JP2000294817A - Surface protection sheet for solar cell module and solar cell module using the same - Google Patents

Abstract

(57) [Summary] PROBLEM TO BE SOLVED: To provide a surface protection sheet constituting a solar cell module.
Although a fluorine-based resin sheet is used as the
Moisture-proof property to prevent invasion of oxygen etc. is remarkably improved, and furthermore, lightfastness, heat resistance, and various robustness such as water resistance,
The long-term performance degradation is minimized, the protection ability is excellent, and the antifouling property is also excellent, and the surface protection sheet constituting a safer and lower cost solar cell module is stable. It is to provide to. SOLUTION: A coating film made of a resin composition containing a fluorine-based resin as a main component of a vehicle and a vapor-deposited thin film of an inorganic oxide are provided, and a metal alkoxide compound and / or A resin film provided with a coating film of a composition containing the hydrolyzate as a main component of a vehicle was laminated, and further, the coating film, a vapor-deposited thin film of inorganic oxide, and a coating film were provided. A surface protection sheet for a solar cell module, characterized in that an antifouling layer and / or an ultraviolet absorber layer is provided on one or both surfaces of a laminate comprising a resin film, and a laminate comprising the same. It relates to the used solar cell module.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a solar cell module.
More specifically, the present invention relates to a surface protection sheet for solar cells and a solar cell module using the same, and more specifically, a solar cell module excellent in light resistance, heat resistance, water resistance, moisture resistance, stain resistance, etc. and having extremely high protection ability. And a solar cell module using the same.

[0002]

2. Description of the Related Art In recent years, attention has been paid to solar cells as a clean energy source due to increasing awareness of environmental issues. At present, solar cell modules of various forms have been developed and proposed. . Thus, the above-mentioned solar cell module usually includes a surface protection sheet layer, a filler layer,
It is manufactured by laminating a solar cell element as a photovoltaic element, a filler layer, a backside protective sheet layer, and the like in that order, vacuum-sucking and heat-compressing, for example, using a lamination method. At present, a glass plate or the like is most commonly used as a surface protection sheet layer constituting the above-mentioned solar cell module, and recently, a resin sheet such as a fluorine-based resin sheet has been used. Is also attracting attention, and its development is proceeding rapidly.

[0003]

By the way, a solar cell generally absorbs sunlight and generates photovoltaic power.
The surface protective sheet layer constituting the solar cell module has a property of transmitting all the incident sunlight, and is excellent in various fastnesses such as light resistance, heat resistance, water resistance, and the like. It has excellent moisture-proof properties to prevent intrusion of the like, and further has a high surface hardness, and prevents accumulation of dirt, dust and the like on the surface, has a high protective ability, and other conditions. . However, a glass plate or the like which is currently most commonly used as a surface protective sheet layer constituting a solar cell module has excellent sunlight permeability, light resistance, heat resistance, and water resistance. It has the advantages of being excellent in various fastnesses such as properties, and also excellent in moisture proofness, hard surface hardness, excellent in antifouling properties, etc., and high in protection ability, but has plasticity, There is a problem that it lacks in impact properties, weight reduction, etc., and is inferior in its workability, workability, etc., and lacks in cost reduction, etc. When a resin sheet such as a fluororesin is used as a surface protection sheet layer constituting the solar cell module, plasticity, impact resistance, Although it is rich in 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. Furthermore, when the above-mentioned fluorine-based resin sheet is used, there is a problem that dusts and the like accumulate on the surface thereof and lack antifouling properties. Accordingly, the present invention provides a fluorine-based resin sheet as a surface protection sheet layer constituting a solar cell module.
Even with the use of heat resistance, the moisture resistance that prevents intrusion of moisture, oxygen, etc. is remarkably improved, and furthermore, with respect to the robustness such as light resistance, heat resistance, water resistance, etc., long-term performance deterioration is minimized. An object of the present invention is to stably provide a low-cost and safe surface protection sheet constituting a solar cell module which is excellent in suppressing, protecting ability, and also excellent in antifouling property.

[0004]

The inventor of the present invention has conducted various studies to solve the problems with respect to the surface protection sheet layer constituting the solar cell module.
Focusing on the properties of the glass plate used as the surface protective sheet layer constituting the film, the fluororesin, the photocatalyst powder, the ultraviolet absorber, etc., first, silicon oxide or aluminum oxide was applied to one side of the resin film. And a transparent glassy inorganic oxide vapor-deposited thin film, and further comprising a metal alkoxide compound and / or a hydrolyzate thereof as a main component of a vehicle on the inorganic oxide vapor-deposited thin film. Then, on one or both surfaces of a resin film provided with a vapor-deposited thin film of the inorganic oxide and the coating film, a fluorine-based resin is used as a main component of the vehicle. Laminate a coating film with a resin composition,
Further, on one or both surfaces of a laminate comprising the coating film and a resin film provided with a vapor-deposited thin film of an inorganic oxide and a coating film, a coating film of a composition containing a photocatalyst powder is formed. An antifouling layer and / or an ultraviolet absorber layer comprising a coating film of a composition containing an ultraviolet absorber is provided to produce a surface protection sheet for a solar cell module, which is used as a surface protection sheet layer. The above-mentioned antifouling layer is the outermost surface, and on the other surface, a filler layer, a solar cell element as a photovoltaic element, a filler layer, and a backside protective sheet layer are sequentially laminated, Next, when a solar cell module was manufactured using a lamination method or the like in which these were integrally vacuum-sucked and heated and pressed, the moisture-proof property for preventing invasion of moisture, oxygen, etc. was remarkably improved. Robustness such as light resistance, heat resistance and water resistance Also, the surface protection sheet for solar cell modules, which minimizes long-term performance deterioration, has excellent protection ability, and is excellent in antifouling properties, etc. The inventors have found that a solar cell module using the same can be manufactured and completed the present invention.

