JP2000340818A - Solar battery module protection sheet and solar battery module using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To be superior in transmission of solar beams, and superior in ruggedness, and superior in various characteristics such as a weather-resistance, a heat-resistance, or the like, and in particular fairly enhance the moisture- proofness. SOLUTION: First, a plastic sheet 1 is used as a substrate sheet, and a deposited thin film 3 of an inorganic oxide of a non-barrier property composed of a silicon oxide, an aluminum oxide, or the like has been previously provided on the one plane, and this is set as a deposition-resistant protection film 2, and further the transparent and vitreous deposited film 3 such as the silicon oxide, aluminum oxide, or the like and of the inorganic oxide superior in a vapor barrier property, an oxide barrier property, or the like is provided on the deposition-resistant protection film 2, thereby manufacturing a solar battery module protection sheet A. Then, this is superior in a transmission of solar beams, is superior in intensity, and further is superior in various characteristics such as weather-resistance, heat-resistance, water-proofness, or the like, and in particular enhances the moisture-proofness for preventing invasion of moisture, oxygen, or the like.

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
More specifically, it has excellent strength and various properties such as weather resistance, heat resistance, water resistance, light resistance, wind pressure resistance, hail resistance, chemical resistance, moisture resistance, stain resistance, etc. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a front or back surface protection sheet for a solar cell module having excellent characteristics, extremely high durability, and excellent protection ability, 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. , Has excellent strength to transmit sunlight, and has excellent strength such as weather resistance, heat resistance, water resistance, light resistance, wind pressure resistance, hail resistance, and chemical resistance. It has excellent moisture resistance to prevent intrusion of oxygen and the like, and also has high surface hardness, and excellent antifouling property to prevent accumulation of dirt and dust on the surface, and is extremely rich in durability.
It is necessary to satisfy conditions such as high protection ability and other conditions, and also in the case of a back surface protection sheet layer,
It is almost necessary to satisfy the same conditions as in the case of the above-mentioned surface protective sheet layer. However, for example, 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, and heat resistance. It is excellent in various fastnesses such as water resistance, light resistance, chemical resistance, etc., also excellent in moisture resistance, and has a hard surface hardness and antifouling property to prevent accumulation of surface dirt, dust, etc. It has advantages such as excellent, high protection ability, but lacks strength, plasticity, impact resistance, light weight, etc., and furthermore, it is inferior in its workability, workability, etc., and lacks in cost reduction, etc. There is a problem.
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. Also, a back surface protection sheet constituting the above solar cell module.
When a resin sheet or the like having excellent strength is used as the layer, it is rich in strength, plasticity, impact resistance, light weight, cost reduction, etc., but has weather resistance, heat resistance, and water resistance. In addition, it is inferior in various fastnesses such as light resistance, chemical resistance and the like, and in particular, 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. , Remarkably enhances the moisture resistance to prevent intrusion of moisture, oxygen, etc., minimizes its long-term performance degradation, is extremely durable, and has excellent protection ability,
Another object of the present invention is to stably provide a front or back surface protection sheet constituting a safer solar cell module at a lower cost.

[0004]

The inventors of the present invention have conducted various studies on a protective sheet layer constituting a solar cell module in order to solve the problems described above. Is used as a substrate sheet, and on one surface thereof, a non-barrier inorganic oxide vapor-deposited thin film made of silicon oxide, aluminum oxide, or the like is provided in advance, and this is used as a vapor-deposited protective film. For a solar cell module, a transparent and inorganic vapor-deposited film made of glassy material such as silicon oxide or aluminum oxide and having excellent water vapor barrier properties and oxygen barrier properties is provided on the vapor deposition resistant protective film. A protection sheet is manufactured, and the protection sheet for a solar cell module is used as a front protection sheet for a solar cell module or a back protection sheet for a solar cell module. For example, the above solar cell module The inorganic oxide deposited film surface of the surface protection sheet for the inside is filled with a filler layer, a solar cell element as a photovoltaic element, a filler layer, and a back protection sheet for a normal solar cell module. Layers are sequentially laminated, and then
When a solar cell module was manufactured using a lamination method in which these were integrally vacuum-sucked and heated and pressed, the solar cell module was excellent in sunlight permeability and strength, and further,
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., especially moisture proofing to prevent moisture and oxygen from entering. It is possible to stably produce a solar cell module that is extremely durable, has excellent protection ability, is lower in cost, and is safer, while significantly improving its performance and minimizing its long-term performance deterioration. Thus, the present invention has been completed.

That is, the present invention is characterized in that an evaporation-resistant protective film is provided on one surface of a plastic sheet, and an inorganic oxide evaporated film is provided on the evaporation-resistant protective film. 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 more specifically with reference to the drawings and the like. FIGS. 1, 2, 3, 4 and 5 show the layers of the protective sheet for a solar cell module according to the present invention. FIG. 6 is a schematic cross-sectional view illustrating a few examples of the configuration, and FIGS. 6, 7 and 8 are manufactured using the protection sheet for a solar cell module according to the present invention shown in FIG. FIG. 4 is a schematic cross-sectional view illustrating some examples of the layer configuration of the solar cell module.

First, a solar cell module according to the present invention
As shown in FIG.
A protective film 2 is provided on one side of
An inorganic oxide vapor-deposited film 3 was provided on the vapor deposition-resistant protective film 2.
The basic structure is composed of a structure. Like this
Thus, the protection sheet for a solar cell module according to the present invention is provided.
To illustrate another example, as shown in FIG.
On one surface of the stick sheet 1, an anti-evaporation protective film 2 is provided.
Further, an inorganic oxide is deposited on the deposition-resistant protective film 2.
Consists of a multilayer film 4 provided with at least two layers of the films 3 and 3
Protection sheet A for solar cell module₁List
be able to. Further, the solar cell module according to the present invention
FIG. 3 shows another example of a protection sheet for a vehicle.
As shown, one side of the plastic sheet 1 is steam resistant.
A deposition protection film 2 is provided.
First, an inorganic oxide vapor deposition film 3a was formed by chemical vapor deposition.
Then, a physical gas is deposited on the inorganic oxide deposited film 3a.
An inorganic oxide vapor-deposited film 3b is provided by a phase growth method,
Composite composed of two or more layers of inorganic oxide deposited films 3a and 3b
Protective sheet for solar cell module composed of membrane 5
A_TwoCan be mentioned. The above examples are not applicable to the present invention.
Some Protection Sheets for Solar Cell Modules
By way of example, the invention is not limited thereby.
Needless to say, it is not done. For example,
Although not shown, the protection module for the solar cell module shown in FIG.
-A _TwoFirst, the physical vapor deposition method
An oxide deposited film is provided, and then a non-deposited film is formed by chemical vapor deposition.
Alternatively, a vapor-deposited film of organic oxide may be provided.

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. Protective sheet A for solar cell module is used as surface protective sheet 11 for solar cell module, and thus, inorganic oxide deposition of surface protective sheet 11 (A) for solar cell module With the surface of the film 3 inside, a filler layer 12, a solar cell element 13 as a photovoltaic element, a filler layer 14, a normal back protection sheet layer 15 for a solar cell module, etc. The solar cell module T is manufactured by integrally forming these layers and integrally forming the above layers by using a normal molding method such as a lamination method of vacuum suction and heat compression. Can be. 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 protection sheet 16 for a solar cell module. First, a normal surface protection sheet 17 for a solar cell module is used.
Filler layer 12, solar cell element 1 as photovoltaic element
3, a filler layer 14, and the above-mentioned back surface protection sheet 16 (A) for a solar cell module are sequentially laminated such that the surfaces of the inorganic oxide vapor-deposited films 3 face each other. the integrally, lamination thermocompression bonding by vacuum suction - 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.

In the present invention, another example of a solar cell module manufactured by using the solar cell module protection sheet according to the present invention described above is as follows. 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. 6, the solar cell module according to the present invention shown in FIG. The solar cell module protection sheet A is used as the solar cell module surface protection sheet 11, and the solar cell module protection sheet A according to the present invention shown in FIG. It is used as a back surface protection sheet 16 for a module, and the surface of the inorganic oxide vapor-deposited film 3 of the above-mentioned surface protection sheet 11 (A) for a solar cell module is turned inside. A filler layer 12, a solar cell element 13 as a photovoltaic element, The filler layer 14 and the back surface protection sheet 16 (A) for a solar cell module are laminated with the inorganic oxide vapor-deposited film 3 facing the surface thereof. Lamine which is sucked and heat pressed
Using conventional molding method Deployment method, a solar cell module as an integral molded product of the above layers - can be produced Le T _2. The above example is a solar cell module manufactured using the protection sheet for a solar cell module according to the present invention.
However, the present invention is not limited to these examples. For example, although not shown, the solar cell module protection sheets shown in FIGS. 2 and 3 and the like are used to manufacture solar cell modules having various forms in the same manner as described above. In the above-mentioned solar cell module, other layers can be optionally added and laminated for the purpose of absorbing sunlight, reinforcing, and the like. .

