JP2000294822A - Surface protection sheet for solar cells and solar cell using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To stably obtain a more low-cost and safe surface protection sheet constituting a solar cell module; the sheet uses a fluoric resin sheet as a surface protection sheet layer constituting the module, greatly improves the moisture proof for blocking moisture, oxygen, etc., from penetrating, suppresses its long- term performance degradation about various resistances such as light resistance, heat resistance and water resistance to minimum and is superior in protection ability, antifouling property, scratch resistance, etc. SOLUTION: A surface protection sheet for solar cell modules and a solar cell module using the same are provided. The sheet comprises a fluoric resin sheet 1, an inorganic oxide-deposited thin film 2 on one surface of the sheet 1, a coating film 3 of a composition contg. a metal alkoxide compound and/or its hydrolyzed product as main components of a vehicle on the deposited thin film 2, and an antifouling layer 4 and/or ultraviolet absorbent layer on one or both surfaces of the resin sheet 1 provided with the deposited thin film 2 and the coating film 3.

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. In the present invention, the sheet means a film or a sheet, and the film means a film or a sheet.

[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. By the way, a glass plate or the like is currently 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 recently 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, the solar light enters, transmits and absorbs sunlight, and has high transparency and absorptivity, and various robustness such as light resistance, heat resistance, and water resistance. It has excellent moisture resistance to prevent intrusion of moisture, oxygen, etc., and also has high surface hardness, prevents accumulation of dirt and dust on the surface, and has excellent abrasion resistance and protection. Conditions such as high ability and other conditions are mentioned. However, a glass plate or the like which is currently most commonly used as a surface protection sheet layer constituting a solar cell module has excellent transmission and absorption of sunlight, and
Light fastness, heat resistance, excellent in various fastnesses such as water resistance, also excellent in moisture proof, furthermore, the surface hardness is hard, excellent in scratch resistance, has the advantages of high protection ability, There is a problem that it lacks in plasticity, impact resistance, weight reduction, etc., and is inferior in its workability, workability, etc., and lacks in cost reduction, etc. Further, when a resin sheet such as a fluororesin is used as the surface protection sheet layer constituting the solar cell module, plasticity,
Although it is rich in 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, in the case of the above-mentioned fluororesin sheet, there is a problem that dust and the like accumulate on the surface, the surface is easily contaminated, the antifouling property is poor, and the abrasion resistance is poor. Therefore, the present invention provides a surface protection sheet layer constituting a solar cell module,
Even with the use of fluororesin sheet, the moisture-proof property to prevent the invasion of moisture, oxygen, etc. is remarkably improved, and the long-term performance of light fastness, heat resistance, water resistance, etc. Deterioration is minimized, the protection ability is excellent, and the contamination resistance and scratch resistance are also excellent. To provide.

[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 the above, photocatalyst powder, ultraviolet absorber, etc., first, use a fluororesin sheet as a base sheet, and use one side of the base sheet. Is provided with a transparent, glassy inorganic oxide vapor-deposited thin film such as silicon oxide or aluminum oxide, and a metal alkoxide compound and / or a hydrolyzate thereof on the inorganic oxide vapor-deposited thin film. Is provided with a coating film of a composition containing as a main component of a vehicle, and furthermore, one of the surfaces of a fluororesin sheet provided with a vapor-deposited thin film of the inorganic oxide and a coating film. Light on both sides A surface protection sheet for a solar cell module is manufactured by providing an antifouling layer composed of a coating film composed of a composition containing a medium powder and / or an ultraviolet absorber layer composed of a coating film composed of a composition containing an ultraviolet absorbent. This is used as a surface protection sheet layer, and a filler layer, a solar cell element as a photovoltaic element, a filler layer, a backside protection sheet layer, and the like are sequentially formed on the inorganic oxide deposited thin film side. The solar cell module was manufactured using a lamination method or the like in which these were integratedly vacuum-sucked and heated and pressed together to obtain a solar cell module. Remarkably improved, and furthermore, with respect to various fastnesses such as light resistance, heat resistance, and water resistance, the long-term performance degradation was minimized,
Excellent protection ability, furthermore, prevents contamination that accumulates dust and contaminates the surface, and is excellent in antifouling property, scratch resistance, etc.
The present invention has been completed by finding that a lower cost and safer surface protection sheet for a solar cell module and a solar cell module using the same can be manufactured.

That is, according to the present invention, a vapor-deposited thin film of an inorganic oxide is provided on one side of a fluororesin sheet, and a metal alkoxide compound and / or a hydrolyzate thereof is deposited on the vapor-deposited thin film of an inorganic oxide. One surface of a fluorine-based resin sheet provided with a coating film made of a composition containing a substance as a main component of a vehicle, and further provided with a vapor-deposited thin film of the inorganic oxide and a coating film. Also, the present invention relates to a surface protection sheet for a solar cell module, which is provided with an antifouling layer and / or an ultraviolet absorber layer on both sides, and a solar cell module using the same.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The above-mentioned present invention will be described below in more detail with reference to the drawings and the like. 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. 4 and 5 are schematic cross-sectional views illustrating a few examples of the layer structure of the surface protection sheet for a solar cell module according to the present invention, and FIG. It is a schematic sectional drawing which illustrates an example about the layer structure of the solar cell module manufactured using the surface protection sheet for solar cell modules concerning this invention.

