JP2000138391A - Surface protective sheet for solar cell module, and solar cell module using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To raise the moistureproofness, by providing a surface protective sheet with an applied film by the resin composition having fluororesin as the main composition, and stacking this and a resin film being provided with a coating film by the resin composition having an ethylene-vinyl alcohol copolymer as the main components on the deposited film of an inorganic oxide. SOLUTION: A surface protective sheet A for a solar cell module is provided with an applied film 1 which has fluororesin as the main components of a vehicle. Then, this is provided with a deposited film 2 of an inorganic oxide on its one side, and further this is constituted by stacking a resin film 4 being provided with a coating film 3 by resin composition having an ethylene-vinyl alcohol copolymer as the main components of a vehicle and the applied sheet 1 on the deposited film 2 of an inorganic oxide. As a result, the protective performance can be elevated by raising the moistureproofness to prevent the penetration of moisture, oxygen, etc., and further, minimizing the long-term performance deterioration as to various solidity such as light resistance, thermalstability, waterproofness, etc.

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. Currently, 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. 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 and the workability are inferior, and the cost is not reduced. When a resin sheet such as a fluororesin is used as the surface protection sheet layer constituting the solar cell module, 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 also significantly improves moisture-proof properties for preventing intrusion of moisture, oxygen, etc. With respect to various robustnesses such as heat resistance and water resistance, the long-term performance deterioration is minimized, the protection ability is excellent, and the solar cell module is excellent in antifouling property, etc., and is lower in cost and safer. 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 transparent, glassy inorganic oxide vapor-deposited thin film such as silicon oxide or aluminum oxide is provided. Further, on the vapor-deposited inorganic oxide thin film, ethylene-vinyl alcohol A coating film made of a resin composition containing a copolymer as a main component of a vehicle, and then on one of the surfaces of the 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. Inside, a filler layer, a solar cell element as a photovoltaic element,
A solar cell module was manufactured by using a lamination method in which a filler layer, a backside protective sheet layer, and the like were sequentially laminated, and then these were integrally vacuum-sucked and heated and pressed. However, it significantly improves moisture resistance to prevent the ingress of moisture, oxygen, etc., and also minimizes long-term performance degradation of light fastness, heat resistance, water resistance, etc., and protects The present invention has been found to be capable of producing a surface protection sheet for a solar cell module which is excellent in antifouling property, furthermore excellent in antifouling property and the like at a lower cost and which is safe, and a solar cell module using the same. Is completed.

That is, the present invention provides a coating film of a resin composition containing a fluorine-based resin as a main component of a vehicle and a thin film of an inorganic oxide deposited thereon. -A surface protection sheet for a solar cell module, characterized by laminating a resin film provided with a coating film of a resin composition containing a vinyl alcohol copolymer as a main component of a vehicle, and It relates to the used solar cell module.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below with reference to the drawings. 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, and 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 resin composition containing an ethylene-vinyl alcohol copolymer as a main component of a vehicle is further provided on the vapor-deposited thin film 2 of inorganic oxide. -A basic structure having a configuration in which a resin film 4 provided with a 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 Film 3 made of a resin composition containing ethylene-vinyl alcohol copolymer as a main component of a vehicle
The provided resin film 4 solar cell module consisting of the construction stacked - can be exemplified bets A ₁ - le for surface protection sheet. 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 inorganic oxide thin film 2a formed by chemical vapor deposition is provided, and then, on the vapor-deposited inorganic oxide thin film 2a, a vapor-deposited inorganic oxide thin film formed by physical vapor deposition is provided. 2b to form a multilayer film 5a composed of two or more layers of inorganic oxide vapor-deposited thin films 2a and 2b, and furthermore, an ethylene-vinyl alcohol film is deposited on the inorganic oxide vapor-deposited thin film 2b constituting the multilayer film 5a. Le copolymer vehicle co Principal component and a resin composition - coating film 3 formed resin film 4 solar cell module consisting of the construction stacked - can be exemplified bets a ₂ - le surface protective sheet . In the above, when laminating a coating film 1 made of a resin composition containing a fluorine-based resin as a main component of a vehicle and a resin film 4 provided with an inorganic oxide deposited thin film 2 and a coating film 3, Oxide deposited thin film 2
A resin composition containing a fluorine-based resin as a main component of a vehicle on the surface of the resin film 4 of the resin film 4 provided with the coating film 3 or the surface of the coating film 3. Alternatively, the coating film 1 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 inward, 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 performed and heat-compression bonding is performed, and the above-described 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 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 as long as they do not affect the transmission of sunlight. Kneading, for example, a solvent type, aqueous type, or, to prepare a resin composition such as an emulsion type, 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, kistrol, air
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-described inorganic oxide vapor-deposited thin film and the 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 two or more kinds of fluororesins made of a 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 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 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 fluorine-based resin, excellent properties of the fluorine-based resin, 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., it is used as a surface protection sheet for a solar cell. 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 properties, 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 salt 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 a 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 using an oxidation reaction deposition method of depositing on a resin film by oxidizing the film, and further using 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 winding type vacuum evaporation apparatus 21,
The resin film 1 fed 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 1 guided on the singing drum 26, and further, if necessary, an oxygen gas outlet 29. Oxygen gas or the like is spouted 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 1 on which a vapor-deposited thin film of an inorganic oxide such as aluminum oxide is formed is fed 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 inorganic oxide thin film can be formed by a growth method.