Next, in the present invention, the protective sheet for a solar cell module according to the present invention and the materials and manufacturing method of the solar cell module using the same will be described in more detail. The protective sheet for the solar cell module according to the present invention, the plastic sheet constituting the solar cell module, and the like are basically formed of an anti-evaporation protective film or an inorganic oxide evaporated film. That it withstands the deposition conditions at the time of the deposition, has excellent adhesion to the deposition-resistant protective film or the inorganic oxide deposited film, etc., and can hold the film without deteriorating the properties of the film. However, since it absorbs sunlight and generates photovoltaic power, it has excellent strength for transmitting sunlight and excellent strength.
Excellent in various robustness such as weather resistance, heat resistance, water resistance, light resistance, wind pressure resistance, hail resistance, chemical resistance, etc.In particular, it is excellent in moisture resistance to prevent intrusion of moisture, oxygen, etc., and surface hardness Films and sheets of various resins that have high antifouling properties, and have excellent antifouling properties to prevent accumulation of dirt and dust on the surface, are extremely durable, and have high protection ability. Can be used. Specifically, examples of the film or sheet of the above various resins include polyethylene resin, polypropylene resin, cyclic polyolefin resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile Ru-butadiene-styrene copolymer (ABS resin), polyvinyl chloride resin, fluorine resin, poly (meth) acrylic resin, polycarbonate resin, polyethylene terephthalate, polyethylene naphthalate Polyester resin such as nylon, various polyamide resin such as nylon, polyimide resin, polyamide imide resin, polyaryl phthalate resin, silicone resin, polysulfone resin, polyphenylene sulfide resin, polyether sulfone Resin, polyurethane resin, aceta System resin, cellulose - scan resin, various resins other such film or sheet - may be used and. In the present invention, among the resin films or sheets described above, a fluorine-based resin sheet, a cyclic polyolefin-based resin sheet,
It is preferable to use a polycarbonate resin sheet, a poly (meth) acrylic resin sheet, or a polyester resin sheet.

Further, in the present invention, among the various resin films or sheets as described above, especially, for example, polytetrafluoroethylene (PTFE), tetrafluoroethylene and perfluoroalkyl vinyl ether
Perfluoroalkoxy resin (PFA) comprising a copolymer with ter, tetrafluoroethylene and hexafluoropropylene copolymer (FEP), tetrafluoroethylene and perfluoroalkylvinyl ether and hexafluoropropylene copolymer (EPE), tetrafluoro Copolymer of ethylene and ethylene or propylene
(ETFE), polychlorotrifluoroethylene resin (PCTFE), copolymer of ethylene and chlorotrifluoroethylene (ECTFE), vinylidene fluoride resin (PVDF), or vinyl fluoride resin (PV
It is preferable to use a transparent fluororesin sheet made of one or more fluororesins such as F). In the present invention, among the above-mentioned fluorine-based resin sheets, in particular, a polyvinyl fluoride-based resin (PVF) or a fluorine-based resin comprising a copolymer of tetrafluoroethylene and ethylene or propylene (ETFE) Sheets have transparency and are particularly preferable from the viewpoint of sunlight permeability and the like.

In the present invention, among the various resin films or sheets described above, particularly, for example, cyclopentadiene and its derivatives, dicyclopentadiene and its derivatives, cyclohexadiene and its derivatives, Norbornadiene and its derivatives,
A polymer obtained by polymerizing a cyclic diene such as another, or one or more of a cyclic diene and an olefin-based monomer such as ethylene, propylene, 4-methyl-1-pentene, styrene, butadiene, isoprene and others; It is preferable to use a transparent cyclic polyolefin resin sheet made of a copolymer or the like obtained by copolymerizing the above. In the present invention, among the above-mentioned transparent cyclic polyolefin-based resin sheets, in particular, cyclopentadiene and derivatives thereof, dicyclopentadiene and derivatives thereof, or cyclic diene polymers such as norbornadiene and derivatives thereof may be used. A transparent cyclic polyolefin resin sheet made of a copolymer,
It is excellent in weather resistance, water resistance, etc., has transparency, and is preferable from the viewpoint of sunlight permeability and the like. Thus, in the present invention, by using the above-mentioned fluorine-based resin sheet or cyclic polyolefin-based resin sheet, the fluorine-based resin sheet or the cyclic polyolefin-based resin sheet has Excellent properties such as mechanical properties, chemical properties, optical properties, etc., specifically, various properties such as weather resistance, heat resistance, water resistance, light resistance, moisture resistance, stain resistance, chemical resistance, etc. It is a protective sheet that constitutes a solar cell by utilizing its characteristics, and thus has the same optical properties, durability, and protective functionality as conventional glass plates and the like, and its flexibility. It is lighter than a glass plate due to its mechanical properties, chemical properties, etc., and has excellent workability and the like, and has advantages such as easy handling.

In the present invention, as the film or sheet of the above-mentioned various resins, for example, one or more of the above-mentioned various resins are used, and the extrusion method, the cast molding method, the T-die method, and the cutting method are used. A method of forming the above various resins alone using a film forming method such as an inflation method, an inflation method, or the like, or a multi-layer coextrusion film forming using two or more kinds of various resins. A film or sheet of various resins is manufactured by a method of forming two or more resins, and a method of mixing and forming a film before forming a film. For example, various resin films or sheets stretched in a uniaxial or biaxial direction using a tenter method or a tuber method can be used. In the present invention, the film thickness of various resin films or sheets is 12 to 300 μm.
And more preferably about 20 to 200 μm.
In the present invention, the film or sheet of various resins has a visible light transmittance of 90% or more, preferably 95% or more, and transmits and absorbs all incident sunlight. It is desirable to have the following properties.

In the above, one or more of the above-mentioned various resins are used, and when forming the film, for example, the processability, heat resistance, weather resistance, mechanical properties, dimensional stability, Antioxidant, slippery, mold release, flame retardant,
Various plastic compounding agents and additives can be added for the purpose of improving or modifying the antifungal property, electric properties, etc., and the amount of addition can be from a very small amount to several tens%. They can be arbitrarily added according to the purpose.
In the above, common additives include, for example, lubricants, crosslinking agents, antioxidants, ultraviolet absorbers, light stabilizers, fillers, reinforcing agents, reinforcing agents, antistatic agents, flame retardants, flame retardants , 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 additives,
It is preferable to use various resin films or sheets obtained by kneading an antioxidant or an ultraviolet absorber. In the present invention, among the above-mentioned additives, it is particularly preferable to use various resin films or sheets 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.
Further, the antioxidant is one that prevents photodeterioration or thermal degradation of the polymer, for example, phenol
Antioxidants such as phenol-based, amine-based, sulfur-based, phosphoric-acid-based, and others can be used. Further, as the above-mentioned ultraviolet absorber or antioxidant, for example, the above-mentioned ultraviolet absorber such as benzophenone or the above antioxidant such as phenol is added to the main chain or side chain constituting the polymer. A polymer-type ultraviolet absorber or an antioxidant obtained by chemically bonding may also be used. The content of the above-mentioned ultraviolet absorber and / or antioxidant varies depending on the particle shape, density and the like, but is about 0.1 to 10
% By weight is preferred.

Further, in the present invention, the surface of the film or sheet made of various resins is used to improve the tight adhesion with a deposition-resistant protective film or an inorganic oxide deposited film.
If necessary, a desired surface treatment layer can be provided in advance. In the present invention, as the surface treatment layer,
For example, 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, an optional treatment such as a pretreatment, etc. A corona treatment layer, an ozone treatment layer, a plasma treatment layer, an oxidation treatment layer, and the like can be formed and provided. The above-mentioned surface pretreatment may be performed in a separate step before forming a deposition-resistant protective film or the like,
For example, in the case of a surface pre-treatment such as a low-temperature plasma treatment or a glow discharge treatment, the pre-treatment for forming the above-described evaporation-resistant protective film or the like can be performed by an in-line treatment as a pre-treatment. There is an advantage that manufacturing costs can be reduced. The above-mentioned surface pretreatment is carried out as a method for improving the tight adhesion between a film or sheet of various resins and an anti-evaporation protective film and the like. In addition, for example, a primer coat layer, an undercoat agent layer, an anchor coat agent layer, an adhesive layer, A surface treatment layer may be formed by arbitrarily forming a vapor-deposited anchor coating agent layer or the like. As the coating agent layer of the above pretreatment, for example,
Polyester resin, polyamide resin, polyurethane resin, epoxy resin, phenol resin, (meth)
Acrylic resin, polyvinyl acetate resin, polyolefin resin such as polyethylene aliha polypropylene or a copolymer or modified resin thereof, cellulose resin,
A resin composition containing other components as a main component of the vehicle can be used.

