JP2000277770A - Surface protection sheet for solar cell module and solar cell module using the same - Google Patents

Abstract

(57) [Summary] PROBLEM TO BE SOLVED: To provide a surface protection sheet constituting a solar cell module.
Even if a fluorine-based resin is used as the layer, the moisture-proof property to prevent the invasion of moisture, oxygen, etc. is remarkably improved, and furthermore, the light fastness, heat resistance, water fastness, etc. By minimizing performance degradation, providing excellent protection ability, and also providing excellent antifouling properties, etc., and stably providing a low-cost and safe surface protection sheet constituting a solar cell module. is there. SOLUTION: A coating film made of a resin composition containing a fluorine-based resin as a main component of a vehicle and a vapor-deposited thin film of an inorganic oxide are provided, and a metal alkoxide compound and / or A surface protection sheet for a solar cell module characterized by laminating a resin film provided with a coating film of a composition containing the hydrolyzate as a main component of a vehicle, and a solar cell using the same It concerns the module.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a solar cell module.
More specifically, the present invention relates to a surface protection sheet for solar cells and a solar cell module using the same, and more specifically, a solar cell module excellent in light resistance, heat resistance, water resistance, moisture resistance, stain resistance, etc. and having extremely high 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. . Thus, the above-mentioned solar cell module usually includes a surface protection 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. At present, a glass plate or the like is most commonly used as a surface protection sheet layer constituting the above-mentioned solar cell module, and recently, a resin sheet such as a fluorine-based resin sheet has been used. Is also attracting attention, and its development is proceeding rapidly.

[0003]

By the way, a solar cell generally absorbs sunlight and generates photovoltaic power.
As the surface protection sheet layer constituting the solar cell module, sunlight is incident, transmits and absorbs the sunlight, and is rich in transmission and absorptivity, and also has various robustness such as light resistance, heat resistance, water resistance and the like. It has excellent moisture resistance to prevent moisture and oxygen from entering, and has high surface hardness and prevents accumulation of dirt and dust on the surface, and has high protection ability. The conditions are as follows. However, a glass plate or the like which is currently most commonly used as a surface protection sheet layer constituting a solar cell module is excellent in sunlight transmission and absorption, light resistance and heat resistance. It has the advantages of excellent water-resistance and other robustness, and also has excellent moisture-proof properties, and has the advantage of having a high surface hardness and a high protective ability, but lacks plasticity, impact resistance, weight reduction, etc. Further, there is a problem that the workability, the workability and the like are inferior, and the cost is not reduced. When a resin sheet such as a fluororesin is used as the surface protection sheet layer constituting the solar cell module, compared with a glass plate or the like,
Although it is rich in plasticity, impact resistance, weight reduction, cost reduction, etc., it is inferior in various fastnesses such as light resistance, heat resistance, water resistance and the like, and in particular, lacks moisture resistance. Further, when the above-mentioned fluorine-based resin sheet is used, there is a problem that dust and the like accumulate on the surface and the surface is contaminated. Therefore, the present invention uses a fluorine-based resin as a surface protection sheet layer constituting a solar cell module, but significantly improves moisture-proof properties for preventing intrusion of moisture, oxygen, and the like, and further improves light resistance, With respect to the robustness such as heat resistance and water resistance, the long-term performance degradation is minimized, the protection performance is excellent, the antifouling property is excellent, and the solar cell module is safer at lower cost. The object is to stably provide a surface protection sheet constituting the shell.

[0004]

The inventor of the present invention has conducted various studies to solve the problems with respect to the surface protective sheet layer constituting the solar cell module as described above. Focusing on the properties of the glass plate used as the surface protection sheet layer constituting and the fluororesin,
First, on one side of a resin film, a silicon oxide, or a transparent, glassy inorganic oxide vapor-deposited thin film such as aluminum oxide is provided, and further, on the vapor-deposited inorganic oxide thin film, a metal alkoxide compound and And / or a coating film made of a composition containing a hydrolyzate thereof as a main component of a vehicle, and further provided on one surface of a resin film provided with a vapor-deposited thin film of the inorganic oxide and a coating film. A surface protection sheet for a solar cell module is manufactured by laminating a coating film of a resin composition containing a fluororesin as a main component of a vehicle, and this is used as a surface protection sheet layer. , A filler layer, a solar cell element as a photovoltaic element, a filler layer, a backside protection sheet layer, and the like are sequentially laminated, and then these are integrally vacuum-evacuated and heat-pressed. Lamine Solar cell module using the Deployment method - was produced Le, water, greatly improves the moisture resistance for preventing intrusion of oxygen or the like, light resistance, heat resistance,
With regard to the robustness such as water resistance, the long-term performance degradation is minimized, the protection ability is excellent, the antifouling property is excellent, and the surface for solar cell modules is safer at lower cost. The inventors have found that a protection sheet and a solar cell module using the same can be manufactured, and completed the present invention.

That is, the present invention provides a coating film made of a resin composition containing a fluorine-based resin as a main component of a vehicle, and a vapor-deposited thin film of an inorganic oxide. A surface protection sheet for a solar cell module, characterized by laminating a resin film provided with a coating film of a composition containing an alkoxide compound and / or a hydrolyzate thereof as a main component of a vehicle, and the same. The present invention relates to 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. The layer structure of the surface protection sheet for a solar cell module according to the present invention and the solar cell module using the same will be described more specifically with reference to the drawings and the like. FIG. 4 is a schematic cross-sectional view illustrating a few examples of the layer configuration of the surface protection sheet for a solar cell module according to the present invention. FIG. FIG. 4 is a schematic cross-sectional view illustrating an example of a layer configuration of a solar cell module manufactured using a surface protection sheet for a solar cell.

First, as shown in FIG. 1, a surface protection sheet A for a solar cell module according to the present invention comprises a coating film 1 made of a resin composition containing a fluorine-based resin as a main component of a vehicle.
A vapor-deposited thin film 2 of inorganic oxide is provided on one side thereof, and a metal alkoxide compound and / or a hydrolyzate thereof is used as a main component of a vehicle on the vapor-deposited thin film 2 of inorganic oxide. The basic structure is that the resin film 4 provided with the coating film 3 is laminated. As another example of the surface protection sheet for a solar cell module according to the present invention, as shown in FIG. 2, coating with a resin composition containing a fluorine-based resin as a main component of a vehicle, as shown in FIG. A multilayer film 5 comprising at least two layers of a film 1 and an inorganic oxide vapor-deposited thin film 2 on one surface thereof, and furthermore, an inorganic oxide vapor-deposited thin film 2 constituting the multilayer film 5 Surface protection sheet A for a solar cell module having a structure in which a resin film 4 provided with a coating film 3 of a composition containing a metal alkoxide compound and / or a hydrolyzate thereof as a main component of a vehicle is laminated. _One can be mentioned. Further, as another example of the surface protection sheet for a solar cell module according to the present invention, as shown in FIG. 3, as shown in FIG. 3, a coating film 1 made of a resin composition containing a fluorine-based resin as a main component of a vehicle. On one side thereof, first, a vapor-deposited thin film 2a of inorganic oxide is provided by chemical vapor deposition, and then a vapor-deposited thin film 2a of the inorganic oxide is formed.
On top of this, a deposited thin film of inorganic oxide by physical vapor deposition 2
b to form an inorganic oxide vapor-deposited thin film 2a, 2b
A multilayer film 5a having at least two layers is formed, and a metal alkoxide compound and / or a hydrolyzate thereof is used as a main component of a vehicle on a vapor-deposited inorganic oxide thin film 2b constituting the multilayer film 5a. A solar cell module having a configuration in which resin films 4 provided with a coating film 3 are laminated.
Le for surface protective sheet - can be exemplified bets A _2. In the above, when laminating the coating film 1 made of a resin composition containing a fluorine-based resin as a main component of the vehicle and the resin film 4 provided with the inorganic oxide deposited thin film 2 and the coating film 3, A surface of the resin film 4 of the resin film 4 provided with the oxide thin film 2 and the coating film 3;
Alternatively, on any surface such as the surface of the coating film 3,
The coating film 1 made of a resin composition containing a fluorine-based resin as a main component of the vehicle may be formed and laminated.

