JP2000332276A - Solar battery module and protective sheet therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance various characteristics such as intensity, weather- resistance, water-resistance, wetness-resistance, stain resistance, and the like, by a method wherein a deposited thin film of an inorganic oxide is provided on one face of a fluoric system resin sheet, and further an annular polyoefinic system resin sheet is provided on the deposited thin film. SOLUTION: First, a fluoric system resin sheet 1 is used as a substrate sheet, and a deposited thin film 2 of a transparent and vitric inorganic oxide composed of a silicon oxide, an aluminum oxide, or the like is provided on the one face, and further an annular polyolefinic system resin sheet 3 is provided on the deposited thin film of the inorganic oxide to manufacture a solar battery module protective sheet A. By use of this solar battery module protective sheet A, it is possible to manufacture a safe solar battery module which is superior in various characteristics such as transmission of solar beams, intensity, weather- resistance, heat-resistance, water-resistance, light-resistance, wind-pressure- resistance, wetness-resistance, stain-resistance, and the like, and restricts a long-term performance deterioration at a minimum.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a solar cell module.
Protection sheet for solar cell and solar cell module using the same
For more details, the strength is excellent, and the weather resistance,
Solar cell module with excellent properties such as heat resistance, water resistance, light resistance, wind pressure resistance, hail resistance, chemical resistance, moisture resistance, antifouling property, etc., extremely high durability and high protection ability The present invention relates to a front or back surface protection sheet and a solar cell module using the same.

[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.

[0003]

By the way, as a protective sheet layer constituting the above solar cell module, for example, in the case of a surface protective sheet layer, a glass plate or the like is currently used.
In addition, resin sheets such as fluororesin sheets have recently attracted attention and are being rapidly developed. In the case of the backside protective sheet layer constituting the solar cell module, a resin sheet or the like having excellent strength is most commonly used at present, and a metal plate or the like is also used. ing. In general, as a protective sheet layer constituting a solar cell module, for example, in the case of a surface protective sheet layer, the solar cell absorbs sunlight and generates photovoltaic power. , It is rich in sunlight permeability and excellent in strength, and is excellent in various robustness such as weather resistance, heat resistance, water resistance, light resistance, wind pressure resistance, hail resistance, chemical resistance, etc.,
Excellent moisture resistance to prevent intrusion of moisture, oxygen, etc., high surface hardness, and excellent antifouling property to prevent accumulation of dirt and dust on the surface, extremely durable, and its protective ability , And other conditions must be satisfied. Also, in the case of the backside protective sheet, it is necessary to satisfy almost the same conditions as in the case of the above-mentioned surface protective sheet layer. It is said to be. However, a glass plate or the like, which is currently most commonly used as a surface protection sheet layer constituting a solar cell module, has excellent sunlight permeability, weather resistance, heat resistance, and water resistance. Excellent in various fastnesses such as light resistance, light resistance, chemical resistance, etc., and also excellent in moisture resistance,
It has the advantages of high surface hardness, excellent antifouling properties to prevent the accumulation of dirt and dust on the surface, and high protection ability, but lacks strength, plasticity, impact resistance, light weight, etc. ,
Further, there is a problem that the workability and the workability are inferior, and the cost is not reduced. When a resin sheet such as a fluororesin is used as the surface protection sheet layer constituting the solar cell module, strength, plasticity, and impact resistance are higher than those of a glass plate or the like. Although it is rich in water resistance, light weight, etc., it is inferior in various fastnesses such as weather resistance, heat resistance, water resistance, light resistance, chemical resistance, etc., and in particular, lacks moisture resistance, stain resistance, etc. is there. When a resin sheet or the like having excellent strength is used as the backside protective sheet layer constituting the solar cell module, the strength, plasticity, impact resistance, light weight, and cost reduction are reduced. Although it is rich,
It is inferior in various fastnesses such as weather resistance, heat resistance, water resistance, light resistance, chemical resistance, etc., and lacks moisture resistance, stain resistance, and the like. Therefore, the present invention is excellent in strength, and is excellent in various properties such as weather resistance, heat resistance, water resistance, light resistance, wind pressure resistance, hail resistance, chemical resistance, moisture resistance, antifouling property, etc. It significantly improves moisture resistance to prevent intrusion of moisture, oxygen, etc., minimizes its long-term performance degradation, is extremely durable, has high protection ability, and is a lower cost and safer solar system. An object is to stably provide a protection sheet constituting a battery module.

[0004]

The present inventor has conducted various studies on the surface protective sheet layer constituting the solar cell module in order to solve the above-mentioned problems, and as a result, has found that a fluorine-based resin sheet has been developed. The substrate is used as a base sheet, and on one surface thereof, a transparent, glassy inorganic oxide vapor-deposited thin film such as silicon oxide or aluminum oxide is provided. A protection sheet for a solar cell module is manufactured by providing a cyclic polyolefin-based resin film thereon, and the protection sheet for a solar cell module is protected by a surface protection sheet layer or a back surface protection. As a sheet layer, for example, the above-mentioned surface protection sheet for a solar cell module is formed by filling a cyclic polyolefin resin film inside, a filler layer, a solar cell element as a photovoltaic element, and a filler layer. And for normal solar cell modules Surface protective sheet - sequentially laminating a coat layer or the like,
Next, when a solar cell module was manufactured using a lamination method or the like in which these were integrally vacuum-sucked and heated and pressed, the solar cell module was excellent in sunlight permeability, excellent in strength, and furthermore weather resistant. Excellent properties such as heat resistance, heat resistance, water resistance, light resistance, wind pressure resistance, hail resistance, chemical resistance, moisture resistance, antifouling property, etc., especially moisture resistance to prevent moisture, oxygen etc. Significantly improve the long-term performance degradation, extremely durable, high protection, and
The present invention has been completed by finding that a safer solar cell module can be stably manufactured at lower cost.

That is, the present invention provides an inorganic oxide vapor-deposited thin film on one surface of a fluororesin sheet, and a cyclic polyolefin resin film on the inorganic oxide vapor-deposited thin film. The present invention relates to a solar cell module protection sheet 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
Protection sheet for solar cell and solar cell module using the same
The layer structure of the solar cell module will be described in more detail with reference to the drawings and the like. FIGS. FIG. 4, FIG. 5 and FIG. 6 show a solar cell module manufactured using the solar cell module protection sheet according to the present invention shown in FIG. It is a schematic sectional drawing which illustrates a few examples about a layer structure.

First, as shown in FIG. 1, a protective sheet A for a solar cell module according to the present invention is provided with a vapor-deposited thin film 2 of an inorganic oxide on one surface of a fluororesin sheet 1. Further, the basic structure is such that a cyclic polyolefin-based resin film 3 is provided on the inorganic oxide vapor-deposited thin film 2. As another example of the protection sheet for a solar cell module according to the present invention, as shown in FIG. 2, an inorganic oxide is deposited on one surface of a fluororesin sheet 1 as shown in FIG. A solar cell comprising a multilayer film 4 having at least two or more thin films 2 provided thereon, and a cyclic polyolefin-based resin film 3 provided on an inorganic oxide vapor-deposited thin film 2 constituting the multilayer film 4 Module protection sheet A ₁
Can be mentioned. Further, as another example of the protection sheet for a solar cell module according to the present invention, as shown in FIG. 3, a chemical vapor deposition method is firstly performed on one surface of a fluororesin sheet 1. And a vapor-deposited inorganic oxide thin film 2b formed by physical vapor deposition on the inorganic oxide vapor-deposited thin film 2a. , 2b, and a solar cell module having a structure in which a cyclic polyolefin-based resin film 3 is provided on a vapor-deposited inorganic oxide thin film 2b constituting the composite film 5. −
Le protective sheet - can be exemplified bets A _2. The above examples illustrate a few examples of the protection sheet for a solar cell module according to the present invention, and it is a matter of course that the present invention is not limited thereto.

Next, in the present invention, an example of a solar cell module manufactured by using the above-mentioned protection sheet for a solar cell module according to the present invention will be described.
An example using the solar cell module protection sheet A according to the present invention shown in FIG. 1 will be described. As shown in FIG. 4, the solar cell module according to the present invention shown in FIG. The protective sheet A for solar cells is used as the surface protective sheet 11 for solar cell modules, and the surface of the cyclic polyolefin resin film 3 of the surface protective sheet 11 (A) for solar cells modules is used. On the inner side, a filler layer 12, a solar cell element 13 as a photovoltaic element, a filler layer 14, a back surface protection sheet layer 15 for a normal solar cell module, and the like are sequentially laminated, and then The solar cell module T can be manufactured by integrally forming these layers and integrally forming each of the above-mentioned layers by using a normal forming method such as a lamination method of vacuum suction and heat compression. Further, in the present invention, another example of the solar cell module manufactured using the solar cell module protection sheet according to the present invention will be described. In the example using the protection sheet A for a solar cell module according to the present invention shown in FIG. 1, as shown in FIG. 5, the protection for the solar cell module according to the present invention shown in FIG. The sheet A is used as a back surface protection sheet 16 for a solar cell module, and a surface protection sheet 17 for a normal solar cell module, a filler layer 12, and a solar cell element as a photovoltaic element. 13, a filler layer 14, and the above-described back surface protection sheet 16 (A) for a solar cell module are sequentially laminated with their cyclic polyolefin resin film 3 facing each other. As a unit, a vacuum suction and heat compression Ne - using conventional molding method Deployment method, a solar cell module as an integral molded product of the above layers - can be produced Le T _1.
Further, in the present invention, another example of the solar cell module manufactured using the solar cell module protection sheet according to the present invention will be described. 1. The solar cell module according to the present invention shown in FIG.
As shown in FIG. 6, the protection sheet A for a solar cell module according to the present invention shown in FIG. 1 is used for a solar cell module. The protective sheet A for a solar cell module according to the present invention as shown in FIG. 1 is used as a back protective sheet 16 for a solar cell module, as shown in FIG. With the surface of the cyclic polyolefin-based resin film 3 of the solar cell module surface protection sheet 11 (A) facing inside, a filler layer 12, a solar cell element 13 as a photovoltaic element, a filler layer 14, Further, the above-mentioned back surface protection sheet 16 (A) for a solar cell module is sequentially laminated with the surface of the cyclic polyolefin resin film 3 opposed to each other. Normal molding method such as lamination method with heat compression Use, the solar cell module as an integral molded product of the above layers - can be produced Le T _2.
The above examples illustrate a few examples of the solar cell module protection sheet according to the present invention and the solar cell module manufactured using the same, and the present invention is not limited thereto. It is not done. For example, although not shown, in the above-described solar cell module, another layer can be arbitrarily added and laminated for the purpose of absorbing sunlight, reinforcing, and the like. is there.

