepared above is used, and, for example,
Using a gravure printing method, offset printing method, letterpress printing method, screen printing method, flexographic printing method, transfer printing method, etc., the deposition film of inorganic oxide provided on the weather-resistant substrate The printed layer according to the present invention can be formed by printing one or more colors on the top. Thus, in the present invention, the printed layer is used to reflect or diffuse the sunlight transmitted from the surface of the solar cell module, thereby achieving reuse, and further improving the design and the like. It is to improve. The thickness of the print layer is preferably from several μm to about 100 μm.

In the above, known vehicles for the ink include, for example, polyethylene resins, polypropylene resins, polystyrene resins, polyvinyl acetate resins, poe vinyl chloride resins, vinyl chloride-vinyl acetate copolymers. , Polyvinylidene chloride resin, polyvinyl butyral resin, (meth) acrylic resin, polyamide resin, polyester resin, alkyd resin, amino resin, epoxy resin, phenol resin, maleic acid Resin, fumaric acid resin, nitrile cellulose, ethyl cellulose, cellulose resins such as acetylbutyl cellulose, ethyloxyethyl cellulose, petroleum resins, chlorinated paraffin, ester gum, chlorinated rubber, and cyclized rubber Etc., rubber resins such as casein, rosin or rosin derivatives, oils S, varnishes, waxes, to one free ink vehicle for other like can be used two or more kinds.

In the above, the colorant is provided with light reflectivity, light diffusivity, and the like in order to reuse the solar light transmitted through the solar cell module by reflecting or diffusing the light. It is added for the purpose of imparting designability and the like, and for example, coloring agents such as various dyes and pigments such as white, black, blue, red and others can be used. Thus, in the present invention, basic lead carbonate, basic lead sulfate, basic lead silicate, zinc white, zinc sulfide, lithopone, antimony trioxide, anatas-type titanium oxide, rutile-type titanium oxide, and the like It is particularly preferred to use one or more white pigments. The amount to be used is 0. 0 in the ink composition.
1% to 30% by weight, preferably 0.5% to
It is desirable to use it by adding about 10% by weight.

The ultraviolet absorber as an additive absorbs harmful ultraviolet rays in sunlight, converts them into harmless heat energy in the molecule, and initiates photodegradation in the polymer. It prevents the active species from being excited. Examples thereof include benzophenone, benzotriazole, saltylate, acrylonitrile, metal complex, and solder.
Doamine-based, ultrafine titanium oxide (particle size, 0.01 to
0.06 μm) or ultrafine zinc oxide (0.01 to
One or more inorganic UV absorbers such as 0.04 μm) can be used. The antioxidant as the above additive is for preventing the above-mentioned polymer from light degradation or thermal degradation, and includes, for example, phenol-based, amine-based, sulfur-based, phosphoric-acid-based, etc. Antioxidants can be used. Further, as the above-mentioned ultraviolet absorber or antioxidant, for example, the above-mentioned ultraviolet absorber such as benzophenone or the above antioxidant such as phenol is added to the main chain or side chain constituting the polymer. A polymer-type ultraviolet absorber or an antioxidant obtained by chemically bonding may also be used. The content of the above-mentioned ultraviolet absorber and / or antioxidant varies depending on the particle shape, density and the like in the ink composition, but is preferably about 0.1 to 10% by weight.

Further, in the present invention, in order to improve the close adhesion between the surface of the inorganic oxide vapor-deposited film and the surface of the printing layer, one or both of the surfaces may be further provided with, for example, A surface treatment layer may be formed by arbitrarily forming a primer layer or the like using a primer composition. Examples of the primer composition include polyester resins, polyamide resins, polyurethane resins, epoxy resins, phenol resins, (meth) acrylic resins, polyvinyl acetate resins, and polyethylene polypropylene. And the like, or a resin composition containing a polyolefin resin or a copolymer or modified resin thereof, a cellulose resin, or the like as a main component of the vehicle. In the present invention, in the above-mentioned primer composition, for example, in order to further improve the tight adhesion, for example, a silane coupling agent, or an antiblocking agent, and other additives such as other additives are optionally added. can do. Thus, in the present invention, for example,
The primer layer can be formed by coating using a coating method such as coating, gravure roll coating, kiss coating, or the like, and the coating amount is 0. 0.1-5 g / m ² (dry state) is desirable.