In the above description, any thin film formed by depositing a metal oxide can be used as the inorganic oxide deposited thin film. For example, silicon (Si), aluminum (Al), magnesium (Mg) can be used. , Calcium (C
a), potassium (K), tin (Sn), sodium (N
a) A vapor-deposited thin film of an oxide of a metal such as boron (B), titanium (Ti), lead (Pb), zirconium (Zr), and yttrium (Y) can be used. Thus, preferred are silicon (Si), aluminum (A
1) and the like. Thus, the 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 °. In the present invention, the inorganic oxide vapor-deposited thin film is not limited to one layer of the inorganic oxide vapor-deposited thin film, but may be a laminate of two or more layers. Alternatively, as the metal oxide, one kind or a mixture of two or more kinds may be used to form a thin film of an inorganic oxide mixed with different materials.

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, in the present invention, the resin film 1 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 via an auxiliary roll 44 to a cooling / electrode drum 45.
Convey on the peripheral surface. 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 1
A plasma is generated by 0, and this is irradiated to form a 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 source 51 disposed outside the chamber, and a magnet 52 is disposed near the cooling / electrode drum 45 to promote the generation of plasma. The above-mentioned resin film 1 on which a deposited thin film of an 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 an inorganic oxide vapor-deposited thin film. In the figure, 55 represents a vacuum pump. The above exemplification is merely an example, and it goes without saying that the present invention is not limited thereby. Although not shown, in the present invention, the inorganic oxide deposited thin film is not limited to one layer of the inorganic oxide deposited thin film,
It may be in the form of a laminate in which two or more layers are laminated, and the material used is one or more of a mixture thereof, and constitutes a vapor-deposited thin film of an inorganic oxide mixed with different materials. You can also.

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.
As the gas, for example, 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 description, as the inert gas, for example, argon gas, helium gas, or the like can be used.