In the present invention, for example, an ultraviolet absorber and / or an antioxidant can be added to the above resin composition in order to improve light resistance and the like. The above-mentioned ultraviolet absorber absorbs the above-mentioned harmful ultraviolet rays in sunlight, converts them into harmless heat energy in the molecule, and excites the active species that initiates photodegradation in the polymer. For example, benzophenone-based,
Benzotriazole type, saltylate type, acrylonitrile type, metal complex salt type, hindered amine type, ultrafine titanium oxide (particle diameter: 0.01 to 0.06 μm) or ultrafine zinc oxide (0.01 to 0 One or more UV absorbers such as inorganic UV absorbers such as .04 μm) can be used. Examples of the antioxidant include those which prevent the aforementioned polymer from light degradation or thermal degradation, and include, for example, phenol-based, amine-based, sulfur-based, phosphoric acid-based, and other antioxidants. Can be used. Further, as the above ultraviolet absorber or antioxidant,
For example, a polymer obtained by chemically bonding the above-mentioned benzophenone-based ultraviolet absorber or the above-mentioned phenol-based antioxidant to the main chain or side chain constituting the polymer.
UV absorbers or antioxidants of the type can also be used. The content of the ultraviolet absorber and / or antioxidant varies depending on the particle shape, density and the like, but is preferably about 0.1 to 10% by weight. In the above, as a method of forming the coating agent layer, for example, a coating agent such as a solvent type, an aqueous type, or an emulsion type is used, and a roll coating method, a gravure roll coating is used. Law,
The coating can be performed by using a coating method such as a kiss coating method or the like. The coating time is determined after the film formation of the fluororesin sheet or after the biaxial stretching treatment. It can be carried out as a post-process, film formation, or in-line processing of biaxial stretching.

Next, in the present invention, a protection sheet for a solar cell module according to the present invention and an anti-evaporation protective film constituting a solar cell module using the same will be described. As will be described later, the plastic sheet is protected on one side of the above-mentioned plastic sheet against vapor deposition conditions when an inorganic oxide vapor-deposited film is formed. It suppresses deformation, deterioration or shrinkage, or cohesive failure in the surface layer or inner layer of the film, and furthermore, a vapor-deposited film of an inorganic oxide is satisfactorily formed on one surface of the plastic sheet, and the plastic In order to improve the tight adhesion between the sheet and the deposited film of the inorganic oxide, etc., the surface is preliminarily formed on one surface of the plastic sheet as a surface pretreatment layer. Thus,
In the present invention, as the above-mentioned deposition-resistant protective film, specifically, for example, a chemical vapor deposition (Chem) such as a plasma chemical vapor deposition, a thermal chemical vapor deposition, or a photochemical vapor deposition.
Ial Vapor Deposition method, CV
D method) or a physical vapor deposition method (P method) such as a vacuum evaporation method, a sputtering method, an ion plating method, or the like.
physical Vapor Deposition
, PVD method) to form a vapor-deposited thin film of an inorganic oxide, whereby a vapor-deposited protective film can be provided.

The above-mentioned chemical vapor deposition method will be described in detail. One side of a plastic sheet is formed by using a monomer gas for vapor deposition of an organic silicon compound or the like as a raw material.
Low-temperature plasma chemical vapor deposition (CVD) using an inert gas such as argon gas or helium gas as the gas, further using an oxygen gas or the like as an oxygen supply gas, and using a low-temperature plasma generator or the like. By forming a vapor-deposited thin film of an inorganic oxide such as silicon oxide using the above method, the vapor deposition-resistant protective film according to the present invention can be provided. In the above, as the low-temperature plasma generator, for example, a generator such as a high-frequency plasma, a pulse wave plasma, or a microwave plasma can be used. Thus, in the present invention, a highly active and stable plasma is obtained. For this purpose, it is desirable to use a generator using a high-frequency plasma method. Specifically, an example of the low-temperature plasma chemical vapor deposition method will be described. FIG. 7 is a schematic configuration diagram of a low-temperature plasma chemical vapor deposition apparatus showing an outline of the low-temperature plasma chemical vapor deposition method. It is. As shown in FIG. 8 described above, according to the present invention, the unwinding roll arranged in the vacuum chamber 22 of the low-temperature plasma chemical vapor deposition apparatus 21 is used.
The plastic sheet 1 is fed out from the roller 23, and the plastic sheet 1 is further conveyed onto the peripheral surface of the cooling / electrode drum 25 at a predetermined speed via the auxiliary roll 24. 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 26 and 27 and the raw material volatile supply device 28 and the like. The vacuum chamber-2 was passed through the material supply nozzle 29 while adjusting the mixed gas composition for vapor deposition consisting of
2 and then, on the plastic sheet 1 conveyed on the peripheral surface of the cooling / electrode drum 25, a glow
Plasma is generated by the discharge plasma 30 and is irradiated with the plasma to form a vapor-deposited thin film of an inorganic oxide such as silicon oxide, whereby a vapor-deposited protective layer can be formed. In the present invention, at that time, predetermined electric power is applied to the cooling / electrode drum 25 from the power supply 31 disposed outside the vacuum chamber 22. The generation of plasma is promoted by arranging the magnet 32, and then the plastic sheet 1 on which the deposited thin film of the inorganic oxide such as silicon oxide is formed is wound up through the auxiliary roll 33. It is possible to form a vapor-deposited protective film composed of a vapor-deposited thin film of an inorganic oxide such as silicon oxide by winding it around a metal layer 34. In addition, in the figure, 35 represents a vacuum pump. The above is an example of a low-temperature plasma-enhanced chemical vapor deposition method for forming a deposition-resistant protective film according to the present invention,
It goes without saying that the present invention is not limited by this.

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, in the silicon oxide deposited thin film formed as described above, a monomer gas such as an organic silicon compound and an oxygen gas chemically react, and the reaction product is formed on a plastic sheet. A thin film that is closely adhered to, dense, and has a high flexibility and the like. Generally, a general formula SiO _x (where X is
It is a continuous vapor-deposited thin film mainly composed of silicon oxide represented by 0 to 2), and further has the formula SiO _x (where X is 1) from the viewpoint of transparency, a vapor deposition-resistant protective layer, and the like. 0.3 to 1.9
Represents the number of It is preferable that the thin film is mainly composed of a silicon oxide deposited film represented by the formula (1). Further, the above-described deposited thin film of silicon oxide is made of a silicon oxide compound containing silicon and oxygen as constituent elements, and carbon, hydrogen, silicon,
Alternatively, it is composed of a vapor-deposited continuous thin film of silicon oxide containing at least one kind of a compound composed of one or more kinds of trace constituent elements composed of oxygen. Further, when the silicon oxide vapor-deposited thin film contains a compound made of carbon, the content of carbon is reduced in the depth direction of the film thickness. In the present invention, the thickness of the deposited silicon oxide thin film is a thin film, and a non-barrier film having no barrier property against water vapor gas, oxygen gas, or the like is sufficient. The film thickness is desirably less than 150 °, specifically, the film thickness is about 10 to 100 °, preferably about 20 to 80 °, and more preferably about 30 to 80 °.
About 60 ° is desirable. Thus, in the above, 150 °
As described above, specifically, 100 °, further, 80 °, and further,
When the thickness is more than 60 °, the deposition conditions and the like become severe, the plastic sheet is yellowed or deteriorated, and further, cohesive failure occurs, and it becomes difficult to form a good deposition-resistant protective film. It is not preferable because cracks and the like easily occur in the film, and if it is less than 10 °, furthermore, 30 °, or even less than 60 °, the function as a deposition-resistant protective layer is lost, and it is difficult to exhibit the effect. This is undesirable because Thus, in the present invention, for the above-mentioned evaporated silicon oxide thin film, for example, an X-ray photoelectron spectrometer (Xray Photoelectron Sp)
, Electroncopy, XPS), Secondary Ion Mass Spectrometer (Secondary Ion Mass Spe
The above-mentioned elemental analysis of a vapor-deposited thin film of an inorganic oxide such as silicon oxide is performed by using a surface analysis apparatus such as stroscopy (SIMS, SIMS) or the like and performing analysis by ion etching in the depth direction. Such physical properties can be confirmed. In the present invention, the film thickness can be measured by a fundamental parameter method using, for example, an X-ray fluorescence analyzer (model name: RIX2000 type) manufactured by Rigaku Corporation. Further, in the above, as a means for changing the thickness of the deposited thin film of the inorganic oxide such as silicon oxide, increasing the volume velocity of the deposited thin film, that is, increasing the amount of the monomer gas and the oxygen gas Or by a method of slowing down the rate of vapor deposition.

Next, the above-mentioned physical vapor deposition method will be described in more detail. As a thin film of inorganic oxide deposited by the physical vapor deposition method, specifically, for example, one surface of a plastic sheet In addition, using a metal oxide as a raw material,
A vacuum deposition method of heating and depositing the material, or an oxidation reaction deposition method of using a metal or a metal oxide as a raw material on one surface of a plastic sheet and introducing and oxidizing oxygen to deposit the material, Further, a vapor-deposited thin film of an inorganic oxide can be formed by using a plasma-assisted oxidation reaction deposition method in which an oxidation reaction is promoted by plasma. In the present invention, a specific example of a method for forming a thin film of an inorganic oxide by a physical vapor deposition method is shown in FIG. 8. FIG. 8 is a schematic configuration diagram showing an example of a roll-up type vacuum evaporation apparatus. As shown in FIG. 8, the plastic sheet 1 unwound from the unwinding roll 43 in the vacuum chamber 42 of the take-up type vacuum evaporation apparatus 41 is cooled via the guide rolls 44 and 45. It is guided to the coating drum 46. Thus, on the plastic sheet 1 guided on the cooled coating drum 46, the evaporation source 48 heated by the crucible 47, for example, metal aluminum or aluminum oxide is evaporated. Further, if necessary, oxygen gas or the like is spouted from the oxygen gas outlet 49, and while being supplied, for example, through the masks 50, 50,
A plastic film formed by depositing a thin film of an inorganic oxide such as aluminum oxide, and then forming a thin film of the inorganic oxide such as aluminum oxide in the above.
The roll 1 is sent out through guide rolls 45 'and 44' and wound up on a take-up roll 51, thereby depositing an inorganic oxide by a physical vapor deposition method as a deposition-resistant protective film according to the present invention. A thin film can be formed.