That is, the present invention provides a coating film made of a resin composition containing a fluorine-based resin as a main component of a vehicle, and a vapor-deposited thin film of an inorganic oxide. A resin film provided with a coating film made of a composition containing an alkoxide compound and / or a hydrolyzate thereof as a main component of a vehicle is laminated, and further, the coating film and a vapor-deposited thin film of an inorganic oxide are coated. A surface protection sheet for a solar cell module, wherein an antifouling layer and / or an ultraviolet absorber layer is provided on one or both surfaces of a laminate comprising a resin film provided with a film. And solar cell modules using the same.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The above-mentioned present invention will be described below in more detail with reference to the drawings and the like. In the present invention, the term "sheet" means either a film or a sheet, and the term "film" means both a film and a sheet. Surface protection sheet for solar cell module according to the present invention
The layer configuration of the solar cell module and the solar cell module using the same will be described in more detail with reference to the drawings and the like. FIGS. FIG. 5 is a schematic cross-sectional view illustrating a few examples of the layer structure of the surface protection sheet for a solar cell module according to the present invention shown in FIG. It is a schematic sectional drawing which illustrates an example about the layer structure of the solar cell module manufactured by the above.

First, as shown in FIG. 1, a surface protection sheet A for a solar cell module according to the present invention comprises a coating film 1 made of a resin composition containing a fluorine-based resin as a main component of a vehicle.
A vapor-deposited thin film 2 of inorganic oxide is provided on one side thereof, and a metal alkoxide compound and / or a hydrolyzate thereof is used as a main component of a vehicle on the vapor-deposited thin film 2 of inorganic oxide. A resin film 4 provided with a coating film 3 is laminated, and a coating film 1 and a laminated body 5 composed of a deposited thin film 2 of inorganic oxide and a resin film 4 provided with a coating film 3 are further formed. The basic structure is such that the antifouling layer 6 and / or the ultraviolet absorber layer 7 is provided on one or both surfaces and the antifouling layer 6 is the outermost surface. As a specific example of the surface protection sheet for a solar cell module according to the present invention, as shown in FIG. 2, a coating film 1 made of a resin composition containing a fluorine-based resin as a main component of a vehicle, On one side, for example, a vapor-deposited thin film 2a of an inorganic oxide by physical vapor deposition
Or a multi-layer film (not shown) of two or more layers thereof, and further, a metal alkoxide compound and / or a hydrolyzate thereof is formed on the vapor-deposited thin film 2a of the inorganic oxide as a main component of the vehicle. And a resin film 4 provided with a coating film 3 of the composition
An antifouling layer 6 and an ultraviolet absorber layer 7 are provided on the surface of a coating film 1 constituting a laminate 5 comprising a resin film 4 provided with a vapor-deposited thin film 2a of an inorganic oxide and a coating film 3. and a solar cell module, characterized in that the antifouling layer 6 outermost surface - can be exemplified bets a ₁ - le for surface protection sheet.

FIG. 3 shows another example of the surface protection sheet for a solar cell module according to the present invention.
As shown in FIG. 1, a coating film 1 made of a resin composition containing a fluorine-based resin as a main component of a vehicle and, for example, one layer of a vapor-deposited inorganic oxide thin film 2b formed by a chemical vapor deposition method, or two or more layers thereof A multilayer film (not shown) 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 further provided on the inorganic oxide deposited thin film 2b. Resin film 4 provided
The coating film 1 and the resin film 4 provided with the inorganic oxide vapor-deposited thin film 2b and the coating film 3 are further laminated on the coating film 1 to form an antifouling surface. A UV absorber layer 7 on the surface of the resin film 4 provided with the deposited thin film 2b of inorganic oxide and the coating film 3 constituting the laminate 5; solar cell module, characterized in that the layer 6 and the uppermost surface - le for surface protective sheet - can be exemplified bets a _2. Further, as another example of the surface protection sheet for a solar cell module according to the present invention, as shown in FIG. 4, a coating film made of a resin composition containing a fluorine-based resin as a main component of a vehicle, as shown in FIG. 1
And a vapor-deposited inorganic oxide thin film 2b formed by, for example, a chemical vapor deposition method on one surface thereof, and a vapor-deposited inorganic oxide thin film formed by a physical vapor deposition method on the inorganic oxide vapor-deposited thin film 2b. 2a to provide a vapor-deposited thin film of the inorganic oxide 2a, 2b
And a multilayer film 8 comprising a metal alkoxide compound and / or a hydrolyzate thereof as a main component of a vehicle.
A resin film 4 provided with a coating film 3 is laminated thereon, and further, a coating film 1 constituting a laminate 5 comprising the coating film 1 and a resin film 4 provided with a multilayer film 8 and a coating film 3 A UV-absorbing layer 7 is provided on the surface of the resin film 4 on which the antifouling layer 6 is provided, and the multilayer film 8 and the coating film 3 constituting the laminate 5 are provided. solar cell module, characterized in that the proofing layer 6 outermost surface - can be exemplified bets a ₃ - Le for surface protection sheet. The above example is a surface protection sheet for a solar cell module according to the present invention.
For example, only a few examples will be described, and the present invention is not limited thereto. For example, although not shown, when laminating the coating film 1 and the resin film 4 provided with the evaporated thin film 2 of inorganic oxide and the coating film 3 in the above, the surface of the coating film 1 and the resin film 4 Or any surface such as the surface of the coating film 1 and the surface of the coating film 3 may be opposed to each other. In the above, the ultraviolet absorbent layer 7
May be provided at any position such as the coating film 1 side or the resin film 4 side, and may be provided between the coating film 1 and the coating film 3.

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. 5 shows an example in which the surface protection sheet A for a tool is used.
As shown in FIG. 1, the surface protection sheet A for a solar cell module according to the present invention shown in FIG. 1 has the antifouling layer 6 as the outermost surface and the other surface as the inner surface. Laminate for laminating a filler layer 11, a solar cell element 12 as a photovoltaic element, a filler layer 13, a backside protective sheet layer 14, etc. The solar cell module T can be manufactured by using the above-mentioned layers as an integrally formed body by using a usual forming method such as a method of forming a solar cell. In the drawings, 1, 2, 3, 4, 5, 7 and the like have the same meaning as described above. The above example is an example of a solar cell module manufactured using the surface protection sheet for a solar cell module according to the present invention, and the present invention is not limited thereto. is not. For example, although not shown, in the above-mentioned solar cell module, other layers may be optionally added and laminated for the purpose of sunlight transmission, absorption, reinforcement, etc. You can do it.