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 vapor-deposited thin film of silicon oxide is represented by the general formula SiO _X (where X represents a number of 1.3 to 1.9) from the viewpoint of transparency, barrier properties and the like. It is preferably 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 changes continuously in the film thickness direction. Further, when the silicon oxide vapor-deposited thin film contains a compound made 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 a deposited silicon oxide thin film using a method of analyzing the surface by ion etching in the depth direction using a surface analyzer such as a 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, if the thickness is more than 1000 ° to 2000 °, cracks and the like are likely to be generated in the film, which is not preferable. 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).
0 type) 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 vapor-deposited inorganic oxide thin films by using both of the chemical vapor deposition methods together, first, on a resin film, dense, An inorganic oxide vapor-deposited thin film which is rich in flexibility and can relatively prevent the occurrence of cracks is provided, and then an inorganic oxide vapor-deposited thin film formed by physical vapor deposition is formed on the inorganic oxide vapor-deposited thin film. It is desirable to provide a deposited thin film of 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 using a plasma surface treatment method or the like in which the surface is modified using a 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 treated 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.
A coating film made of a resin composition containing an ethylene-vinyl alcohol copolymer as a main component of a vehicle will be described. As the coating film, for example, an ethylene-vinyl alcohol copolymer is used. One or more of the following as the main component of the vehicle,
Further, if necessary, for example, fillers, stabilizers, plasticizers,
Add optional additives such as light stabilizers such as antioxidants and ultraviolet absorbers, dispersants, thickeners, drying agents, lubricants, antistatic agents, crosslinking agents, etc. A resin composition composed of a solvent type, an aqueous type, or an emulsion type is prepared by kneading the resin composition, and the resin composition is used, for example, by a roll coating method, gravure roll coating, or the like. Method, kiss roll coat method, squeeze roll coat method,
The coating amount, for example, 0.1 g / m ^{2 to} 10 g / m ² (dry state) is determined by a coating method such as a reverse roll coating method, a curtain flow coating method, or the like. preferably, co to be ^{0.5g / m 2 ~5g / m 2} ( dry state) position - and coating, and then drying by heating, and further, e - is subjected to treatment for aging, etc., according to the present invention A coating film can be formed. In the above, as the resin composition, an ethylene-vinyl alcohol copolymer or the like is dissolved or kneaded, and further, these are cured, so that the resin composition adjusted using an alcohol-water-based solution or the like is used. It is preferable to use an alcohol component such as n-propyl alcohol, isopropyl alcohol, n-butanol, or t-type alcohol.
-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 as follows:
For example, alcohol, 50 to 70 parts by weight of water, 50 parts by weight
It is desirable to prepare an alcohol-water solution by blending in an amount of up to 30 parts by weight.

In the above, ethylene-vinyl alcohol
Examples of the ethylene-vinyl acetate copolymer include ethylene-vinyl acetate copolymer having an ethylene content of 25 to 50 mol%, which is obtained by completely saponifying an ethylene-vinyl acetate copolymer having a vinyl acetate content of about 79 to 92 wt%. Coalescing can be used. The ethylene-vinyl alcohol copolymer has a high gas barrier property, and is further excellent in fragrance retention, transparency, and the like. % Or less is not preferred because the oxygen gas barrier property is rapidly lowered and the transparency is deteriorated, and if less than 25 mol%, the thin film becomes brittle and It is not preferable because the gas barrier property is lowered.

In the above, specifically, the additive reacts with the hydroxyl or the like of the ethylene-vinyl alcohol copolymer to form molecules of the ethylene-vinyl alcohol copolymer by chemical bonding with each other. A polyfunctional compound capable of forming a three-dimensional network structure (cured) polymer compound or the like can be used in combination, for example, an alkoxysilane compound such as tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, or the like. Zirconium alkoxide compounds such as methoxyzirconium and tetraethoxyzirconium, and metal alkoxide compounds such as tetramethoxytitanium and tetraethoxytitanium titanium alkoxide compounds can be used. Further, in the present invention, as the additive, for example, a compound having a functional group that reacts with active hydrogen such as a —CH ＝ CH ₂ group, ＝ C ＝ O group, —C≡N group, epoxy group, ethyleneimine group, etc. , -OH group, -SH group, -COOH
Group, compound having active hydrogen, such as -NH ₂ group, and other,
A crosslinking agent comprising a compound having a halogen group, a salt, a chelate-forming group, or the like can be used. Specifically, for example, a dialdehyde compound, a dicarboxylic acid compound, a diimide compound, a di- or polyhydric alcohol compound, a diamine compound, a diisocyanate compound, a bisepoxy compound, a bisethyleneimine compound, a divinyl compound, a zirconium compound, Titanium chelate compounds and the like can be used.

Furthermore, in the present invention, a polymer having a good adhesion to a deposited thin film of an inorganic oxide, for example, N-unsubstituted polyalkyleneimine such as polyethyleneimine;
Polyethyleneimine-based polymers such as N-alkyl-substituted polyalkyleneimines and N-acyl-substituted polyalkyleneimines; polycarbodiimide-based polymers such as polycarbodiimide; polyvinylpyrrolidone; polyalkylated vinylpyrrolidone; A polymer, a polyvinylpyrrolidone-based polymer such as a copolymer of vinylpyrrolidone and styrene, and the like can be used.