In the above description, as the thin film of the inorganic oxide, any thin film obtained by basically depositing a metal oxide can be used. 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 above-described inorganic oxide vapor-deposited thin film varies depending on the type of metal used, or the type of metal oxide, and the like. A non-barrier film having no barrier property against oxygen gas or the like is sufficient. For example, the film thickness is desirably less than 150 °, and specifically, the film thickness is about 10 to 100 °, preferably 20 °.
The angle is preferably about 80 to about 80, and more preferably about 30 to 60. Thus, in the above, when the thickness is less than 150 °, specifically, 100 °, further 80 °, and more than 60 °, the plastic sheet is yellowed or deteriorated,
Furthermore, it causes cohesive failure and the like, and it is difficult to form a satisfactory evaporation-resistant protective film. Further, cracks and the like are easily generated in the film, which is not preferable. If the angle is less than 60 °, the function as a deposition-resistant protective layer is lost, and it is difficult to achieve the effect.

In the present invention, as the deposition-resistant protective film, in the case of a deposited thin film of an inorganic oxide formed by a low-temperature plasma-enhanced chemical vapor deposition method, one surface of a plastic sheet is coated with a monomer such as an organic silicon compound. -The gas is decomposed, the decomposed product chemically reacts with oxygen gas, etc., and the reaction product adheres tightly in a molecular state, and can form a dense, flexible, etc. thin film. Smoothness, tight adhesion,
It is excellent in flexibility and the like, and is desirable as a deposition-resistant protective film.

Next, in the present invention, a deposited film of an inorganic oxide constituting a protective sheet for a solar cell module, a solar cell module and the like according to the present invention will be described. As the film, unlike the above-described deposition-resistant protective film, a film having excellent water vapor barrier properties and oxygen barrier properties capable of preventing permeation of water vapor gas, oxygen gas and the like is desirable. Thus, the deposited film of the inorganic oxide according to the present invention is, for example, the above-described physical vapor deposition method, or the chemical vapor deposition method, or a combination thereof, to form a vapor-deposited thin film of the inorganic oxide. It can be provided by forming a multilayer film composed of one or two or more layers, or a composite film composed of two or more layers of vapor-deposited thin films of different inorganic oxides. That is, in the present invention, as described above, after forming an evaporation-resistant protective film on one surface of a plastic sheet, a monomer gas for evaporation such as an organosilicon compound is formed on the evaporation-resistant protective film. Low-temperature plasma chemical vapor using an inert gas such as argon gas or helium gas as a carrier gas, oxygen gas as an oxygen supply gas, and a low-temperature plasma generator. By forming a deposited film of an inorganic oxide such as silicon oxide using a growth method (CVD method), the deposited film of an inorganic oxide according to the present invention can be provided. In the above, a low-temperature plasma generator, a specific low-temperature plasma chemical vapor deposition apparatus using a low-temperature plasma chemical vapor deposition method (FIG. 7), and materials to be used can be the same as those described above. It is. In the present invention, as described above, one surface of the plastic sheet is
After forming the deposition-resistant protective film, a metal oxide is used as a raw material, and a vacuum deposition method of heating and depositing the metal oxide on one side of the plastic sheet, After forming a vapor deposition protective film, an oxidation reaction vapor deposition method in which a metal or a metal oxide is used as a raw material and oxygen is introduced and oxidized to deposit on the vapor deposition protective film, and the oxidation reaction is further performed by plasma. The inorganic oxide deposited film according to the present invention can be provided by forming a deposited film of an inorganic oxide such as aluminum oxide by using a plasma-assisted oxidation reaction vapor deposition method or the like that supports. In the above, the roll-up type vacuum vapor deposition apparatus (FIG. 8) by the above-mentioned physical vapor deposition method, the materials to be used, and the like can be used as they are.

In the present invention, the inorganic oxide vapor-deposited film according to the present invention is one of the inorganic oxide vapor-deposited films.
Not only the layers but also a laminate of two or more layers may be used, and one or two materials may be used.
It is also possible to use a mixture of more than one kind, and to form a deposited film of an inorganic oxide mixed with different materials. For example,
In the present invention, a first layer of an inorganic oxide vapor-deposited film is first formed using the above-described low-temperature plasma chemical vapor deposition apparatus (FIG. 7), and then the inorganic oxide vapor-deposited film is similarly formed. On the film, a vapor-deposited film of an inorganic oxide is further formed, or the film is connected in series using a low-temperature plasma-enhanced chemical vapor deposition apparatus (FIG. 7) as described above, and continuously. By forming a vapor-deposited thin film of an inorganic oxide, a vapor-deposited thin film of an inorganic oxide composed of two or more multilayer films can be formed. Further, in the present invention, a first layer of an inorganic oxide vapor-deposited thin film is first formed using the above-mentioned roll-up vacuum vapor deposition apparatus (FIG. 8), and then the inorganic oxide vapor-deposited film is similarly formed. An inorganic oxide deposited thin film is further formed on the deposited thin film, or is connected in series using the above-described roll-up vacuum deposition apparatus (FIG. 8), and is continuously connected. By forming a vapor-deposited thin film of an inorganic oxide, a vapor-deposited thin film of an inorganic oxide composed of two or more multilayer films can be formed. Further, in the present invention, the solar cell module protection sheet and the solar cell module according to the present invention are provided.
For example, a composite film composed of two or more vapor-deposited thin films of different kinds of inorganic oxides by using both the above-described physical vapor deposition method and chemical vapor deposition method as a vapor-deposited film of inorganic oxide constituting Can be formed to form an inorganic oxide deposited film. Thus, when forming a composite film composed of two or more layers of the above-mentioned vapor-deposited thin films of the above-mentioned different kinds of inorganic oxides, first, a vapor-deposited protective film is formed on a plastic sheet. On the vapor-deposited protective film, a vapor-deposited film of an inorganic oxide is provided by a chemical vapor deposition method, which is dense, rich in flexibility, and can relatively prevent the occurrence of cracks. It is desirable to provide a vapor-deposited inorganic oxide film formed by physical vapor deposition on top of this to form a vapor-deposited inorganic oxide film composed of a composite film of two or more layers of different kinds of inorganic oxide vapor-deposited films It is. Of course, in the present invention, contrary to the above, after forming a deposition-resistant protective film on a plastic sheet,
First, on the deposition-resistant protective film, by physical vapor deposition,
An inorganic oxide vapor deposition film is provided, and then a dense, flexible, and relatively inorganic oxide vapor deposition film capable of relatively preventing the occurrence of cracks is provided by a chemical vapor deposition method. An inorganic oxide vapor-deposited thin film composed of a composite film of two or more oxide vapor-deposited films can also be formed.

In the present invention, the thickness of the inorganic oxide vapor deposition film according to the present invention is excellent in a water vapor barrier property, an oxygen barrier property, etc., which can prevent permeation of water vapor gas, oxygen gas and the like. The film thickness is desirably, specifically, the film thickness is desirably 150 ° or more to 4000 °, more preferably 200 ° to 2000 °, and further preferably 300 ° to 1000 °. , The film thickness is 1000 °, further 2000 °,
Further, if the thickness is more than 4000 °, cracks and the like are generated in the film, and the film tends to be inferior in water vapor barrier properties, oxygen barrier properties, and the like.
Further, if the angle is less than 200 ° or even less than 150 °, it becomes difficult to exhibit the barrier properties such as the water vapor barrier property and the oxygen barrier property. In the present invention, in order to form a vapor-deposited film of an inorganic oxide having the above-described film thickness, by changing the vapor deposition conditions and the like when forming the above-described vapor deposition-resistant protective film, a vapor-deposited film of an inorganic oxide is formed. To form. For example, by changing the amount of an evaporation monomer such as an organic silicon compound as an evaporation material, or the amount of an evaporation material such as a metal or a metal oxide, an evaporation speed or an evaporation time, a degree of vacuum, and the like, the conditions described above are changed. In this case, an inorganic oxide vapor-deposited film having a thickness larger than the thickness of the vapor-deposited protective film is formed.