Next, in the present invention, the surface protection sheet for a solar cell module according to the present invention, the material constituting the solar cell module using the same, the manufacturing method, and the like will be described in more detail. A coating film made of a resin composition containing a fluorine-based resin as a main component of a vehicle and constituting a surface protection sheet for a solar cell module, a solar cell module and the like according to the present invention will be described. For formation, first, one or more kinds of fluororesins are used as a main component of the vehicle, and if necessary, for example, processability, heat resistance, light resistance, water resistance, and weather resistance of a coating film. , Mechanical or chemical properties, dimensional stability, antioxidant,
Additives of various plastics for the purpose of improving or modifying the sliding properties, mold release properties, flame retardancy, anti-mold properties, electrical properties, etc., for example, lubricants, cross-linking agents, antioxidants, ultraviolet absorbers , Light stabilizer, filler, reinforcing agent, reinforcing agent, antistatic agent,
One or more additives such as a flame retardant, a flame retardant, a foaming agent, an anti-mold agent, a colorant, etc. are arbitrarily added within a range not affecting the transmission of sunlight, and a solvent, a diluent. The mixture is sufficiently kneaded to prepare a resin composition of, for example, a solvent type, an aqueous type, or an emulsion type. Next, the above-prepared resin composition is subjected to, for example, a floating knife coating method, a knife over roll coating method, an inverted knife coating method, a squeeze roll coating method, Reverse roll coating method, roll coating method, gravure roll coating method, kiss roll coating method, air blade coating method, extrusion coating method, curtain coating method Co
Or a coating method such as gravure printing, offset printing, silk screen printing, transfer printing, etc. Can be applied or printed on one surface or both surfaces of the resin film provided with and dried to form a coating film. Thus,
In the present invention, by forming a coating film on the resin film provided with the vapor-deposited inorganic oxide thin film and the coating film as described above, the coated film, the vapor-deposited inorganic oxide thin film and the coating film are formed. A laminated body obtained by laminating a resin film provided with a method can be manufactured. In the above, the thickness of the coating film, 1~75g / m ² (dry state) position, more preferably, 10 to 50 g / m ² (dry state) position is desirable.

In the above, examples of the fluorine resin include polytetrafluoroethylene (PTFE), tetrafluoroethylene and perfluoroalkyl vinyl ether.
Perfluoroalkoxy resin (PFA) comprising a copolymer with ter, tetrafluoroethylene and hexafluoropropylene copolymer (FEP), tetrafluoroethylene and perfluoroalkylvinyl ether and hexafluoropropylene copolymer (EPE), tetrafluoro Copolymer of ethylene and ethylene or propylene
(ETFE), polychlorotrifluoroethylene resin (PCTFE), copolymer of ethylene and chlorotrifluoroethylene (ECTFE), vinylidene fluoride resin (PVDF), vinyl fluoride resin (PVF), trade name, CYTOP (Cytop, a registered trademark), or
One or two or more fluororesins made of a trade name, transparent fluororesin made of Lumiflon (registered trademark) (both made by Asahi Glass Co., Ltd.) and the like can be used. In the present invention, it is desirable that the fluororesin has a visible light transmittance of 90% or more, preferably 93% or more, and has a property of transmitting all incident sunlight. In the present invention, among the above-mentioned fluororesins, in particular, a transparent fluororesin made of trade name, CYTOP (Cytop, registered trademark) or trade name, Lumiflon (registered trademark) has transparency. However, it is preferable from the viewpoint of sunlight permeability and the like.
Thus, in the present invention, by using the above-mentioned fluorine-based resin, excellent properties of the fluorine-based resin, particularly, mechanical properties, chemical properties, optical properties, and the like,
Utilizing various properties such as light resistance, heat resistance, water resistance, etc., such as super weather resistance, contamination resistance, chemical resistance, etc., it is used as a surface protection sheet constituting a solar cell. It has the same optical properties and durability as conventional glass plates, etc.,
Due to its flexibility and mechanical properties, it is lighter than a glass plate or the like, has excellent workability, and has advantages such as easy handling. In the present invention, various additives may be added to the resin composition containing the above-mentioned fluororesin as a main component of the vehicle, and among them, an ultraviolet absorber and / or an antioxidant may be added. It is preferable to do so.