First, as shown in FIG. 1, a surface protection sheet A for a solar cell module according to the present invention is provided with an inorganic oxide vapor-deposited thin film 2 on one surface of a fluororesin sheet 1. ,
Further, a coating film 3 made of a composition containing a metal alkoxide compound and / or a hydrolyzate thereof as a main component of the vehicle is provided on the vapor-deposited thin film 2 of the inorganic oxide. Evaporated thin film 2 and coating film 3
The basic structure is that the antifouling layer 4 and / or the ultraviolet absorbent layer 5 are provided on one or both surfaces of the fluororesin sheet 1 provided with the above. As a specific example of the surface protection sheet for a solar cell module according to the present invention, as shown in FIG. 2, an inorganic oxide is deposited on one surface of a fluororesin sheet 1. A thin film 2 is provided, and 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 provided on the inorganic oxide vapor-deposited thin film 2. Evaporated inorganic oxide thin film 2
An antifouling layer 4 is provided on the fluororesin sheet 1 of the fluororesin sheet 1 provided with the coating film 3 and an ultraviolet absorber is provided on the surface of the coating film 3. Providing layer 5,
-Proof solar cell module, characterized in that the smudge layer 4 a top surface - can be exemplified bets A ₁ - le for surface protection sheet.
Further, as another specific example of the surface protection sheet for a solar cell module according to the present invention, as shown in FIG. 3, an inorganic oxide is deposited on one surface of a fluororesin sheet 1. A thin film 2 is provided, and 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 provided on the inorganic oxide vapor-deposited thin film 2. An antifouling layer 4 and a UV absorber layer 5 are provided on the surface of the fluororesin sheet 1 of the fluororesin sheet 1 provided with the inorganic oxide vapor-deposited thin film 2 and the coating film 3. solar cell module, characterized in that the antifouling layer 4 and the outermost surface - can be exemplified bets a ₂ - le for surface protection sheet. Further, as another specific example of the surface protection sheet for a solar cell module according to the present invention, as shown in FIG. 4, one surface of a fluororesin sheet 1 is coated with an inorganic oxide. A multilayer film 6 composed of at least two or more layers of the vapor-deposited thin film 2 is provided. A fluorine-based resin sheet provided with a coating film 3 of a composition as a component and further provided with the multilayer film 6 and the coating film 3;
On one or both sides of any sheet 1, the antifouling layer 4 and / or UV absorber layer solar cell module comprising 5 structure provided with - le surface protective sheet - it can be exemplified bets A _3. Further, as another specific example of the surface protection sheet for a solar cell module according to the present invention, as shown in FIG. Providing a deposited thin film 2a of an inorganic oxide by a growth method,
Next, on the inorganic oxide vapor-deposited thin film 2a, an inorganic oxide vapor-deposited thin film 2b is provided by physical vapor deposition to form a multilayer film 6 composed of two or more inorganic oxide vapor-deposited thin films 2a and 2b.
a, and a coating film 3 of a composition containing a metal alkoxide compound and / or a hydrolyzate thereof as a main component of a vehicle on the inorganic oxide deposited thin film 2b constituting the multilayer film 6a. And an antifouling layer 4 and / or an ultraviolet absorber layer 5 on one or both surfaces of the fluororesin sheet 1 provided with the multilayer film 6a and the coating film 3. the provided was composed of configuration solar cell module - can be exemplified bets a ₄ - le for surface protection sheet.

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. 6 illustrates an example in which a surface protection sheet A for a tool is used.
As shown in FIG. 1, the surface of the surface protecting sheet A for a solar cell module according to the present invention shown in FIG. A lamination method of laminating a solar cell element 12, a filler layer 13, a backside protective sheet layer 14, etc. as an electromotive element, and then vacuum-suctioning and heat-compressing them as a single unit. By using the molding method described above, the solar cell module T can be manufactured by using each of the above-mentioned layers as an integral molded body. In the drawing, reference numerals 1, 2, 3, 4, 5, etc. have the same meanings as described above. The above examples are only examples of the surface protection sheet for a solar cell module according to the present invention and a solar cell module manufactured using the same, and the present invention is not limited thereto. Not something.
For example, although not shown, in the above-described solar cell module, another layer can be arbitrarily added and laminated for the purpose of absorbing sunlight, reinforcing, and the like. is there. Further, in the present invention, when producing the surface protection sheet for a solar cell module according to the present invention, a step of providing a vapor-deposited thin film of an inorganic oxide, a step of providing a coating film, and providing an antifouling layer. The order of the steps, the step of providing the ultraviolet absorbent layer, and the like can be arbitrarily performed.

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. Examples of the fluorine resin sheet constituting the surface protection sheet for a solar cell module, the solar cell module and the like according to the present invention include polytetrafluoroethylene (PTFE), tetrafluoroethylene and perfluoroethylene. Perfluoroalkoxy resin (PF) consisting of a copolymer with alkyl vinyl ether
A), tetrafluoroethylene and hexafluoropropylene copolymer (FEP), tetrafluoroethylene and perfluoroalkylvinyl ether and hexafluoropropylene copolymer (EPE), copolymer of tetrafluoroethylene and ethylene or propylene (ET
FE), polychlorotrifluoroethylene resin (PCT)
FE), a copolymer of ethylene and chlorotrifluoroethylene (ECTFE), a vinylidene fluoride resin (P
VDF) or a transparent fluororesin film or sheet made of vinyl fluoride resin (PVF)
Can be used. In the present invention, among the above-mentioned fluororesin films or sheets, a vinyl fluoride resin (PVF) or a copolymer of tetrafluoroethylene and ethylene or propylene is used.
A fluororesin sheet made of (ETFE) has transparency, and is particularly preferable from the viewpoints of sunlight transmission and absorption. Thus, in the present invention, by using the above-mentioned fluorine-based resin sheet, the excellent properties of the fluorine-based resin sheet, particularly, mechanical properties, heat resistance, optical properties, etc. Furthermore, a surface protection sheet constituting a solar cell utilizing various properties such as super weather resistance such as light resistance, heat resistance, water resistance, etc., stain resistance, chemical resistance, and scratch resistance. With this, it has the same optical properties and durability as conventional glass plates, etc., and is lighter than glass plates due to its flexibility and mechanical properties, and has excellent workability, etc. It has advantages such as easy operation.