Next, in the present invention, the solar cell module
Protection module for ordinary solar cell module
Explaining about the sheet, such a surface protection sheet has sunlight permeability, insulation property, etc., and furthermore, weather resistance,
Has various properties such as heat resistance, light resistance, water resistance, wind pressure resistance, hail resistance, chemical resistance, moisture resistance, antifouling property, etc., and has excellent physical or chemical strength, toughness, etc. It is required to be extremely durable and to be excellent in scratch resistance, shock absorption and the like because of its protection of a solar cell element as a photovoltaic element. Specific examples of the above surface protection sheet include, for example, a known glass plate and the like, and further, for example, a fluorine resin, a polyamide resin (various nylons), a polyester resin, and a polyethylene resin. Films of various resins such as resin, polypropylene resin, cyclic polyolefin resin, polystyrene resin, (meth) acrylic resin, polycarbonate resin, acetal resin, cellulose resin, and others. Alternatively, a sheet can be used. As the above resin film or sheet, for example, a biaxially stretched resin film or sheet can also be used. Further, in the above resin film or sheet, the film thickness is about 12 to 200 μm, more preferably 25 to 200 μm.
About 150 μm is desirable.

Next, in the present invention, the solar cell module
The filler layer laminated below the surface protection sheet for a solar cell module constituting the solar cell module will be described. The filler layer is transparent because sunlight enters and transmits and absorbs sunlight. It is necessary that the photovoltaic element has an adhesive property with a surface protection sheet, and has a function of maintaining the smoothness of the surface of a solar cell element as a photovoltaic element. Having thermoplasticity for
Further, since the solar cell element as a photovoltaic element is to be protected, it is necessary to have excellent scratch resistance, shock absorption and the like. Specifically, as the filler layer, for example, a fluorine resin, an ethylene-vinyl acetate copolymer, an ionomer resin, an ethylene-acrylic acid, or a methacrylic acid copolymer, a polyethylene resin, a polypropylene resin, Acrylic acid, itaconic acid, polyolefin resin such as polyethylene or polypropylene
Acid-modified polyolene fin resin modified with unsaturated carboxylic acids such as maleic acid and fumaric acid, polyvinyl butyral
Resin, silicone resin, epoxy resin, (meth)
A mixture of one or more resins such as acrylic resins and other resins can be used. In the present invention, in order to improve the heat resistance, light resistance, weather resistance such as water resistance, etc. of the resin constituting the above-mentioned filler layer, in a range where the transparency is not impaired, for example, crosslinking is performed. Additives such as an agent, a thermal antioxidant, a light stabilizer, an ultraviolet absorber, a photooxidant, and the like can be arbitrarily added and mixed. Therefore, in the present invention, as the filler on the incident side of sunlight, in consideration of light resistance, heat resistance, and weather resistance such as water resistance, a fluororesin or an ethylene-vinyl acetate resin is a desirable material. is there. The thickness of the filler layer is about 200 to 1000 μm, preferably 350 μm.
About 600 μm is desirable.

Next, in the present invention, the solar cell module
The solar cell element as a photovoltaic element constituting the solar cell element will be described. As such a solar cell element, a conventionally known one, for example, a crystalline silicon such as a single-crystal silicon-type solar cell element, a polycrystalline silicon-type solar cell element, etc. Solar electronic devices, single-junction or tandem-structure amorphous silicon solar cell devices, gallium arsenide (G
III-V compound semiconductor solar devices such as aAs) and indium phosphide (InP), cadmium telluride (CdTe)
And copper indium selenide (CuInSe ₂ )
Group VI compound semiconductor solar electronic devices and others can be used. Further, a thin-film polycrystalline silicon solar cell element, a thin-film microcrystalline silicon solar cell element, a hybrid element of a thin-film crystalline silicon solar cell element and an amorphous silicon solar cell element, and the like can also be used. Thus, in the present invention, a solar cell element is formed, for example, on a substrate such as a glass substrate, a plastic substrate, a metal substrate, or the like, by forming crystalline silicon such as a pn junction structure or amorphous silicon such as a pin junction structure. An electromotive force portion such as silicon or a compound semiconductor is formed to constitute a solar cell element.