Next, in the present invention, the protective sheet for a solar cell module according to the present invention and the material and manufacturing method of the solar cell module using the same will be described in more detail. Examples of the fluorine-based resin sheet constituting the protection sheet for a solar cell module, the solar cell module and the like according to the present invention include polytetrafluoroethylene (PTFE), tetrafluoroethylene and perfluoroalkylvinyl. A perfluoroalkoxy resin (PFA) composed of a copolymer with ether, tetrafluoroethylene and hexafluoropropylene copolymer (FEP), tetrafluoroethylene and perfluoroalkylvinyl ether and hexafluoropropylene copolymer (EPE), Tetrafluoroethylene and ethylene or propylene Copolymers of - (ETFE), polychlorotrifluoroethylene resin (PCTFE), copolymers of ethylene and chlorotrifluoroethylene - (E
A transparent fluororesin film or sheet made of CTFE), vinylidene fluoride resin (PVDF), or vinyl fluoride resin (PVF) can be used. In the present invention, among the above-mentioned fluororesin films or sheets, vinyl fluoride resin (PVF) or copolymer of tetrafluoroethylene and ethylene or propylene (ETFE)
The fluororesin sheet comprising is particularly preferred from the viewpoint of transparency and sunlight permeability. Thus, in the present invention, by using the above-mentioned fluororesin sheet, excellent characteristics of the fluororesin sheet, particularly, mechanical properties, heat resistance, optical properties, etc.
In addition, light resistance, heat resistance, water resistance, and other super weather resistance,
It is a protective sheet that constitutes a solar cell by utilizing various properties such as contamination resistance and chemical resistance, and has optical properties and durability equivalent to those of a conventional glass plate, etc. Also,
Due to its flexibility and mechanical properties, it is lighter than a glass plate, has excellent workability and the like, and has advantages such as easy handling.

In the present invention, as the above-mentioned fluororesin film or sheet, for example, one or more of the above-mentioned fluororesins is used, and the extrusion method, cast molding method, T-die method , Cutting method, inflation
A method of forming a film of the above-mentioned fluororesin alone, or a method of forming a multi-layer co-extrusion film using two or more kinds of fluororesins, Furthermore, by using two or more kinds of fluorine-based resins, a method of mixing and forming a film before forming a film to produce a film or sheet of a fluorine-based resin, and further, if necessary,
For example, a fluororesin film or sheet stretched in a uniaxial or biaxial direction using a tenter method or a tuber method can be used.
In the present invention, the thickness of the fluororesin film or sheet is preferably about 12 to 200 μm, more preferably about 25 to 150 μm. Further, in the present invention, as a film or sheet of a fluororesin,
It is desirable that the visible light transmittance is 90% or more, preferably 95% or more, and that it has a property of transmitting and absorbing all incident sunlight.

[0011] In the above, when the fluororesin is formed into a film, for example, the processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant property, slipperiness, releasability, and difficulty of the film are considered. Improve flammability, anti-mold, electrical properties, etc.,
For the purpose of reforming, various plastic compounding agents and additives can be added, and the amount of addition 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, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, a reinforcing agent, an antistatic agent,
A flame retardant, a flame retardant, a foaming agent, a fungicide, a pigment, and the like can be used, and further, a modifying resin and the like can be used. In the present invention, among the above-mentioned additives, it is particularly preferable to use a film or sheet of a cyclic polyolefin-based resin obtained by kneading and processing an ultraviolet absorber and / or an antioxidant. . As the above-mentioned ultraviolet absorber, it absorbs harmful ultraviolet rays in sunlight, converts it into harmless heat energy in the molecule, and prevents excitation of the active species that initiates photodegradation in the polymer. For example, benzophenone-based, benzotriazole-based, saltylate-based, acrylonitrile-based, metal complex salt-based, hindered amine-based, ultrafine titanium oxide (particle diameter: 0.01 to 0.06 μm) or One or more inorganic absorbers such as ultrafine zinc oxide (0.01 to 0.04 μm) can be used. In addition, the antioxidant is one that prevents photodeterioration or thermal degradation of the polymer, for example,
Phenol-based, amine-based, sulfur-based, phosphoric acid-based, and other 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 ultraviolet absorber and / or the antioxidant varies depending on the particle shape, density and the like, but is about 0.1%.
About 1 to 10% by weight is preferable.

In the present invention, the surface of the fluororesin film or sheet may be, for example,
Pretreatment such as corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment using chemicals or the like, and the like can be arbitrarily performed. The above-mentioned surface pretreatment may be performed in a separate step before forming a vapor-deposited thin film of an inorganic oxide.For example, in the case of a surface treatment such as a low-temperature plasma treatment or a glow discharge treatment, As a pretreatment for forming a vapor-deposited thin film of an oxide, pretreatment can be performed by in-line treatment. In such a case, there is an advantage that the production cost can be reduced. The surface pretreatment is performed as a method for improving the adhesion between the film or sheet of the fluororesin and the vapor-deposited thin film of the inorganic oxide. In addition, for example, a primer coat agent layer, an undercoat agent layer, a vapor-deposited anchor coat agent layer, or the like may be optionally formed on the surface of a fluororesin film or sheet in advance. It can also be formed. As the coating agent layer for the above pretreatment, for example, a resin composition containing a polyester-based resin, a polyurethane-based resin, or the like as a main component of the vehicle can be used. In the above, as a method of forming the coating agent layer, for example, a solvent type, an aqueous type,
Alternatively, using a coating agent such as an emulsion type,
Rucote method, gravure roll method, kiss coat method,
The coating can be performed by using a coating method such as other methods, and the coating is performed after the film formation of the fluororesin film or sheet, or after the biaxial stretching treatment. Or by in-line processing of biaxial stretching or the like.

Next, in the present invention, a vapor-deposited thin film of an inorganic oxide constituting a solar cell module protection sheet, a solar cell module and the like according to the present invention will be described.
As such a deposited thin film of an inorganic oxide, for example, one layer or two of a deposited thin film of an inorganic oxide may be formed by physical vapor deposition, chemical vapor deposition, or a combination thereof.
It can be manufactured by forming a multilayer film having two or more layers or a composite film composed of two or more layers of vapor-deposited thin films of different inorganic oxides. The inorganic oxide vapor-deposited thin film formed by the above-described physical vapor deposition method will be described in further detail. Examples of the inorganic oxide vapor-deposited thin film formed by the physical vapor deposition method include a vacuum vapor deposition method, a sputtering method, and an ion plating method. Physical vapor deposition (Physical)
A vapor-deposited thin film of an inorganic oxide can be formed by using a vapor deposition method (PVD method).
In the present invention, specifically, a metal oxide is used as a raw material, which is heated to form a fluororesin film or sheet.
Vacuum evaporation method to deposit on metal or oxidation reaction deposition method to use metal or metal oxide as raw material, introduce oxygen and oxidize to deposit on fluorine-based resin film or sheet Further, a vapor-deposited film can be formed by using a plasma-assisted oxidation reaction vapor deposition method that promotes an oxidation reaction with plasma.

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. 7. FIG. 7 is a schematic structural diagram showing an example of a roll-up type vacuum evaporation apparatus. It is. As shown in FIG. 7, a fluororesin film or sheet 1 fed from an unwinding roll 23 in a vacuum chamber 22 of a take-up type vacuum evaporation apparatus 21 is provided with guide rolls 24 and 25. Through,
It is guided to the cooled coating drum 26. Thus, on the fluororesin film or sheet 1 guided on the cooled coating drum 26, an evaporation source 28 heated by a crucible 27, for example, metal aluminum or oxidized material Aluminum or the like is evaporated, and if necessary, an oxygen gas or the like is blown out from the oxygen gas blow-out port 29, and while supplying the gas, an inorganic oxide such as aluminum oxide is deposited through the masks 30 and 30, for example. A thin film is formed, and then a film or sheet 1 made of a fluorine-based resin on which an evaporated thin film of, for example, an inorganic oxide such as aluminum oxide is formed, is placed on a guide roll 2.
By feeding the film through 5 'and 24' and winding it on a take-up roll 31, a vapor-deposited thin film of inorganic oxide can be formed by physical vapor deposition according to the present invention.
In the present invention, first, a first layer of an inorganic oxide vapor-deposited thin film is formed using the above-mentioned winding vacuum vapor deposition apparatus, and then, similarly, the inorganic oxide vapor-deposited thin film is formed. On top of this, an inorganic oxide deposited thin film is formed, or this is connected in series using a roll-up vacuum deposition apparatus as described above, and the inorganic oxide is continuously deposited. By forming a thin film, an inorganic oxide vapor-deposited thin film including two or more multilayer films can be formed.