In the present invention, as the above-mentioned fluororesin sheet, for example, one or more of the above-mentioned fluororesins is used, and the extrusion method, cast molding method, T-die method, and cutting method are used. A method of forming the above-mentioned fluororesin alone by using a film-forming method such as an inflation method or other method, or a method of forming a multilayer co-extrusion film using two or more kinds of fluororesins. A film or sheet of a fluorine-based resin is produced by a method of mixing two or more kinds of fluorine-based resins before the formation of the film to form a film. In this case, for example, a film or sheet made of a fluororesin that is stretched in a uniaxial or biaxial direction using a tenter method or a tuber method can be used. In the present invention, the thickness of the fluororesin sheet is 12 to 200 μm.
And more preferably about 25 to 150 μm.
Further, in the present invention, as the fluororesin sheet,
It is desirable that the visible light transmittance is 90% or more, preferably 93% or more, and that it has a property of transmitting all incident sunlight. In the above, at the time of film formation of the fluororesin, for example, processability of the film, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, sliding properties, mold release properties, flame retardancy, Anti-mold, electrical properties,
For the purpose of improving and modifying others, various plastic compounding agents and additives can be added, and the amount of addition can be from a very small amount to several tens%, depending on the purpose.
It can be arbitrarily added. Further, in the above, common additives include, for example, lubricants, crosslinking agents, antioxidants, ultraviolet absorbers, light stabilizers, fillers, reinforcing agents, reinforcing agents, antistatic agents, flame retardants, flame retardants , Foaming agent, fungicide,
Pigments, others, and the like can be used, and further, a modifying resin and the like can be used. In the present invention, among the above-mentioned additives, in particular, an antioxidant, or a fluororesin screen obtained by kneading and processing an ultraviolet absorber or the like.
It is desirable to use

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

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 the metal oxide is used as a raw material, or a vacuum evaporation method in which the metal oxide is heated and vapor-deposited on a fluororesin sheet. A vapor deposition film is formed using an oxidation reaction vapor deposition method in which oxygen is introduced and oxidized to vapor-deposit on a fluorine-based resin sheet, and a plasma-assisted oxidation reaction vapor deposition method in which the oxidation reaction is promoted by plasma. be able to. 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. 7. FIG. 7 is a schematic configuration diagram showing an example of a roll-up type vacuum evaporation apparatus. As shown in FIG. 7, in a vacuum chamber 22 of a take-up type vacuum evaporation apparatus 21, a fluororesin sheet 1 fed from an unwinding roll 23 is guided via guide rolls 24 and 25.
It is guided to the cooled coating drum 26. Then, on the fluorine-based resin sheet 1 guided on the cooled coating drum 26, a vapor deposition source 28 heated by a crucible 27, for example, metal aluminum or aluminum oxide, is placed. It is evaporated, and if necessary, oxygen gas or the like is spouted from the oxygen gas outlet 29 and supplied, for example, through the masks 30, 30.
Forming a vapor-deposited thin film of an inorganic oxide such as aluminum oxide, and then forming a vapor-deposited thin film of an inorganic oxide such as aluminum oxide on the fluorine-based resin screen above;
The roll 1 is sent out through guide rolls 25 'and 24' and wound up on a take-up roll 31 to form a vapor-deposited inorganic oxide thin film by physical vapor deposition according to the present invention. it can. 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.
Further, in the present invention, as the metal or the 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 side of the fluororesin sheet, a monomer gas for vapor deposition such as an organic silicon compound is used as a raw material, and an inert gas such as an argon gas or a helium gas is used as a carrier gas. Use oxygen gas, etc.
A deposited thin film of an inorganic oxide such as silicon oxide can be formed by using a low-temperature plasma chemical vapor deposition (CVD) method using a low-temperature plasma generator or the like. In the above, as the low-temperature plasma generator, for example, high-frequency plasma, pulse wave plasma, it is possible to use a generator such as microwave plasma, in the present invention,
In order to obtain highly active and stable plasma, it is desirable to use a generator using a high-frequency plasma method.

More specifically, an example of a method of forming a vapor-deposited thin film of an inorganic oxide by the above-described low-temperature plasma chemical vapor deposition method will be described. FIG. FIG. 1 is a schematic configuration diagram of a low-temperature plasma chemical vapor deposition apparatus showing an outline of a method for forming a vapor-deposited oxide thin film. As shown in FIG. 8, in the present invention, the fluororesin sheet 1 is fed out from an unwinding roll 43 disposed in a vacuum chamber 42 of a plasma enhanced chemical vapor deposition apparatus 41. The fluororesin sheath
The roller 1 is conveyed on the peripheral surface of the cooling / electrode drum 45 at a predetermined speed via the auxiliary roll 44. 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 vapor-deposition mixed gas composition, the vapor-deposition mixed gas composition was introduced into the vacuum chamber 42 through the raw material supply nozzle 49, and the cooling / electrode drum 4
Plasma is generated by the glow discharge plasma 50 on the fluororesin sheet 1 conveyed on the 5 peripheral surfaces, and the plasma is irradiated to form a vapor-deposited thin film of an inorganic oxide such as silicon oxide. Film forming. In the present invention, at this time, a predetermined power is applied to the cooling / electrode drum 45 from a power source 51 disposed outside the chamber.
The generation of plasma is promoted by disposing a magnet 52 near the electrode drum 45. Next, the fluorine-based resin sheet 1 on which the deposited thin film of inorganic oxide such as silicon oxide is formed, Take-up roll 5 via roll 53
4 to produce a vapor-deposited inorganic oxide thin film by the plasma enhanced chemical vapor deposition method according to the present invention. In the figure, 55 represents a vacuum pump.
Further, 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 as described above are connected, and two or more layers are laminated. An inorganic oxide vapor-deposited thin film composed of layers or more can be formed. In the present invention,
A monomer gas for vapor deposition or the like may be used as one kind or a mixture of two or more kinds, and a thin film of an inorganic oxide mixed with different materials may be formed. The above exemplification is merely an example, and it goes without saying that the present invention is not limited thereby.