Next, in the present invention, an example of a solar cell module manufactured by using the above-mentioned surface protection sheet for a solar cell module according to the present invention is illustrated in FIG. The solar cell module according to the present invention shown
FIG. 4 shows an example in which a surface protection sheet A for a tool is used.
As shown in FIG. 1, the surface protection sheet A for a solar cell module according to the present invention shown in FIG. 1 has one surface on the inside, and the filler layer 11 and the photovoltaic element are sequentially formed. The solar cell element 12, the filler layer 13, and the backside protective sheet layer 14 are laminated, and then these are integrated into one.
The solar cell module T can be manufactured by using a normal molding method such as a lamination method in which vacuum suction is applied and heat-compression bonding is performed, and the above layers are integrally formed. The above example is a surface protection sheet for a solar cell module according to the present invention.
The present invention is not limited to these examples, and illustrates an example of a solar cell module manufactured using the same. For example, although not shown,
In the above-mentioned solar cell module, other layers can be optionally added and laminated for the purpose of transmitting, absorbing, reinforcing, etc. sunlight.

Next, in the present invention, the surface protection sheet for a solar cell module according to the present invention and the material constituting the solar cell module using the same, the manufacturing method, and the like will be described in more detail. The coating film made of a resin composition containing a fluorine-based resin as a main component of a vehicle and constituting a surface protection sheet for a solar cell module, a solar cell module, and the like according to the present invention may be a fluororesin. Seed or two or more as main components of the vehicle, if necessary, for example, a lubricant, a crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, a reinforcing agent, an antistatic agent ,
One or more additives such as a flame retardant, a flame retardant, a fungicide, a colorant, etc. are arbitrarily added within a range that does not affect the transmission of sunlight, and a solvent, a diluent, etc. are sufficient. Kneading to, for example, a solvent type, aqueous type, or, to prepare a resin composition such as an emulsion type, and then, the resin composition,
For example, floating knife coat, knife over
Roll coat, inverted knife coat, squeeze
Roll coat, roll roll coat, roll coat
G, gravure roll coat, kis roll coat, air
A coating method such as blade coating, extrusion coating, curtain coating, etc., or
Using a printing method such as gravure printing, offset printing, silk screen printing, transfer printing, etc., the surface of the coating film of the resin film provided with the above-mentioned vapor-deposited inorganic oxide thin film and coating film. Alternatively, a coating film can be formed on any surface of the resin film by coating or printing to form a laminate. In the above,
The thickness of the coating film is 1 to 75 g / m ² (dry state)
And preferably in the order of 10 to 50 g / m ² .

In the above, as the fluororesin, for example, polytetrafluoroethylene (PTF)
E), perfluoroalkoxy resin (PFA) comprising a copolymer of tetrafluoroethylene and perfluoroalkylvinyl ether, tetrafluoroethylene and hexafluoropropylene copolymer (FEP), tetrafluoroethylene and perfluoroalkylvinyl ether And hexafluoropropylene copolymer (EPE); copolymer of tetrafluoroethylene and ethylene or propylene (ETFE); polychlorotrifluoroethylene resin (PCTFE); copolymer of ethylene and chlorotrifluoroethylene (ECTFE); Vinylidene fluoride resin (PVDF), vinyl fluoride resin (PV
F) or one or more kinds of fluororesins made of transparent fluororesin made of trade name, CYTOP (registered trademark) or trade name, Lumiflon (registered trademark) (both made by Asahi Glass Co., Ltd.), etc. can do. In the present invention, the fluororesin has a property of transmitting visible light of 90% or more, preferably 93% or more, and transmitting and absorbing all the incident sunlight. Is desirable. In the present invention, among the above-mentioned fluorine-based resins, particularly, a vinyl fluoride-based resin (PVF), a copolymer of tetrafluoroethylene and ethylene or propylene (ETF).
E), trade name, CYTOP (Cytop, registered trademark),
Alternatively, a transparent fluororesin made of a trade name, Lumiflon (registered trademark) has transparency and is preferable from the viewpoint of sunlight permeability and the like. Thus, in the present invention, by using the above-mentioned fluororesin, the excellent properties of the fluororesin, particularly, mechanical properties, chemical properties, optical properties, etc., furthermore, light resistance, heat resistance Utilizing various properties such as super weather resistance, durability, contamination resistance, chemical resistance, etc., such as water resistance, water resistance, etc., a surface protection sheet constituting a solar cell is obtained. It has the same optical properties, weather resistance, durability, etc. as glass plates, etc., and is lighter than glass plates, etc. due to its flexibility and mechanical characteristics, and has excellent workability, etc. It has advantages such as easiness.

By the way, various additives may be added to the resin composition containing the above-mentioned fluororesin as a main component of the vehicle, and among them, particularly, an ultraviolet absorber and / or an antioxidant may be used. It is preferable to add and include them. As the above-mentioned ultraviolet absorber, for example, it absorbs harmful ultraviolet rays in sunlight, converts it into harmless heat energy in the molecule, and excites the active species that initiates photodegradation in the polymer. And specifically,
Benzophenone type, benzotriazole type, saltile
Type, acrylonitrile type, metal complex type, hindered amine type, ultrafine titanium oxide (particle size, 0.01 to 0.0
6 μm) or ultrafine zinc oxide (particle size, 0.01 to
One or more inorganic UV absorbers such as 0.04 μm) can be used. In the above description, the antioxidant is, for example, one that prevents photodeterioration or thermal deterioration of the polymer, and specifically, includes phenol-based, amine-based, sulfur-based, phosphoric-acid-based, and others. And the like. One or more known antioxidants can be used. The amount of the ultraviolet absorber and / or antioxidant to be added is preferably 0.1 to 10 parts by weight which does not affect the transmission of sunlight.

Next, in the present invention, a surface protection sheet for a solar cell module and a solar cell module according to the present invention.
When the vapor-deposited thin film of the inorganic oxide constituting the metal or the like is described, as the vapor-deposited thin film of the inorganic oxide, for example, a physical vapor deposition method, or a chemical vapor deposition method, or a combination thereof, It can be manufactured by forming one or two or more multilayer films of a deposited thin film of an inorganic oxide. The inorganic oxide vapor-deposited thin film formed by the above-mentioned physical vapor deposition method will be described in further detail. Examples of the inorganic oxide vapor-deposited thin film formed by the physical vapor deposition method include a vacuum vapor deposition method, a sputtering method, and an ion plating method. Physical Vap (Physical Vap)
or Deposition method, PVD method) to form a deposited thin film of inorganic oxide. In the present invention, specifically, a metal oxide is used as a raw material, and a vacuum evaporation method in which the metal oxide is heated and vapor-deposited on a resin film, or a metal or a metal oxide is used as a raw material, and oxygen is introduced. Then, the deposited film can be formed by an oxidation reaction deposition method of depositing on the resin film by oxidizing the film, and further, a plasma-assisted oxidation reaction deposition method of promoting the oxidation reaction by plasma. In the present invention, a specific example of a method of forming a thin film of an inorganic oxide by a physical vapor deposition method is shown in FIG. 5. FIG. 5 is a schematic configuration diagram showing an example of a roll-up type vacuum evaporation apparatus. As shown in FIG. 5, in a vacuum chamber 22 of a take-up type vacuum evaporation apparatus 21,
The resin film 4 unwound from the unwinding roll 23 is guided to a cooled coating drum 26 via guide rolls 24 and 25. Thus, the above cooled core
An evaporation source 28 heated by a crucible 27, for example, metal aluminum or aluminum oxide, is evaporated on the resin film 4 guided on the singing drum 26, and further, if necessary, an oxygen gas outlet 29. Oxygen gas or the like is jetted out, and the masks 30 and 30 are supplied while supplying the gas.
Through, for example, to form a deposited thin film of an inorganic oxide such as aluminum oxide, and then, in the above, for example,
The resin film 4 on which a vapor-deposited thin film of an inorganic oxide such as aluminum oxide is formed is sent out through guide rolls 25 'and 24' and wound up on a take-up roll 31, whereby the physical vapor phase according to the present invention is obtained. A vapor-deposited thin film of an inorganic oxide can be formed by a growth method. In the present invention, the method for forming a vapor-deposited thin film of an inorganic oxide as described above is based on 2 methods.
It may be repeated twice or more times, or two or more vacuum evaporation apparatuses as described above may be connected, and two or more layers may be stacked to form a two or more inorganic oxide evaporated thin film. In the present invention, as the metal or metal oxide to be used, one kind or a mixture of two or more kinds can be used to form a thin film of an inorganic oxide mixed with different materials.

In the above, 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 thin film of the inorganic oxide as described above varies depending on the type of the metal or the metal oxide to be used.
It is desirable to arbitrarily select and form it within the range of 0 °, preferably 100 to 1000 °.