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

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

Next, in the present invention, the solar cell module
A solar cell element as a photovoltaic element constituting a cell will be described. As such a solar cell element, a conventionally known solar cell element, 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, in the present invention, a thin-film polycrystalline silicon solar cell element, a thin-film microcrystalline silicon solar cell element, a hybrid element of a thin-film crystalline silicon solar cell element and an amorphous solar cell element, and the like 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. One or more resins such as an acid-modified polyolefin resin modified with a saturated carboxylic acid, a polyvinyl butyral resin, a silicone resin, an epoxy resin, a (meth) acrylic resin, and the like. Mixtures can be used. In the present invention, in order to improve the heat resistance, light resistance, weather resistance such as water resistance, etc. of the resin constituting the above-mentioned filler layer, in a range where the transparency is not impaired, for example, crosslinking is performed. Additives such as an agent, a thermal antioxidant, a light stabilizer, an ultraviolet absorber, a photooxidant, and the like can be arbitrarily added and mixed. The thickness of the filler layer is 200 to
About 1000 μm, more preferably 350 to 600 μm
Position is desirable.

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, in the present invention, a method for manufacturing a solar cell module using the above-mentioned materials will be described. Using the protection sheet for a solar cell module according to (1) as a front protection sheet for the solar cell module or a back protection sheet for the solar cell module;
For example, the surface of the deposited thin film of the inorganic oxide of the surface protection sheet for a solar cell module according to the present invention is directed to the inside,
A filler layer, a solar cell element as a photovoltaic element, a filler layer, a back surface protection sheet layer for a normal solar cell module, and the like are sequentially laminated, and further, if necessary, between each layer. In addition, arbitrarily laminated other materials, and then, these
A solar cell module can be manufactured by using a normal molding method such as a lamination method in which the layers are integrated by vacuum suction or the like and heat-pressed, and the above-described layers are formed into an integrally formed body by thermo-compression bonding. In the above, if necessary, (meth) acrylic resin,
A heat-melt adhesive, a solvent-based adhesive, a photo-curable adhesive, or the like containing a resin such as an olefin-based resin, a vinyl-based resin, or the like as a main component of the vehicle can be used. Further, in the above-mentioned lamination, on each lamination facing surface, in order to improve the tight adhesion, if necessary, for example, corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas or nitrogen gas, Pretreatment such as glow discharge treatment, oxidation treatment using a chemical agent, or the like, or the like can be optionally performed. Further, in the above lamination,
A primer coating layer, an undercoat agent layer, an adhesive layer, an anchor coating agent layer, or the like is arbitrarily formed in advance on each of the laminated opposing surfaces, and surface pretreatment is performed. You can also. Examples of the coating agent layer for the above pretreatment include polyester resin, polyamide resin, polyurethane resin, epoxy resin, phenol resin, (meth) acrylic resin, polyvinyl acetate resin, A resin composition containing, as a main component of the vehicle, a polyolefin resin such as polyethylene aliha polypropylene or a copolymer or modified resin thereof, a cellulose resin, or the like can be used. In the above, as a method for forming the coating agent layer, for example, a coating agent such as a solvent type, an aqueous type, or an emulsion type is used, and a roll coating method, a gravure roll coating is used. The coating can be performed by using a coating method such as a method, a kiss coating method, or the like.

[0034]

EXAMPLES The present invention will be described more specifically below with reference to examples. Example 1 (1). A 50 μm thick polyvinyl fluoride resin sheet (PVF) was used, which was mounted on a delivery roll of a plasma-enhanced chemical vapor deposition apparatus. Formed on the treated surface, an anti-evaporation protective film was provided. (Evaporation conditions) Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 5: 5: 5 (unit: slm) Degree of vacuum in vacuum chamber: 7.0 × 10 ⁻⁶ mbar In evaporation chamber Degree of vacuum: 3.8 × 10 ^-2 mbar Cooling / electrode drum supply power: 15 kW Sheet transfer speed: 100 m / min (2). Next, the thickness of 50 μm provided with the above-described evaporation-resistant protective film.
m, a polyvinyl fluoride resin film (PVF) was mounted on a delivery roll of a plasma-enhanced chemical vapor deposition apparatus in the same manner as described above. The film was formed on the surface of the above-mentioned polyvinyl fluoride resin film having a vapor-proof protective 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 transfer speed: 80 m / min. Immediately after the deposition, the surface of the deposited silicon oxide film was subjected to corona discharge treatment at an output of 10 kW and at a processing speed of 100 m / min to increase the surface tension of the deposited film surface from 35 dyne to 60 dyne. Was formed to produce a protective sheet for a solar cell module according to the present invention. (3). Next, the protective sheet for a solar cell module produced above was used as a surface protective sheet for a solar cell module, and a 400 μm-thick ethylene film was formed on the corona-treated surface of the silicon oxide vapor deposition film. -Biaxially stretched polyethylene terephthalate having a thickness of 38 µm and having solar cell elements made of vinyl acetate copolymer sheet and amorphous silicon arranged in parallel.
A film, a 400 μm-thick ethylene-vinyl acetate copolymer sheet, and a 50 μm-thick biaxially stretched polyethylene terephthalate film, with the solar cell element surface facing upward, an acrylic resin adhesive The solar cell module according to the present invention was manufactured by laminating through the layers. (4). In the above, a fluororesin sheet (ETFE) made of ethylene-tetrafluoroethylene copolymer having a thickness of 50 μm is used in place of the above-mentioned 50 μm-thick polyvinyl fluoride resin sheet (PVF) as the base material. )
In the same manner as described above, the same surface protection sheet and solar cell module according to the present invention could be produced.

Embodiment 2 (1). A 50 μm-thick polyvinyl fluoride resin sheet provided with the anti-evaporation protective film produced in Example 1 above was used, and it was mounted on a delivery roll of a take-up type vacuum evaporator. On a coating drum, and using aluminum as a deposition source under the following conditions,
Electron beam (EB) while supplying oxygen gas
By a reactive vacuum deposition method using a heating method, a film thickness of 800
An aluminum oxide vapor-deposited film was formed. (Evaporation conditions) Evaporation source: Aluminum Degree of vacuum in vacuum chamber: 7.5 × 10 ⁻⁶ mbar Degree of vacuum in evaporation chamber: 2.1 × 10 ⁻⁶ mbar EB output: 40 KW Film transport speed: 600 m / Next, about the polyvinyl fluoride resin film on which the aluminum oxide vapor-deposited film having a film thickness of 800 ° was formed as described above, immediately after the vapor deposition, the aluminum oxide vapor-deposited film surface was coated with a plasma using a glow discharge plasma generator. Output, 1
500 W, oxygen gas (O ₂ ): argon gas (Ar) =
Using a mixed gas of 19: 1, a mixed gas pressure of 6 × 1
A plasma treated surface is formed by performing oxygen / argon mixed gas plasma treatment at a processing speed of 420 m / min at 0 ^-5 Tool, thereby forming a protective sheet for a solar cell module according to the present invention.
Manufactured. (2). Next, the protective sheet for a solar cell module produced above was used as a surface protective sheet for a solar cell module, and a 400 μm-thick ethylene film was deposited on the plasma-treated surface of the deposited aluminum oxide thin film. A 38 μm-thick biaxially stretched polyethylene terephthalate film in which solar cell elements made of a vinyl acetate copolymer sheet and amorphous silicon are arranged in parallel, ethylene having a thickness of 400 μm
Vinyl acetate copolymer sheet and 50 μm thick 2
The solar cell module according to the present invention was manufactured by laminating an axially stretched polyethylene terephthalate film with the solar cell element surface facing upward via an adhesive layer of an acrylic resin. (3). In the above, a fluororesin sheet (ETFE) made of ethylene-tetrafluoroethylene copolymer having a thickness of 50 μm is used in place of the above-mentioned 50 μm-thick polyvinyl fluoride resin sheet (PVF) as the base material. )
In 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.

Embodiment 3 (1). A 50 μm-thick polyvinyl fluoride resin sheet (PV) on which a deposition-resistant protective film produced in Example 1 was formed.
F), which was mounted on a delivery roll of a plasma-enhanced chemical vapor deposition apparatus, and under the following conditions, a vapor-deposited silicon oxide film having a thickness of 500.degree. It was formed on the film surface. (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 Next, a 500-nm-thick silicon oxide evaporation film was formed as described above. Immediately after the deposition of the polyvinyl fluoride resin sheet, a corona discharge treatment was performed on the surface of the deposited silicon oxide film at an output of 10 kW and at a processing speed of 100 m / min, and the surface tension of the deposited film surface was changed from 35 dyne to 60 dyne. And a corona treated surface was formed. (2). Next, using a polyvinyl fluoride resin sheet on which a silicon oxide vapor-deposited film subjected to the corona treatment was formed,
This was mounted on a delivery roll of a take-up type vacuum evaporation apparatus, and then was unwound onto a coating drum. Under the following conditions, aluminum was used as an evaporation source and oxygen gas was supplied. A reactive vacuum deposition method using an electron beam (EB) heating method was used to apply a corona-treated surface of the deposited film of silicon oxide on the polyvinyl fluoride resin sheet to
A deposited film of aluminum oxide having a thickness of 500 ° was formed. (Evaporation conditions) Evaporation source: Aluminum Degree of vacuum in vacuum chamber: 7.5 × 10 ⁻⁶ mbar Degree of vacuum in evaporation chamber: 2.1 × 10 ⁻⁶ mbar EB output: 40 KW Film transport speed: 600 m / Next, immediately after the vapor deposition of the polyvinyl fluoride resin sheet on which the aluminum oxide vapor-deposited film having a film thickness of 500 ° was formed, a glow discharge plasma generator was used on the aluminum oxide vapor-deposited film surface. , Plasma power, 15
00 W, oxygen gas (O ₂ ): argon gas (Ar) = 1
9: 1 mixed gas, mixed gas pressure 6 × 10
^The protective sheet for a solar cell module according to the present invention was manufactured by performing oxygen / argon mixed gas plasma processing at a processing speed of 420 m / min at ^-5 Tool. (3). Next, the protective sheet for a solar cell module produced above was used as a surface protective sheet for a solar cell module, and a 400 μm-thick ethylene film was deposited on the plasma-treated surface of the deposited aluminum oxide thin film. A 38 μm-thick biaxially stretched polyethylene terephthalate film in which solar cell elements made of a vinyl acetate copolymer sheet and amorphous silicon are arranged in parallel, ethylene having a thickness of 400 μm
Vinyl acetate copolymer sheet and 50 μm thick 2
The solar cell module according to the present invention was manufactured by laminating an axially stretched polyethylene terephthalate film with the solar cell element surface facing upward via an adhesive layer of an acrylic resin. (4). In the above, instead 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 ethylene-kneaded kneaded ultraviolet absorber was used. Fluorinated resin sheet made of tetrafluoroethylene copolymer (ETF
Using E), the same surface protection sheet and solar cell module according to the present invention could be produced in exactly the same manner as described above.