Next, in the present invention, a surface protection sheet for a solar cell module and a solar cell module according to the present invention.
When the vapor-deposited thin film of the inorganic oxide constituting the metal or the like is described, as the vapor-deposited thin film of the inorganic oxide, for example, a physical vapor deposition method, or a chemical vapor deposition method, or a combination thereof, It can be manufactured by forming one or two or more multilayer films of a deposited thin film of an inorganic oxide. The inorganic oxide vapor-deposited thin film formed by the above-mentioned physical vapor deposition method will be described in further detail. Examples of the inorganic oxide vapor-deposited thin film formed by the physical vapor deposition method include a vacuum vapor deposition method, a sputtering method, and an ion plating method. Physical Vap (Physical Vap)
or Deposition method, PVD method) to form a deposited thin film of inorganic oxide. In the present invention, specifically, a metal oxide is used as a raw material, and a vacuum evaporation method in which the metal oxide is heated and vapor-deposited on a resin film, or a metal or a metal oxide is used as a raw material, and oxygen is introduced. Then, the deposited film can be formed by an oxidation reaction deposition method of depositing on the resin film by oxidizing the film, and further, a plasma-assisted oxidation reaction deposition method of promoting the oxidation reaction by plasma. In the present invention, a specific example of a method of forming a thin film of an inorganic oxide by a physical vapor deposition method is shown in FIG. 6. FIG. 6 is a schematic configuration diagram showing an example of a roll-up type vacuum evaporation apparatus. As shown in FIG. 6, in a vacuum chamber 22 of a take-up type vacuum evaporation apparatus 21,
The resin film 4 unwound from the unwinding roll 23 is guided to a cooled coating drum 26 via guide rolls 24 and 25. Thus, the above cooled core
An evaporation source 28 heated by a crucible 27, for example, metal aluminum or aluminum oxide, is evaporated on the resin film 4 guided on the singing drum 26, and further, if necessary, an oxygen gas outlet 29. Oxygen gas or the like is jetted out, and the masks 30 and 30 are supplied while supplying the gas.
Through, for example, to form a deposited thin film of an inorganic oxide such as aluminum oxide, and then, in the above, for example,
The resin film 4 on which a vapor-deposited thin film of an inorganic oxide such as aluminum oxide is formed is sent out through guide rolls 25 'and 24' and wound up on a take-up roll 31, whereby the physical vapor phase according to the present invention is obtained. A vapor-deposited thin film of an inorganic oxide can be formed by a growth method. In the present invention, the method for forming a vapor-deposited thin film of an inorganic oxide as described above is based on 2 methods.
It can be repeated two or more times, or two or more vacuum deposition apparatuses as described above can be connected, and two or more layers can be stacked to form a two or more inorganic oxide deposited thin film. 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 surface of the resin film, a monomer gas for vapor deposition such as an organic silicon compound is used as a raw material, an inert gas such as an argon gas or a helium gas is used as a carrier gas, and an oxygen gas is used as an oxygen supply gas. By using a low-temperature plasma-enhanced chemical vapor deposition (CVD) method using a low-temperature plasma generator or the like, a deposited thin film of an inorganic oxide such as silicon oxide can be formed. In the above description, as the low-temperature plasma generator, for example, a generator such as a high-frequency plasma, a pulse wave plasma, or a microwave plasma can be used. Thus, in the present invention, a highly active and stable plasma is obtained. For this purpose, it is desirable to use a generator using a high-frequency plasma method.

More specifically, an example of a method for forming a vapor-deposited thin film of an inorganic oxide by the above-described low-temperature plasma chemical vapor deposition method will be described. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic configuration diagram of a low-temperature plasma-enhanced chemical vapor deposition apparatus showing an outline of a method for forming a vapor-deposited thin film of an oxide. As shown in FIG. 7, in the present invention, the resin film 4 is unwound from an unwinding roll 43 disposed in a vacuum chamber 42 of a plasma enhanced chemical vapor deposition apparatus 41. Is cooled at a predetermined speed through an auxiliary roll 44 at the cooling / electrode drum 45.
Convey on the peripheral surface. Thus, in the present invention, oxygen gas, an inert gas, a monomer gas for vapor deposition such as an organic silicon compound, and the like are supplied from the gas supply devices 46 and 47 and the raw material volatile supply device 48 and the like. While adjusting the mixed gas composition for vapor deposition, the mixed gas composition for vapor deposition was introduced into the vacuum chamber -42 through the raw material supply nozzle 49, and was conveyed onto the peripheral surface of the cooling / electrode drum 45 described above. Glow discharge plasma 5 on resin film 4
A plasma is generated by 0, and this is irradiated to form a vapor-deposited thin film of an inorganic oxide such as silicon oxide, thereby forming a film.
In the present invention, the cooling / electrode drum 45
A predetermined power is applied from a power supply 51 disposed outside the chamber, and a magnet 52 is disposed near the cooling / electrode drum 45 to promote the generation of plasma. The resin film 4 on which the deposited thin film of the inorganic oxide such as silicon oxide is formed is wound on a winding roll 54 via an auxiliary roll 53, and the plasma chemical vapor deposition method according to the present invention is performed. To produce a vapor-deposited thin film of an inorganic oxide. In the figure, 55 represents a vacuum pump. In the present invention, the above-described method for forming a vapor-deposited thin film of an inorganic oxide is repeated two or more times, or two or more vacuum vapor deposition apparatuses are connected and two or more An inorganic oxide vapor-deposited thin film composed of layers or more can be formed. In the present invention, one or a mixture of two or more kinds of monomer gases for vapor deposition may be used to form a thin film of an inorganic oxide mixed with different materials. The above examples illustrate one example thereof,
It goes without saying that the present invention is not limited by this.

In the above, a monomer for vapor deposition of an organic silicon compound or the like forming a vapor deposited thin film of an inorganic oxide such as silicon oxide.
Examples of the gas include 1.1.3.3-tetramethyldisiloxane, hexamethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, Phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, and the like can be used. In the present invention, among the organic silicon compounds as described above, the use of 1.1.3.3-tetramethyldisiloxane or hexamethyldisiloxane as a raw material is advantageous in terms of handleability and formed deposited film. It is a particularly preferable raw material in view of its characteristics and the like. In the above, for example, an argon gas, a helium gas, or the like can be used as the inert gas.

In the present invention, the silicon oxide vapor-deposited thin film formed as described above undergoes a chemical reaction between a monomer gas such as an organosilicon compound and oxygen gas, and the reaction product adheres tightly to the resin film. dense, it is possible to form a thin film rich in flexibility or the like, usually, the general formula SiO _X (provided that, X
Represents a number of 0 to 2). Thus, the above-mentioned silicon oxide vapor-deposited thin film is represented by a general formula SiO _X (where X represents a number of 1.3 to 1.9) in terms of transparency, barrier properties, and the like. It is preferable to use a thin film mainly composed of a deposited silicon oxide film. In the above, the value of X changes depending on the molar ratio of the monomer gas to the oxygen gas, the energy of the plasma, etc. In general, the gas permeability decreases as the value of X decreases, but the film itself has It has a yellow color and poor transparency. Further, the above-described deposited silicon oxide thin film has silicon (Si) and oxygen (O) as essential constituent elements, and further has one of carbon (C) and hydrogen (H);
Alternatively, it is composed of a deposited film of silicon oxide containing both elements as trace constituent elements and has a thickness of 50 °.
2,000 [deg.], And the composition ratio of the essential constituent elements and the trace constituent elements changes continuously in the film thickness direction. Further, when the above-mentioned vapor-deposited silicon oxide thin film contains a compound composed of carbon, the carbon content is reduced in the depth direction of the film thickness. Thus, in the present invention, for the above-mentioned evaporated silicon oxide thin film, for example, an X-ray photoelectron spectrometer (Xray Photoelectron)
n Spectroscopy, XPS), Secondary Ion Mass Spectrometer (Secondary Ion Mass)
The physical properties as described above were confirmed by performing elemental analysis of the deposited thin film of silicon oxide using a method of analyzing the surface by ion etching in the depth direction using a surface analyzer such as Spectroscopy (SIMS). Is what you can do. In the present invention, the film thickness of the silicon oxide vapor-deposited thin film is 50 to 2000 mm.
And more specifically, the film thickness is more preferably in the range of about 100 to 1000 °.
When the thickness is more than 00 °, cracks and the like are easily generated in the film, which is not preferable.
If it is less than 0 °, it is not preferable because it is difficult to exhibit the effect of the barrier property. 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.