Next, in the present invention, the vapor-deposited thin film of inorganic oxide by the above-mentioned chemical vapor deposition method will be further described. Chemical vapor deposition (Chemical Vapor Deposition) such as vapor phase epitaxy, thermochemical vapor phase epitaxy, and photochemical vapor phase epitaxy
A vapor-deposited thin film of an inorganic oxide can be formed using an n method, a CVD method, or the like. In the present invention, specifically,
On one surface of the resin film, a monomer gas for vapor deposition such as an organic silicon compound is used as a raw material, an inert gas such as an argon gas or a helium gas is used as a carrier gas, and an oxygen gas is used as an oxygen supply gas. By using a low-temperature plasma-enhanced chemical vapor deposition (CVD) method using a low-temperature plasma generator or the like, a deposited thin film of an inorganic oxide such as silicon oxide can be formed. In the above description, 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.

More specifically, an example of a method for forming a vapor-deposited thin film of an inorganic oxide by the low-temperature plasma enhanced chemical vapor deposition method will be described. FIG. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic configuration diagram of a low-temperature plasma-enhanced chemical vapor deposition apparatus showing an outline of a method for forming a vapor-deposited thin film of an oxide. As shown in FIG. 6 described above, in the present invention, the resin film 4 is unwound from an unwinding roll 43 disposed in a vacuum chamber 42 of a plasma enhanced chemical vapor deposition apparatus 41. Is cooled at a predetermined speed through an auxiliary roll 44 at the cooling / electrode drum 45.
Convey on the peripheral surface. Thus, in the present invention, oxygen gas, an inert gas, a monomer gas for vapor deposition such as an organic silicon compound, and the like are supplied from the gas supply devices 46 and 47 and the raw material volatile supply device 48 and the like. While adjusting the mixed gas composition for vapor deposition, the mixed gas composition for vapor deposition was introduced into the vacuum chamber -42 through the raw material supply nozzle 49, and was conveyed onto the peripheral surface of the cooling / electrode drum 45 described above. Glow discharge plasma 5 on resin film 4
A plasma is generated by 0, and this is irradiated to form a vapor-deposited thin film of an inorganic oxide such as silicon oxide, thereby forming a film.
In the present invention, the cooling / electrode drum 45
A predetermined power is applied from a power supply 51 disposed outside the chamber, and a magnet 52 is disposed near the cooling / electrode drum 45 to promote the generation of plasma. The resin film 4 on which the deposited thin film of the inorganic oxide such as silicon oxide is formed is wound on a winding roll 54 via an auxiliary roll 53, and the plasma chemical vapor deposition method according to the present invention is performed. To produce a vapor-deposited thin film of an inorganic oxide. In the figure, 55 represents a vacuum pump. In the present invention, the above-described method for forming a vapor-deposited thin film of an inorganic oxide is repeated two or more times, or two or more vacuum vapor deposition apparatuses are connected and two or more An inorganic oxide vapor-deposited thin film composed of layers or more can be formed. In the present invention, one or a mixture of two or more kinds of monomer gases for vapor deposition may be used to form a thin film of an inorganic oxide mixed with different materials. The above examples illustrate one example thereof,
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 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 properties and the like. In the above, for example, an argon gas, a helium gas, or the like can be used as the inert gas.

In the present invention, the silicon oxide vapor-deposited thin film formed as described above undergoes a chemical reaction between a monomer gas such as an organosilicon compound and oxygen gas, and the reaction product adheres tightly to the resin film. dense, it is possible to form a thin film rich in flexibility or the like, usually, the general formula SiO _X (provided that, X
Represents a number of 0 to 2). Thus, the above-mentioned silicon oxide vapor-deposited thin film is represented by a general formula SiO _X (where X represents a number of 1.3 to 1.9) in terms of transparency, barrier properties, and the like. It is preferable to use a thin film mainly composed of a deposited silicon oxide film. In the above, the value of X changes depending on the molar ratio of the monomer gas to the oxygen gas, the energy of the plasma, etc. In general, the gas permeability decreases as the value of X decreases, but the film itself has It has a yellow color and poor transparency. Further, the above-described deposited silicon oxide thin film has silicon (Si) and oxygen (O) as essential constituent elements, and further has one of carbon (C) and hydrogen (H);
Alternatively, it is composed of a deposited film of silicon oxide containing both elements as trace constituent elements and has a thickness of 50 °.
And the constituent ratio between the essential constituent elements and the trace constituent elements continuously changes in the film thickness direction. Further, when the above-mentioned vapor-deposited silicon oxide thin film contains a compound composed of carbon, the carbon content is reduced in the depth direction of the film thickness. Thus, in the present invention,
Regarding the above-mentioned silicon oxide vapor-deposited thin film, for example, an X-ray photoelectron spectrometer (Xray Photoelectron)
Spectroscopy, XPS), Secondary Ion Mass Spectrometer (Secondary Ion Mass S)
The above physical properties are confirmed by performing elemental analysis of the deposited thin film of silicon oxide using a method of performing analysis such as ion etching in the depth direction using a surface analysis device such as Spectroscopy (SIMS). Is what you can do. Further, in the present invention, the thickness of the deposited silicon oxide thin film is desirably about 50 to 2000 °, and specifically, the thickness is as follows:
About 100-1000 °, more preferably 100-50
0 ° is desirable, so in the above, 500 °,
Further, when the thickness is more than 1000 ° to 2000 °, cracks and the like are easily generated in the film, which is not preferable, and when it is less than 100 °, furthermore, when the thickness is less than 50 °, it becomes difficult to exhibit a barrier effect. It is undesirable. In the above description, the film thickness is determined, for example, by a fluorescent X-ray analyzer (model name, RIX200 manufactured by Rigaku Corporation).
(Type 0) and can be measured by a fundamental parameter method. Further, in the above, as means for changing the thickness of the deposited silicon oxide thin film, increasing the volume velocity of the deposited film, that is, a method of increasing the amount of the monomer gas and the oxygen gas or the rate of the deposition. It can be performed by a method of slowing down.

Incidentally, in the present invention, as a vapor-deposited thin film of an inorganic oxide constituting a surface protection sheet for a solar cell module, a solar cell module or the like according to the present invention, for example, a physical vapor deposition method can be used. When forming a multilayer film composed of two or more layers of a vapor-deposited thin film of an inorganic oxide by using both of the chemical vapor deposition methods together, first, on a resin film, dense and dense by a chemical vapor deposition method, Provide a vapor-deposited thin film of an inorganic oxide which is rich in flexibility and can relatively prevent the occurrence of cracks, and then, on the vapor-deposited thin film of the inorganic oxide, deposit a vapor-deposited thin film of the inorganic oxide by physical vapor deposition. It is desirable to provide a deposited thin film of an inorganic oxide composed of two or more multilayer films. In the present invention, the above-mentioned vapor-deposited thin film of the inorganic oxide has a close adhesion with a coating film or the like provided thereon, in order to improve the affinity and the like, for example,
A plasma-treated surface is formed by using a plasma surface treatment method in which surface modification is performed using plasma gas generated by ionizing a gas by arc discharge, or corona discharge is performed by a corona discharge treatment method or the like. It can be processed to form a corona treated surface or the like.

Next, in the present invention, the surface protection sheet for a solar cell module and the solar cell module according to the present invention.
The coating film formed of a composition containing a metal alkoxide compound and / or a hydrolyzate thereof as a main component of a vehicle will be described. For example, mainly, a general formula, M (0R) _n (where M is Si, Ti, Al, B, Zr, W, or
Represents a metal atom consisting of ta, R represents an alkyl group consisting of C ₁ -C _10, n is an integer of 1-4. ), A hydrolyzate thereof, or a mixture thereof. In the above, as the metal alkoxide compound, specifically, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetraisobutoxysilane, tetra-sec-butoxysilane,
Tetra-tert-butoxysilane, tetra-n-amyloxysilane, tetraisoamyloxysilane, tetrahexyloxysilane, tetraheptyloxysilane, tetraoctyloxysila, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, Methyltributoxysila, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylbutoxysilane, vinyltrimethoxysilane, γ-
(Methacryloxypropyl) trimethoxysilane, γ-
Glycidoxypropyltrimethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, and other alkoxysilane compounds; trimethoxyaluminum,
Aluminum alkoxide compounds such as triethoxyaluminum, triisopropoxyaluminum and others;
Zirconium alkoxide compounds such as tetramethoxyzirconium, tetraethoxyzirconium, tetraisopropoxyzirconium, tetrabutoxyzirconium and others; titanium alkoxide compounds such as tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium, tetrabutoxytitanium and others; tantalum penta Tantalum alkoxide compounds such as propoxide, tantalum pentaboxy and others;
Boron alkoxide compounds such as boron trimethoxide, boron tributoxide, and others; and one or more mixtures of others can be used.