In the above description, the inorganic oxide deposited thin 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 thin film of a metal oxide 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 vapor-deposited thin film of the above-described metal oxide can be referred to as a metal oxide such as silicon oxide, aluminum oxide, and magnesium oxide.
For example, SiO _X, AlO _X, as such as MgO _X MO
_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 thin film of the inorganic oxide as described above varies depending on the type of the metal or the metal oxide to be used.
It is desirable to arbitrarily select and form it within the range of 0 °, preferably 100 to 1000 °. Further, in the present invention, as the metal or metal oxide to be used, one or a mixture of two or more thereof may be used to form a vapor-deposited thin film of an inorganic oxide mixed with different materials.

Next, in the present invention, the vapor-deposited thin film of an inorganic oxide formed by the above-described chemical vapor deposition method will be further described. Chemical vapor deposition (Chemical Vapor Deposition) such as vapor phase epitaxy, thermochemical vapor phase epitaxy, and photochemical vapor phase epitaxy
A vapor-deposited thin film of an inorganic oxide can be formed using an n method, a CVD method, or the like. In the present invention, specifically,
On one surface of a fluororesin film or sheet, a monomer gas for vapor deposition such as an organic silicon compound is used as a raw material, and an inert gas such as an argon gas or a helium gas is used as a carrier gas. A vapor-deposited thin film of an inorganic oxide such as silicon oxide can be formed using a low-temperature plasma chemical vapor deposition (CVD) method using an oxygen gas or the like as an oxygen supply gas and a low-temperature plasma generator or the like. . In the above, as the low-temperature plasma generator, for example,
It is possible to use a generator such as a high-frequency plasma, a pulsed-wave plasma, a microwave plasma, etc. Therefore, in the present invention, in order to obtain a highly active and stable plasma, a generator using a high-frequency plasma method is used. It is desirable to do.

More specifically, an example of a method of forming a vapor-deposited thin film of an inorganic oxide by the low-temperature plasma chemical vapor deposition method will be described. FIG. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic configuration diagram of a low-temperature plasma-enhanced chemical vapor deposition apparatus showing an outline of a method for forming a vapor-deposited thin film of an oxide. As shown in FIG. 8, in the present invention, a film or sheet 1 made of a fluororesin is fed from an unwinding roll 43 disposed in a vacuum chamber 42 of a plasma enhanced chemical vapor deposition apparatus 41. Further, the fluororesin film or sheet 1 is conveyed onto the peripheral surface of the cooling / electrode drum 45 at a predetermined speed via the auxiliary roll 44. Thus, in the present invention, oxygen gas, an inert gas, a monomer gas for vapor deposition such as an organic silicon compound, and the like are supplied from the gas supply devices 46 and 47 and the raw material volatile supply device 48 and the like. While adjusting the mixed gas composition for vapor deposition, the mixed gas composition for vapor deposition was introduced into the vacuum chamber 42 through the raw material supply nozzle 49,
Next, a glow is placed on the fluororesin film or sheet 1 conveyed on the cooling / electrode drum 45 peripheral surface.
Plasma is generated by the discharge plasma 50 and is irradiated to form a deposited thin film of an inorganic oxide such as silicon oxide, thereby forming a film. In the present invention, at that time,
A predetermined power is applied to the electrode drum 45 from a power supply 51 disposed outside the chamber, and a magnet 52 is disposed near the cooling / electrode drum 45 to promote generation of plasma. Then, the fluororesin film or sheet 1 on which the vapor-deposited thin film of the inorganic oxide such as silicon oxide is formed as described above is wound up on a winding roll 54 via an auxiliary roll 53, According to the present invention, a vapor-deposited thin film of an inorganic oxide can be manufactured by the plasma enhanced chemical vapor deposition method. 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 vapor-deposited thin film is not limited to one layer of the inorganic oxide vapor-deposited thin film, but may be a laminate of two or more layers. The materials may be used alone or as a mixture of two or more kinds, and a vapor-deposited thin film of an inorganic oxide mixed with different materials may be used. In the present invention, for example, using a low-temperature plasma-enhanced chemical vapor deposition apparatus as described above, first, a first layer of an inorganic oxide vapor-deposited thin film is formed, and then the inorganic oxide vapor deposition is performed in the same manner. An inorganic oxide deposited thin film is further formed on the thin film, or the thin film is continuously connected to the inorganic oxide by using a low-temperature plasma chemical vapor deposition apparatus as described above. By forming a vapor-deposited thin film of above, a vapor-deposited thin film of inorganic oxide composed of two or more multilayer films can be formed.

In the above, a monomer for vapor deposition of an organic silicon compound or the like for forming a vapor deposited thin film of an inorganic oxide such as silicon oxide.
Examples of the gas include 1.1.3.3-tetramethyldisiloxane, hexamethyldisiloxane, 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 above-mentioned organosilicon compounds, 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 characteristics 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 silicon oxide vapor-deposited thin film formed as described above undergoes a chemical reaction between a monomer gas such as an organic silicon compound and oxygen gas and the like, and the reaction product is a fluorine resin film or sheet. Silicon oxide represented by the general formula SiO _x (where X represents a number from 0 to 2). Is a continuous vapor-deposited thin film mainly composed of In view of transparency, barrier properties, and the like, the silicon oxide vapor-deposited thin film has the general formula SiO _x (where X is 1.
Represents a number from 3 to 1.9. It is preferable that the thin film is mainly composed of a silicon oxide deposited film represented by the formula (1). In the above, the value of X changes depending on the molar ratio of the monomer gas and the oxygen gas, the energy of the plasma, and the like. Generally, as the value of X decreases, the gas permeability decreases.
The film itself becomes yellowish and the transparency becomes poor. Further, the above-mentioned deposited thin film of silicon oxide has silicon (Si) and oxygen (O) as essential constituent elements, and furthermore, one of carbon (C) and hydrogen (H), or both elements Consisting of a deposited film of silicon oxide containing as a trace constituent element, and the thickness thereof is in the range of 50 ° to 500 °, and the constituent ratio of the essential constituent element and the trace constituent element is:
It changes continuously in the film thickness direction. Further, when the above-mentioned vapor-deposited silicon oxide thin film contains a compound composed of carbon, the carbon content is reduced in the depth direction of the film thickness.

Thus, in the present invention, the above-mentioned deposited silicon oxide thin film is, for example, an X-ray photoelectron spectrometer (X
ray Photoelectron Spectro
, XPS), secondary ion mass spectrometer (Se
condary Ion Mass Spectros
(Copies, SIMS), etc. to confirm the above physical properties by performing elemental analysis of the deposited silicon oxide thin film using a method of analyzing by ion etching in the depth direction, etc. using a surface analyzer such as SIMS. Is what you can do. In the present invention, the thickness of the above-described silicon oxide vapor-deposited thin film is desirably about 50 to 2000 °, and specifically, the thickness is about 100 to 100.
The 0 ° position is desirable, and in the above, 1000
If the thickness is more than 2000 °, cracks and the like are likely to occur in the film, which is not preferable.
If it is 0 ° or less than 50 °, it is difficult to achieve the barrier effect, which is not preferable. In the above description, the film thickness can be measured by a fundamental parameter method using, for example, a fluorescent X-ray analyzer (model name: RIX2000) manufactured by Rigaku Corporation. Further, in the above, as means for changing the thickness of the deposited silicon oxide thin film, 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.

In the present invention, the protection sheet for a solar cell module and the solar cell module according to the present invention are provided.
As a vapor-deposited thin film of an inorganic oxide constituting
When forming a composite film composed of two or more vapor-deposited thin films of different kinds of inorganic oxides by using both physical vapor deposition and chemical vapor deposition together, first, a fluororesin film or sheet is formed. On the substrate, a dense, flexible, and relatively thin cracked inorganic oxide deposition film is provided by a chemical vapor deposition method, and then the inorganic oxide deposited thin film is deposited on the inorganic oxide deposited thin film. It is desirable to provide a vapor-deposited inorganic oxide thin film by physical vapor deposition to form a vapor-deposited inorganic oxide thin film composed of a composite film composed of two or more layers. Of course,
In the present invention, contrary to the above, the fluorine-based resin
First, a vapor-deposited thin film of inorganic oxide is provided by physical vapor deposition, and then dense, flexible, and relatively free of cracks by chemical vapor deposition. It is also possible to provide a deposited thin film of an inorganic oxide which can be formed to form a deposited thin film of an inorganic oxide composed of a composite film composed of two or more layers.

In the present invention, for example, a gas is applied to the surface of the inorganic oxide vapor-deposited thin film in order to improve, for example, close adhesion with a cyclic polyolefin resin film.
A plasma-treated surface can be formed by using a plasma surface treatment method or the like in which surface modification is performed using a plasma gas generated by ionization due to arc discharge. That is, in the present invention, the plasma processing surface can be formed by performing the plasma processing using a gas such as an oxygen gas, a nitrogen gas, an argon gas, or a helium gas as a plasma gas. Therefore, in the present invention, it is preferable that the plasma treatment is performed by using an oxygen gas or a mixed gas of an oxygen gas and an argon gas or a helium gas during the plasma discharge treatment. By such a plasma treatment, it is possible to perform the plasma treatment at a lower voltage, thereby preventing the deterioration of the deposited thin film of the inorganic oxide and the like, and providing a good plasma treatment surface on its surface. Is what you can do.