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

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

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

Next, in the present invention, in the composition containing the above-mentioned metal alkoxide compound and / or hydrolyzate thereof as a main component of the vehicle, the content of the metal alkoxide compound and / or hydrolyzate thereof is as follows. 0.1% by weight or more, preferably 0.1 to 70% by weight, more preferably 0.1 to 70% by weight in terms of SiO ₂ generated as a result of 100% hydrolysis and condensation of the metal alkoxide compound.
It is desirable to use it 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. If it exceeds 70% by weight, it is not preferable because it is difficult to form a transparent uniform film.

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

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

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

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

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

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

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

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

Next, the antifouling layer composed of a coating film made of a composition containing a photocatalyst powder constituting a surface protection sheet for a solar cell module, a solar cell module and the like according to the present invention will be described. The antifouling layer is provided on the outermost surface of the surface protection sheet. That is, in the present invention, dust and dust are formed on the other surface (outermost surface) of a coating film of a resin composition containing a fluorine-based resin constituting a surface protection sheet for a solar cell module as a main component of a vehicle. Is to form an antifouling layer for preventing accumulation of the like. Thus, as the antifouling layer, a photocatalyst powder or a photocatalyst sol (hereinafter, referred to as a photocatalyst sol)
The photocatalyst powder may be composed of a coating film containing a composition containing a photocatalyst sol). In the above, as a coating film of the composition containing the photocatalyst powder, first, for example, one or two or more of the binders as vehicles are added to one or more of the photocatalyst powders, and if necessary, For example, for example, lubricants, crosslinking agents, antioxidants, ultraviolet absorbers, light stabilizers, fillers, reinforcing agents, reinforcing agents, antistatic agents, flame retardants, flame retardants, foaming agents, antifungal agents, pigments, etc. Arbitrarily add one or more kinds of additives within a range not affecting the transmission of sunlight,
After sufficiently kneading with a solvent, a diluent or the like, a composition of, for example, a solvent type, an aqueous type, or an emulsion type is prepared. Next, in the present invention, the composition prepared above is used, and is used, for example, by a knife coating method, a squeeze roll coating method, a reverse roll coating method, a roll coating method. Coating method, gravure roll coating method, kiss roll coating method, extrusion coating method, curtain coating method
Coating or printing using a coating method such as gravure printing, offset printing, silk screen printing, transfer printing, etc., and then drying to form a coating film. By forming, the antifouling layer according to the present invention can be constituted. In the above, the thickness of the coating film is 0.1 to 10 g / m
^2nd place (dry state), more preferably 0.5 to 1 g / m
^Second place is desirable.

In the above, as the photocatalyst powder, for example, the resin is degraded, destroyed, or decomposed or degraded by the action of light such as sunlight due to oxidation or the like.
It is possible to use a chemical substance 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 description, the antifouling layer is desirably made 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, 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-based resin, polypropylene-based resin, 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, poly (meth) acrylic resin, polyacrylonitrile Resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin),
Polyester resin, polyamide resin, polycarbonate resin, polyvinyl alcohol resin, ethylene
Saponified vinyl acetate copolymer, fluororesin, diene resin, polyacetal resin, polyurethane resin,
Various natural or semi- or synthetic resins such as epoxy resins, phenol resins, aminoplast resins, silicone resins, nitrocellulose, inorganic polymers, and others, inorganic polymers, and others. One or more kinds of known resins, modified resins thereof, and others can be used. Thus, in the present invention, among the above binders, the binder not affected by the photocatalyst powder is particularly low-melting glass, alkali metal silicate, phosphate, or colloidal silica. ,
It is preferred to use one or more of other inorganic polymers.

In the present invention, the photoactivity of the photocatalyst powder in the coating film constituting the antifouling layer affects the lower layer of the antifouling layer, for example, a fluororesin sheet. And an activity blocking layer for blocking the activity of the photocatalyst powder comprising an inorganic film or the like for blocking mutual contact so as not to cause deterioration, decomposition, destruction, or the like. The above-mentioned activity blocking layer is usually provided below the antifouling layer. As the inorganic film constituting the above-mentioned activity blocking layer, for example, the above-mentioned vapor-deposited film of inorganic oxide such as silicon oxide or aluminum oxide can be used. The above-mentioned inorganic oxide vapor-deposited film can be formed into a film in the same manner as described above to form an active cutoff layer.
It is preferably about 000 °, more preferably about 100 to 1500 °. Further, in the present invention, in order to strengthen the tight adhesion of the antifouling layer, when providing a coating film of a composition containing a photocatalyst powder constituting the antifouling layer, if necessary, a fluorine-based resin An adhesive primer layer or the like can be provided on the surface of the sheet. As a material constituting the above-mentioned primer layer, for example, it is desirable to form using a material constituting an inorganic primer layer which is not decomposed by the photoactivity of the photocatalyst powder in the antifouling layer. . Specifically, typical examples of organic titanium compounds include tetraisopropyl titanate, tetrabutyl titanate,
Alkyl titanates such as tetrastearyl titanate and products obtained by hydrolysis such as titanium chelate can be used. In addition, inorganic polysilazane (perhydropolysilazalane) and the like can also be used. In the present invention, particularly preferred are tetraisopropyl titanate and tetrabutyl titanate, which have a very high hydrolysis rate and can be decomposed after coating the solution.