Next, in the present invention, the solar cell module
The filler layer laminated below the photovoltaic element constituting the solar cell module will be described. The filler layer is the same as the filler layer laminated below the solar cell module surface protection sheet. In addition, it is necessary to have an adhesive property with a back surface protection sheet, and further, to have a function of maintaining the smoothness of the back surface of the solar cell element as a photovoltaic element, and to have thermoplasticity. In order to protect a solar cell element as a photovoltaic element, it is necessary to have excellent scratch resistance, shock absorption and the like. However, the filler layer laminated below the photovoltaic element constituting the solar cell module is different from the filler layer laminated below the surface protection sheet for the solar cell module. ,
It is not necessary to have transparency. Specifically, as the above-mentioned filler layer, for example, as in the case of the above-mentioned filler layer laminated below the surface protection sheet for a solar cell module, for example, a fluorine-based resin, ethylene-vinyl acetate copolymer may be used. A polyolefin resin such as coalesced, ionomer resin, ethylene-acrylic acid, or methacrylic acid copolymer, polyethylene resin, polypropylene resin, polyethylene or polypropylene can be mixed with acrylic acid, itaconic acid, maleic acid, fumaric acid, etc. One or more resins such as an acid-modified polyolefin resin modified with a saturated carboxylic acid, a polyvinyl butyral resin, a silicone resin, an epoxy resin, a (meth) acrylic resin, and the like. Mixtures can be used. In the present invention, in order to improve the heat resistance, light resistance, weather resistance such as water resistance, etc. of the resin constituting the above-mentioned filler layer, in a range where the transparency is not impaired, for example, crosslinking is performed. Additives such as an agent, a thermal antioxidant, a light stabilizer, an ultraviolet absorber, a photooxidant, and the like can be arbitrarily added and mixed. The thickness of the filler layer is 200 to
About 1000 μm, more preferably 350 to 600 μm
Position is desirable.

In the present invention, when the solar cell module according to the present invention is manufactured, in order to improve its various strengths such as strength, weather resistance, scratch resistance, etc. Material, for example, low density polyethylene,
Medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid or methacrylic Acid copolymer, methylpentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer, poly (meth) acrylic resin, poly Acrylic nitrile resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, polyamide resin, polycarbonate resin , Polyvinyl alcohol tree , Ethylene - saponified vinyl acetate copolymer, fluorine resin, diene resin, polyacetal - Le resins, polyurethane resins, nitrocellulose -
And any other known resin film or sheet. In the present invention, the above-mentioned film or sheet may be any of unstretched and uniaxially or biaxially stretched. The thickness is arbitrary,
It can be used by selecting from the range of several μm to 300 μm. Further, in the present invention, the film or sheet may be any film such as an extruded film, an inflation film, or a coating film.

Next, in the present invention, a method for manufacturing a solar cell module using the back surface protection sheet for a solar cell module according to the present invention will be described. A method, for example, the above-mentioned surface protection sheet for a solar cell module, a filler layer, a solar cell element as a photovoltaic element, a filler layer, and the backside protection for a solar cell module according to the present invention. The sheets are sequentially laminated with their printing layers facing each other, and if necessary, other materials are optionally laminated between the layers,
Using a normal molding method such as a lamination method in which these are integrated by vacuum suction or the like and then heated and pressed, the above-mentioned layers are formed as an integrally formed body by thermocompression bonding to produce a solar cell module. Can be. In the above, if necessary, a heat-melt adhesive containing a resin such as a (meth) acrylic resin, an olefin-based resin, a vinyl-based resin, or the like as a main component of the vehicle, in order to enhance adhesion between the layers, Solvent-based adhesives, photo-curable adhesives, and others can be used.

In the above-mentioned lamination, each lamination facing surface may be provided, if necessary, for example, with a corona discharge treatment, an ozone treatment, a low-temperature treatment using an oxygen gas or a nitrogen gas or the like, in order to improve the tight adhesion. Pretreatments such as a plasma treatment, a glow discharge treatment, an oxidation treatment using a chemical agent, and the like can be arbitrarily performed. Further, in the above-mentioned lamination, a primer coat agent layer, an undercoat agent layer, an adhesive layer, an anchor coat agent layer, or the like is arbitrarily formed on each of the laminated opposing surfaces in advance. Then, surface pretreatment can be performed. Examples of the coating agent layer for the above pretreatment include polyester resin, polyamide resin, polyurethane resin, epoxy resin, phenol resin, (meth) acrylic resin, polyvinyl acetate resin, A resin composition containing, as a main component of the vehicle, a polyolefin resin such as polyethylene aliha polypropylene or a copolymer or modified resin thereof, a cellulose resin, or the like can be used. In the above, as a method of forming the coating agent layer, for example, a coating agent such as a solvent type, an aqueous type, or an emulsion type is used, and a roll coating is used.
The coating can be performed by using a coating method such as a coating method, a gravure roll coating method, a kiss coating method and others.