In the present invention, it is most preferable that the plasma processing be performed using a mixed gas of oxygen gas and argon gas or helium gas. It is desirable to perform the process in-line immediately after forming the deposited thin film of the object. That is, in the present invention, on the surface of the inorganic oxide deposited thin film, for example, immediately after its formation, and before the deposited thin film comes into contact with a guide roll or the like,
By performing in-line plasma treatment, impurities, dust and the like adhering to the surface of the deposited thin film of inorganic oxide are removed, and furthermore, a hydrocarbon group (for example, C -C, CH, C =
Etc.) and the degree of oxidation of the surface increases, and a large number of carboxyl groups, keto groups, aceto groups, OH groups, etc. are formed on the surface, and the surface wettability is greatly improved, and Post-processing suitability such as close adhesion, printability and coating property is improved. Thus, in the present invention, by providing a cyclic polyolefin-based resin film on the above-mentioned plasma-treated surface as described later, the tight adhesion is enhanced, and the protection excellent in the laminate strength and the like is provided. A sheet can be formed, and a barrier film composed of two layers, a vapor-deposited thin film of an inorganic oxide and a cyclic polyolefin resin film, has a sufficiently high barrier property against oxygen gas or water vapor. In addition, it can be used to produce protective sheets of various forms. In addition, in the present invention, since the adhesiveness is excellent and the laminating strength can be increased, for example, in the post-processing such as film winding, printing, laminating, or bag-making. In addition, cracks and the like can be prevented from being generated in the above-mentioned vapor-deposited thin film of inorganic oxide, and so-called post-processing suitability can be improved. Further, in the present invention, since the plasma processing is performed in-line, the manufacturing cost is extremely excellent. In the present invention, as a method of generating plasma in the plasma processing, for example, DC glow discharge, high frequency (Audio Frequency: AF, Radio)
(Frequency: RF) discharge, microwave discharge, and the like. Thus,
In the present invention, it can be usually performed using a high frequency (AF) discharge device of 13.56 MHz.

Next, in the present invention, the cyclic polyolefin resin film constituting the solar cell module protection sheet, the solar cell module and the like according to the present invention will be described. Can be formed in various ways. First, in the present invention, as a first method, a solvent type containing one or more cyclic polyolefin-based resins as a main component of a vehicle,
An aqueous type, or a resin composition comprising an emulsion type or the like is prepared, and thus the resin composition is used.
For example, a roll coat method, a gravure roll coat method, a kiss roll coat method, a squeeze roll coat method, a reverse roll coat method may be formed on the above-mentioned inorganic oxide vapor-deposited thin film. Coating amount, for example, from 0.1 g / m ² to 0.1 g / m ² by a coating method such as a coating method, a curtain coating method, and others
About 20 g / m ² (dry state), preferably 0.5 g / m ²
m ^{2 to} 10 g / m ² (dry state) is coated and then subjected to heat drying, aging treatment and the like to form the cyclic polyolefin resin film according to the present invention. be able to.

In the present invention, as a second method, similarly to the above, a resin composition for melt extrusion coating containing one or more cyclic polyolefin-based resins as a main component of a vehicle is prepared. Thus, the resin composition is used, and the film thickness is, for example, 0.1 μm to 300 μm on the above-mentioned vapor-deposited inorganic oxide thin film by, for example, a melt extrusion coating method. Position, preferably 0.5μ
melt extrusion coating so as to be about m to 200 μm,
Next, drying and further aging treatment are performed to form the cyclic polyolefin-based resin film according to the present invention. In the second method, the cyclic polyolefin-based resin film according to the present invention may be a single or co-extruded film of a cyclic polyolefin-based resin, or
A co-extruded film obtained by co-extruding the cyclic polyolefin-based resin and another resin may be used.

Further, in the present invention, as a third method, similarly to the above, a film-forming resin composition containing one or more cyclic polyolefin-based resins as a main component of a vehicle is prepared. Using the resin composition,
This is formed into a single film or a multilayer co-extrusion film by using, for example, an extrusion method, a cast molding method, a T-die method, a cutting method, an inflation method, or the like. To form a film or sheet of a cyclic polyolefin-based resin, and if necessary, for example, a one-axis or two-axis system using a tenter system or a tuber system. To produce a cyclic polyolefin-based resin film or sheet which is stretched in the direction, and thereafter, use the cyclic polyolefin-based resin film or sheet, and apply it to the surface of the inorganic oxide vapor-deposited thin film. For example, the cyclic polyolefin-based resin film according to the present invention may be formed by laminating by a dry laminating method, a wet laminating method, a solventless dry laminating method, or the like. Kill. In the above, the film thickness of the cyclic polyolefin resin film or sheet is about 12 to 500 μm, preferably 20 to 300 μm.
The m-th position is desirable. The above examples are only a few examples of the method for forming the cyclic polyolefin-based resin film according to the present invention, and the present invention is not limited thereto.

In the present invention, the resin composition for forming the above-mentioned cyclic polyolefin resin film includes, for example, processability, heat resistance, weather resistance, mechanical properties, dimensional stability, and the like of a film (film). Various plastic compounding agents and additives can be added for the purpose of improving and modifying the antioxidant properties, slip properties, mold release properties, flame retardancy, anti-mold properties, electrical properties, etc. 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, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, a reinforcing agent, an antistatic agent, a flame retardant,
Flameproofing agents, foaming agents, mildewproofing agents, pigments, and the like can be used, and further, modifying resins and the like can be used. In the present invention, among the above-mentioned additives, it is particularly preferable to use the above-mentioned antioxidant, ultraviolet absorber or the like.

In the present invention, when forming a cyclic polyolefin-based resin film, the surface of a vapor-deposited thin film of an inorganic oxide, or the surface of a cyclic polyolefin-based resin film or sheet may be, if necessary, For example, a pretreatment such as a corona discharge treatment, an ozone treatment, a low-temperature plasma treatment using an oxygen gas or a nitrogen gas, a glow discharge treatment, an oxidation treatment using a chemical agent or the like, and the like can be optionally performed. . The above-mentioned surface pretreatment may be performed in a separate step after forming a vapor-deposited thin film of an inorganic oxide, and, for example, in the case of a surface treatment such as a low-temperature plasma treatment or a glow discharge treatment, the above-mentioned inorganic oxide After forming the vapor-deposited thin film, pre-processing can be performed by in-line processing. In such a case, there is an advantage that the manufacturing cost can be reduced. The above-mentioned surface pretreatment is performed as a method for improving the adhesion between the cyclic polyolefin-based resin film and the deposited thin film of the inorganic oxide.However, as a method for improving the adhesion, for example, Alternatively, a primer coating agent layer, an undercoating agent layer, an anchor coating agent layer, or the like can be arbitrarily formed in advance on the surface of the deposited inorganic oxide thin film. As the coating agent layer of the above pretreatment, for example, a resin composition containing a polyester-based resin, a polyurethane-based resin, an acrylic-based resin, or the like as a main component of the vehicle 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 method, a gravure roll coating is used. Law,
The coating can be performed by using a coating method such as a kiss coating method or the like.

In the second method, in order to obtain a stronger adhesive strength, for example, an adhesion aid such as an anchor coat agent is used, and the anchor coat agent layer is used. Through this, a cyclic polyolefin-based resin film can be formed. Examples of the above-mentioned anchor coating agent include various aqueous or oily anchor coating agents such as organotitanium, isocyanate, polyethyleneimine, polybutadiene, etc. such as alkyl titanate. Can be used. The anchor coating agent is, for example,
Coating can be performed by using a coating method such as roll coating, gravure coating, kiss coating, and the like. The coating amount is 0.1 to 5 g / g.
m ² (dry state) is desirable. In the third method, a laminating adhesive is used, and the lamination can be performed via the adhesive layer. In the above description, examples of the laminating adhesive include one-pack or two-pack curable or non-curable vinyl, (meth) acrylic, polyamide, polyester, polyurethane,
Adhesives for laminating such as solvent type, aqueous type or emulsion type such as epoxy type, phenol type, rubber type and others can be used. In the above-mentioned adhesive for laminating, for example, an adhesion promoter such as a silane coupling agent, or an ultraviolet absorber, an antioxidant,
Additives such as stabilizers and others can be optionally added. Examples of the method of coating the above-mentioned adhesive for laminating include roll coat, gravure roll coat, and the like.
Coating can be performed by using a coating method such as kiss coating or the like.
0.1 to 10 g / m ² (dry state) is desirable.

In the above description, examples of the cyclic polyolefin resin include, for example, polymerized cyclic dienes such as cyclopentadiene and its derivatives, dicyclopentadiene and its derivatives, cyclohexadiene and its derivatives, norbornadiene and its derivatives, and others. Or an olefinic monomer such as ethylene, propylene, 4-methyl-1-pentene, styrene, butadiene, isoprene, etc.
A copolymer obtained by copolymerizing one or more of the following:
One or more transparent cyclic polyolefin-based resins consisting of In the present invention, among the above-mentioned transparent cyclic polyolefin-based resins, in particular, from cyclopentadiene and its derivatives, dicyclopentadiene and its derivatives, or cyclic diene polymers and copolymers such as norbornadiene and its derivatives. Transparent cyclic polyolefin-based resin is excellent in weather resistance, water resistance, etc., and further, has transparency,
It is preferable from the viewpoint of the transmittance of sunlight and the like. Thus, in the present invention, by adopting the cyclic polyolefin-based resin as described above, the excellent properties of the cyclic polyolefin-based resin, particularly, mechanical properties, optical properties, etc., further, weather resistance, heat resistance It is intended to be used as a protection sheet constituting a solar cell by utilizing various properties such as water resistance, light resistance, moisture resistance, stain resistance, chemical resistance, and others.
As a result, it has the same optical properties and durability as conventional glass plates, etc., and is lighter than glass plates due to its flexibility and mechanical properties, and has excellent workability and is easy to handle. And the like. In the present invention, the cyclic polyolefin resin has a visible light transmittance of 90% or more, preferably 95% or more.
As described above, it is desirable to have a transmissivity for transmitting all the incident sunlight. By the way, in the present invention, the above-mentioned cyclic polyolefin-based resin film has excellent close-adhesiveness to a vapor-deposited thin film of an inorganic oxide, the adhesive strength between the two is extremely strong, and no phenomenon such as peeling between the layers is observed. Further, in the present invention, a barrier film composed of two layers of a vapor-deposited thin film of an inorganic oxide and a cyclic polyolefin-based resin film is formed, whereby the barrier property against oxygen gas, water vapor gas, etc., The barrier properties are remarkably improved, and transparency, heat resistance, hot water resistance, suitability for lamination, etc. are excellent, and a very good surface protection sheet can be produced.