Embodiment 4 (1). A 50 μm thick polyvinyl fluoride resin sheet (PVF) was used, which was mounted on a delivery roll of a take-up type vacuum evaporation apparatus, and then fed out onto a coating drum. Then, while using aluminum as a deposition source and supplying oxygen gas,
A vapor-deposited thin film of aluminum oxide having a thickness of 50 ° was formed on the surface of the above-mentioned polyvinyl fluoride resin sheet which had been easily vapor-deposited by a reactive vacuum vapor deposition method using a heating (EB) heating method, and a vapor deposition-resistant protective film was provided. . (Evaporation conditions) Evaporation source: Aluminum Degree of vacuum in vacuum chamber: 7.5 × 10 ⁻⁶ mbar Degree of vacuum in evaporation chamber: 2.1 × 10 ⁻⁶ mbar EB output: 20 KW Film transport speed: 500 m / Minutes (2). Next, the thickness of 50 μm provided with the above-described evaporation-resistant protective film.
Then, in the same manner as in (2) of Example 2 described above, a film thickness of 8 was obtained by a reactive vacuum evaporation method using an electron beam (EB) heating method, using a polyvinyl fluoride resin sheet having a thickness of 8 m.
A protective film for a solar cell module according to the present invention is manufactured by forming a deposited film of aluminum oxide with a thickness of 00 ° and performing a plasma treatment on the surface of the deposited film of aluminum oxide to form a plasma-treated surface. did. (3). Next, the protective sheet for a solar cell module produced above was used as a surface protective sheet for a solar cell module, and a 400 μm-thick ethylene film was deposited on the plasma-treated surface of the deposited aluminum oxide thin film. A 38 μm-thick biaxially stretched polyethylene terephthalate film in which solar cell elements made of a vinyl acetate copolymer sheet and amorphous silicon are arranged in parallel, ethylene having a thickness of 400 μm
Vinyl acetate copolymer sheet and 50 μm thick 2
The solar cell module according to the present invention was manufactured by laminating an axially stretched polyethylene terephthalate film with the solar cell element surface facing upward via an adhesive layer of an acrylic resin. (4). In the above, a fluororesin sheet (ETFE) made of ethylene-tetrafluoroethylene copolymer having a thickness of 50 μm is used in place of the above-mentioned 50 μm-thick polyvinyl fluoride resin sheet (PVF) as the base material. )
In 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.

Embodiment 5 (1). Using a polyvinyl fluoride resin sheet having a thickness of 50 μm provided with an anti-evaporation protective film manufactured in Example 4 above, the surface of the anti-evaporation protective film was coated with the (2) of Example 2 above.
In the same manner as described above, a 500-mm-thick aluminum oxide vapor-deposited film was formed by a reactive vacuum vapor deposition method using an electron beam (EB) heating method, and a plasma-treated surface was further formed. Further, in the same manner as in (2) of Example 2 above, a 500-nm-thick aluminum oxide deposited film was similarly formed on the plasma-treated surface of the 500-mm-thick aluminum oxide-deposited film formed above. Further, a plasma-treated surface was formed to produce a protective sheet for a solar cell module according to the present invention comprising a two-layer aluminum oxide film. (2). Next, the protective sheet for a solar cell module produced above was used as a surface protective sheet for a solar cell module, and a 400 μm-thick ethylene film was deposited on the plasma-treated surface of the deposited aluminum oxide thin film. A 38 μm-thick biaxially stretched polyethylene terephthalate film in which solar cell elements made of a vinyl acetate copolymer sheet and amorphous silicon are arranged in parallel, ethylene having a thickness of 400 μm
Vinyl acetate copolymer sheet and 50 μm thick 2
The solar cell module according to the present invention was manufactured by laminating an axially stretched polyethylene terephthalate film with the solar cell element surface facing upward via an adhesive layer of an acrylic resin. (3). In the above, a fluororesin sheet (ETFE) made of ethylene-tetrafluoroethylene copolymer having a thickness of 50 μm is used in place of the above-mentioned 50 μm-thick polyvinyl fluoride resin sheet (PVF) as the base material. )
In the same manner as described above, the same surface protection sheet and solar cell module according to the present invention could be produced.

Embodiment 6 (1). Using a 50 μm thick polyvinyl fluoride resin sheet provided with an anti-evaporation protective film produced in Example 1 above, the same as (2) of Example 1 above on the surface of the anti-evaporation protective film. Then, a vapor-deposited silicon oxide film having a thickness of 500 ° was formed, and a corona-treated surface was further formed. Further, in the same manner as in (2) of Example 1 described above, the film thickness
Similarly, on the corona-treated surface of the silicon oxide vapor-deposited film, a 500-nm-thick silicon oxide vapor-deposited film is formed, and further, a corona-treated surface is formed to form a two-layer silicon oxide vapor-deposited film. A protection sheet for a solar cell module according to the invention was manufactured. (2). Next, the protective sheet for a solar cell module manufactured above was used as a surface protective sheet for a solar cell module, and a 400 μm-thick ethylene film was coated on the corona-treated surface of the silicon oxide vapor-deposited thin film. A vinyl acetate copolymer sheet,
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 terephthalate film was laminated with the solar cell element surface facing upward via an adhesive layer of an acrylic resin to produce a solar cell module according to the present invention. (3). In the above, a fluororesin sheet (ETFE) made of ethylene-tetrafluoroethylene copolymer having a thickness of 50 μm is used in place of the above-mentioned 50 μm-thick polyvinyl fluoride resin sheet (PVF) as the base material. )
In the same manner as described above, the same surface protection sheet and solar cell module according to the present invention could be produced.

Embodiment 7 (1). The protection sheet for a solar cell module manufactured in Example 1 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 having a thickness of 400 μm and amorphous silicon arranged in parallel on a corona-treated surface of a silicon oxide vapor-deposited film of a surface protection sheet for use with a thickness of 38 μm; Biaxially stretched polyethylene terephthalate film, thickness 400μ
m, an ethylene-vinyl acetate copolymer sheet, and a back surface protection sheet for a solar cell module as described above, wherein the corona-treated surface of the silicon oxide vapor-deposited film is opposed to the solar cell element. The solar cell module according to the present invention was manufactured by laminating with an acrylic resin adhesive layer facing upward. (2). In the above, a fluororesin sheet (ETFE) made of ethylene-tetrafluoroethylene copolymer having a thickness of 50 μm is used in place of the above-mentioned 50 μm-thick polyvinyl fluoride resin sheet (PVF) as the base material. )
In the same manner as described above, the same surface protection sheet and solar cell module according to the present invention could be produced.

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. 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 a plasma-treated surface of an aluminum oxide vapor-deposited film of a surface protection sheet for sealing;
m, a biaxially stretched polyethylene terephthalate film, a 400 μm-thick ethylene-vinyl acetate copolymer sheet,
An acrylic resin adhesive is provided on the back surface protection sheet for a solar cell module, with the plasma-treated surface of the aluminum oxide vapor-deposited film facing the solar cell element surface facing upward. The solar cell module according to the present invention was manufactured by laminating through the layers. (2). In the above, a fluororesin sheet (ETFE) made of ethylene-tetrafluoroethylene copolymer having a thickness of 50 μm is used in place of the above-mentioned 50 μm-thick polyvinyl fluoride resin sheet (PVF) as the base material. )
In the same manner as described above, the same surface protection sheet and solar cell module according to the present invention could be produced.