Next, an ultraviolet absorbent layer composed of a coating film of a composition containing an ultraviolet absorbent constituting the surface protective sheet for a solar cell module according to the present invention will be described. As such an ultraviolet absorber layer, for example, one or more binders as a vehicle are added to one or more ultraviolet absorbers,
Further, if necessary, for example, a lubricant, a crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, a reinforcing agent, an antistatic agent, a flame retardant, a flame retardant, a foaming agent, a fungicide ,
One or more additives such as pigments and other additives are arbitrarily added within a range that does not affect the transmission of sunlight, and further kneaded sufficiently with a solvent, a diluent, etc., for example, a solvent type, an aqueous type. A composition such as a mold or an emulsion type is prepared, and then the composition is subjected to, for example, a knife coating method, a square coating method, and the like.
Roll coat method, reverse roll coat method, roll coat method, gravure roll coat method, kiss roll coat method, extrude coat method, curtain flow method
Coating method such as coating method, other printing method, or printing method such as gravure printing, offset printing, silk screen printing, transfer printing, etc. An absorbent layer can be provided. In the above, the thickness of the coating film is set to 0.
1 to 10 g / m ² (dry state), more preferably
1.0-5 g / m ² is desirable.

In the above description, the ultraviolet absorber absorbs harmful ultraviolet rays in sunlight, converts the harmful ultraviolet rays into harmless heat energy in the molecule, and excites the active species that initiates photodegradation in the polymer. Specifically, benzophenone, benzotriazole, saltylate,
Acrylic nitrile type, metal complex salt type, hindered amine type, ultrafine titanium oxide (particle size, 0.01 to 0.06μ)
m), ultrafine zinc oxide (particle size, 0.01 to 0.04 μm)
One or two or more inorganic UV absorbers such as m) can be used. In the above composition, the content of the ultraviolet absorber is desirably about 0.1 to 20% by weight. Further, in the above, the above composition, an antioxidant for preventing photodegradation or thermal degradation of the polymer,
Specifically, it is desirable to use an antioxidant such as a phenol type, an amine type, a sulfur type, a phosphoric acid type or the like. In the above-mentioned composition, as the binder as the vehicle, the binder exemplified when the above-mentioned antifouling layer is formed can be used in the same manner.

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 module will be described. The filler layer needs to have transparency having a property of transmitting incident sunlight. It is also necessary to have an adhesive property with a surface protection sheet, and furthermore, to have a function of maintaining the smoothness of the surface of the solar cell element as a photovoltaic element, it has a thermoplastic property. In order to protect the solar cell element as a photovoltaic element, it is necessary to have excellent scratch resistance, shock absorption and the like. Specifically, as the filler layer, for example,
Fluorine resin, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid, or methacrylic acid copolymer, polyethylene resin, polypropylene resin, polyolefin resin such as polyethylene or polypropylene, acrylic acid, itaconic acid, Maleic acid,
Resins such as acid-modified polyolefin-based resins modified with unsaturated carboxylic acids such as fumaric acid, polyvinyl butyral resins, silicone resins, epoxy resins, (meth) acrylic resins, and others One or more 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. Thus, in the present invention, as the filler on the incident side of sunlight, light resistance, heat resistance, considering weather resistance such as water resistance,
Fluorine resins and ethylene-vinyl acetate resins are desirable materials. The thickness of the filler layer is 2
About 00/1000 μm, more preferably 350-60
About 0 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, a thin-film polycrystalline silicon solar cell element, a thin-film microcrystalline silicon solar cell element, a hybrid element of a thin-film crystalline silicon solar cell element and an amorphous silicon solar cell element, and the like can 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 /
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.
It is desirably about 0 μm, preferably about 25 to 150 μm.