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 solar cell module protection sheet constituting the solar cell module will be described. As the filler layer, sunlight enters and transmits and absorbs sunlight. In addition, it is necessary to have an adhesive property with a surface protection sheet, and further, to fulfill the function of maintaining the smoothness of the surface of a solar cell element as a photovoltaic element. In order to protect the solar cell element as a photovoltaic element, it is necessary to have excellent scratch resistance, shock absorption and the like. Specifically, as the filler layer, for example, a fluorine-based resin, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid, or methacrylic acid copolymer, polyethylene resin, polypropylene resin, Acid-modified polyolene fin resins, cyclic polyolefin resins, polyvinyl butyral resins obtained by modifying polyolefin resins such as polyethylene or polypropylene with unsaturated carboxylic acids such as acrylic acid, itaconic acid, maleic acid and fumaric acid , Silicone resin,
Mixtures of one or more resins such as epoxy resins, (meth) acrylic resins, and others 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, etc.,
What can be mixed. Thus, in the present invention, as the filler on the incident side of sunlight, light resistance, heat resistance, considering the weather resistance such as water resistance, a fluororesin,
Ethylene-vinyl acetate copolymer, cyclic polyolefin resin, and silicone resin are preferred materials. In addition,
The thickness of the filler layer is 200 to 1000 μm
And more preferably about 350 to 600 μm.

Next, in the present invention, the solar cell module
A solar cell element as a photovoltaic element constituting a solar cell will be described. As such a solar cell element, a conventionally known one, for example, a crystalline silicon solar cell element, a polycrystalline silicon solar cell element, an amorphous silicon solar cell element , A copper indium selenide solar cell element, a compound semiconductor solar cell element, and the like can be used.
Further, for example, a thin-film polycrystalline silicon solar cell element, a thin-film microcrystalline silicon solar cell element, or a hybrid element of a thin-film crystalline silicon solar electronic element and an amorphous solar cell element can be used.

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 adhesiveness to the backside protection sheet, and further to have thermoplasticity to fulfill the function of maintaining the smoothness of the backside of the solar cell element as a photovoltaic element. 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. , Surely,
It is not necessary to have transparency. Specifically, as the above-mentioned filler layer, for example, as in the case of the above-described filler layer laminated under 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. Acid-modified polyolefin-based resin modified with a saturated carboxylic acid, cyclic polyolefin-based resin, polyvinyl butyral resin, silicone-based resin,
Mixtures of one or more resins such as epoxy resins, (meth) acrylic resins, and others 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, etc.,
What can be mixed. The thickness of the filler layer is desirably about 200 to 1000 μm, and more desirably about 350 to 600 μm.

Next, in the present invention, the solar cell module
Back protection sheet for normal solar cell module that constitutes module
When the back layer is described, an insulating resin film or sheet can be used as the back surface protection sheet, and further, has heat resistance, light resistance, weather resistance such as water resistance, Excellent physical or chemical strength, toughness, etc.,
Furthermore, 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. Specific examples of the backside protective sheet include polyamide resins (various nylons), polyester resins, polyethylene resins, polypropylene resins, cyclic polyolefin resins, polystyrene resins, polycarbonate resins, and the like. Films or sheets of various resins, such as methacrylate resins, acetal resins, cellulose resins, (meth) acrylic resins, fluorine resins, and others can be used. As the above resin film or sheet, for example, a biaxially stretched resin film or sheet can also be used. In the resin film or sheet, the film thickness is about 12 to 200 μm, more preferably 25 to 1 μm.
About 50 μm 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 Acrylonitrile 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. Also, the thickness is arbitrary,
It can be used by selecting from a range of several μm to about 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, a method of manufacturing a solar cell module using the above-mentioned materials in the present invention will be described. Such a manufacturing method may be a known method, for example, the above-described method of the present invention. The protective sheet for a solar cell module according to the above is used, and this is used as a front or back surface protective sheet for the solar cell module.
A filler layer, a solar cell element as a photovoltaic element, a filler layer, and a normal back protection sheet for a solar cell module are sequentially added to the above surface protection sheet for a solar cell module. Layers, etc., and if necessary, any other material between the layers, and then integrate them by vacuum suction or the like and integrate them by heat and pressure. The solar cell module can be manufactured by heat-press molding each of the above-mentioned layers as an integrally molded body by utilizing the method. 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. Also,
In the present invention, on each of the facing surfaces to be laminated, if necessary, for example, a corona discharge treatment, an ozone treatment, a low-temperature plasma treatment using an oxygen gas or a nitrogen gas, or an atmospheric pressure, 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, as the above-mentioned surface pretreatment, as a method for improving its adhesion,
In addition, a primer coat agent layer, an undercoat agent layer, an anchor coat agent layer, or the like can be arbitrarily formed in advance. As the coating agent layer of the above pretreatment,
For example, a resin composition containing a polyester resin, a polyurethane resin, an acrylic resin, or the like as a main component of the vehicle can be used. Also, in the above,
As a method for forming the coating agent layer, for example, a solvent type, an aqueous type, or an emulsion type coating agent is used.
The coating can be performed by using a coating method such as a roll coating method, a gravure roll coating method, a kiss coating method, and the like. Further, as the above-mentioned surface pretreatment, as a method for improving the adhesion, a film thickness of about 20 to 100 °, preferably 30 to It is also possible to form an inorganic oxide vapor-deposited thin film having a thickness of about 60 ° and having no barrier performance, and use this as a surface pretreatment layer.

[0038]

Next, the present invention will be described more specifically with reference to examples. Example 1 (1). As a base material, a polyvinyl fluoride resin sheet (PVF) having a thickness of 50 μm is used, which is mounted on a delivery roll of a take-up type vacuum evaporation apparatus, and then placed on a coating drum. And then, under the following conditions, using aluminum as a deposition source and supplying oxygen gas,
By a reactive vacuum evaporation method using an electron beam (EB) heating method, an aluminum oxide deposited thin film having a thickness of 500 ° was formed on the surface of the polyvinyl fluoride resin film which had been subjected to the easy adhesion treatment. (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 / Minutes (2). Next, after the above-mentioned vapor-deposited thin film of aluminum oxide having a film thickness of 500 ° was formed, immediately after the vapor deposition, a plasma output of 1500 W, oxygen gas (O
₂ ): Using a mixed gas of argon gas (Ar) = 19: 1, an oxygen / argon mixed gas plasma process was performed at a mixed gas pressure of 6 × 10 ⁻⁵ Tool and a processing speed of 420 m / min to form a plasma processed surface. . (3). Next, a two-component curing type polyurethane laminating film was applied to the plasma-treated surface of the above-mentioned evaporated aluminum oxide thin film.
The adhesive for coating is coated by a gravure roll coating method to form an adhesive layer for laminating having a thickness of 1.0 g / m ² (dry state), and then the adhesive for laminating is applied. A 100 μm-thick polydicyclopentadiene resin film was dry-laminated on the surface of the agent layer to produce a solar cell module protection sheet according to the present invention. (4). Next, the protective sheet for a solar cell module produced above was used as a surface protective sheet for a solar cell module, and the polydicyclopentadiene resin film surface was coated with 400 μm thick ethylene-vinyl acetate. A copolymer sheet, a 38 μm-thick biaxially stretched polyethylene terephthalate film in which solar cell elements made of amorphous silicon are arranged in parallel, a 400 μm-thick ethylene-vinyl acetate copolymer sheet, and a thickness A biaxially stretched polyethylene terephthalate film having a thickness of 50 μm was laminated via an adhesive layer of an acrylic resin, with the solar cell element surface facing upward, to produce a solar cell module according to the present invention. . (5). In the above, instead of the above-mentioned 50 μm-thick polyvinyl fluoride resin sheet (PVF) as the base material, a 50 μm-thick fluororesin sheet made of tetrafluoroethylene-ethylene copolymer (ETF) was used.
Using E), the same protection sheet for solar cell module and solar cell module according to the present invention could be manufactured in the same manner as described above. Further, in the above, a 100 μm-thick polycyclopentadiene resin film is used in place of the 100 μm-thick polydicyclopentadiene resin film. The protection sheet and the solar cell module could be manufactured.