Next, in the present invention, a silane coupling agent having binary reactivity can be added. Examples of the silane coupling agent include, 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- One or more of aminopropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane, bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane, γ-aminopropylsilicone can be used. As the amount of use, only a small amount may be added. Furthermore, in the present invention, when a hydroxyl group or the like of the ethylene-vinyl alcohol copolymer and the above-mentioned metal alkoxide compound, a cross-linking agent or the like reacts to form a cross-linked structure, for example, a curing catalyst or the like is added. can do. 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, mineral acids such as sulfuric acid, hydrochloric acid and nitric acid, and 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 ethylene-vinyl alcohol copolymer is used as a main component of the vehicle, and if necessary, an additive is optionally added thereto to form an alcohol-water-based solvent and a diluent. A resin composition which is sufficiently kneaded is prepared by a method such as the above, coated by a usual coating method, and then heated and dried, and further subjected to an aging treatment or the like to thereby obtain a coating. A film can be formed. 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 no phenomenon such as peeling between the layers is observed. In the present invention, a barrier film composed of two layers of a vapor-deposited thin film of an inorganic oxide and the above-described coating film is formed, thereby further improving the barrier properties against oxygen gas, water vapor gas, and the like, and It is excellent in transparency, heat resistance, hot water resistance, laminating suitability, etc., and can produce an extremely good laminated material.