In the present invention, when the solar cell module according to the present invention is manufactured, in order to improve various robustness such as strength, weather resistance, scratch resistance, etc. Material, for example, polyethylene resin,
Polypropylene-based resin, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-
Acrylic or methacrylic acid copolymer, methylpentene polymer, polybutene resin, polyvinyl acetate resin, poly (meth) acrylic resin, polyacrylonitrile resin, polystyrene resin, acrylonitrile-styrene copolymer (AS Resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, polyamide resin, polycarbonate resin, polyvinyl alcohol resin, and ethylene-vinyl acetate copolymer Any known resin film or sheet such as a compound, a fluorine resin, a diene resin, a polyacetal resin, a polyurethane resin, nitrocellulose, or the like can be used. In the present invention, the film or sheet is unstretched,
Any material such as one stretched in a uniaxial or biaxial direction can be used. The thickness is arbitrary, but can be selected 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 biaxially stretched polyethylene terephthalate film having a thickness of 50 μm was used, mounted on a delivery roll of a take-up type vacuum evaporation apparatus, and then fed out onto a coating drum. Under the following evaporation conditions, aluminum was used as an evaporation source, and oxygen gas was supplied, and a film thickness of 30 was applied to the easily-adhesion-treated surface by a reactive vacuum evaporation method using an electron beam (EB) heating method.
A deposited thin film of 0 ° aluminum oxide was formed. (Evaporation conditions) Evaporation source: Aluminum Degree of vacuum in vacuum chamber: 7.5 × 10 ⁻⁶ mbar Degree of vacuum in evaporation chamber: 2.1 × 10 ⁻⁶ mbar EB output: 40 KW Film transport speed: 600 m / Next, immediately after the deposition, a glow discharge plasma generator was used to apply a plasma output of 1500 W, oxygen gas (O ₂ ): argon on the thin film of aluminum oxide having a thickness of 300 ° formed as described above. Using a mixed gas consisting of gas (Ar) = 19: 1, a mixed gas pressure of 6 × 10 ⁻⁵ Toor,
An oxygen / argon mixed gas plasma treatment was performed at a treatment speed of 420 m / min to form a plasma treated surface. (2). On the other hand, 2 parts by weight of dimethyldimethoxysilane, 1 part by weight of ethanol and 0.2 part by weight of 0.1N hydrochloric acid were mixed at the same ratio and refluxed at 50 ° C. for 2 hours. A ratio of 25 parts by weight of methyltrimethoxysilane, 5 parts by weight of ethanol, and 20 parts by weight of a toluene solution (20%) of polymethyl methacrylate (PMMA) to the obtained partially hydrolyzed solution of dimethyldimethoxysilane. And further stirred at room temperature for 2 hours to prepare a coating composition.
Next, the coating composition obtained above was used on the plasma-treated surface of the above-mentioned aluminum oxide vapor-deposited thin film, and the composition was coated by a gravure roll coating method to a thickness of 1.0 g. / M ² (dry state), and then heat-treated at 120 ° C. for 5 minutes to form a cured coating film. (3). Further, on the surface of the cured coating film produced above, using a fluororesin coating liquid (trade name, Lumiflon, manufactured by Asahi Glass Co., Ltd.), and coating by a gravure roll coating method, A layered product was produced by forming a coating film of 10 g / m ² (dry state). Next, 5 parts by weight of ultrafine titanium oxide particles of 0.03 μm and an ethylene-vinyl alcohol copolymer liquid (solid content: 20 μm) were placed on the biaxially stretched polyethylene terephthalate film surface of the laminate produced above.
% Solution) of 95 parts by weight was coated by a gravure roll coating method to form an ultraviolet absorber layer having a thickness of 0.5 g / m ² (dry state). A surface protection sheet according to the present invention 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 fluororesin coating liquid (trade name, Lumiflon, manufactured by Asahi Glass Co., Ltd.),
Using a fluororesin liquid comprising a copolymer of tetrafluoroethylene and ethylene, except for the above, producing the same surface protection sheet and solar cell module according to the present invention in exactly the same manner as described above. We were able to.

Embodiment 2 (1). A biaxially stretched polyethylene terephthalate film having a thickness of 50 μm was used as a base material, and was mounted on a delivery roll of a plasma enhanced chemical vapor deposition apparatus, and a silicon oxide film having a thickness of 300 mm was deposited under the following deposition conditions. Apply the thin film
It was formed on the easily-adhered surface of an axially stretched polyethylene terephthalate 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 In evaporation chamber Degree of vacuum: 6.0 × 10 ⁻² mbar Cooling / electrode drum supply power: 20 kW Film transfer speed: 80 m / min Evaporation surface: Corona treated surface Next, a 300 mm thick silicon oxide evaporated thin film was formed as described above. Then, immediately after the vapor deposition, a corona discharge treatment is performed on the silicon oxide vapor-deposited thin film surface at an output of 10 kW and a processing speed of 100 m / min to form a corona-treated surface, and the surface tension of the vapor-deposited thin film surface is increased from 35 dyne. Increased to 60 dyne. (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 a solution of the partial hydrolyzate of the obtained tetraethoxysilane, a toluene solution of polymethyl methacrylate (PMMA) (20
%), And the mixture was further stirred at room temperature for 2 hours to prepare a coating composition. Next, the above coating composition was used on the corona-treated surface of the above-mentioned silicon oxide vapor-deposited thin film, and was coated by a gravure roll coating method to have a thickness of 1.5 g / m2. ² (dry state) was formed, and then heat-treated at 120 ° C. for 1 minute to form a cured coating film. (3). Further, on the surface of the cured coating film produced above, using a fluororesin coating liquid (trade name, Lumiflon, manufactured by Asahi Glass Co., Ltd.), and coating by a gravure roll coating method, A layered product was produced by forming a coating film of 10 g / m ² (dry state). Next, an ultraviolet ray comprising 1 part by weight of a benzophenone-based ultraviolet absorber and 99 parts by weight of a thermosetting acrylic resin liquid (solid content: 20%) is applied on the biaxially stretched polyethylene terephthalate film surface of the laminate produced above. The absorbent composition is coated by a gravure roll coating method to form an ultraviolet absorbent layer having a thickness of 2.0 g / m ² (dry state), and the surface protective sheet according to the present invention is formed. Was manufactured. (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 fluororesin coating liquid (trade name, Lumiflon, manufactured by Asahi Glass Co., Ltd.),
Using a fluororesin liquid comprising a copolymer of tetrafluoroethylene and ethylene, except for the above, producing the same surface protection sheet and solar cell module according to the present invention in exactly the same manner as described above. We were able to.