Next, in the present invention, the hydrolyzate of the metal alkoxide compound is obtained by dissolving one or more of the above metal alkoxide compounds in an appropriate solvent, A complete hydrolyzate can be obtained. In the above, as the solvent, water, methanol, ethanol, isopropyl alcohol, butanol, alcohols such as others, the above-mentioned mixed solvent comprising water-alcohol, etc., methyl ethyl ketone, Ketones such as methyl isobutyl ketone and others, esters such as ethyl acetate and butyl acetate and others, halogenated hydrocarbons, aromatic hydrocarbons such as toluene and xylene, and others can be used. In addition,
In the present invention, when performing the above-described hydrolysis, for example, a small amount of a mineral acid such as sulfuric acid, hydrochloric acid, or nitric acid, or an organic acid such as acetic acid or tartaric acid can be added and used as a catalyst.

Next, in the present invention, in the composition containing the above-mentioned metal alkoxide compound and / or hydrolyzate thereof as a main component of the vehicle, the content of the metal alkoxide compound and / or hydrolyzate thereof is as follows. 0.1% by weight or more, preferably 0.1 to 70% by weight, more preferably 0.1 to 70% by weight in terms of SiO ₂ generated as a result of 100% hydrolysis and condensation of the metal alkoxide compound.
It is desirable to use it after dissolving it in a solvent so as to be about 20% by weight. In the above, if the amount is less than 0.1% by weight, the formed coating film cannot form a film having desired characteristics, that is, a desired barrier performance. If it exceeds 70% by weight, it is not preferable because it is difficult to form a transparent uniform film.

In the present invention, in order to form a coating film of a composition containing the above-mentioned metal alkoxide compound and / or its hydrolyzate as a main component of the vehicle, first, for example, a metal alkoxide compound And / or one or more of its hydrolysates are the main components of the vehicle, and if necessary, furthermore, for example, resins as binders, fillers, stabilizers, plasticizers, antioxidants, Add additives such as light stabilizers such as ultraviolet absorbers, dispersants, thickeners, drying agents, lubricants, antistatic agents, crosslinking agents, etc., and knead thoroughly with solvents, diluents, etc. A composition comprising a solvent type, an aqueous type or an emulsion type is prepared. Thus, in the present invention, the composition prepared above is used, for example, a roll coat method, a gravure roll coat method, a kiss roll coat method, a squeeze roll coat method. The coating amount, for example, 0.1 g / m ^{2 to} 10 g, by a coating method such as a reverse roll coating method, a curtain flow coating method, etc.
/ M ² (dry state), preferably 0.5 g / m ² to
Coating is carried out to a level of about 5 g / m ² (dry state), followed by heat drying and further aging treatment to form a coating film according to the present invention. In the above, as the above composition, a metal alkoxide compound and / or a hydrolyzate thereof is dissolved or kneaded, and further, these are cured.
It is preferable to use a composition prepared using water or an alcohol-water solution, and the above-mentioned alcohol components include, for example, n-propyl alcohol and isopropyl alcohol. -N-butanol, t-
Butanol, ethyl alcohol, methyl alcohol and the like can be used. In the above-mentioned alcohol-water solution, the mixing ratio of alcohol and water is, for example, alcohol, 50 to 70 parts by weight of water, 50 to 70 parts by weight
It is desirable to prepare an alcohol-water solution by mixing at a ratio of 30 parts by weight.

In the above composition, the additives include
For example, it is preferable to mix and use an inorganic filler such as metal oxide fine particles at the same time. In such a case, when the SiO ₂ mixed sol having a large number of hydroxyl groups on its surface forms an SiO ₂ gel film by heating or the like, the surface of the metal oxide fine particles has a hard structure by itself. This has the advantage that it reacts with the hydroxyl groups of the above to reinforce the coating film. As the above-mentioned metal oxide fine particles, for example, silica, alumina, titania, zirconia, etc. can be used. It can be added and used.

Further, in the above-mentioned composition, for example, water-soluble, hydrophilic, etc. One or two or more of various resins such as hydrophobic, hydrophobic, etc. can also be added. In the above, as the resin, for example, a polyethylene resin, a polyolefin resin such as a polypropylene resin, or an acid-modified polyolefin resin thereof, a polyvinyl acetate resin,
Polyacrylic or methacrylic resin, polystyrene resin, polyvinyl alcohol resin, ethylene-vinyl alcohol copolymer, polyvinyl butyral resin,
Polyvinylpyrrolidone resin, methylcellulose, ethylcellulose, carboxymethylcellulose, nitrocellulose, polyester resin, polyamide resin,
Phenol resins, melamine resins, urea resins, polyurethane resins, and others can be used.

Further, in the above composition, for example, a binary reactive silane coupling agent or an isocyanate compound can be added as a crosslinking agent. As the above silane coupling agent,
For example, γ-chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,
4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N -Β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ
One or more of ureidopropyltriethoxysilane, bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane and γ-aminopropylsilicone can be used. Further, as the above-mentioned isocyanate compound, those having two or more isocyanate groups in the molecule can be used.
Tolylene diisocyanate, triphenylmethane triisocyanate, tetramethyl xylene diisocyanate
And others can be used. Only a small amount may be used.

Further, in the present invention, in order to cross-link and cure the metal alkoxide compound and / or the hydrolysis thereof, and furthermore, it is reacted with a cross-linking agent or the like to form a cross-linking structure. Can be added. Examples of the above-mentioned curing catalyst include, for example, tertiary amines which are substantially insoluble in water and soluble in an organic solvent. N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine and the like, and as the acids, for example, sulfuric acid, hydrochloric acid, mineral acids such as nitric acid,
Organic acids such as acetic acid and tartaric acid can be used. It is sufficient to add a small amount as the amount used.

In the present invention, the above-mentioned metal alkoxide compound and / or a hydrolyzate thereof are used as a main component of the vehicle, and if necessary, a desired additive is optionally added thereto. -Aqueous solvent, a composition obtained by sufficiently kneading with a diluent or the like is prepared, and coated by a usual coating method,
A coating film can be formed by subjecting it to heat drying, aging treatment and the like. Thus,
The above-mentioned coating film is excellent in close adhesion to a vapor-deposited thin film of an inorganic oxide, the bonding strength between the two is extremely strong, and a phenomenon such as peeling between layers is not recognized. Forming a barrier film consisting of two layers of a vapor-deposited thin film of an inorganic oxide and the above-mentioned coating film, thereby further improving the barrier property against oxygen gas, water vapor gas, etc., and It is excellent in heat resistance, hot water resistance, laminating suitability, etc., and can produce an extremely good laminated material.

Next, in the present invention, the surface protection sheet for a solar cell module and the solar cell module according to the present invention.
In a resin film having a vapor-deposited thin film of an inorganic oxide constituting a film and a coating film, examples of the resin film include polyolefin resins such as polyethylene and polypropylene, polyethylene terephthalate, and polyethylene naphthalate. Polyester resins such as polyester resin, polyamide resin, polycarbonate resin, polystyrene resin, polyvinyl alcohol, polyvinyl alcohol resin such as saponified portion of ethylene-vinyl acetate copolymer,
Polyacrylonitrile resin, polyvinyl chloride resin,
Films or sheets of various resins such as polyvinyl acetal-based resin, polyvinyl butyral-based resin, fluorine-based resin and others can be used. Thus, in the present invention, as the film or sheet of the above resin, for example, one or more of the above resins are used to form a film by inflation method, T-die method, etc. Using a method, a method of forming a film of the above resin alone, or a method of forming a multilayer co-extrusion film using two or more different resins, further using two or more resins, A resin film or sheet is manufactured by, for example, a method of mixing and forming a film before forming a film, and further, for example, a uniaxial method using a tenter method or a tuber method. Alternatively, a resin film or sheet stretched in a biaxial direction can be used. In the present invention, the thickness of the resin film is preferably about 5 to 200 μm, more preferably about 10 to 50 μm. In the above, when forming a resin into a film, for example, the processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slip properties, mold release properties, flame retardancy, anti-mold Properties, electrical properties,
Various plastic compounding agents and additives can be added for the purpose of improving and modifying others.
Up to the above, it can be arbitrarily added according to the purpose. Further, in the above, as a general additive, for example, a lubricant, a crosslinking agent, an antioxidant, an ultraviolet absorber, a filler, a reinforcing agent, a reinforcing agent, an antistatic agent, a flame retardant, a flame retardant, a foaming agent, A fungicide, a pigment, and the like can be used, and further, a modifying resin and the like can be used.