Next, in the present invention, a surface protection sheet for a solar cell module and a solar cell module according to the present invention.
In a resin film having a vapor-deposited thin film of an inorganic oxide constituting a resin or the like, examples of the resin film include polyolefin resins such as polyethylene and polypropylene, and polyester resins such as polyethylene terephthalate and polyethylene naphthalate. , Polyamide-based resin, polycarbonate-based resin, polystyrene-based resin, polyvinyl alcohol, polyvinyl alcohol-based resin such as saponified portion of ethylene-vinyl acetate copolymer, polyacrylonitrile-based resin, polychlorinated resin Films or sheets of various resins such as vinyl resin, polyvinyl acetal resin, polyvinyl butyral resin, fluorine 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, and a film forming method such as an inflation method, a T-die method, and the like is used. Using the method, a method of forming the above resin alone into a film, 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, using a tenter method or a tuber method to form a uniaxial film. 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 about 5 to 200 μm, more preferably 10 to 50 μm.
The m-th position is desirable. In the above, at the time of film formation of the resin, for example, the workability of the film, heat resistance, weather resistance,
Mechanical properties, dimensional stability, antioxidant properties, slipperiness, mold release,
Various plastic compounding agents and additives can be added for the purpose of improving and modifying the flame retardancy, mold resistance, electrical properties, etc. It can be added arbitrarily according to the purpose from a very small amount to several tens% without affecting. Further, in the above, as a general additive, for example, a lubricant, a crosslinking agent,
Antioxidants, ultraviolet absorbers, fillers, reinforcing agents, reinforcing agents,
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 comprises:
If necessary, for example, corona discharge treatment, ozone treatment,
Pretreatment such as low-temperature plasma treatment using oxygen gas, nitrogen gas, or the like, glow discharge treatment, oxidation treatment using chemicals, or the like, and the like can be arbitrarily performed. The surface pre-treatment 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 oxide, pretreatment can be performed by in-line treatment. In such a case, there is an advantage that the manufacturing cost can be reduced. The above-mentioned surface pretreatment is to be carried out as a method for improving the adhesion between the resin film and the deposited thin film of the inorganic oxide. 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 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 coating method, a kiss coating method, or the like. It can be carried out by in-line processing or the like of axial stretching processing. 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 surface protection sheet for a solar cell module, the solar cell module and the like 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, a resin is degraded, broken down or decomposed by oxidation or the like by the action of light such as sunlight, or the molecular weight is reduced.
It is possible to use a chemical substance having an action of destroying the adhesiveness of the 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 maintaining 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 Coupling (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 resins, polyacetal resins, polyurethane resins, epoxy resins, phenol resins, aminoplast resins, silicone resins, nitrocellulose, inorganic polymers, 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 the lower layer of the antifouling layer, for example, a coating film.
In order not to cause deterioration, decomposition, destruction, or the like, an activity blocking layer for blocking the activity of the photocatalyst powder formed of an inorganic film or the like for blocking mutual contact can be provided. The above-mentioned activity blocking 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 above-mentioned inorganic oxide vapor-deposited film can be formed into a film in the same manner as described above to form an active cutoff 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 which is not decomposed by the photoactivity of the photocatalyst powder in the antifouling layer can be used. Tetrabutyl titane
Alkyl titanates such as tert-tetrastearyl titanate
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, transmits and absorbs sunlight. It is necessary to have a property to adhere to the surface protection sheet, and also to function to maintain the smoothness of the surface of the solar cell element as a photovoltaic element. Having thermoplasticity for
Further, since the solar cell element as a photovoltaic element is 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-based 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 filler layer, as long as the transparency is not impaired, for example, crosslinking may be performed. Additives such as an agent, a thermal antioxidant, a light stabilizer, an ultraviolet absorber, a photooxidant, and others can be arbitrarily added and mixed. Thus, 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 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 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 surface protection sheet for a solar cell module. In addition, it is necessary to have an adhesive property with a back surface protection sheet, and further, to have a function of maintaining the smoothness of the back surface of the solar cell element as a photovoltaic element, and to have thermoplasticity. In order to protect a solar cell element as a photovoltaic element, it is necessary to have excellent scratch resistance, shock absorption and the like. However, the filler layer laminated below the photovoltaic element constituting the solar cell module is different from the filler layer laminated below the surface protection sheet for the solar cell module. ,
It is not necessary to have transparency. Specifically, as the above-mentioned filler layer, for example, as in the case of the above-mentioned filler layer laminated below the surface protection sheet for a solar cell module, for example, a fluorine-based resin, ethylene-vinyl acetate copolymer may be used. Coalesced, ionomer resin, ethylene-acrylic acid, or polyolefin-based resin such as methacrylic acid copolymer, polyethylene resin, polypropylene resin, polyethylene or polypropylene, etc., 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 filler layer, as long as the transparency is not impaired, for example, crosslinking may be performed. Additives such as an agent, a thermal antioxidant, a light stabilizer, an ultraviolet absorber, a photooxidant, and others 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 sheet will be described. As the backside protective sheet, an insulating resin film or sheet can be used, and further, heat resistance, light resistance, and water resistance With weather resistance such as, physical or chemical strength, excellent in 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 back surface 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-based resin, a cellulose-based 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. The film thickness of the resin film or sheet 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, in the present invention, a method for manufacturing a solar cell module using the above-mentioned materials will be described. 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.

[0038]