Embodiment 9 (1). The protection sheet for a solar cell module manufactured in Example 3 above 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 plasma-treated surface of the deposited aluminum oxide thin film of the surface protection sheet for sealing;
μm biaxially stretched polyethylene terephthalate film,
400 μm thick ethylene-vinyl acetate copolymer sheath
And a back surface protection sheet for the solar cell module described above.
The solar cell according to the present invention is stacked with the plasma-treated surface of the vapor-deposited thin film of aluminum oxide facing and the solar cell element surface facing upward, with an adhesive layer of an acrylic resin interposed therebetween. Modules were manufactured. (2). In the above, instead 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 ethylene-kneaded kneaded ultraviolet absorber was used. Fluorinated resin sheet made of tetrafluoroethylene copolymer (ETF
Using E), the same surface protection sheet and solar cell module according to the present invention could be produced in exactly the same manner as described above.

Embodiment 10 (1). The protection sheet for a solar cell module manufactured in Example 4 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 a plasma-treated surface of a deposited thin film of aluminum oxide as a surface protection sheet for sealing.
μm biaxially stretched polyethylene terephthalate film,
400 μm thick ethylene-vinyl acetate copolymer sheath
And a back surface protection sheet for the solar cell module described above.
The solar cell according to the present invention is stacked with the plasma-treated surface of the vapor-deposited thin film of aluminum oxide facing and the solar cell element surface facing upward, with an adhesive layer of an acrylic resin interposed therebetween. Modules were manufactured. (2). In the above, a fluororesin sheet (ETFE) made of ethylene-tetrafluoroethylene copolymer having a thickness of 50 μm is used in place of the above-mentioned 50 μm-thick polyvinyl fluoride resin sheet (PVF) as the base material. )
In the same manner as described above, the same surface protection sheet and solar cell module according to the present invention could be produced.

Embodiment 11 (1). The protection sheet for a solar cell module manufactured in 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 a plasma-treated surface of a deposited thin film of aluminum oxide as a surface protection sheet for sealing.
μm biaxially stretched polyethylene terephthalate film,
400 μm thick ethylene-vinyl acetate copolymer sheath
And a back surface protection sheet for the solar cell module described above.
The solar cell according to the present invention is stacked with the plasma-treated surface of the vapor-deposited thin film of aluminum oxide facing and the solar cell element surface facing upward, with an adhesive layer of an acrylic resin interposed therebetween. Modules were manufactured. (2). In the above, a fluororesin sheet (ETFE) made of ethylene-tetrafluoroethylene copolymer having a thickness of 50 μm is used in place of the above-mentioned 50 μm-thick polyvinyl fluoride resin sheet (PVF) as the base material. )
In the same manner as described above, the same surface protection sheet and solar cell module according to the present invention could be produced.

Embodiment 12 (1). The protection sheet for a solar cell module manufactured in Example 6 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 having a thickness of 400 μm and amorphous silicon arranged in parallel on a corona-treated surface of a silicon oxide vapor deposited film of a surface protection sheet for sealing, a thickness of 38 μm; Biaxially stretched polyethylene terephthalate film, thickness 400μ
m, an ethylene-vinyl acetate copolymer sheet, and a back surface protection sheet for a solar cell module as described above, wherein the corona-treated surface of the silicon oxide vapor-deposited film is opposed to the solar cell module. The solar cell module according to the present invention is laminated with the element surface facing upward via an adhesive layer of an acrylic resin.
Manufactured. (2). In the above, a fluororesin sheet (ETFE) made of ethylene-tetrafluoroethylene copolymer having a thickness of 50 μm is used in place of the above-mentioned 50 μm-thick polyvinyl fluoride resin sheet (PVF) as the base material. )
In the same manner as described above, the same surface protection sheet and solar cell module according to the present invention could be produced.

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 a backside protective sheet for a solar cell module as described above, wherein the corona-treated surface of the silicon oxide vapor-deposited film is opposed, and the solar cell element surface is faced up with an acrylic resin. To form a solar cell module according to the present invention. (2). In the above, a fluororesin sheet (ETFE) made of ethylene-tetrafluoroethylene copolymer having a thickness of 50 μm is used in place of the above-mentioned 50 μm-thick polyvinyl fluoride resin sheet (PVF) as the base material. )
In the same manner as described above, the same surface protection sheet and solar cell module according to the present invention could be produced.

Embodiment 14 (1). The protective sheet for a solar cell module manufactured in Example 2 above was used as a back surface protective sheet for a solar cell module, and a 50 μm thick polyvinyl fluoride resin sheet was used.
38 μm thick biaxially stretched polyethylene terephthalate film in which solar cell elements made of PVF, a 400 μm thick ethylene-vinyl acetate copolymer sheet, and amorphous silicon are arranged in parallel, 400 μm thick ethylene -The vinyl acetate copolymer sheet and the backside protection sheet for a solar cell module described above, with the plasma-treated surface of the aluminum oxide vapor-deposited film facing up and the solar cell element surface facing upward; Toward the solar cell module according to the present invention by laminating via an adhesive layer of an acrylic resin.
Manufactured. (2). In the above, a fluororesin sheet (ETFE) made of ethylene-tetrafluoroethylene copolymer having a thickness of 50 μm is used in place of the above-mentioned 50 μm-thick polyvinyl fluoride resin sheet (PVF) as the base material. )
In the same manner as described above, the same surface protection sheet and solar cell module according to the present invention could be produced.

Embodiment 15 (1). The protective sheet for a solar cell module manufactured in Example 3 was used as a back surface protective sheet for a solar cell module, and was a 50 μm thick polyvinyl fluoride resin sheet.
38 μm thick biaxially stretched polyethylene terephthalate film in which solar cell elements made of PVF, 400 μm thick ethylene-vinyl acetate copolymer sheet and amorphous silicon are arranged in parallel, 400 μm thick ethylene -The vinyl acetate copolymer sheet and the backside protection sheet for a solar cell module described above, with the plasma-treated surface of the vapor-deposited thin film of aluminum oxide facing the solar cell element surface and the solar cell element surface facing 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, a fluororesin sheet (ETFE) made of ethylene-tetrafluoroethylene copolymer having a thickness of 50 μm is used in place of the above-mentioned 50 μm-thick polyvinyl fluoride resin sheet (PVF) as the base material. )
In the same manner as described above, the same surface protection sheet and solar cell module according to the present invention could be produced.

Examples 16 to 19 Instead of using the polyvinyl fluoride resin sheet (PVF) having a thickness of 50 μm in the above-mentioned Example 1, the plastic sheets shown in the following Examples 16 to 19 were used. And
Other than that, the surface protection sheet and the solar cell module according to the present invention could be manufactured in the same manner as in Example 1 described above. Embodiment 16 FIG. Polydicyclopentadiene resin sheet having a thickness of 100 μm. Polycarbonate resin sheet having a thickness of 100 μm. Polyacrylic resin sheet having a thickness of 100 μm. 100 μm thick polyethylene terephthalate resin sheet

Examples 20 to 23 Instead of using a polyvinyl fluoride resin sheet (PVF) having a thickness of 50 μm in the above Example 2, a plastic sheet shown in the following Examples 20 to 23 was used. And
Except for this, the surface protection sheet and the solar cell module according to the present invention were produced in the same manner as in Example 2 described above. Embodiment 20 FIG. Polydicyclopentadiene resin sheet having a thickness of 100 μm. Polycarbonate resin sheet having a thickness of 100 μm. Polyacryl resin sheet having a thickness of 100 μm. 100 μm thick polyethylene terephthalate resin sheet

Comparative Example 1 A glass plate having a thickness of 3 mm was used as a base material for a solar cell module.
And a solar cell element composed of an ethylene-vinyl acetate copolymer sheet and amorphous silicon having a thickness of 400 μm arranged in parallel on one surface of the sheet. A 38 μm biaxially stretched polyethylene terephthalate film, a 400 μm thick ethylene-vinyl acetate copolymer sheet, and a 50 μm thick biaxially stretched polyethylene terephthalate film were placed with their solar cell element surfaces facing up. In this way, the solar cell module was manufactured by laminating 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.
Having a thickness of 3 in which solar cell elements made of ethylene-vinyl acetate copolymer sheet and amorphous silicon are arranged in parallel.
An 8-μm biaxially oriented polyethylene terephthalate film, a 400 μm-thick ethylene-vinyl acetate copolymer sheet, and a 50 μm-thick biaxially oriented polyethylene terephthalate film were placed with their solar cell element surfaces facing up. In this way, a solar cell module was manufactured by laminating through an adhesive layer of an acrylic resin.

Comparative Example 3 As a substrate, a polydicyclopentadiene resin sheet having a thickness of 100 μm was used as a surface protection sheet for a solar cell module.
Having a thickness of 3 in which solar cell elements made of ethylene-vinyl acetate copolymer sheet and amorphous silicon are arranged in parallel.
An 8-μm biaxially oriented polyethylene terephthalate film, a 400 μm-thick ethylene-vinyl acetate copolymer sheet, and a 50 μm-thick biaxially oriented polyethylene terephthalate film were placed with their solar cell element surfaces facing up. In this way, a solar cell module was manufactured by laminating through an adhesive layer of an acrylic resin.