In the present invention, in the method of manufacturing a solar cell module using the back protection sheet for a solar cell module according to the present invention, the solar cell module according to the present invention is previously prepared. A filler layer is laminated on the surface of the printed layer of the solar cell module backside protection sheet to produce a laminate comprising the solar cell module backside protection sheet and the filler layer. Similarly, a filler layer and a surface protection sheet for a solar cell module are preliminarily laminated to produce a laminate comprising both of them, and then the above two laminates are placed on the surface of the filler layer. , Facing each other, furthermore, a solar cell element as a photovoltaic element is laminated between the layers, and further, if necessary, other materials are optionally laminated between the respective layers. Lamination method, etc., which is integrated by vacuum suction and heat-pressed Using a normal molding method, and heat pressing molding integrally molded body of the above layers, the solar cell module - can be produced Le.

[0041]

EXAMPLES The present invention will be described below more specifically with reference to examples. Example 1 (1). A fluororesin sheet made of a copolymer of tetrafluoroethylene and ethylene (ETFE) having a thickness of 50 .mu.m is used, and the sheet is mounted on a delivery roll of a plasma enhanced chemical vapor deposition apparatus. On the corona-treated surface of the base resin sheet, a silicon oxide deposited film having a thickness of 800 mm was formed under the following conditions. (Evaporation conditions) Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 1: 10: 10 (unit: slm) Degree of vacuum in vacuum chamber: 5.0 × 10 ⁻⁶ mbar In evaporation chamber Degree of vacuum: 6.0 × 10 ⁻² mbar Cooling / electrode drum supply power: 20 kW Film transport speed: 80 m / min Next, immediately after forming the above-described 800 nm-thick silicon oxide deposited film, the silicon oxide Using a glow discharge plasma generator, a plasma output of 1500 W, a mixed gas consisting of oxygen gas (O ₂ ): argon gas (Ar) = 19: 1, and a mixed gas pressure of 6 × 10 ^-5 Tor
r, a plasma treatment was performed with an oxygen / argon mixed gas at a treatment speed of 420 m / min to form a plasma treated surface. (2). Next, an epoxy-based silane coupling agent (8.0% by weight) and an anti-blocking agent were added to the plasma-treated surface of the silicon oxide vapor-deposited film formed in the above (1). 1.0% by weight)
A sufficiently kneaded primer-resin composition is used, and this is applied to a film thickness of 0.5 g / m by a gravure roll coating method.
² (dry state) to form a primer layer. On the other hand, a polyamide resin and nitrocellulose are used as a vehicle for the ink, and titanium oxide (8% by weight) as a white pigment and ultrafine titanium oxide (particle size, 0.01 to 0.
06 μm, 3% by weight), and other necessary additives, and kneaded well to prepare an ink composition.
Next, on the primer layer formed above, similarly, using the white ink composition formed above, this was printed many times by a gravure printing method to form a print layer having a film thickness of 50 μm. A back protection sheet for a solar cell module according to the present invention was manufactured. (3). Next, a glass plate having a thickness of 3 mm and a thickness of 4
A 38 μm-thick biaxially stretched polyethylene terephthalate film in which solar cell elements made of an amorphous silicon are arranged in parallel, and a 400 μm-thick ethylene-vinyl acetate copolymer sheet The backsheet for solar cell module and the backsheet for solar cell module are printed with their printed layers facing each other, and the solar cell element surface is directed upward, and an acrylic resin is bonded between the layers. The solar cell module according to the present invention was manufactured by laminating through the agent layer.