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, which was 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 method 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 the above-mentioned 300 ° -thick aluminum oxide vapor-deposited thin film, immediately after the vapor deposition, a plasma output of 1500 W, oxygen gas was applied to the aluminum oxide vapor-deposited thin film 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). Next, using a gravure printing machine, a gravure coat roll is placed on the first color of the plasma-treated surface of the aluminum oxide vapor-deposited thin film, and an ethylene-vinyl alcohol copolymer (ethylene A resin composition consisting of 100 parts by weight of a 15% solution of ion-exchanged water having a content of 32 mol% and n-propyl alcohol (1/1) solvent was used, and this was coated by a gravure roll coating method. To form a coating film having a thickness of 1.1 g / m ² (dry state), followed by heat treatment at 120 ° C. for 5 minutes 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.
10 g / m ² (dry state)
Was formed to produce a surface protective 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 surfaces thereof facing each other with an acrylic resin adhesive layer 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 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 In evaporation 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 surface at an output of 10 kW at a processing speed of 100 m / min. Perform processing to reduce the surface tension of the vapor-deposited thin film surface to 35 dy.
ne to 60 dyne. (3). Next, using a gravure printing machine, a gravure coat roll was placed on the first color of the silicon oxide vapor-deposited thin film on the corona-treated surface, and ethylene-vinyl alcohol was applied.
Copolymer (ethylene content: 32 mol%) 10 parts by weight,
34 parts by weight of tetraethoxysilane, 15 parts by weight of water, 10 parts by weight of isopropyl alcohol, tertiary amine catalyst 0.1
An aqueous resin composition consisting of 7 parts by weight and 3.4 parts by weight of epoxy silane was used.
A coating film having a thickness of 0.9 g / m ² (dry state) was formed by a coating method.
Heat treatment was performed for a minute to form a coating cured film. Furthermore,
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 oriented polyethylene terephthalate film having a thickness of 50 μm as a substrate by a gravure coating method. Apply, film thickness 10g /
An m ² (dry state) coating film was formed 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 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 so as to face each other and interposing an acrylic resin adhesive layer 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 base material, 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). Next, using a gravure printing machine, a gravure coat roll was placed in the first color on the plasma-treated surface of the above-mentioned evaporated aluminum oxide thin film, and an ethylene-vinyl alcohol copolymer (ethylene Content 32 mol%) 1
An aqueous resin composition comprising 0 parts by weight, 34 parts by weight of tetraethoxysilane, 15 parts by weight of water, 10 parts by weight of isopropyl alcohol, 0.17 parts by weight of a tertiary amine catalyst, and 3.4 parts by weight of epoxysilane. This was coated by a gravure roll coating method and had a thickness of 0.9 g / m2.
² (dry state) coating film is formed.
Heat treatment was performed at 20 ° C. for 1 minute to form a cured coating film. 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 so as to face each other and interposing an acrylic resin adhesive layer 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.

Example 4 A gravure printing machine was used on the plasma-treated surface of the aluminum oxide vapor-deposited thin film manufactured in exactly the same manner as in Example 1 above, and a gravure coat roll was used for the first color. And a 15% solution of ethylene-vinyl alcohol copolymer (ethylene content 32 mol%) in ion-exchanged water and n-propyl alcohol (1/1) solvent was added to 100 parts by weight of polyethyleneimine ( Nippon Shokubai Chemical Co., Ltd.)
Using a 5% solution of 20% by weight of a resin composition, this is coated by a gravure roll coating method to form a coating film having a thickness of 1.1 g / m ² (dry state). Then, heat treatment was performed at 120 ° C. for 5 minutes to form a cured coating film. Next, 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 except for the above. Further, a solar cell module according to the present invention was manufactured in the same manner as in Example 1 using the surface protection sheet manufactured as described above.

Example 5 The ion-exchanged water of an ethylene-vinyl alcohol copolymer (ethylene content of 32 mol%) was applied to the corona-treated surface of a silicon oxide vapor-deposited thin film produced in exactly the same manner as in Example 2 above. 15% by n-propyl alcohol (1/1) solvent
A resin composition was used in which 1 part by weight of a 30% solution of zirconium acetate in the same solvent was added to 100 parts by weight of the solution, and the resin composition was coated by a gravure roll coating method to have a thickness of 1%. A coating film of 0.1 g / m 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 2 above. Furthermore, 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.

Example 6 An ion-exchanged water of ethylene-vinyl alcohol copolymer (ethylene content: 32 mol%) was applied to the plasma-treated surface of the deposited aluminum oxide thin film produced in exactly the same manner as in Example 1 above. A resin composition obtained by adding 1 part by weight of a 30% solution of carbodiimide in the same solvent to 100 parts by weight of a 15% solution in n-propyl alcohol (1/1) solvent is used. A coating film having a thickness of 1.1 g / m ² (dry state) is formed by a coating method, and then heat-treated at 120 ° C. for 5 minutes to form a cured coating film. did. Next, 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 except for the above.
Furthermore, the solar cell module according to the present invention was prepared in the same manner as in Example 1 using the surface protection sheet manufactured as described above.
Manufactured.