In the present invention, the resin film is
If necessary, for example, corona discharge treatment, ozone treatment,
Pretreatment such as low-temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment using chemicals, or the like can be arbitrarily performed. The above-mentioned surface pretreatment may be performed in a separate step before forming a vapor-deposited thin film of an inorganic oxide.For example, in the case of a surface treatment such as a low-temperature plasma treatment or a glow discharge treatment, As a pretreatment for forming a vapor-deposited thin film of an oxide, pretreatment can be performed by in-line treatment. In such a case, there is an advantage that the production cost can be reduced. The above-mentioned surface pretreatment is to be performed as a method for improving the adhesion between the resin film and the deposited thin film of the inorganic oxide, but as a method for improving the adhesion, other, for example, a substrate On the surface of the film, a primer coat agent layer, an undercoat agent layer, a vapor-deposited anchor coat agent layer, or the like can be arbitrarily formed in advance. As the coating agent layer for the above pretreatment, for example, a resin composition containing a polyester-based resin, a polyurethane-based resin, or the like as a main component of the vehicle can be used. In the above, as a method of forming the coating agent layer, for example, a coating agent such as a solvent type, an aqueous type, or an emulsion type is used, and a roll coating method, a gravure roll coating is used. The coating can be performed by using a coating method such as a coating method, a kiss coating method, or the like. It can be carried out by in-line processing of axial stretching processing or the like. In the present invention, as the substrate film, specifically, a biaxially oriented polypropylene resin film such as a biaxially oriented polypropylene film, a biaxially oriented polyester resin film such as a biaxially oriented polyethylene terephthalate film, Alternatively, it is desirable to use a biaxially stretched polyamide resin film such as a biaxially stretched nylon film.

In the solar cell module surface protection sheet and solar cell module according to the present invention,
An antifouling layer can be formed on the outermost surface. That is, in the present invention, the other one surface (outermost surface) of the coating film made of the resin composition containing the fluorine-based resin constituting the surface protection sheet for the solar cell module as a main component of the vehicle has dust or the like. An antifouling layer for preventing accumulation of water can be formed. The antifouling layer is formed of a coating film of a composition containing a photocatalyst powder or a photocatalyst sol (both are collectively referred to as a photocatalyst powder). In the above, as a coating film of the composition containing the photocatalyst powder, for example, one or more of the photocatalyst powder, one or more of the binder as a vehicle is added, and if necessary, For example, lubricants, crosslinking agents, antioxidants, ultraviolet absorbers, light stabilizers, fillers, reinforcing agents,
One or more additives such as a reinforcing agent, an antistatic agent, a flame retardant, a flame retardant, a foaming agent, a fungicide, a pigment, and other additives are arbitrarily added within a range that does not affect sunlight transmission. Furthermore,
Solvent, sufficiently kneaded with a diluent, for example, a solvent type, aqueous type, or, to prepare a composition such as an emulsion type,
Subsequently, the composition is subjected to, for example, a floating knife coating method, a knife over roll coating method, an inverted knife coating method, a squeeze roll coating method, and a reverse coating method.
Roll coat method, roll coat method, gravure roll coat method, kiss roll coat method, air blade coat method, extrude coat method, curtain coat method
Coating method such as gravure printing, offset printing, silk screen printing, transfer printing, etc. to form a coating film by applying or printing. it can. In the above description, the thickness of the coating film is preferably about 0.1 to 10 g / m ² (dry state), more preferably about 1.0 to 1 g / m ² .

In the above, as the photocatalyst powder, for example, the resin is degraded, destroyed, or decomposed or degraded by the action of light such as sunlight due to oxidation or the like.
It is possible to use a chemical substance that has an effect of destroying the adhesiveness of dust and the like adhered to the surface of the antifouling layer, washing and removing the dust and the like by wind and rain, and easily holding the surface for cleaning. . Specifically, for example, as a photocatalyst powder,
For example, TiO ₂ , ZnO, SrTiO ₃ , CdS, C
aP, InP, GaAs, BaTiO ₂ , K ₂ Ti
O ₃ , K ₂ NbO ₃ , Fe ₂ O ₃ , Ta ₂ O ₃ , W
O ₃ , SnO ₂ , Bi ₂ O ₈ , NiO, Cu ₂ O, Si
C, SiO ₂ , MoS ₂ , InPb, RuO ₂ , CeO
₂ etc., or Pt, Rh, RuO ₂ , N
A composition in which a metal such as b, Cu, Sn, Ni, and Fe and / or a metal oxide thereof is mixed can be used. In the above composition, the content of the photocatalyst powder varies depending on the particle shape, density and the like, but is preferably about 0.1 to 30% by weight.

In the above, the binder as a vehicle has film-forming properties, and further has light resistance, heat resistance,
It is excellent in various fastnesses such as water resistance, it also increases the hardness of the coating film, it has excellent scratch resistance, abrasion resistance, etc., especially, it is possible to use a binder that is not affected by the photoactivity of the photocatalyst powder. Can,
Specifically, for example, polyethylene resin, polypropylene resin, 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, vinyl chloride-vinylidene chloride copolymer, poly (meth) acrylic resin, polyacrylonitrile resin, polystyrene resin, acrylonitrile-styrene copolymer Copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, polyamide resin, polycarbonate resin, polyvinyl alcohol resin, ethylene-vinyl acetate copolymer Combined saponified product, fluororesin,
Known resins such as diene resin, polyacetal resin, polyurethane resin, epoxy resin, phenol resin, aminoplast resin, silicone resin, nitrocellulose, inorganic polymer and others Alternatively, one or more kinds of modified resins, others, and the like can be used. Thus, in the present invention, among the binders not affected by the photocatalyst powder, among the binders described above, particularly, low-melting glass and alkali metal silicate
It is preferable to use one or more of inorganic polymers such as silica, phosphate and colloidal silica.

In the present invention, the photoactivity of the photocatalyst powder in the coating film constituting the antifouling layer affects, for example, a coating film located below the antifouling layer,
An activity blocking layer for blocking the activity of the photocatalyst powder made of an inorganic film or the like for blocking mutual contact can be provided so as not to cause the deterioration, decomposition, destruction, or the like. The above-mentioned active barrier layer is usually provided below the antifouling layer. As the inorganic film constituting the above-mentioned activity blocking layer, for example, the above-mentioned vapor-deposited film of inorganic oxide such as silicon oxide or aluminum oxide can be used. The formation of the above-mentioned inorganic oxide vapor-deposited film can be carried out in the same manner as described above to form an active barrier layer.
And more preferably about 100 to 1500 °.

In the present invention, in order to strengthen the tight adhesion of the antifouling layer, when providing a coating film of a composition containing a photocatalyst powder constituting the antifouling layer, if necessary, An adhesive primer layer or the like can be provided.
As a material constituting the above-mentioned primer layer, for example,
A material constituting an inorganic primer layer that is not decomposed by the photoactivity of the photocatalyst powder in the antifouling layer can be used. Specifically, tetraisopropyl titanate, which is a typical example of an organic titanium compound, Tetrabutyl titane
Alkyl titanates such as tert., Tetrastearyl titanate, etc.
And products produced by hydrolysis of titanium chelate and the like. In addition, inorganic polysilazane (perhydropolysilazaran) and the like can also be used. In the present invention, particularly preferred are tetraisopropyl titanate and tetrabutyl titanate, which have a very high rate of hydrolysis and can be decomposed after coating the solution.

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. In addition, the thickness of the above-mentioned filler layer is about 200 to 1000 μm, more preferably about 3 μm.
About 50 to 600 μm is desirable.

Next, in the present invention, the solar cell module
A solar cell element as a photovoltaic element constituting a solar cell will be described. As such a solar cell element, a conventionally known one, for example, a crystalline silicon solar cell element, a polycrystalline silicon solar cell element, an amorphous silicon solar cell element , A copper indium selenide solar cell element, a compound semiconductor solar cell element, and the like can be used.
Further, 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 silicon solar cell element, and the like can also 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
The backside protective sheet layer constituting the film will be described. As the backside protective sheet, an insulating resin film or sheet can be used, and furthermore, heat resistance, light resistance, and water resistance can be used. It has weather resistance such as, physical or chemical strength, excellent toughness, etc., furthermore, from the protection of the solar cell element as a photovoltaic element, scratch resistance,
It is necessary to be excellent in shock absorption and the like. Specific examples of the backside protection sheet include polyamide resins (various nylons), polyester resins, polyethylene resins, polypropylene resins, polystyrene resins, polycarbonate resins, and the like. Films or sheets of various resins such as an acetal resin, a cellulose resin, a (meth) acrylic resin 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 above resin film or sheet, the film thickness is 12 to 20.
About 0 μm, more preferably about 25 to 150 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 can be used in any of unstretched and uniaxially or biaxially stretched. The thickness is arbitrary,
It can be used by selecting from a range of several μm to about 300 μm. Further, in the present invention, the film or sheet may be any film such as an extruded film, an inflation film or a coating film.