Examples 2 to 7 In the above Example 1, instead of using a fluororesin sheet having a thickness of 50 μm, the following weather-resistant base material was used. Go exactly the same as
Similar to the first embodiment, similar back surface protection sheets and solar cell modules according to the present invention could be manufactured. Embodiment 2. FIG. 50μm thick polyvinyl fluoride resin screen
Example 3 (PVF) Polydicyclopentadiene resin sheet having a thickness of 100 μm. Polycarbonate resin sheet having a thickness of 50 μm. Polyacrylic resin sheet having a thickness of 50 μm. Biaxially stretched nylon film having a thickness of 20 μm. Biaxially stretched polyethylene terephthalate film with a thickness of 20 μm

Embodiment 8 (1). A fluororesin sheet made of a copolymer of tetrafluoroethylene and ethylene (ETFE) having a thickness of 50 μm is used, and the sheet is attached to a delivery roll of a roll-up type vacuum evaporation apparatus. -The above-mentioned fluorine-based resin film is fed out on a singing drum and subjected to a reactive vacuum deposition method using an electron beam (EB) heating method while supplying oxygen gas while using aluminum as a deposition source under the following conditions. Film thickness of 80 on the corona treated surface
A 0 ° aluminum oxide deposited film was formed. (Evaporation conditions) Evaporation source: Aluminum Degree of vacuum in vacuum chamber: 7.5 × 10 ⁻⁶ mbar Degree of vacuum in evaporation chamber: 2.1 × 10 ⁻⁶ mbar EB output: 40 KW Film transport speed: 600 m / Immediately after the above-described 800-nm-thick aluminum oxide vapor-deposited film was formed, a plasma output of 1500 W and oxygen gas (O ₂₎ were applied to the aluminum oxide vapor-deposited film surface using a glow discharge plasma generator. ): Argon gas (A
r) = 19: 1, using a mixed gas pressure of 6 × 10 ⁻⁵ Tool and a processing speed of 420 m / min to perform an oxygen / argon mixed gas plasma process to form a plasma-treated surface. (2). Next, on the plasma-treated surface of the aluminum oxide vapor-deposited film produced in the above (1), an epoxy-based silane coupling agent (8.0% by weight) and an anti-blocking agent ( 1.0% by weight) and sufficiently kneaded to obtain a primer-resin composition, which is obtained by a gravure roll coating method so as to have a film thickness of 0.5 g / m ² (dry state). To form a primer layer. On the other hand, a polyamide resin and nitrocellulose are used as a vehicle for the ink, and titanium oxide (8% by weight) as a white pigment and ultrafine titanium oxide (particle size, 0.01 to 0.06 μm, 3% by weight)
In addition, necessary additives were added and kneaded well to prepare an ink composition. Next, on the primer layer formed above, similarly, using the white ink composition formed above, this was printed many times by a gravure printing method to form a print layer having a film thickness of 50 μm. A back protection sheet for a solar cell module according to the present invention was manufactured. (3). Next, a glass plate having a thickness of 3 mm and a thickness of 4
A 38 μm-thick biaxially stretched polyethylene terephthalate film in which solar cell elements made of an amorphous silicon are arranged in parallel, and a 400 μm-thick ethylene-vinyl acetate copolymer sheet The backsheet for solar cell module and the backsheet for solar cell module are printed with their printed layers facing each other, and the solar cell element surface is directed upward, and an acrylic resin is bonded between the layers. The solar cell module according to the present invention was manufactured by laminating through the agent layer.

Examples 9 to 13 Instead of using the fluororesin sheet having a thickness of 50 μm in Example 7 described above, the following weather-resistant base material was used. Go exactly the same as
In the same manner as in Example 7 above, a similar back surface protection sheet and solar cell module according to the present invention could be manufactured. Embodiment 9 FIG. 50μm thick polyvinyl fluoride resin screen
G (PVF) Embodiment 10 Polydicyclopentadiene resin sheet having a thickness of 100 μm. 50μm thick polycarbonate resin sheet
G. Embodiment 12 FIG. Example 13 Polyacrylic resin sheet having a thickness of 50 μm Biaxially stretched polyethylene terephthalate film with a thickness of 20 μm

Embodiment 14 (1). A 50 μm-thick polyvinyl fluoride resin sheet (PVF) is used, which is mounted on a delivery roll of a plasma-enhanced chemical vapor deposition apparatus, and then a corona treatment of the polyvinyl fluoride resin sheet (PVF) is performed. On the surface, a vapor-deposited thin film of silicon oxide having a thickness of 50 ° was formed under the following conditions to provide a vapor deposition-resistant protective film. (Evaporation conditions) Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 5: 5: 5 (unit: slm) Degree of vacuum in vacuum chamber: 7.0 × 10 ⁻⁶ mbar In evaporation chamber Vacuum degree: 3.8 × 10 ^-2 mbar Cooling / electrode drum supply power: 15 kW Sheet transfer speed: 100 m / min Next, the above-mentioned Example 1 Similarly, an evaporated silicon oxide film having a thickness of 800 ° was formed, and a plasma-treated surface was formed on the deposited silicon oxide film. (2). Next, on the plasma-treated surface of the deposited silicon oxide film having a thickness of 800 ° formed as described above, the same process as in the above-described embodiment 1 was performed. Such a back surface protection sheet and a solar cell module could be manufactured.