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.
And 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 side, with the solar cell element surfaces facing each other. 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 liquid (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 dry state) coating film 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 deposited aluminum oxide thin film of the above-mentioned surface protection sheet. 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 liquid (trade name,
(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 Examples The total light transmittance of the surface protective sheets according to the present invention produced 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. (3). Measurement of Water Vapor Permeability and Oxygen Permeability The water vapor permeability was determined by the surface protection sheet according to the present invention manufactured in Examples 1 to 6 and the surface protection sheet according to Comparative Examples 1 to 3.
Under the conditions of a temperature of 40 ° C. and a humidity of 90% RH, a measuring instrument manufactured by MOCON, USA [model name, part
MATTRAN (PERMATRAN)]
Oxygen permeability was measured at a temperature of 23 for the same object as described above.
C., humidity 90% RH, USA, MOCON (MOCO
N) [Model name, OXTRA
N)]. The above measurement results are shown in Table 1 below.

[0048]

[Table 1] In Table 1 above, the water vapor barrier property is represented by [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 property and oxygen barrier property. 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.

[0050]

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 on the vapor-deposited inorganic oxide thin film, a resin composition containing an ethylene-vinyl alcohol copolymer as a main component of a vehicle is further provided. Coating film, and then, on one surface of the resin film provided with the vapor-deposited thin film of the inorganic oxide and the coating film, a coating film of a resin composition containing a fluorine-based resin as a main component of a vehicle is formed. To produce a surface protection sheet for a solar cell module, which is used as a surface protection sheet layer, one side of which is inside, a filler layer, and a solar cell element as a photovoltaic element. ,filler And a backside protective sheet layer and the like are sequentially laminated, and then a solar cell module is manufactured using a lamination method or the like in which these are integrally vacuum-suctioned and heated and pressed to obtain a water-soluble module. It significantly improves the moisture resistance to prevent the intrusion of oxygen, etc., and also minimizes the long-term performance degradation of light resistance, heat resistance, water resistance, etc., and has excellent protection ability In addition, it is excellent in antifouling properties, etc., and is a lower cost and safer surface protection module for solar cell modules.
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 photovoltaic module manufactured using the surface protection sheet for a photovoltaic module according to the present invention shown in FIG.
FIG. 3 is a schematic cross-sectional view schematically showing 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 of forming a 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) 4F006 AA12 AA13 AA18 AA19 AA22 AA34 AA42 AA55 AB19 AB20 AB64 AB65 AB66 AB67 AB68 AB74 AB76 BA03 BA04 BA05 BA11 CA08 DA01 DA03 DA04 4F100 AA17B AA19 AH06A A01A08A01C AK07D AK17A AK41D AK42 AK46D AK69C AL05A AL05C AR00E BA04 BA05 BA07 BA10A BA10D BA10E BA13 CA02A CA02C CA06A CA07A EH66B EJ38D EJ55B EJ61B GB41 JB07 JD03 JD04 EJ03 JK12A01

Claims (17)

[Claims] 1. 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.
What is claimed is: 1. A surface protection sheet for a solar cell module, comprising a resin film provided with a coating film of a resin composition containing a vinyl alcohol copolymer 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 is composed of one or more multilayer films of the chemical vapor-deposited inorganic oxide vapor-deposited thin film. 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 formed of a multilayer film of two or more layers by a physical vapor deposition method and a chemical vapor deposition method. 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 seal for a solar cell module according to claim 1, wherein the ethylene-vinyl alcohol copolymer has an ethylene content of 25 to 50 mol%. G. 12. The surface protection sheet for a solar cell module according to claim 1, wherein the resin composition contains a metal alkoxide compound. 13. The surface protection sheet for a solar cell module according to claim 1, wherein the resin composition contains a crosslinking agent. 14. The surface protection for a solar cell module according to claim 1, wherein the resin composition contains a polymer having a high adhesiveness to a deposited thin film of an inorganic oxide. Sheet. 15. The surface protection sheet for a solar cell module according to claim 1, wherein the resin composition contains a silane coupling agent. 16. The resin film according to claim 1, wherein the resin film comprises a biaxially oriented polyester resin film, a biaxially oriented polyamide resin film, or a biaxially oriented polypropylene resin film. Protection sheet for solar cell module. 17. 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. A filler layer and a photovoltaic layer are provided on one surface of a solar cell module surface protection sheet in which a resin film provided with a coating film of a resin composition containing a copolymer as a main component of a vehicle is laminated. A solar cell element as a power element, a filler layer, and a backside protective 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.