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 characteristics and the like. In the above, for example, an argon gas, a helium gas, or the like can be used as the inert gas.

In the present invention, in the silicon oxide vapor-deposited thin film formed as described above, a monomer gas such as an organic silicon compound chemically reacts with oxygen gas or the like, and the reaction product is formed on a fluorine-based resin sheet. To form a dense, thin film having high flexibility and the like. Usually, silicon oxide represented by the general formula SiO _x (where X represents a number of 0 to 2) is mainly used. It is a continuous vapor-deposited thin film. 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, and the like. Generally, as the value of X decreases, the gas permeability decreases, but the film itself exhibits yellowness. Takes on, the transparency becomes worse. Further, the above-mentioned deposited thin film of silicon oxide has silicon (Si) and oxygen (O) as essential constituent elements, and furthermore, one of carbon (C) and hydrogen (H), or both elements Consisting of a silicon oxide deposited film containing as a trace constituent element, and the film thickness thereof,
It is in the range of 50 ° to 2000 °, and the composition ratio of 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, the above-mentioned deposited silicon oxide thin film is, for example, an X-ray photoelectron spectrometer (X
ray Photoelectron Spectro
, XPS), secondary ion mass spectrometer (Se
condary Ion Mass Spectros
(Copies, SIMS), etc. to confirm the above physical properties by performing elemental analysis of the deposited silicon oxide thin film using a method of analyzing by ion etching in the depth direction, etc. using a surface analyzer such as SIMS. Is what you can do. In the present invention, the thickness of the above-described silicon oxide vapor-deposited thin film is desirably about 50 to 2000 °, and specifically, the thickness is about 100 to 100.
The 0 ° position is desirable, and in the above, 1000
If the thickness is more than 2000 °, cracks and the like are likely to occur in the film, which is not preferable.
If it is 0 ° or less than 50 °, it is difficult to achieve the barrier effect, which is not preferable. In the above description, the film thickness can be measured by a fundamental parameter method using, for example, a fluorescent X-ray analyzer (model name: RIX2000) manufactured by Rigaku Corporation. Further, in the above, as means for changing the thickness of the deposited silicon oxide thin film, increasing the volume velocity of the deposited film, that is, a method of increasing the amount of the monomer gas and the oxygen gas or the rate of the deposition. It can be performed by a method of slowing down.

In the present invention, 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 inorganic oxide thin film by using both of the chemical vapor deposition methods together, first, a chemical vapor deposition method is performed on a fluororesin sheet. A dense, highly flexible, thin film of inorganic oxide capable of relatively preventing cracks is provided, and then the inorganic oxide is formed on the thin film of inorganic oxide by physical vapor deposition. It is desirable to provide an evaporated thin film of inorganic oxide composed of two or more multilayer films by providing an evaporated thin film. In the present invention, for example, a gas is applied to the surface of the vapor-deposited inorganic oxide thin film formed above in order to improve the close adhesion and affinity with the coating film provided thereon. Oxygen gas, nitrogen gas, argon gas generated by ionization by
A plasma-treated surface or a corona-treated surface can be formed by utilizing a plasma surface treatment method in which surface modification is performed using a plasma gas such as helium gas, or a corona discharge treatment method.

Next, in the present invention, a surface protection sheet for a solar cell module and a 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 by dissolving it in a solvent so as to be about 50% by weight. In the above, if the content is less than 0.1% by weight, the formed coating film cannot form a film having desired properties, that is, a desired barrier performance. When the content exceeds 70% by weight, it is difficult to form a transparent uniform film, which is not preferable.

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 component of the vehicle, and if necessary, furthermore, for example, resins as binders, fillers, stabilizers, plasticizers, antioxidants, Light stabilizers such as ultraviolet absorbers, dispersants, thickeners, drying agents, lubricants, antistatic agents, cross-linking agents, and other additives are optionally added, and thoroughly kneaded with a solvent, diluent, 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., from the viewpoint of the coating property of the coating film, the close adhesion of the coating film to the deposited thin film of the inorganic oxide, and the like. 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 silane coupling agent having dual reactivity or an isocyanate compound may 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 to obtain water or alcohol. -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.
The antifouling layer constituting the metal layer or the like will be described. The antifouling layer is formed of a photocatalyst powder containing titanium oxide as a main component or a coating film of a composition including fine particles contained in a sol. 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, reinforcing agents, antistatic agents, flame retardants,
One or more kinds of flame retardants, foaming agents, fungicides, pigments, etc. are arbitrarily added within a range not affecting the transmission of sunlight, and further kneaded sufficiently with a solvent, a diluent or the like. For example, a composition such as a solvent type, an aqueous type, or an emulsion type is prepared, and then the composition is subjected to, for example, a floating knife coating method, a knife over roll coating method, Inverted knife coating, squeeze roll coating, reverse roll coating, roll coating,
Gravure roll coating, kiss roll coating, air
Blade coating method, extrusion coating method, car coating
A coating method such as a ten-flow coating method and others, or gravure printing, offset printing, silk screen printing, etc.
A coating film can be formed by applying or printing using a printing method such as printing, transfer printing, or the like. In the above, the thickness of the coating film is 0.1 to 1
0 g / m ² (dry state), more preferably 0.5 to
1 g / m ² is desirable.

In the above, as the photocatalyst powder, for example, the resin is deteriorated, destroyed, or decomposed by oxidation or the like by the action of light such as sunlight,
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 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.