Embodiment 15 (1). A polyvinyl fluoride resin sheet (PVF) having a thickness of 50 μm was used, mounted on a delivery roll of a take-up type vacuum evaporation apparatus, and then fed out onto a coating drum. Under conditions, aluminum was used as a vapor deposition source, and an electron beam was supplied while supplying oxygen gas.
A vapor-deposited thin film of aluminum oxide having a thickness of 50 ° is formed on the corona-treated surface of the polyvinyl fluoride resin sheet (PVF) by a reactive vacuum deposition method using a heating method (EB). Was provided. (Evaporation conditions) Evaporation source: Aluminum Degree of vacuum in vacuum chamber: 7.5 × 10 ⁻⁶ mbar Degree of vacuum in evaporation chamber: 2.1 × 10 ⁻⁶ mbar EB output: 20 KW Film transport speed: 500 m / Further, an aluminum oxide deposited film having a film thickness of 800 ° was formed on the deposited anti-evaporation protective film in the same manner as in Example 7 above. A treated surface was formed. (2). Next, on the plasma-treated surface of the deposited aluminum oxide film having a thickness of 800 ° formed above, the same procedure as in the above-described Example 7 was performed.
A similar backside protection sheet and solar cell module according to the present invention could be manufactured.

Embodiment 16 (1). A polyvinyl fluoride resin sheet (PVF) having a thickness of 50 μm is used, and 1 × 10 ^-4
Purity 99.9 by high-frequency dielectric heating under Torr vacuum
% Silicon monoxide (SiO) was heated and evaporated to form a deposited film of silicon oxide of 500 °. Next, the film thickness of 500
Immediately after forming the silicon oxide vapor deposition film, the power of 10 kW and the processing speed of 100 m / m were applied to the silicon oxide vapor deposition film surface.
The corona discharge treatment was carried out at "in" to form a corona treated surface in which the surface tension of the vapor-deposited film surface was increased from 35 dyne to 60 dyne. (2). Next, on the corona-treated surface of the deposited silicon oxide film having a thickness of 500 ° formed as described above, the same process as in the above-described Example 1 was performed. Such a back surface protection sheet and a solar cell module
Could be manufactured.

Embodiment 17 (1). Using a polyvinyl fluoride resin sheet (PVF) having a thickness of 50 μm, a vapor-deposited silicon oxide film having a film thickness of 500 ° is formed in the same manner as in the first embodiment. A corona treated surface was formed on the surface. Next, on the corona-treated surface formed above, a vapor-deposited film of aluminum oxide having a thickness of 500 ° was formed in the same manner as in Example 7 described above, and a plasma-treated surface was further formed on the vapor-deposited film of aluminum oxide. Formed. (2). Next, the above-described 500-nm-thick aluminum oxide vapor-deposited film is subjected to the same process as in Example 7 above, and the same process as in Example 7 is performed.
A similar backside protection sheet and solar cell module according to the present invention could be manufactured.

Embodiment 18 (1). Using a polyvinyl fluoride resin sheet (PVF) having a thickness of 50 μm, a vapor-deposited silicon oxide film having a film thickness of 500 ° is formed in the same manner as in the first embodiment. A plasma treated surface was formed on the surface. next,
On the plasma-processed surface formed above, a 500-nm-thick silicon oxide vapor-deposited film was formed in the same manner as in Example 1 above, and a plasma-treated surface was further formed on the silicon oxide-deposited film. did. (2). Next, on the plasma-treated surface of the deposited silicon oxide film having a thickness of 500 ° formed as described above, the same process as in the above-described embodiment 1 is performed. Such a back surface protection sheet and a solar cell module could be manufactured.

COMPARATIVE EXAMPLE 1 A 38 μm-thick biaxially stretched polyethylene terephthalate having a thickness of 3 mm, a solar cell element made of a 400 μm-thick ethylene-vinyl acetate copolymer sheet, and amorphous silicon was arranged in parallel. -Film, thickness 400μ
m-ethylene-vinyl acetate copolymer sheet and 50 μm thick white biaxially stretched polyethylene terephthalate
The solar cell module was manufactured by laminating a photo film with the solar cell element surface facing upward through an adhesive layer of an acrylic resin.