Next, a method of manufacturing a solar cell module using the above-mentioned materials in the present invention will be described. Such a manufacturing method may be a known method, for example, the above-described method of the present invention. Using a surface protection sheet for a solar cell module according to the above, with the surface of the inorganic oxide vapor-deposited thin film inside, a filler layer, a solar cell element as a photovoltaic element, A filler layer, a backside protective sheet layer, etc. are laminated, and if necessary, other materials are laminated arbitrarily between the respective layers. The solar cell module can be manufactured by using a conventional molding method such as a lamination method and forming the above-mentioned layers into an integrally molded body by thermocompression bonding. In the above, if necessary, a heat-melt adhesive containing a resin such as a (meth) acrylic resin, an olefin-based resin, a vinyl-based resin, or the like as a main component of the vehicle, in order to enhance adhesion between the layers, Solvent-based adhesives, photo-curable adhesives, and others can be used.

[0041]

Next, the present invention will be described more specifically with reference to examples. Example 1 (1). As a base material, a biaxially stretched polyethylene terephthalate film having a thickness of 50 μm was used, mounted on a delivery roll of a take-up type vacuum evaporation apparatus, and then fed out onto a coating drum. Under the following conditions, the above-mentioned biaxially stretched polyethylene terephthalate film is easily bonded by a reactive vacuum deposition method using an electron beam (EB) heating system while supplying oxygen gas while using aluminum as a deposition source. An aluminum oxide deposited thin film having a thickness of 300 ° was formed on the surface. (Evaporation conditions) Evaporation source: Aluminum Degree of vacuum in vacuum chamber: 7.5 × 10 ⁻⁶ mbar Degree of vacuum in evaporation chamber: 2.1 × 10 ⁻⁶ mbar EB output: 40 KW Film transport speed: 600 m / Minutes (2). Next, after forming a thin film of aluminum oxide having a thickness of 300 ° above, immediately after the deposition, a plasma output of 1500 W and oxygen gas were applied to the surface of the thin film of aluminum oxide using a glow discharge plasma generator. (O
₂ ): Oxygen / argon mixed gas plasma processing was performed using a mixed gas consisting of argon gas (Ar) = 19: 1 at a mixed gas pressure of 6 × 10 ⁻⁵ Tool and a processing speed of 420 m / min. (3). On the other hand, 2 parts by weight of dimethyldimethoxysilane, 1 part by weight of ethanol and 0.2 part by weight of 0.1N hydrochloric acid were mixed at the same ratio and refluxed at 50 ° C. for 2 hours. A ratio of 25 parts by weight of methyltrimethoxysilane, 5 parts by weight of ethanol, and 20 parts by weight of a toluene solution (20%) of polymethyl methacrylate (PMMA) to the obtained partially hydrolyzed solution of dimethyldimethoxysilane. And further stirred at room temperature for 2 hours to prepare a coating composition.
Next, the coating composition obtained above was used on the plasma-treated surface of the above-mentioned aluminum oxide vapor-deposited thin film, and the composition was coated by a gravure roll coating method to a thickness of 1.0 g. / M ² (dry state), and then heat-treated at 120 ° C. for 5 minutes to form a cured coating film. Furthermore, the thickness as a substrate is 50 μm
A fluororesin coating solution (trade name, Lumiflon, manufactured by Asahi Glass Co., Ltd.) is applied to the non-coated cured film surface of the biaxially stretched polyethylene terephthalate film by a gravure coating method, and the film thickness is 10 g. / M ² (dry state) to form a coating film to produce a surface protection sheet according to the present invention. (4). Next, a 38 μm-thick biaxially stretched polyethylene terephthalate film (light receiving surface) in which solar cell elements made of amorphous silicon are arranged in parallel is coated on the coating cured film of the surface protection sheet manufactured as described above. The photovoltaic module according to the present invention was manufactured by laminating the photovoltaic cell elements with the surface facing the photovoltaic cell and an adhesive layer of an acrylic resin. (5). In the above, instead of the fluororesin coating liquid (trade name, Lumiflon, manufactured by Asahi Glass Co., Ltd.), a fluororesin liquid composed of a copolymer of tetrafluoroethylene and ethylene is used, and otherwise is exactly the same as above. Thus, a surface protection sheet and a solar cell module were manufactured in the same manner as described above.

Embodiment 2 (1). A biaxially stretched polyethylene terephthalate film having a thickness of 50 μm was used as a base material, and was mounted on a delivery roll of a plasma enhanced chemical vapor deposition apparatus. Was formed on the surface of the above-mentioned biaxially stretched polyethylene terephthalate film which had been subjected to easy adhesion. (Evaporation conditions) Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 1: 10: 10 (unit: slm) Degree of vacuum in vacuum chamber: 5.0 × 10 ⁻⁶ mbar Inside vapor deposition chamber Degree of vacuum: 6.0 × 10 ^-2 mbar Cooling / electrode drum supply power: 20 kW Film transport speed: 80 m / min Evaporation surface: Corona treated surface (2). Immediately after the deposition of the biaxially stretched polyethylene terephthalate film on which a 300-mm-thick silicon oxide vapor-deposited thin film was formed, a corona discharge was applied to the silicon oxide vapor-deposited thin film at an output of 10 kW and at a processing speed of 100 m / min. Perform processing to reduce the surface tension of the deposited thin film surface to 35 dy.
ne to 60 dyne. (3). On the other hand, 25 parts by weight of tetraethoxysilane, 10 parts by weight of ethanol and 5 parts by weight of 0.1 N hydrochloric acid were mixed at the same ratio and refluxed at 50 ° C. for 3 hours. To a solution of the partial hydrolyzate of the obtained tetraethoxysilane, a toluene solution of polymethyl methacrylate (PMMA) (20
%), And the mixture was further stirred at room temperature for 2 hours to prepare a coating composition. Next, the above coating composition was used on the corona-treated surface of the above-mentioned silicon oxide vapor-deposited thin film, and was coated by a gravure roll coating method to have a thickness of 1.5 g / m2. ² (dry state) was formed, and then heat-treated at 120 ° C. for 1 minute to form a cured coating film. Further, a fluororesin coating solution (trade name, Lumiflon, manufactured by Asahi Glass Co., Ltd.) is applied to the non-coated cured film surface of a biaxially stretched polyethylene terephthalate film having a thickness of 50 μm as a substrate by gravure coating.
The surface protection sheet according to the present invention was produced by applying a coating method to form a coating film having a thickness of 10 g / m ² (dry state). (4). Next, a 38 μm-thick biaxially stretched polyethylene terephthalate film (light-receiving surface) in which solar cell elements made of amorphous silicon are arranged in parallel on the coating cured film surface of the surface protection sheet manufactured as described above. The photovoltaic module according to the present invention was manufactured by laminating the photovoltaic cell elements with their faces facing each other with an adhesive layer of an acrylic resin interposed therebetween. (5). In the above, instead of the fluororesin coating liquid (trade name, Lumiflon, manufactured by Asahi Glass Co., Ltd.), a fluororesin liquid composed of a copolymer of tetrafluoroethylene and ethylene is used, and otherwise is exactly the same as above. Thus, a surface protection sheet and a solar cell module were manufactured in the same manner as described above.