Incidentally, in the present invention, the photoactivity of the photocatalyst powder in the coating film constituting the antifouling layer is such that the photoactivity is located below the antifouling layer, for example, an ultraviolet absorber layer or a fluorine-based layer. Provide an activity blocking layer for blocking the activity of the photocatalyst powder consisting of an inorganic film or the like that blocks the mutual contact so as not to affect the resin sheet, etc. and to cause its degradation, decomposition, destruction, etc. Can be. The above-mentioned activity blocking layer is usually provided below the antifouling layer. Examples of the inorganic film constituting the above-mentioned activity blocking layer include, for example,
The above-described transparent silicon oxide or a deposited film of an inorganic oxide such as 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 the thickness thereof is about 100 to 3000 °, more preferably 100 to 1500 °. Position is desirable.

In the present invention, in order to strengthen the close 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, a surface protection sheet for a solar cell module and a solar cell module according to the present invention.
The UV absorber layer that constitutes the UV absorber or the like will be described. As the UV absorber layer, for example, one or more binders as a vehicle are added to one or more UV absorbers. And, if necessary, for example,
Lubricants, crosslinking agents, antioxidants, stabilizers, fillers, reinforcing agents,
One or more of a reinforcing agent, an antistatic agent, a flame retardant, a flame retardant, a foaming agent, a fungicide, a pigment, etc. are arbitrarily added within a range not affecting the transmission of sunlight, and a solvent is further added. By sufficiently kneading with a diluent or the like, for example, a solvent type, an aqueous type, or a composition such as an emulsion type is prepared,
A coating method for forming the antifouling layer using the composition,
Alternatively, a coating film can be formed by similarly applying or printing similarly using a printing method or the like. In the above, the thickness of the coating film is 0.1 to 10 g /
m ² (dry state), more preferably 1 to 5 g / m ²
Position is desirable.

In the above, the ultraviolet absorber 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. Benzophenone, benzotriazole, saltyl, acrylonitrile, metal complex salt, hindered amine, etc.
Ultrafine titanium oxide (particle size, 0.01-0.06μ
m) or ultrafine zinc oxide (0.01 to 0.04 μm)
m), one or more of inorganic UV absorbers such as ultrafine talc, kaolin, calcium carbonate and other white powders can be used. In the above composition, the content of the ultraviolet absorber varies depending on the particle shape, density and the like, but is preferably about 0.1 to 20% by weight. In the above description, as the binder as a vehicle, the binder used when forming a coating film of the composition containing the photocatalyst powder constituting the above-described antifouling layer can be similarly used.

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, for example, a thin-film polycrystalline silicon solar cell element, a thin-film microcrystalline silicon solar cell element, or a hybrid element of a thin-film crystalline silicon solar electronic element and an amorphous solar cell element can be used.

Next, in the present invention, the solar cell module
The filler layer laminated below the photovoltaic element constituting the solar cell module will be described. The filler layer is the same as the filler layer laminated below the solar cell module surface protection sheet. In addition, it is necessary to have adhesiveness to the backside protection sheet, and further to have thermoplasticity to fulfill the function of maintaining the smoothness of the backside of the solar cell element as a photovoltaic element. In order to protect a solar cell element as a photovoltaic element, it is necessary to have excellent scratch resistance, shock absorption and the like. However, the filler layer laminated below the photovoltaic element constituting the solar cell module is different from the filler layer laminated below the surface protection sheet for the solar cell module. , Surely,
It is not necessary to have transparency. Specifically, as the above-mentioned filler layer, for example, as in the case of the above-described filler layer laminated under the surface protection sheet for a solar cell module, for example, a fluorine-based resin, ethylene-vinyl acetate copolymer may be used. A polyolefin resin such as coalesced, ionomer resin, ethylene-acrylic acid, or methacrylic acid copolymer, polyethylene resin, polypropylene resin, polyethylene or polypropylene can be mixed with acrylic acid, itaconic acid, maleic acid, fumaric acid, etc. 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 may be 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 present invention described above. 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.

[0042]

Next, the present invention will be described more specifically with reference to examples. Example 1 (1). As a base material, a polyvinyl fluoride resin sheet (PVF) having a thickness of 50 μm is used, which is mounted on a delivery roll of a take-up type vacuum evaporation apparatus, and then placed on a coating drum. And then, under the following conditions, using aluminum as a deposition source and supplying oxygen gas,
By a reactive vacuum evaporation method using an electron beam (EB) heating method, an evaporated thin film of aluminum oxide having a thickness of 300 ° was formed on the surface of the above-mentioned polyvinyl fluoride resin film which had been subjected to the easy adhesion treatment. (Evaporation conditions) Evaporation source: Aluminum Degree of vacuum in vacuum chamber: 7.5 × 10 ⁻⁶ mbar Degree of vacuum in evaporation chamber: 2.1 × 10 ⁻⁶ mbar EB output: 40 KW Film transport speed: 600 m / Minutes (2). Then, immediately after the deposition, the glow discharge plasma generator was used to apply a plasma output of 1500 W and an oxygen gas (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 in the mixing ratio, and the mixture was refluxed at 50 ° C. for 2 hours.
25 parts by weight of methyltrimethoxysilane and ethanol were added to the obtained partially hydrolyzed solution of dimethyldimethoxysilane.
Then, 5 parts by weight of toluene and 20 parts by weight of a toluene solution (20%) of polymethyl methacrylate (PMMA) were added, and the mixture was further stirred at room temperature for 2 hours to prepare a coating composition. Next, on the plasma-treated surface of the deposited aluminum oxide thin film, using the composition for coating obtained above,
This was coated by a gravure roll coating method to form a coating film having a thickness of 1.0 g / m ² (dry state), and then subjected to a heating treatment at 120 ° C. for 5 minutes. A cured film was formed. Next, an ultraviolet absorbent composition comprising 5 parts by weight of ultrafine titanium oxide particles of 0.03 μm and 95 parts by weight of ethylene-vinyl alcohol copolymer (solid content: 25%) was applied to the surface of the cured coating film formed above. The product is applied by a gravure roll coating method to form a film having a thickness of 0.5 g / m ^2.
An (ultra-dry) ultraviolet absorber layer was formed to produce a surface protection sheet for a solar cell module 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 surface of the ultraviolet absorbent layer 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 an acrylic resin adhesive layer facing each other. (5). In the above, instead of the above-mentioned 50 μm-thick polyvinyl fluoride resin sheet (PVF) as the base material, a 50 μm-thick fluororesin sheet made of tetrafluoroethylene-ethylene copolymer (ETF) was used.
Using E), in the same manner as described above, a similar surface protection sheet for a solar cell module according to the present invention, and
The solar cell module could be manufactured.