Embodiment 2 (1). As a base material, a polyvinyl fluoride resin film (PVF) having a thickness of 50 μm was used, which was mounted on a delivery roll of a plasma-enhanced chemical vapor deposition apparatus, and a deposited thin film of silicon oxide having a thickness of 500 mm under the following conditions. Was formed on the easily treated surface of the polyvinyl fluoride resin film. (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 Inside vapor deposition chamber Degree of vacuum: 6.0 × 10 ^-2 mbar Cooling / electrode drum supply power: 20 kW Film transport speed: 80 m / min Evaporation surface: Corona treated surface (2). Next, after the above-mentioned vapor deposition thin film of silicon oxide having a film thickness of 500 ° was formed, immediately after the vapor deposition, an output of 10 kW and a processing speed of 100 m / min were applied to the vapor deposition thin film surface of the silicon oxide.
To perform a corona discharge treatment to reduce the surface tension of the deposited thin film surface to 3.
It was improved from 5 dyne to 60 dyne. (3). Next, a two-part curable polyurethane-based adhesive for laminating is coated on the corona-treated surface of the silicon oxide vapor-deposited thin film by a gravure roll coating method to have a thickness of 1.0 g / m 2. ² (in a dry state) to form an adhesive layer for laminating, and then apply a thickness of 1 to the surface of the laminating adhesive layer.
A solar cell module according to the present invention is obtained by dry laminating a 50 μm polydicyclopentadiene resin film.
A protective sheet was prepared for this purpose. (4). Next, the protective sheet for a solar cell module produced above was used as a surface protective sheet for a solar cell module, and the polydicyclopentadiene resin film surface was coated with 400 μm thick ethylene-vinyl acetate. A copolymer sheet, a 38 μm-thick biaxially stretched polyethylene terephthalate film in which solar cell elements made of amorphous silicon are arranged in parallel, a 400 μm-thick ethylene-vinyl acetate copolymer sheet, and a thickness A biaxially stretched polyethylene terephthalate film having a thickness of 50 μm was laminated via an adhesive layer of an acrylic resin, with the solar cell element surface facing upward, to produce a solar cell module according to the present invention. . (5). In the above, instead of the above-mentioned 50 μm-thick polyvinyl fluoride resin sheet (PVF) as the base material, a 50 μm-thick fluororesin sheet made of tetrafluoroethylene-ethylene copolymer (ETF) was used.
Using E), the same protection sheet for solar cell module and solar cell module according to the present invention could be manufactured in the same manner as described above. Further, in the above, a polycyclopentadiene resin film having a thickness of 150 μm was used in place of the polydicyclopentadiene resin film having a thickness of 150 μm. The protection sheet and the solar cell module could be manufactured.

Embodiment 3 (1). As a base material, a 50 μm-thick polyvinyl fluoride resin film (PV
F), a vapor-deposited thin film of silicon oxide having a thickness of 500 ° was formed on the easily-adhesion-treated surface in the same manner as in Example 2 described above, and the corona discharge was further formed on the vapor-deposited thin film of silicon oxide. Perform processing to reduce the surface tension of the vapor-deposited thin film surface to 35 dyne.
60 dyne. (2). Next, using the polyvinyl fluoride resin film on which the vapor-deposited silicon oxide thin film subjected to the corona treatment was formed, the silicon oxide vapor deposition of the polyvinyl fluoride resin film was performed in exactly the same manner as in Example 1 above. An aluminum oxide deposited thin film having a thickness of 500 ° was formed on the corona-treated surface of the thin film, and plasma treatment was further performed on the aluminum oxide deposited thin film surface to form a plasma-treated surface. (3). Next, a two-component curing type polyurethane laminating film was applied to the plasma-treated surface of the above-mentioned evaporated aluminum oxide thin film.
The adhesive for coating is coated by a gravure roll coating method to form an adhesive layer for laminating having a thickness of 1.0 g / m ² (dry state), and then the adhesive for laminating is applied. A 200 μm-thick polydicyclopentadiene resin film was dry-laminated on the surface of the agent layer to produce a protective sheet for a solar cell module according to the present invention. (4). Next, the protective sheet for a solar cell module produced above was used as a surface protective sheet for a solar cell module, and the polydicyclopentadiene resin film surface was coated with 400 μm thick ethylene-vinyl acetate. A copolymer sheet, a 38 μm-thick biaxially stretched polyethylene terephthalate film in which solar cell elements made of amorphous silicon are arranged in parallel, a 400 μm-thick ethylene-vinyl acetate copolymer sheet, and a thickness A biaxially stretched polyethylene terephthalate film having a thickness of 50 μm was laminated via an adhesive layer of an acrylic resin, with the solar cell element surface facing upward, to produce a solar cell module according to the present invention. . (5). In the above, in place of the above-mentioned 50 μm-thick polyvinyl fluoride resin sheet (PVF) kneaded with an ultraviolet absorber as a base material, a 50 μm-thick tetrafluoroethylene-kneaded tetrafluoroethylene resin sheet is used. Using a fluororesin sheet (ETFE) composed of a fluoroethylene-ethylene copolymer, in exactly the same manner as described above, a similar protection sheet for a solar cell module and a solar cell module according to the present invention. -Can be manufactured. In the above, a 200 μm-thick polynorbornadiene resin film is used in place of the 200 μm-thick polydicyclopentadiene resin film. Sheets and solar cell modules could be manufactured.

Example 4 A polyurethane-based anchor coating agent was coated on the plasma-treated surface of the deposited aluminum oxide thin film produced in Example 1 by a gravure roll coating method.
An anchor coating agent layer having a thickness of 0.5 g / m ² (dry state) was formed, and then a polydicyclopentadiene resin was used on the surface of the anchor coating agent layer, and this was melted and extruded. Then, a polydicyclopentadiene resin film having a thickness of 150 μm was formed, and the solar cell module according to the present invention was formed.
A protective sheet was prepared for this purpose. Next, the solar cell module according to the present invention was manufactured in the same manner as in Example 1 above, using the solar cell module protection sheet manufactured above using the solar cell module surface protection sheet. Was manufactured. Also,
In the above description, a polycyclopentadiene resin is used in place of the polydicyclopentadiene resin, and in exactly the same manner as described above, a similar protection sheet for a solar cell module according to the present invention and a solar cell module Could be manufactured.

Example 5 A polyurethane anchor coating agent was coated by a gravure roll coating method on the corona-treated surface of the silicon oxide vapor-deposited thin film produced in the above-mentioned Example 2 to a thickness of 0%. .5
g / m ² (dry state) to form an anchor coat agent layer,
Next, a polydicyclopentadiene resin is used on the surface of the anchor coating agent layer, and is melt-extruded and coated to form a polydicyclopentadiene resin film having a thickness of 300 μm. A protective sheet for the module was manufactured. Next, the solar cell module according to the present invention was manufactured in the same manner as in Example 2 above, using the solar cell module protection sheet manufactured above using the solar cell module surface protection sheet. Was manufactured. Further, in the above, a polynorbornadiene resin is used in place of the polydicyclopentadiene resin, and in the same manner as described above, a similar surface protection sheet for a solar cell module and a solar cell module according to the present invention. -Can be manufactured.

EXAMPLE 6 10 parts by weight of polydicyclopentadiene resin and 90 parts by weight of a mixed solvent of toluene and methyl ethyl ketone (1: 1) were applied to the plasma-treated surface of the deposited aluminum oxide thin film produced in Example 1 above. Is coated by a gravure roll coating method to form a coating film having a thickness of 5.0 g / m ² (dry state). Heat for a minute
A polydicyclopentadiene resin film was formed by hardening to prepare a protective sheet for a solar cell module according to the present invention. Further, the protection sheet for a solar cell module manufactured above is replaced with a surface protection sheet for a solar cell module.
A solar cell module according to the present invention was manufactured in the same manner as in Example 1 using the above-described method. Further, in the above, a polycyclopentadiene resin is used in place of the polydicyclopentadiene resin, and a solar cell module protection sheet and a solar cell module according to the present invention are provided in the same manner as described above. -Can be manufactured.

Embodiment 7 (1). The solar cell module protection sheet manufactured in Example 1 is used as a solar cell module surface protection sheet and a solar cell module back surface protection sheet. 38 μm thick solar cell elements made of 400 μm thick ethylene-vinyl acetate copolymer sheet and amorphous silicon are arranged in parallel on the surface of the polydicyclopentadiene resin film of the surface protection sheet for the module.
m, a biaxially stretched polyethylene terephthalate film, a 400 μm-thick ethylene-vinyl acetate copolymer sheet,
Further, the back surface protection sheet for a solar cell module is provided with the polydicyclopentadiene resin film surface facing the solar cell element surface and the acrylic resin adhesive layer interposed therebetween. By laminating, a solar cell module according to the present invention was manufactured. (2). In the above, instead of the above-mentioned 50 μm-thick polyvinyl fluoride resin sheet (PVF) as the base material, a 50 μm-thick fluororesin sheet made of tetrafluoroethylene-ethylene copolymer (ETF) was used.
Using E), the same protection sheet for solar cell module and solar cell module according to the present invention could be manufactured in the same manner as described above. Further, in the above, a 100 μm-thick polycyclopentadiene resin film is used in place of the 100 μm-thick polydicyclopentadiene resin film. The protection sheet and the solar cell module could be manufactured.

Embodiment 8 (1). The protection sheet for a solar cell module manufactured in Example 2 is used as a front protection sheet for a solar cell module and a back protection sheet for a solar cell module. 38 μm thick solar cell elements made of 400 μm thick ethylene-vinyl acetate copolymer sheet and amorphous silicon are arranged in parallel on the surface of the polydicyclopentadiene resin film of the surface protection sheet for the module.
m, a biaxially stretched polyethylene terephthalate film, a 400 μm-thick ethylene-vinyl acetate copolymer sheet,
Further, the back surface protection sheet for a solar cell module is provided with the polydicyclopentadiene resin film surface facing the solar cell element surface and the acrylic resin adhesive layer interposed therebetween. By laminating, a solar cell module according to the present invention was manufactured. (2). In the above, instead of the above-mentioned 50 μm-thick polyvinyl fluoride resin sheet (PVF) as the base material, a 50 μm-thick fluororesin sheet made of tetrafluoroethylene-ethylene copolymer (ETF) was used.
Using E), the same protection sheet for solar cell module and solar cell module according to the present invention could be manufactured in the same manner as described above. Further, in the above, a polycyclopentadiene resin film having a thickness of 150 μm was used in place of the polydicyclopentadiene resin film having a thickness of 150 μm. The protection sheet and the solar cell module could be manufactured.