Comparative Example 2 A 38 μm-thick biaxially stretched polyethylene terephthalate having a 3 mm-thick glass plate, 400 μm-thick ethylene-vinyl acetate copolymer sheet, and solar cell elements made of amorphous silicon arranged in parallel. -Film, thickness 400μ
m of an ethylene-vinyl acetate copolymer sheet and a 50 μm-thick white polyvinyl fluoride resin sheet are opposed to each other, and the solar cell element surface thereof faces upward. The solar cell module was manufactured by laminating through an adhesive layer.

EXPERIMENTAL EXAMPLES The reflectances of the back protection sheets for solar cell modules according to the present invention manufactured in Examples 1 to 18 and the back protection sheets according to Comparative Examples 1 and 2 were measured. Further, a solar cell module evaluation test was performed on the solar cell modules manufactured in Examples 1 to 18 and the solar cell modules manufactured in Comparative Examples 1 and 2. (1). Measurement of reflectivity This is based on the base film, which is the back protection sheet for the solar cell module according to the present invention manufactured in Examples 1 to 18 and the back protection sheet according to Comparative Examples 1 and 2. about,
The reflectance (%) with respect to a light having a wavelength of 550 nm was measured with a spectrophotometer. (2). Solar cell module evaluation test This is based on JIS standard C8917-1989.
An environmental test of the solar cell module was performed, and the output of the photovoltaic power before and after the test was measured and compared and evaluated. (3). Measurement of Water Vapor Permeability and Oxygen Permeability The water vapor permeability was determined by comparing the back surface protection sheet for solar cell module according to the present invention manufactured in Examples 1 to 18 with the comparative example 1
2 under a condition of a temperature of 40 ° C. and a humidity of 90% RH under the conditions of a temperature of 40 ° C. and a humidity of 90% [model name, PERMATRA (PERMATRA)]
N)], and the oxygen permeability was measured using the same object as described above under the conditions of a temperature of 23 ° C. and a humidity of 90% RH. OXTRAN]. (4). Measurement of lamination strength This means that the back surface protection sheet for solar cell module is 15m
m width and a tensile tester [A & D
(A & D) Co., Ltd. (Model name: Tensilon) was used to measure the peel strength of the laminate constituting the back protective sheet for a solar cell module. The results of the above measurements are shown in Table 1 below.

[0053] In Table 1 above, the unit of the reflectance is [%],
The unit of the water vapor barrier property is [g / m ² / day · 40 ° C.
100% RH], and the unit of the oxygen barrier property is [c
c / m ² / day · 23 ° C. · 90% RH], the unit of the output reduction rate is [%], and the unit of the lamination strength is:
[Kg / 15 mm width].

As is clear from the measurement results shown in Table 1 above, the back protective sheets for solar cell modules according to Examples 1 to 18 have a high reflectance, a water vapor barrier property and an oxygen barrier property. Excellent in properties and lamination strength. Furthermore, the solar cell modules using the solar cell module protection sheets according to Examples 1 to 18 had a low output reduction rate. On the other hand, the solar cell module protection sheets according to Comparative Examples 1 and 2 have high reflectance but low water vapor barrier properties and low oxygen barrier properties. The battery module is
There were problems such as a high output reduction rate.

[0055]

As is apparent from the above description, the present invention provides:
On one surface of the weather-resistant substrate, a silicon oxide, or a transparent glassy material such as aluminum oxide, and a vapor-deposited film of an inorganic oxide excellent in water vapor barrier properties, oxygen barrier properties, etc. are provided. On the oxide film, a printing layer of an ink composition comprising an ink vehicle as a main component, a coloring agent such as a dye and a pigment, and the like added thereto, and sufficiently kneaded to form a solar cell. A back surface protection sheet for a module is manufactured, and the back surface protection sheet for a solar cell module is manufactured.
For example, a surface protection sheet for a normal solar cell module made of a glass plate or the like, a filler layer, a solar cell element as a photovoltaic element, a filler layer, and the above solar cell A back surface protection sheet for a module is sequentially laminated with the printed layers facing each other, and then a solar cell is applied by using a lamination method or the like in which these are integrally vacuum-sucked and heated and pressed. By manufacturing modules, excellent strength, furthermore
Excellent in various properties such as weather resistance, heat resistance, water resistance, light resistance, wind pressure resistance, hail resistance, chemical resistance, antifouling property, etc., and especially excellent in moisture resistance to prevent intrusion of moisture, oxygen, etc. In addition, light reflectivity, light diffusion, design, etc. are significantly improved, and their long-term performance deterioration is minimized, and they are extremely durable, have excellent protection ability, and are manufactured at lower cost. That is, a safe solar cell module can be stably manufactured.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view schematically showing a layer configuration of an example of a back surface protection sheet for a solar cell module according to the present invention.