Embodiment 2 (1). As a base material, a polyvinyl fluoride resin film (PVF) having a thickness of 50 μm was used, which was mounted on a delivery roll of a plasma enhanced chemical vapor deposition apparatus, and a silicon oxide vapor-deposited thin film having a thickness of 300 ° was formed under the following conditions. Was formed on the easily treated surface of the polyvinyl fluoride resin film. (Evaporation conditions) Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 1: 10: 10 (unit: slm) Degree of vacuum in vacuum chamber: 5.0 × 10 ⁻⁶ mbar Inside vapor deposition chamber Degree of vacuum: 6.0 × 10 ^-2 mbar Cooling / electrode drum supply power: 20 kW Film transport speed: 80 m / min Evaporation surface: Corona treated surface (2). Next, immediately after the deposition, an output of 10 kW and a processing speed of 100
Corona discharge treatment was performed at m / min to increase the surface tension of the vapor-deposited thin film surface from 35 dyne to 60 dyne. (3). 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. A solution of polymethyl methacrylate (PMMA) in toluene (20%) was added to the resulting partially hydrolyzed solution of tetraethoxysilane.
0 parts by weight were added, 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. Next, 1 part by weight of a benzophenone-based ultraviolet absorber and 99 parts by weight of a thermosetting acrylic resin liquid (solid content 2
5%) by applying a gravure roll coating method to form an ultraviolet absorber layer having a thickness of 2 g / m ² (dry state). -A surface protection sheet for steel was produced. (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 surface of the ultraviolet absorbent layer 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 an acrylic resin adhesive layer facing each other. (5). In the above, instead of the above-mentioned 50 μm-thick polyvinyl fluoride resin sheet (PVF) as the base material, a 50 μm-thick fluororesin sheet made of tetrafluoroethylene-ethylene copolymer (ETF) was used.
Using E), in the same manner as described above, a similar surface protection sheet for a solar cell module according to the present invention, and
The solar cell module could be manufactured.

Embodiment 3 (1). Using a polyvinyl fluoride resin film (PVF) having a thickness of 50 μm as a base material, a silicon oxide vapor-deposited thin film having a thickness of 300 mm was formed in exactly the same manner as in Example 2 above.
The surface for easy adhesion treatment was formed, and the surface of the thin film of silicon oxide was subjected to a corona discharge treatment to increase the surface tension of the surface of the thin film from 35 dyne to 60 dyne. (2). Next, using a polyvinyl fluoride resin film on which a vapor-deposited silicon oxide thin film subjected to the corona treatment was formed, the silicon oxide vapor deposition of the polyvinyl fluoride resin film was performed in exactly the same manner as in Example 1 above. An aluminum oxide deposited thin film having a thickness of 300 ° was formed on the corona-treated surface of the thin film, and plasma treatment was further performed on the aluminum oxide deposited thin film surface. (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.
Then, 3 parts by weight of toluene and 10 parts by weight of a cyclohexane solution of cycloolefin (30%) were added, and the mixture was further stirred at room temperature for 2 hours to prepare a coating composition. Next, the coating composition obtained above was used for the plasma-treated surface of the aluminum oxide vapor-deposited thin film, 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, and then
Heat treatment was performed at 0 ° C. for 1 minute to form a cured coating film. Next, 0.03 μm is applied to the coating cured film surface.
m of zinc oxide ultrafine particles and 95 parts by weight of ethylene-vinyl alcohol copolymer solution (solid content: 25%) was applied by a gravure roll coating method to form an ultraviolet absorbent composition. An ultraviolet absorber layer of 0.5 g / m ² (dry state) was formed to produce a surface protection sheet for a solar cell module 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 surface of the ultraviolet absorbent layer 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 an acrylic resin adhesive layer facing each other. (5). In the above, instead of the above-mentioned 50 μm-thick polyvinyl fluoride resin sheet (PVF) as the base material, a 50 μm-thick fluororesin sheet made of tetrafluoroethylene-ethylene copolymer (ETF) was used.
Using E), in the same manner as described above, a similar surface protection sheet for a solar cell module according to the present invention, and
The solar cell module could be manufactured.

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). 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 the obtained partial hydrolyzate solution of tetraethoxysilane, 25 parts by weight of a fluorinated acrylic resin solution (trade name, Lumiflon, manufactured by Asahi Glass Co., Ltd.) was added, and the mixture was further stirred at room temperature for 2 hours. The composition was prepared. 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. (3). Next, on the surface of the coating cured film formed above, an ultraviolet absorber layer was formed in the same manner as in (3) of Example 1, and then a 50 μm-thick polyvinyl fluoride as a base material was further formed. On the other surface (outermost surface) of the resin film,
A photocatalyst composition comprising 10 parts by weight of ultrafine titanium oxide particles having a particle size of 0.03 μm and 90 parts by weight of tetraethoxysilane solution (solid content: 20%) is applied by a gravure roll coating method, and the film thickness is 1 g / m 2. ^{2 A} (dry state) antifouling layer is formed to provide a solar cell module surface protection seal according to the present invention.
Manufactured. 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.