Embodiment 3 (1). As a substrate, a thickness of 5 kneaded with an ultraviolet absorber
A biaxially oriented polyethylene terephthalate film of 0 μm was used, and the thickness was 30
A vapor-deposited thin film of 0 ° silicon oxide was formed, and the surface of the vapor-deposited thin film of silicon oxide was subjected to corona discharge treatment to increase the surface tension of the vapor-deposited thin film surface from 35 dyne to 60 dyne. (2). Next, a vapor-deposited aluminum oxide thin film having a thickness of 300 ° was formed on the corona-treated surface of the silicon oxide vapor-deposited thin film of the biaxially stretched polyethylene terephthalate film in exactly the same manner as in Example 1 described above. Then, a plasma treatment was performed on the surface of the deposited thin film of aluminum oxide. (3). On the other hand, 5 parts by weight of dimethyldimethoxysilane, 2.5 parts by weight of ethanol and 0.5 parts by weight of 0.1N hydrochloric acid were mixed at the same ratio and refluxed at 50 ° C. for 2 hours.
15 parts by weight of methyltrimethoxysilane and ethanol were added to the resulting partially hydrolyzed solution of dimethyldimethoxysilane.
At a ratio of 3 parts by weight of the catalyst and 10 parts by weight of a cyclohexane solution of a cyclic polyolefin (30%).
After stirring for an hour, a composition for coating was prepared. Next, the coating composition obtained above was used on the plasma-treated surface of the above-mentioned deposited thin film of aluminum oxide, and the composition was coated by a gravure roll coating method to a thickness of 2.0 g. / M
² (dry state) coating film is formed.
The coating was cured by heating at 20 ° C. for 1 minute. Furthermore, a fluororesin coating solution containing a benzophenone-based ultraviolet absorber (trade name, Lumiflon, manufactured by Asahi Glass Co., Ltd.) is applied to the non-coated cured film surface of a biaxially stretched polyethylene terephthalate film having a thickness of 50 μm as a substrate. Was applied using a gravure coating method to form a coating film having a thickness of 10 g / m ² (dry state). Further, a photocatalyst coating solution comprising 10 parts by weight of ultrafine titanium oxide particles having a particle size of 0.03 μm and 90 parts by weight of a tetraethoxysilane solution (solid content: 20%) was applied to the above coating film surface (outermost surface) by gravure coating. The surface protection sheet according to the present invention was produced by applying a coating method to form an antifouling layer having a thickness of 1.0 g / m ² . (4). Next, a 38 μm-thick biaxially stretched polyethylene terephthalate film (light-receiving surface) in which solar cell elements made of amorphous silicon are arranged in parallel on the coating cured film surface of the surface protection sheet manufactured as described above. The photovoltaic module according to the present invention was manufactured by laminating the photovoltaic cell elements with their faces facing each other with an adhesive layer of an acrylic resin interposed therebetween. (5). In the above, instead of the fluororesin coating liquid containing a benzophenone-based ultraviolet absorber (trade name, Lumiflon, manufactured by Asahi Glass Co., Ltd.), a fluororesin liquid comprising a copolymer of tetrafluoroethylene and ethylene containing a benzophenone-based ultraviolet absorber The surface protection sheet and the solar cell module were produced in the same manner as described above except for using the above.

Embodiment 4 (1). On the plasma-treated surface of the deposited aluminum oxide thin film having a thickness of 300 ° produced in Example 1 above, a deposited aluminum oxide thin film having a thickness of 300 ° was formed in exactly the same manner as in Example 1 above. Plasma deposition was performed on the aluminum thin film deposition surface to form two aluminum oxide thin films. (2). Separately, 25 parts by weight of tetraethoxysilane, 10 parts by weight of ethanol and 5 parts by weight of 0.1 N hydrochloric acid were mixed and refluxed at 50 ° C. for 3 hours. To the obtained partially hydrolyzed solution of tetraethoxysilane, add a fluorine-based acrylic resin solution (trade name, Lumiflon) manufactured by Asahi Glass Co., Ltd. 25
The mixture was stirred at room temperature for 2 hours to prepare a coating composition. Next, the above-mentioned composition for coating was used on the plasma-treated surface of the above-mentioned vapor-deposited thin film of aluminum oxide, and was coated by a gravure roll coating method to have a thickness of 0.5 g / m 2. ² (dry state) was formed, and then heat-treated at 120 ° C. for 5 minutes to form a cured coating film. Then, otherwise,
A surface protection sheet for a solar cell module according to the present invention was manufactured in exactly the same manner as in Example 1 described above. Further, using the surface protection sheet manufactured as described above,
A solar cell module according to the present invention was manufactured in the same manner as in the above.

Embodiment 5 (1). On the corona-treated surface of the silicon oxide vapor-deposited thin film produced in Example 2 above, a silicon oxide vapor-deposited thin film having a thickness of 300 ° was formed in exactly the same manner as in Example 2 above. The surface was subjected to corona discharge treatment to form two layers of silicon oxide vapor-deposited thin films. (2). On the other hand, 20 parts by weight of tetraethoxysilane and water 5
0 parts by weight, 30 parts by weight of ethanol and 0.1 N hydrochloric acid 5
Parts by weight and the mixture was refluxed at 50 ° C. for 3 hours. To the obtained partial hydrolyzate solution of tetraethoxysilane, 50 parts by weight of a solution of ethylene-vinyl alcohol copolymer in water-isopropyl alcohol (solid content: 8%) was added, and the mixture was further added at room temperature for 2 hours. The composition for coating was prepared by stirring. Next, the above-mentioned composition for coating was used on the plasma-treated surface of the above-mentioned silicon oxide vapor-deposited thin film, and was coated by a gravure roll coating method to have a thickness of 1.0 g / m 2. ² (dry state) was formed, and then heat-treated at 120 ° C. for 5 minutes to form a cured coating film. Hereinafter, a surface protection sheet for a solar cell module according to the present invention was manufactured in exactly the same manner as in Example 2 described above. Further, the surface protection sheet manufactured as described above is used.
A solar cell module according to the present invention was manufactured in exactly the same manner as in Example 2 described above.

Embodiment 6 (1). As a substrate, a thickness of 5 kneaded with an ultraviolet absorber
A biaxially stretched polyethylene terephthalate film of 0 μm was used and the thickness was 30
A 0 ° aluminum oxide deposited thin film was formed, and a plasma treatment was performed on the aluminum oxide deposited thin film surface. (2). Next, in the same manner as in Example 2 described above, the plasma-treated surface of the aluminum oxide vapor-deposited thin film of the biaxially stretched polyethylene terephthalate film was coated with a film thickness of 30%.
A 0 ° silicon oxide deposited thin film was formed, and a corona discharge treatment was further performed on the silicon oxide deposited thin film surface. Next, a surface protection sheet for a solar cell module according to the present invention was manufactured on the corona-treated surface of the silicon oxide vapor-deposited thin film in the same manner as in Example 2 above. Further, a solar cell module according to the present invention was manufactured in exactly the same manner as in Example 2 above, using the surface protection sheet manufactured as described above.

Comparative Example 1 (1). As a base material, a 50 μm thick polyvinyl fluoride resin film (PVF) was used, and this was used as a surface protection sheet.
A 38 μm-thick biaxially stretched polyethylene terephthalate film (light-receiving surface) in which solar cell elements made of amorphous silicon are arranged in parallel on one surface thereof, with the solar cell element surfaces facing each other, and an acrylic resin The solar cell module was manufactured by laminating via an adhesive layer.

COMPARATIVE EXAMPLE 2 A biaxially stretched polyethylene terephthalate film having a thickness of 50 μm was used as a substrate, and a vapor-deposited thin film of aluminum oxide having a thickness of 300 ° was formed in the same manner as in Example 1 above. Further, a plasma treatment was performed on the surface of the deposited thin film of aluminum oxide. Furthermore, the thickness as a substrate is 50 μm
A fluororesin coating solution (trade name, Lumiflon, manufactured by Asahi Glass Co., Ltd.) is applied to the non-plasma-treated surface of the biaxially stretched polyethylene terephthalate film by a gravure coating method, and the film thickness is 10 g / m ² ( A coating film (in a dry state) was formed to produce a surface protection sheet. Next, a 38 μm-thick biaxially stretched polyethylene terephthalate film (light receiving surface) in which solar cell elements made of amorphous silicon are arranged in parallel on the plasma-treated surface of the above-mentioned surface protection sheet on which a thin film of aluminum oxide is deposited. Were laminated with an adhesive layer of an acrylic resin facing the solar cell element surface to produce a solar cell module.

COMPARATIVE EXAMPLE 3 A biaxially stretched polyethylene terephthalate film having a thickness of 50 μm was used as a base material. A corona discharge treatment was performed on the surface of the silicon oxide film on which the silicon oxide was deposited. Further, a fluororesin coating solution (trade name, product name) is applied to the non-corona treated surface of a biaxially stretched polyethylene terephthalate film having a thickness of 50 μm as a substrate.
(Lumiflon, manufactured by Asahi Glass Co., Ltd.) using a gravure coating method to form a coating film having a thickness of 10 g / m ² (dry state), thereby producing a surface protection sheet. Next, a 38 μm-thick biaxially stretched polyethylene terephthalate film (light-receiving surface) in which solar cell elements made of amorphous silicon were arranged in parallel on the corona-treated surface of the deposited silicon oxide thin film of the surface protection sheet. The photovoltaic module was manufactured by stacking the photovoltaic cell elements with their surfaces facing each other with an acrylic resin adhesive layer interposed therebetween.