Comparative Example 4 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 backside protection sheet for a solar cell module, and one of them is a 50 μm thick polyvinyl fluoride resin sheet. On the (PVF) surface, ethylene-400 μm thick
38 μm-thick biaxially stretched polyethylene terephthalate film having a thickness of 38 μm, in which solar cell elements made of a vinyl acetate copolymer sheet and amorphous silicon are arranged in parallel, a thickness of 400
μm ethylene-vinyl acetate copolymer sheet, and
The other 50 μm-thick polyvinyl fluoride resin sheet (P
VF) is laminated with an adhesive layer of an acrylic resin, with the solar cell element surface facing upward, to form a solar cell module.
Manufactured.

Comparative Example 5 As a substrate, a polydicyclopentadiene resin sheet having a thickness of 100 μm was used as a surface protection sheet for a solar cell module and a backside protection sheet for a solar cell module. Then, on one side of the polydicyclopentadiene resin sheet having a thickness of 100 μm,
38 μm-thick biaxially stretched polyethylene terephthalate film having a thickness of 38 μm, in which solar cell elements made of a vinyl acetate copolymer sheet and amorphous silicon are arranged in parallel, a thickness of 400
μm ethylene-vinyl acetate copolymer sheet, and
The other 100 μm-thick polydicyclopentadiene resin sheet is laminated via an adhesive layer of an acrylic resin, with the solar cell element surface facing upward, to form a solar cell module.
Manufactured.

Experimental Example The total light transmittance of the protective sheets according to the present invention produced in Examples 1 to 23 and the protective sheets according to Comparative Examples 1 to 5 was measured. Solar cell module evaluation tests were performed on the solar cell modules manufactured in Examples 1 to 23 and the solar cell modules manufactured in Comparative Examples 1 to 5. (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 23 and the protective sheets according to Comparative Examples 1 to 5. The total light transmittance (%) was measured according to-. (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 23 and the protective sheets according to Comparative Examples 1 to 5 at a temperature of 40 ° C and a humidity of 90. % RH, measured with a measuring instrument (model name, PERMATRAN) manufactured by MOCON, USA. Measuring instrument manufactured by MOCON, USA [model name: OXTRAN] under conditions of ° C and humidity of 90% RH
Was measured. The results of the above measurements are shown in Table 1 below.

[0057] In Table 1 above, the water vapor barrier is [g / m ² / d
ay · 40 ° C. · 100% RH], and the oxygen barrier 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 23 have a high total light transmittance, a water vapor barrier property, and an oxygen barrier. Excellent barrier properties. Further, the first embodiment described above
The solar cell modules using the solar cell module protective sheets according to any one of Examples to 23 had a low output reduction rate. On the other hand, the protective sheets for solar cell modules according to Comparative Examples 1 to 5 have high total light transmittance, but low water vapor barrier properties and oxygen barrier properties, and are therefore manufactured using them. The resulting solar cell module has problems such as a high output reduction rate.

[0059]

As is apparent from the above description, the present invention
First, using a plastic sheet as a base sheet,
On one surface thereof, in advance, a non-barrier inorganic oxide vapor-deposited thin film made of silicon oxide, aluminum oxide, or the like is provided, and this is used as a vapor-proof protective film.
A protective sheet for a solar cell module is manufactured by providing a transparent film made of a glassy material such as silicon oxide or aluminum oxide and having an excellent water vapor barrier property, an excellent oxygen barrier property and the like. The protection sheet for a solar cell module is used as a surface protection sheet for a solar cell module or a back surface protection sheet for a solar cell module,
For example, the filler layer, a solar cell element as a photovoltaic element, a filler layer, and a normal solar cell may be formed such that the surface of the inorganic oxide deposited film of the surface protection sheet for a solar cell module is on the inside. A solar cell module is manufactured using a lamination method or the like in which a back surface protection sheet layer for a battery module and the like are sequentially laminated, and then these are integrally vacuum-sucked and heated and pressed. , Excellent sunlight permeability, and excellent strength,
Furthermore, it is excellent in various properties such as weather resistance, heat resistance, water resistance, light resistance, wind pressure resistance, hail resistance, chemical resistance, moisture resistance, stain resistance, etc. Remarkably improved moisture resistance, minimized its long-term performance degradation, and stably manufactures a highly durable, excellent protective ability, lower cost and safer solar cell module. That you can do.

[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 low-temperature plasma-enhanced 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.

FIG. 8 is a schematic configuration diagram of a roll-up type vacuum deposition apparatus showing an outline of a method of forming a deposited thin film of an inorganic oxide by a physical 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 Plastic sheet 2 Deposition resistant protective film 3 Inorganic oxide deposited film 3b inorganic oxide deposited film 4 multilayer film 5 composite membrane T solar cell module of the deposited film 3a inorganic oxides - Le T ₁ solar cell module - Le T ₂ solar cell module - le 11 solar cell module - surface for Le Protective sheet 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-Kaga-cho, Shinjuku-ku, Tokyo Inside Nippon Printing Co., Ltd. (72) Inventor Kazuyuki Takasawa 1-chome, Ichigaya-cho, Shinjuku-ku, Tokyo No. 1 Dai Nippon Printing Co., Ltd. F-term (reference) 5F051 BA14 BA18 EA01 EA18 JA05

Claims (16)

[Claims] 1. A solar cell module, comprising: a protective sheet on one side of a plastic sheet; and a vapor-deposited inorganic oxide layer on the protective layer. -Protective sheet for the tool. 2. A protective sheet for a solar cell module, wherein a protective film is provided on one side of a plastic sheet, and a vapor-deposited inorganic oxide film is provided on the protective film. A protection sheet for a solar cell module, comprising a sheet. 3. A backside protection for a solar cell module by providing a deposition-resistant protective film on one surface of a plastic sheet, and further providing an inorganic oxide deposited film on the deposition-resistant protective film. A protection sheet for a solar cell module, comprising a sheet. 4. A plastic 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 plastic sheet contains an ultraviolet absorber and / or an antioxidant. 6. A plastic sheet comprising a fluorine resin sheet, a cyclic polyolefin resin sheet, a polycarbonate resin sheet, and a poly (meth) acrylic resin sheet.
The protection sheet for a solar cell module according to any one of claims 1 to 5, wherein the protection sheet comprises a sheet or a polyester resin sheet. 7. The solar cell module according to claim 1, wherein the deposition-resistant protective thin film comprises a deposited thin film of an inorganic oxide formed by a chemical vapor deposition method or a physical vapor deposition method. Protection sheet. 8. The protection sheet for a solar cell module according to claim 1, wherein the deposition-resistant protective thin film comprises an inorganic oxide deposited thin film formed by a plasma enhanced chemical vapor deposition method. 9. The protection sheet for a solar cell module according to claim 1, wherein the deposition-resistant protective thin film comprises a silicon oxide deposited thin film by a plasma chemical vapor deposition method. 10. The anti-evaporation protective thin film comprises a silicon oxide compound having silicon and oxygen as constituent elements, and the silicon oxide compound further contains at least one of carbon or hydrogen as a trace constituent element. The protection sheet for a solar cell module according to any one of claims 1 to 9, characterized by containing the following element. 11. The deposition-resistant protective thin film has a thickness of 10 ° or more.
2. The method of claim 1, wherein the angle is less than 150 degrees.
10. The protection sheet for a solar cell module according to any one of items 10 to 10. 12. The inorganic oxide vapor-deposited film is composed of one or two or more multilayers of inorganic oxide vapor-deposited films or a composite film of two or more inorganic oxide vapor-deposited films. The protection sheet for a solar cell module according to any one of claims 1 to 11, characterized in that: 13. An inorganic oxide deposited film having a thickness of 150 °
The protection sheet for a solar cell module according to any one of claims 1 to 12, wherein the protection sheet has a thickness of not more than 4,000 °. 14. A solar cell module comprising a plastic sheet provided with an anti-evaporation protective film on one surface, and an inorganic oxide evaporative film provided on the anti-evaporation protective film. A filler layer on the surface of the deposited inorganic oxide film of the surface protection sheet,
A solar cell element as a photovoltaic element, a filler layer, and a backside protection sheet layer for a solar cell module are sequentially laminated, and these are vacuum-suctioned and integrally formed by a heat compression lamination method or the like. A solar cell module having a body. 15. A surface protection seal for a solar cell module.
A filler layer, a solar cell element as a photovoltaic element, a filler layer, and a vapor-proof protective film provided on one surface of a plastic sheet, and further on the vapor-proof protective film, A back surface protection sheet for a solar cell module comprising an inorganic oxide vapor-deposited film is sequentially laminated with the inorganic oxide vapor-deposited film surfaces facing each other. -A solar cell module characterized by being made into an integrally formed body by a method such as a method. 16. A solar cell module comprising a plastic sheet provided with a deposition-resistant protective film on one surface thereof, and further provided with an inorganic oxide deposited film on the deposition-resistant protective film. A filler layer on the surface of the deposited inorganic oxide film of the surface protection sheet,
A solar cell element as a photovoltaic element, a filler layer, and a vapor-deposited protective film provided on one surface of a plastic sheet, and a vapor-deposited inorganic oxide film on the vapor-deposited protective film. Back protection sheet for solar cell module
A solar cell module, comprising: laminating layers sequentially with their inorganic oxide vapor-deposited film surfaces facing each other, and vacuum-suctioning them to form an integrally formed body by a heat compression lamination method or the like.