Embodiment 9 (1). The solar cell module protection sheet manufactured in Example 3 is used as a solar cell module surface protection sheet and a solar cell module back surface protection sheet. 38 μm thick solar cell elements made of 400 μm thick ethylene-vinyl acetate copolymer sheet and amorphous silicon are arranged in parallel on the surface of the polydicyclopentadiene resin film of the surface protection sheet for the module.
m, a biaxially stretched polyethylene terephthalate film, a 400 μm-thick ethylene-vinyl acetate copolymer sheet,
Further, the back surface protection sheet for a solar cell module is provided with the polydicyclopentadiene resin film surface facing the solar cell element surface and the acrylic resin adhesive layer interposed therebetween. By laminating, a solar cell module according to the present invention was manufactured. (2). In the above, in place of the above-mentioned 50 μm-thick polyvinyl fluoride resin sheet (PVF) kneaded with an ultraviolet absorber as a base material, a 50 μm-thick tetrafluoroethylene-kneaded tetrafluoroethylene resin sheet is used. Using a fluororesin sheet (ETFE) composed of a fluoroethylene-ethylene copolymer, in exactly the same manner as described above, a similar protection sheet for a solar cell module and a solar cell module according to the present invention. -Can be manufactured. In the above, a 200 μm-thick polynorbornadiene resin film is used in place of the 200 μm-thick polydicyclopentadiene resin film. Sheets and solar cell modules could be manufactured.

Example 10 The protection sheet for a solar cell module manufactured in the above Example 4 was used as a front protection sheet for a solar cell module and a back protection sheet for a solar cell module. A solar cell element made of an ethylene-vinyl acetate copolymer sheet and amorphous silicon having a thickness of 400 μm is arranged in parallel on the surface of the polydicyclopentadiene resin film of the surface protection sheet for a solar cell module. A 38 μm-thick biaxially stretched polyethylene terephthalate film, a 400 μm-thick ethylene-vinyl acetate copolymer sheet, and the above-mentioned back surface protection sheet for a solar cell module were prepared by using polydicyclopentadiene The solar cell module according to the present invention is laminated with the resin film surface facing and the solar cell element surface facing upward with an adhesive layer of an acrylic resin interposed therebetween. Was manufactured. Further, in the above, a polycyclopentadiene resin is used in place of the polydicyclopentadiene resin, and a solar cell module protection sheet and a solar cell module according to the present invention are provided in the same manner as described above. -Can be manufactured.

Embodiment 11 The protection sheet for a solar cell module manufactured in the above Example 5 is used as a front protection sheet for a solar cell module and a back protection sheet for a solar cell module. A solar cell element made of an ethylene-vinyl acetate copolymer sheet and amorphous silicon having a thickness of 400 μm is arranged in parallel on the surface of the polydicyclopentadiene resin film of the surface protection sheet for a solar cell module. A 38 μm-thick biaxially stretched polyethylene terephthalate film, a 400 μm-thick ethylene-vinyl acetate copolymer sheet, and the above-mentioned back surface protection sheet for a solar cell module were prepared by using polydicyclopentadiene The solar cell module according to the present invention is laminated with the resin film surface facing the solar cell element surface facing upward and an acrylic resin adhesive layer interposed therebetween. Was manufactured. Further, in the above, a polynorbornadiene resin is used in place of the polydicyclopentadiene resin, and in the same manner as described above, a similar surface protection sheet for a solar cell module and a solar cell module according to the present invention. -Can be manufactured.

Embodiment 12 The protection sheet for a solar cell module manufactured in the above-mentioned embodiment 6 is used as a front protection sheet for a solar cell module and a back protection sheet for a solar cell module. A solar cell element made of an ethylene-vinyl acetate copolymer sheet and amorphous silicon having a thickness of 400 μm is arranged in parallel on the surface of the polydicyclopentadiene resin film of the surface protection sheet for a solar cell module. A 38 μm-thick biaxially stretched polyethylene terephthalate film, a 400 μm-thick ethylene-vinyl acetate copolymer sheet, and the above-mentioned back surface protection sheet for a solar cell module were prepared by using polydicyclopentadiene The solar cell module according to the present invention is laminated with the resin film surface facing and the solar cell element surface facing upward with an adhesive layer of an acrylic resin interposed therebetween. Was manufactured. Further, in the above, a polycyclopentadiene resin is used in place of the polydicyclopentadiene resin, and the same surface protection sheet for a solar cell module according to the present invention, The module could be manufactured.

Embodiment 13 (1). The protection sheet for a solar cell module manufactured in Example 1 was used as a back surface protection sheet for a solar cell module. First, a glass plate having a thickness of 3 mm and a thickness of 400 mm were used.
μm ethylene-vinyl acetate copolymer sheet, 38 μm-thick biaxially stretched polyethylene terephthalate film in which solar cell elements made of amorphous silicon are arranged in parallel, 400 μm thickness ethylene-vinyl acetate copolymer sheet -, And the back surface protection sheet for a solar cell module, the polydicyclopentadiene resin film surface is opposed, and the solar cell element surface is directed upward,
The solar cell module according to the present invention was manufactured by laminating through an adhesive layer of an acrylic resin. (2). In the above, instead of the above-mentioned 50 μm-thick polyvinyl fluoride resin sheet (PVF) as the base material, a 50 μm-thick fluororesin sheet made of tetrafluoroethylene-ethylene copolymer (ETF) was used.
Using E), the same protection sheet for solar cell module and solar cell module according to the present invention could be manufactured in the same manner as described above. Further, in the above, a 100 μm-thick polycyclopentadiene resin film is used in place of the 100 μm-thick polydicyclopentadiene resin film. The protection sheet and the solar cell module could be manufactured.

Embodiment 14 (1). The protective sheet for a solar cell module manufactured in Example 2 was used as a back protective sheet for a solar cell module. First, a 50 μm-thick polyvinyl fluoride resin sheet (PVF) was used. A 38 μm-thick biaxially stretched polyethylene terephthalate film in which solar cell elements made of an ethylene-vinyl acetate copolymer sheet and amorphous silicon having a thickness of 400 μm are arranged in parallel, a thickness of 400 μm
The ethylene-vinyl acetate copolymer sheet and the back surface protection sheet for a solar cell module described above, with their polydicyclopentadiene resin film surfaces facing each other, and
The solar cell module according to the present invention was manufactured by laminating the solar cell element face up with an acrylic resin adhesive layer interposed therebetween. (2). In the above, instead of the above-mentioned 50 μm-thick polyvinyl fluoride resin sheet (PVF) as the base material, a 50 μm-thick fluororesin sheet made of tetrafluoroethylene-ethylene copolymer (ETF) was used.
Using E), the same protection sheet for solar cell module and solar cell module according to the present invention could be manufactured in the same manner as described above. Further, in the above, a polycyclopentadiene resin film having a thickness of 150 μm was used in place of the polydicyclopentadiene resin film having a thickness of 150 μm. The protection sheet and the solar cell module could be manufactured.

Embodiment 15 (1). The protection sheet for the solar cell module manufactured in Example 3 was used as a back protection sheet for the solar cell module. First, a 50 μm thick polyvinyl fluoride resin sheet (PVF) was used. A 38 μm-thick biaxially stretched polyethylene terephthalate film in which solar cell elements made of an ethylene-vinyl acetate copolymer sheet and amorphous silicon having a thickness of 400 μm are arranged in parallel, a thickness of 400 μm
The ethylene-vinyl acetate copolymer sheet and the back surface protection sheet for a solar cell module described above, with their polydicyclopentadiene resin film surfaces facing each other, and
The solar cell module according to the present invention was manufactured by laminating the solar cell element face up with an acrylic resin adhesive layer interposed therebetween. (2). In the above, in place of the above-mentioned 50 μm-thick polyvinyl fluoride resin sheet (PVF) kneaded with an ultraviolet absorber as a base material, a 50 μm-thick tetrafluoroethylene-kneaded tetrafluoroethylene resin sheet is used. Using a fluororesin sheet (ETFE) composed of a fluoroethylene-ethylene copolymer, in exactly the same manner as described above, a similar protection sheet for a solar cell module and a solar cell module according to the present invention. -Can be manufactured. In the above, a 200 μm-thick polynorbornadiene resin film is used in place of the 200 μm-thick polydicyclopentadiene resin film. Sheets and solar cell modules could be manufactured.

Comparative Example 1 A glass plate having a thickness of 3 mm was used as a base material for a solar cell module.
400 μm thick ethylene-vinyl acetate copolymer sheet on one surface.
38 μm thick biaxially oriented polyethylene terephthalate film in which solar cell elements made of amorphous silicon are arranged in parallel, 400 μm thick ethylene-vinyl acetate copolymer sheet, and 50 μm thick biaxially oriented polyethylene The solar cell module was manufactured by laminating a terephthalate film with the solar cell element surface facing upward through an adhesive layer of an acrylic resin.

Comparative Example 2 A 50 μm thick polyvinyl fluoride resin screen was used as a substrate.
(PVF) is used as a surface protection sheet for a solar cell module, and a solar cell element made of an ethylene-vinyl acetate copolymer sheet having a thickness of 400 μm and amorphous silicon is arranged in parallel on one surface thereof. 38 μm thick biaxially stretched polyethylene terephthalate film, thickness 4
00 μm ethylene-vinyl acetate copolymer sheet and 50 μm thick 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 3 A 50 μm thick polyvinyl fluoride resin screen was used as a substrate.
Sheet (PVF) is used as a surface protection sheet for a solar cell module and a back surface protection sheet for a solar cell module, and one of the 50 μm-thick polyvinyl fluoride resin sheet (PVF) is used. A 38 μm-thick biaxially stretched polyethylene terephthalate film having a 400 μm-thick ethylene-vinyl acetate copolymer sheet and amorphous silicon solar cell elements arranged in parallel, a 400 μm-thick ethylene-acetic acid film Vinyl copolymer sheet and the other 50 μm thick polyvinyl fluoride resin sheet (PVF)
Were laminated via an adhesive layer of an acrylic resin with the solar cell element surface facing upward to produce a solar cell module.