Embodiment 5 (1). Vaporization of the silicon oxide produced in Example 2 above
On the corona-treated surface of the deposited thin film, exactly the same as in Example 2 above
Then, a silicon oxide deposited thin film having a thickness of 300 mm is formed.
Next, a corona discharge treatment is applied to the surface of the silicon oxide film.
Then, two layers of deposited silicon oxide thin films were formed. (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.
did. Partial hydrolyzate of the obtained tetraethoxysilane
The water-aqueous ethylene-vinyl alcohol copolymer is added to the solution.
50 parts by weight of isopropyl alcohol solution (solid content 8%)
, And further stirred at room temperature for 2 hours to obtain a composition for coating.
I adjusted things. Next, the roller of the above-mentioned silicon oxide deposited thin film
On the treated surface, use the composition for application described above,
Coating by gravure roll coating method, thickness 1.
0 g / m^Two(Dry state) coating film is formed,
Next, heat-treat at 120 ° C for 5 minutes to coat and cure
A film was formed. Next, a cured coating film is formed as described above.
After the formation, a 50 μm thick polyvinyl fluoride
Surface of resin sheet (outermost surface, non-coated cured film surface)
Then, in the same manner as in (3) of Example 2 above,
Using the absorbent composition, forming an ultraviolet absorbent layer,
Then, an oxidized particle having a particle size of 0.03 μm
10 parts by weight of titanium ultra-fine particles and tetraethoxysilane liquid 9
0 parts by weight (solid content: 20%) of a photocatalyst composition
Coating using a via roll coating method, film thickness 1 g / m
^Two(Dry state) antifouling layer is formed, and
A surface protection sheet for a solar cell module was manufactured. Furthermore,
Using the surface protection sheet manufactured above,
2. A solar cell module according to the present invention was manufactured in the same manner as in 2.
Built.

Embodiment 6 (1). 50μm thick polyvinyl fluoride as base material
Using resin film (PVF)
In the same way, depositing aluminum oxide with a thickness of 300mm
A thin film is formed on the surface for easy adhesion treatment, and
Plasma treatment was performed on the surface of the deposited thin film of minium. 0d
yne. Next, plasma treatment is performed as described above.
Polyfluorinated Aluminum Oxide Deposited Thin Film
Exactly the same as in Example 2 above, using a vinyl resin film
The above-mentioned oxidation of the polyvinyl fluoride resin film
On the plasma treated surface of the deposited thin film of luminium, a film thickness of 300
蒸 着 A silicon oxide vapor deposition thin film is formed.
Corona discharge treatment was performed on the deposited thin film surface. (2). Next, the core of the deposited silicon oxide thin film formed above was used.
In the same manner as in Example 2 above,
A hardened film was formed. Next, the core formed above
In the same manner as in (3) of Example 2 above,
After forming an ultraviolet absorber layer, and further as a substrate
The other side of the 50 μm thick polyvinyl fluoride resin film
Ultrafine titanium oxide particles with a particle size of 0.03 μm on the surface (outermost surface)
10 parts by weight of the polymer and 90 parts by weight of the tetraethoxysilane solution (solid
(Photoform composition 20%)
-Using a coating method, and a film thickness of 1 g / m ^Two(Dry)
A solar cell module according to the present invention having an antifouling layer formed thereon
A surface protection sheet for use was manufactured. In addition, the table produced above
Using a surface protection sheet, similar to the third embodiment,
A solar cell module according to the invention was manufactured.

Comparative Example 1 A 50 μm-thick polyvinyl fluoride resin film (PVF) was used as a substrate, 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, and an adhesive layer of an acrylic resin with the solar cell element surfaces facing each other. To produce a solar cell module.

COMPARATIVE EXAMPLE 2 Using a polyvinyl fluoride resin film (PVF) having a thickness of 50 μm as a substrate, a vapor-deposited thin film of aluminum oxide having a thickness of 300 ° was formed in the same manner as in Example 1 described above. Further, the surface of the deposited thin film of aluminum oxide was subjected to plasma treatment to produce a surface protection sheet. Then
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,
The photovoltaic module was manufactured by laminating the photovoltaic cell elements so as to face each other with an adhesive layer of an acrylic resin interposed therebetween.

COMPARATIVE EXAMPLE 3 A 50 μm thick polyvinyl fluoride resin film (PVF) was used as a base material. Adhesion processing surface formed, further, on the silicon oxide deposited thin film surface,
A corona discharge treatment was performed 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 corona-treated surface, with the solar cell element surfaces facing each other, The solar cell module was manufactured by laminating through a resin adhesive layer.

Experimental Example 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 protection 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. Total light transmittance (%) using-
Was measured. (2). Solar cell module evaluation test This is based on JIS standard C8917-1989.
Of the photovoltaic power before and after the test, 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.
Measured with a measuring device (model name, PERMATRAN) manufactured by MOCON, USA, under the conditions of a temperature of 40 ° C. and a humidity of 90% RH. The object was measured at a temperature of 23 ° C. and a humidity of 90% RH using a measuring device (model name, OXTRAN) manufactured by MOCON, USA. The results of the above measurements are shown in Table 1 below.

[0052] In Table 1 above, the water vapor permeability is [g / m ² / d
ay.40 ° C. · 100% RH], and the oxygen permeability is [cc / m ² / day · 23 ° C. · 90% RH].
H].

As is evident from the measurement results shown in Table 1 above, the surface protection sheets for solar cell modules according to Examples 1 to 6 have high total light transmittance, high water vapor barrier properties, It had excellent oxygen barrier properties. Examples 1 to 6
The solar cell module using the surface protection sheet according to (1) also has a low output reduction rate. In contrast,
Although the surface protection sheet according to Comparative Example 1 has a high total light transmittance, it has low water vapor barrier properties and oxygen barrier properties. Therefore, a solar cell module using the same has a high output reduction rate. There was a problem. Furthermore, the surface protection sheets according to Comparative Examples 2 and 3 had high total light transmittance, excellent water vapor barrier properties and oxygen barrier properties, and had low output reduction rates. As compared with those of Examples 1 to 6, the water vapor barrier property and the oxygen barrier property were slightly inferior, and the output reduction rate was slightly higher.