Experimental Example The total light transmittance of the surface protective sheets according to the present invention manufactured in Examples 1 to 6 and the surface protective sheets according to Comparative Examples 1 to 3 was measured. Examples 1 to 6
A solar cell module evaluation test was conducted for the solar cell modules manufactured in Comparative Examples 1 to 3 and the solar cell modules manufactured in Comparative Examples 1 to 3. (1). Measurement of Total Light Transmittance This is based on the base film and the color of the surface protection sheets according to the present invention manufactured in Examples 1 to 6 and the surface protection sheets according to Comparative Examples 1 to 3. The total light transmittance (%) was measured by a computer. (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 measured for the surface protection sheets according to the present invention manufactured in Examples 1 to 6 and the surface protection sheets according to Comparative Examples 1 to 3.
Under the conditions of a temperature of 40 ° C. and a humidity of 90% RH, a measuring device manufactured by MOCON, USA [model name, part
MATTRAN (PERMATRAN)]
Oxygen permeability was measured at a temperature of 23
℃, humidity 90% RH, USA, Mocon (MOCO
N) Company [Model name, OXTRA
N)]. The results of the above measurements are shown in Table 1 below.

[0051] In Table 1 above, the water vapor barrier property is expressed as [g / m ² /
day • 40 ° C • 100% RH], and
The oxygen barrier property is as follows: [cc / m ² / day · 23 ° C. · 90
% RH].

As is clear from the measurement results shown in Table 1 above, the surface protection sheets according to Examples 1 to 6 have high total light transmittance, and are excellent in water vapor barrier properties and oxygen barrier properties. Furthermore, solar cell modules using them are:
The output reduction rate was low. On the other hand, the surface protective sheet according to Comparative Example 1 has a high total light transmittance, but is inferior in water vapor barrier property and oxygen barrier property.
The solar cell module using it, the output reduction rate,
There was a problem that it was expensive. Further, the surface protection sheets according to Comparative Examples 2 and 3 are different from those according to Examples 1 to 6 in terms of water vapor barrier property, oxygen barrier property, and the like.
It was slightly inferior.

[0053]

As is apparent from the above description, the present invention
Focusing on the properties of the glass plate used as the surface protection sheet layer constituting the solar cell module and the fluorine-based resin, first, one side of the resin film is coated with silicon oxide or aluminum oxide. A transparent glassy inorganic oxide vapor-deposited thin film is provided, and a metal alkoxide compound and / or a hydrolyzate thereof is used as a main component of a vehicle. Forming a coating film of a resin composition containing a fluorine-based resin as a main component of a vehicle on one surface of a resin film provided with a deposited thin film of the inorganic oxide and a coating film. To form a surface protection sheet for a solar cell module, which is used as a surface protection sheet layer, one side of which is on the inside, a filler layer, and a solar cell as a photovoltaic element. The solar cell module is formed by sequentially laminating a cell, a filler layer, a backside protective sheet layer, and the like, and then using a lamination method or the like in which these are integrally vacuum-evacuated and heat-pressed. Manufactured to significantly improve moisture resistance to prevent intrusion of moisture, oxygen, etc., and also minimize light-resistance, heat-resistance, water-resistance, etc. A low-cost and safe surface protection sheet for a solar cell module that is excellent in protection ability, furthermore excellent in antifouling properties and the like, and a solar cell module using the same.
Can be manufactured.

[Brief description of the drawings]

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

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

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

FIG. 4 is a solar cell module manufactured using the surface protection sheet for a solar cell module according to the present invention shown in FIG.
FIG. 3 is a schematic cross-sectional view schematically illustrating a layer configuration of an example of the structure.

FIG. 5 is a schematic configuration diagram of a take-up type vacuum evaporation apparatus showing an outline of a method of forming an evaporated thin film of an inorganic oxide by a physical vapor deposition method.

FIG. 6 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.

[Explanation of symbols]

A Surface protection sheet for solar cell module A ₁ Surface protection sheet for solar cell module A ₂ Surface protection sheet for solar cell module 1 Coating film 2 Evaporated thin film of inorganic oxide 2a Inorganic Evaporated thin film of oxide 2b Evaporated thin film of inorganic oxide 3 Coating film 4 Resin film 5 Multilayer film 5a Multilayer film T Solar cell module 11 Filler layer 12 Solar cell element 13 Filler layer 14 Backside protection sheet

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hiroshi Yamamoto 1-1-1, Ichigaya-Kagacho, Shinjuku-ku, Tokyo Inside Dai Nippon Printing Co., Ltd. (72) Katsutoshi Konno 1-chome, Ichigaya-cho, Shinjuku-ku, Tokyo No. 1 Dai Nippon Printing Co., Ltd. F-term (reference) 5F051 BA18 CB12 CB13 CB14 CB22 GA05 GA06

Claims (17)

[Claims] 1. A coating film of a resin composition containing a fluorine-based resin as a main component of a vehicle, and a vapor-deposited thin film of an inorganic oxide are provided, and a metal alkoxide compound and / or Alternatively, a surface protection sheet for a solar cell module characterized by laminating a resin film provided with a coating film of a composition containing a hydrolyzate thereof as a main component of a vehicle. 2. The surface protection seal for a solar cell module according to claim 1, wherein the coating film is made of a transparent fluororesin having a visible light transmittance of 90% or more.
G. 3. The coating film according to claim 1, wherein the coating film is made of a transparent fluororesin made of CYTOP (trade name) or Lumiflon (trade name) (both manufactured by Asahi Glass Co., Ltd.). Protection sheet for solar cell module. 4. The coating film according to claim 1, wherein the coating film contains an ultraviolet absorber and / or an antioxidant.
2. A surface protection sheet for a solar cell module according to item 1. 5. The surface protection sheet for a solar cell module according to claim 1, wherein the coating film has an antifouling layer on the outermost surface. 6. The method according to claim 1, wherein the inorganic oxide vapor-deposited thin film is formed of one or more multilayer films of the inorganic oxide vapor-deposited thin film formed by physical vapor deposition. A surface protection sheet for a solar cell module to be described. 7. The method according to claim 1, wherein the inorganic oxide vapor-deposited thin film comprises one or more multilayer films of the inorganic oxide vapor-deposited thin film formed by chemical vapor deposition. A surface protection sheet for a solar cell module to be described. 8. The solar cell according to claim 1, wherein the inorganic oxide vapor-deposited thin film is composed of two or more multilayer films formed by physical vapor deposition and chemical vapor deposition. Surface protection sheet for modules. 9. A vapor-deposited thin film of an inorganic oxide, wherein a vapor-deposited thin film of an inorganic oxide is provided by a chemical vapor deposition method, and then the inorganic oxide is deposited on the vapor-deposited thin film of the inorganic oxide by a physical vapor deposition method. 9. The solar cell module according to claim 8, comprising a multilayer film of two or more layers provided with a deposited thin film of an object.
Surface protection sheet for 10. The surface protection seal for a solar cell module according to claim 1, wherein the vapor-deposited thin film of an inorganic oxide forms a plasma-treated surface or a corona-treated surface. G. 11. The surface protection sheet for a solar cell module according to claim 1, wherein the composition contains a resin component. 12. The surface protection sheet for a solar cell module according to claim 11, wherein the resin component is a water-soluble or hydrophilic resin. 13. The surface protection sheet for a solar cell module according to claim 1, wherein the composition contains a curing catalyst for a metal alkoxide compound and / or a hydrolyzate thereof. . 14. The surface protection sheet for a solar cell module according to claim 1, wherein the composition contains inorganic oxide fine particles. 15. The solar cell module according to claim 1, wherein the composition comprises a crosslinking agent.
Surface protection sheet for 16. The resin film comprises a biaxially stretched polyester resin film, a biaxially stretched polyamide resin film, a biaxially stretched polypropylene resin film, a cyclic polyolefin resin film, or a (meth) acrylic resin film. The surface protection sheet for a solar cell module according to any one of claims 1 to 15, wherein:
G. 17. A coating film made of a resin composition containing a fluorine-based resin as a main component of a vehicle, and a vapor-deposited thin film of an inorganic oxide are provided, and a metal alkoxide compound and / or Alternatively, on one surface of a solar cell module surface protection sheet in which a resin film provided with a coating film of a composition containing a hydrolyzate thereof as a main component of a vehicle, a filler layer and a light A solar cell element as an electromotive element, a filler layer, and a backside protection sheet layer are sequentially laminated, and these are vacuum-suctioned to form an integrally formed body by a heat compression lamination method or the like. Solar cell module.