EXPERIMENTAL EXAMPLES The total light transmittance of the protective sheets according to the present invention produced in Examples 1 to 15 and the protective sheets according to Comparative Examples 1 to 3 was measured. Solar cell module evaluation tests were performed on the solar cell modules manufactured in Examples 1 to 15 and the solar cell modules manufactured in Comparative Examples 1 to 3. (1). Measurement of total light transmittance This is based on the base film and the color computer for the protective sheets according to the present invention manufactured in Examples 1 to 15 and the protective sheets according to Comparative Examples 1 to 3. -Was used to measure the total light transmittance (%). (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 for the protective sheets according to the present invention manufactured in Examples 1 to 15 and the protective sheets according to Comparative Examples 1 to 3 at a temperature of 40 ° C. and a humidity of 90. % RH, and measured with a measuring device (model name, PERMATRAN) manufactured by MOCON, USA. Measuring instrument manufactured by MOCON, USA [model name: OXTRAN] under the conditions of ° C and 90% RH.
Was measured. The results of the above measurements are shown in Table 1 below.

[0057] In Table 1 above, the water vapor permeability is [g / m ² / d
ay.40 ° C. · 100% RH], and the oxygen permeability is [cc / m ² / day · 23 ° C. · 90% RH].
H].

As is clear from the measurement results shown in Table 1 above, the protective sheets for solar cell modules according to Examples 1 to 15 have a high total light transmittance, a water vapor barrier property, and oxygen. Excellent barrier properties. Examples 1 to 15
The solar cell module using the protection sheet according to
The output reduction rate was also low. On the other hand, although the protective sheets according to Comparative Examples 1 to 3 have high total light transmittance, they have low water vapor barrier property and low oxygen barrier property. There were problems such as a high rate.

[0059]

As is apparent from the above description, the present invention
First, using a fluororesin sheet as a base sheet,
On one surface thereof, silicon oxide, or a transparent, glassy inorganic oxide vapor-deposited thin film such as aluminum oxide is provided, and a cyclic polyolefin-based resin film is further provided on the inorganic oxide vapor-deposited thin film. A protection sheet for a solar cell module is manufactured, and the protection sheet for a solar cell module is used as a front or back surface protection sheet layer for a solar cell module. With the above-mentioned cyclic polyolefin resin film of the surface protection sheet for a solar cell module inside, a filler layer, a solar cell element as a photovoltaic element, a filler layer, and a normal solar cell module A solar cell module is manufactured by using a lamination method in which a back protective sheet layer and the like are sequentially laminated, and then these are integrally vacuum-evacuated and heat-pressed to produce a solar cell module. Excellent permeability and strength Are further, weather resistance, heat resistance, water resistance, light resistance, resistance to wind pressure resistance, hail resistance, chemical resistance, moisture resistance,
Excellent in anti-fouling properties and other properties, in particular, significantly improves moisture resistance to prevent intrusion of moisture, oxygen, etc., minimizes its long-term performance degradation, is extremely durable, and has a protective ability Therefore, a safe solar cell module can be stably manufactured at a lower cost and at a lower cost.

[Brief description of the drawings]

FIG. 1 is a protective seal for a solar cell module according to the present invention.
FIG. 2 is a schematic cross-sectional view schematically illustrating a layer configuration of an example of the layer.

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

FIG. 3 is a protective sheet for a solar cell module according to the present invention.
FIG. 2 is a schematic cross-sectional view schematically illustrating a layer configuration of an example of the layer.

FIG. 4 is a schematic sectional view schematically showing a layer configuration of an example of a solar cell module manufactured using the solar cell module protection sheet according to the present invention shown in FIG. 1;

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

FIG. 6 is a schematic cross-sectional view schematically showing a layer configuration of an example of a solar cell module manufactured using the solar cell module protection sheet according to the present invention shown in FIG.

FIG. 7 is a schematic configuration diagram of a take-up type vacuum evaporation apparatus showing an outline of a method for forming a deposited thin film of an inorganic oxide by a physical vapor deposition method.

FIG. 8 is a schematic configuration diagram of a low-temperature plasma chemical vapor deposition apparatus showing an outline of a method for forming a vapor-deposited thin film of an inorganic oxide by a chemical vapor deposition method.

[Explanation of symbols]

A Protective sheet for solar cell module A ₁ Protective sheet for solar cell module A ₂ Protective sheet for solar cell module 1 Fluorine resin sheet 2 Deposited thin film of inorganic oxide 2a depositing thin film 3 cyclic polyolefin resin film 4 multilayer film 5 composite membrane T solar cell module of the deposited thin film 2b inorganic oxide of the inorganic oxide - Le T ₁ solar cell module - Le T ₂ solar cell module - le 11 solar cell module - Surface protection sheet for module 12 Filler layer 13 Solar cell element 14 Filler layer 15 Backside protection sheet 16 Backside protection sheet for solar cell module 17 Surface protection sheet

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yasuki Suzuura 1-1-1, Ichigaya-Kagacho, Shinjuku-ku, Tokyo Inside Dai Nippon Printing Co., Ltd. (72) Inventor Takakazu Goto 1-chome, Ichigaya-cho, Shinjuku-ku, Tokyo No. 1-1 Inside Dai Nippon Printing Co., Ltd. (72) Inventor Eiki Niio 1-1-1, Ichigaya Kagacho, Shinjuku-ku, Tokyo Inside Dai Nippon Printing Co., Ltd. (72) Inventor Junro Suzuki Ichigaya, Shinjuku-ku, Tokyo 1-1-1 Kagacho F-term in Dai Nippon Printing Co., Ltd. (reference) 4F100 AA17B AA19B AA20B AG00B AK03C AK17A AK80C BA03 BA07 BA10A BA10C CA06A CA07A EH66B GB41 JB01 JB06 JJ03 JK01 JK01 JL01 JN01 JN01 JL01 EA18 EA20 HA19 JA03 JA04 JA05

Claims (10)

[Claims] An inorganic oxide vapor-deposited thin film is provided on one side of a fluorine-based resin sheet, and a cyclic polyolefin resin film is further provided on the inorganic oxide vapor-deposited thin film. Protection sheet for solar cell module. 2. A solar cell module comprising: a vapor-deposited thin film of an inorganic oxide provided on one side of a fluororesin sheet; and a cyclic polyolefin-based resin film provided on the vapor-deposited thin film of the inorganic oxide. A protection sheet for a solar cell module, comprising a surface protection sheet for a solar cell module. 3. A solar cell module comprising: an inorganic oxide vapor-deposited thin film provided on one side of a fluororesin sheet; and a cyclic polyolefin-based resin film provided on the inorganic oxide vapor-deposited thin film. A protection sheet for a solar cell module, comprising a back protection sheet for a solar cell module. 4. A fluororesin sheet having a visible light transmittance of 9%.
The protection sheet for a solar cell module according to any one of claims 1 to 3, wherein the content is 0% or more. 5. The protective sheet for a solar cell module according to claim 1, wherein the fluororesin sheet contains an ultraviolet absorber and / or an antioxidant. . 6. The inorganic oxide vapor-deposited thin film is composed of one or two or more layers of inorganic oxide vapor-deposited thin films or a composite film composed of two or more different inorganic oxide vapor-deposited thin films. The protection sheet for a solar cell module according to any one of claims 1 to 5, wherein: 7. The solar cell module according to claim 1, wherein the cyclic polyolefin-based resin film is made of a polycyclopentadiene resin film, a polydicyclopentadiene resin film, or a polynorbornadiene resin film. -Protective sheet for the tool. 8. A solar cell module comprising: an inorganic oxide vapor-deposited thin film provided on one surface of a fluorine-based resin sheet; and a cyclic polyolefin-based resin film provided on the inorganic oxide vapor-deposited thin film. A filler layer, a solar cell element as a photovoltaic element, a filler layer, and a back surface protection sheet layer for a solar cell module are sequentially formed on the surface of the cyclic polyolefin resin film of the surface protection sheet for use. A solar cell module, wherein the solar battery module is formed by laminating, vacuum-suctioning these, and forming them into an integrally formed body by a heat compression lamination method or the like. 9. A surface protection sheet for a solar cell module,
A filler layer, a solar cell element as a photovoltaic element, a filler layer, and a vapor-deposited inorganic oxide thin film provided on one surface of a fluororesin sheet. Then, a back protection sheet for a solar cell module provided with a cyclic polyolefin-based resin film is sequentially laminated with the cyclic polyolefin-based resin film surfaces facing each other. A solar cell module characterized by being formed into an integral body by an application method or the like. 10. A solar cell module comprising: a vapor-deposited inorganic oxide thin film provided on one side of a fluorine-based resin sheet; and a cyclic polyolefin-based resin film provided on the inorganic oxide vapor-deposited thin film. A filler layer, a solar cell element as a photovoltaic element, a filler layer, and one surface of a fluorine-based resin sheet on the surface of the cyclic polyolefin resin film of the surface protection sheet for
An inorganic oxide vapor-deposited thin film is provided, and further, a cyclic polyolefin-based resin film is provided on the inorganic oxide vapor-deposited thin film. Are laminated one by one, facing each other, and are vacuum-suctioned to form an integrally molded body by a heat compression lamination method or the like.
Le.