[0054]

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, the photocatalyst powder, the ultraviolet absorber, etc., first, a fluororesin sheet is used as the base sheet.
Used on one side, a silicon oxide, or a transparent, glassy inorganic oxide vapor-deposited thin film such as aluminum oxide is provided, and a metal alkoxide compound is further formed on the inorganic oxide vapor-deposited thin film. And / or a fluorine-containing resin sheet provided with a coating film made of a composition containing a hydrolyzate thereof as a main component of a vehicle, and further provided with a vapor-deposited thin film of an inorganic oxide and a coating film as described above. A surface protection sheet for a solar cell module is manufactured by providing an antifouling layer and / or an ultraviolet absorber layer on one or both surfaces of the above, and this is used as a surface protection sheet layer. Co
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 on the side of the coating film, and then these are integrally vacuum-heated and heated. A solar cell module is manufactured by using a lamination method for pressure bonding, etc., and the moisture-proof property for preventing intrusion of moisture, oxygen, etc. is remarkably improved, and various properties such as light resistance, heat resistance, water resistance, etc. In terms of robustness, it is a low cost and safe surface for solar cell modules that minimizes long-term performance deterioration, has excellent protection ability, and is also excellent in antifouling and scratch resistance. Protection sheet and solar cell module using the same
Can be manufactured.

[Brief description of the drawings]

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

FIG. 4 is a schematic cross-sectional view showing a layer configuration of an example of a surface protection sheet for a solar cell module according to the present invention.

FIG. 5 is a schematic cross-sectional view showing a layer configuration of an example of a surface protection sheet for a solar cell module according to the present invention.

FIG. 6 shows 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. 7 is a schematic configuration diagram of a take-up type vacuum evaporation apparatus showing an outline of a method for forming a deposited thin film of an inorganic oxide by a physical vapor deposition method.

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

[Explanation of symbols]

A solar cell module - le for surface protective sheet - DOO A ₁ to A ₄ solar cell module - le for surface protective sheet - sheet 1 fluororesin sheet - DOO 2 deposition film 2b of the inorganic oxide vapor deposition film 2a inorganic oxides Inorganic oxide deposited thin film 3 Coating film 4 Antifouling layer 5 UV absorber layer 6 Multilayer film 6a 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 EA01 EA18 HA20 JA05

Claims (17)

[Claims] 1. An inorganic oxide vapor-deposited thin film is provided on one side of a fluororesin sheet, and a metal alkoxide compound and / or a hydrolyzate thereof is added to a vehicle on the inorganic oxide vapor-deposited thin film. A coating film of a composition as a main component is provided, and further, on one or both surfaces of a fluorine-based resin sheet provided with a vapor-deposited thin film of the inorganic oxide and a coating film, A surface protection sheet for a solar cell module, comprising an antifouling layer and / or an ultraviolet absorber layer. 2. An antifouling layer is provided on a fluororesin sheet surface, while an ultraviolet absorber layer is provided on a coating film surface, and the antifouling layer constitutes the outermost surface. The surface protection sheet for a solar cell module according to claim 1, characterized in that: 3. An antifouling layer and an ultraviolet absorber layer are provided on a fluororesin sheet surface, and the antifouling layer constitutes the outermost surface. Surface protection sheet for solar cell module. 4. The solar cell module according to claim 1, wherein the fluororesin sheet is a transparent fluororesin sheet having a visible light transmittance of 90% or more. -Surface protection sheet for steel. 5. A sheet according to claim 1, wherein the fluororesin sheet is a vinyl fluoride resin or a transparent fluororesin sheet made of ethylene-tetrafluoroethylene copolymer. 4. A surface protection sheet for a solar cell module according to item 4. 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 solar cell module according to claim 1, wherein the composition contains a resin component.
Surface protection sheet for 11. The surface protection sheet for a solar cell module according to claim 1, wherein the resin component comprises a water-soluble or hydrophilic resin. 12. The surface protection sheet for a solar cell module according to claim 1, wherein the composition comprises a curing catalyst for a metal alkoxide compound and / or a hydrolyzate thereof. . 13. The surface protection sheet for a solar cell module according to claim 1, wherein the composition contains inorganic oxide fine particles. 14. The solar cell module according to claim 1, wherein the composition contains a crosslinking agent.
Surface protection sheet for 15. The antifouling layer according to claim 1, wherein the antifouling layer comprises a coating film of a photocatalyst powder containing titanium oxide as a main component or a composition comprising fine particles contained in a sol. Surface protection sheet for solar cell module. 16. The surface protection sheet for a solar cell module according to claim 1, wherein the ultraviolet absorbent layer comprises a coating film of a composition containing the ultraviolet absorbent. 17. A vapor-deposited thin film of an inorganic oxide is provided on one side of a fluorine-based resin sheet, and a metal alkoxide compound and / or a hydrolyzate thereof is added to a vehicle on the vapor-deposited thin film of an inorganic oxide. A coating film made of a resin composition as a main component is provided, and further, on one or both surfaces of a fluorine-based resin sheet provided with a vapor-deposited thin film of the inorganic oxide and a coating film. A filler layer, a solar cell element as a photovoltaic element, and a filler, on the inorganic oxide deposited thin film side of the surface protection sheet for a solar cell module provided with an antifouling layer and / or an ultraviolet absorber layer. A solar cell module, comprising: an agent layer and a backside protective sheet layer sequentially laminated, and vacuum-suctioning these layers to form an integrally formed body by a heat-compression lamination method or the like.