FIG. 2 is a schematic cross-sectional view schematically showing a layer configuration of an example of a back surface protection sheet for a solar cell module according to the present invention.

FIG. 3 is a schematic cross-sectional view schematically showing a layer configuration of another example of a deposited film of an inorganic oxide.

FIG. 4 is a schematic cross-sectional view schematically illustrating a layer configuration of another example of a deposited film of an inorganic oxide.

FIG. 5 is a photovoltaic module manufactured by using the solar cell module back protection sheet according to the present invention shown in FIG.
FIG. 2 is a schematic cross-sectional view schematically showing a layer configuration of an example of the structure.

FIG. 6 is a schematic configuration diagram illustrating an example of a take-up type vacuum evaporation apparatus.

FIG. 7 is a schematic configuration diagram illustrating an example of a plasma chemical vapor deposition apparatus.

[Explanation of symbols]

A solar cell module - for the backside Le protective sheet - DOO A ₁ solar cell module - for the backside Le protective sheet - DOO deposited film 2c inorganic oxide deposited film 2a multilayer film 2b inorganic oxide 1 weatherable substrate 2 inorganic oxide Deposition film 2d Composite film 3 Print layer 4 Primer layer T Solar cell module 11 Surface protection sheet for solar cell module 12 Filler layer 13 Solar cell element 14 Filler layer 15 Solar cell module Back protection sheet

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kojiro Okawa 1-1-1, Ichigaya-Kagacho, Shinjuku-ku, Tokyo Inside Dai Nippon Printing Co., Ltd. No. 1-1, Dai Nippon Printing Co., Ltd. (72) Inventor Kazuyuki Takazawa 1-1-1, Ichigaya Kagacho, Shinjuku-ku, Tokyo F-term in Dai Nippon Printing Co., Ltd. 5F051 BA17 BA18 EA18 GA03 GA11 JA04

Claims (8)

[Claims] 1. A solar cell module comprising: a weather-resistant substrate having an inorganic oxide vapor-deposited film provided on one surface thereof; and a printed layer provided on the inorganic oxide vapor-deposited film. Back protection sheet. 2. A weather-resistant substrate made of a film or sheet of a fluororesin, a cyclic polyolefin resin, a polyester resin, a polyamide resin, a polycarbonate resin, or a poly (meth) acrylic resin. 2. The backside protection sheet for a solar cell module according to claim 1, wherein: 3. The method according to claim 1, wherein the inorganic oxide vapor-deposited film is a multilayer film of one or more inorganic oxide vapor-deposited films or a composite film of two or more different inorganic oxide vapor-deposited films. The back surface protection sheet for a solar cell module according to claim 1 or 2, characterized in that: 4. The backside protection sheet for a solar cell module according to claim 1, wherein the inorganic oxide vapor-deposited film has a thickness of 50 to 4000 °.
G. 5. The back protection sheet for a solar cell module according to claim 1, wherein the printing layer comprises a printing layer made of an ink composition containing an ink vehicle as a main component. -G. 6. The back protection sheet for a solar cell module according to claim 1, wherein the printing layer is a printing layer formed by a gravure printing method. 7. The backside protection for a solar cell module according to claim 1, wherein the printing layer comprises a printing layer having light reflectivity or light diffusivity and a design property. Sheet. 8. A surface protection sheet for a solar cell module,
Filler layer, a solar cell element as a photovoltaic element, a filler layer, and, on one side of the weather-resistant substrate, provided a deposited film of an inorganic oxide, further, on the deposited film of the inorganic oxide, Backside protection sheet for solar cell module having a structure provided with a printed layer
The solar cell module is characterized in that the solar cell module is formed by sequentially laminating the printed layers with their printed layers facing each other, and vacuum-suctioning them to form an integrally formed body by a heat-compression lamination method or the like.