Embodiment 3 (1). As a substrate, a biaxially oriented polyethylene terephthalate film having a thickness of 50 μm was used.
In the same manner as above, a 300-mm-thick silicon oxide vapor-deposited thin film is formed on the easily-adhesion-treated surface, and further, the silicon oxide vapor-deposited thin-film surface is subjected to corona discharge treatment to form a corona-treated surface. The surface tension of the vapor-deposited thin film was increased from 35 dyne to 60 dyne. Next, a vapor-deposited aluminum oxide thin film having a thickness of 300 ° was formed on the corona-treated surface of the silicon oxide vapor-deposited thin film of the biaxially stretched polyethylene terephthalate film in exactly the same manner as in Example 1 described above. A plasma treatment was performed on the surface of the deposited aluminum oxide thin film to form a plasma treatment surface. (2). On the other hand, 5 parts by weight of dimethyldimethoxysilane, 2.5 parts by weight of ethanol and 0.5 parts by weight of 0.1N hydrochloric acid were mixed at the same ratio and refluxed at 50 ° C. for 2 hours.
15 parts by weight of methyltrimethoxysilane and ethanol were added to the resulting partially hydrolyzed solution of dimethyldimethoxysilane.
At a ratio of 3 parts by weight of the catalyst and 10 parts by weight of a cyclohexane solution of a cyclic polyolefin (30%).
After stirring for an hour, a composition for coating was prepared. Next, the coating composition obtained above was used on the plasma-treated surface of the above-mentioned deposited thin film of aluminum oxide, and the composition was coated by a gravure roll coating method to a thickness of 2.0 g. / M
² (dry state) coating film is formed.
The coating was cured by heating at 20 ° C. for 1 minute. (3). Next, on the surface of the coating cured film produced as described above, ultraviolet absorption comprising 5 parts by weight of ultrafine titanium oxide particles of 0.03 μm and 95 parts by weight of an ethylene-vinyl alcohol copolymer liquid (20% solid solution) was applied. The composition was coated by a gravure roll coating method to obtain a film thickness of 0.5
g / m ² (dry state) of an ultraviolet absorbent layer was formed. Further, a fluororesin coating solution (trade name, Lumiflon, manufactured by Asahi Glass Co., Ltd.) is used on the above-mentioned ultraviolet absorber layer,
Coating was performed by a gravure roll coating method to form a coating film having a thickness of 10 g / m ² (dry state), thereby producing a laminate. Next, a photocatalyst consisting of 10 parts by weight of ultrafine titanium oxide particles having a particle size of 0.03 μm and 90 parts by weight of a tetraethoxysilane solution (solid content: 20%) was formed on the coating film surface (outermost surface) of the laminate produced above. The coating solution was applied by a gravure roll coating method to form an antifouling layer having a thickness of 1 g / m ² (dry state), thereby producing a surface protection sheet according to the present invention. (4). Next, a 38 μm-thick biaxially stretched polyethylene terephthalate film (light-receiving) in which solar cell elements made of amorphous silicon were arranged in parallel on the biaxially stretched polyethylene terephthalate film surface of the surface protection sheet produced above. The photovoltaic module according to the present invention was manufactured by laminating the photovoltaic module of the present invention with the photovoltaic cell face facing the photovoltaic cell element face and an adhesive layer of an acrylic resin. (5). In the above, instead of the above fluororesin coating liquid (trade name, Lumiflon, manufactured by Asahi Glass Co., Ltd.),
Using a fluororesin liquid comprising a copolymer of tetrafluoroethylene and ethylene, except for the above, producing the same surface protection sheet and solar cell module according to the present invention in exactly the same manner as described above. We were able to.

Embodiment 4 (1). On the plasma-treated surface of the 300-mm-thick aluminum oxide vapor-deposited thin film produced in the first embodiment, a 300-mm-thick aluminum oxide vapor-deposited thin film is further formed in exactly the same manner as in the first embodiment. Then, plasma treatment was performed on the aluminum oxide deposited thin film surface to form two layers of aluminum oxide deposited thin films. (2). Separately, 25 parts by weight of tetraethoxysilane, 10 parts by weight of ethanol and 5 parts by weight of 0.1 N hydrochloric acid were mixed and refluxed at 50 ° C. for 3 hours. To the obtained partially hydrolyzed solution of tetraethoxysilane, add a fluorine-based acrylic resin solution (trade name, Lumiflon) manufactured by Asahi Glass Co., Ltd. 25
The mixture was stirred at room temperature for 2 hours to prepare a coating composition. Next, the above-mentioned composition for coating was used on the plasma-treated surface of the above-mentioned vapor-deposited thin film of aluminum oxide, and was coated by a gravure roll coating method to have a thickness of 0.5 g / m 2. ² (dry state) was formed, and then heat-treated at 120 ° C. for 5 minutes to form a cured coating film. (3). Next, on the surface of the coating cured film formed above, an ultraviolet absorber layer was provided in exactly the same manner as in Example 3 above, and a coating film was further provided on the ultraviolet absorber layer to form a laminate. Then, on the coating film surface (outermost surface) of the laminate, a particle size of 0.03
A photocatalyst coating solution consisting of 10 parts by weight of ultrafine titanium oxide particles of 90 μm and 90 parts by weight of tetraethoxysilane solution (solid content: 20%) was applied by a gravure roll coating method, and the film thickness was 1 g / m ² ( An antifouling layer (in a dry state) was formed to produce a surface protection sheet according to the present invention. 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). On the corona-treated surface of the silicon oxide vapor-deposited thin film produced in Example 2 above, a silicon oxide vapor-deposited thin film having a thickness of 300 ° was further formed in exactly the same manner as in Example 2 above. Corona discharge treatment was performed on the surface of the deposited thin film to form two deposited silicon oxide thin films. (2). On the other hand, 20 parts by weight of tetraethoxysilane and water 5
0 parts by weight, 30 parts by weight of ethanol and 0.1 N hydrochloric acid 5
Parts by weight and the mixture was refluxed at 50 ° C. for 3 hours. To the obtained partial hydrolyzate solution of tetraethoxysilane, 50 parts by weight of a solution of ethylene-vinyl alcohol copolymer in water-isopropyl alcohol (solid content: 8%) was added, and the mixture was further added at room temperature for 2 hours. The composition for coating was prepared by stirring. Next, the above-mentioned composition for coating was used on the plasma-treated surface of the above-mentioned silicon oxide vapor-deposited thin film, and was coated by a gravure roll coating method to have a thickness of 1.0 g / m 2. ² (dry state) was formed, and then heat-treated at 120 ° C. for 5 minutes to form a cured coating film. (3). Next, on the surface of the coating cured film formed above, an ultraviolet absorber layer was formed in exactly the same manner as in Example 3, and a coating film was formed on the ultraviolet absorber layer. A laminate was formed, and then 10 parts by weight of ultrafine titanium oxide particles having a particle size of 0.03 μm and a tetraethoxysilane solution were formed on the coating film surface (outermost surface) of the laminate in exactly the same manner as in Example 3 described above. A photocatalyst coating solution consisting of 90 parts by weight (solid content: 20%) is applied by a gravure roll coating method to form an antifouling layer consisting of a coating film having a thickness of 1 g / m ² (dry state). Thus, a surface protection sheet according to the present invention was manufactured. Further, a solar cell module according to the present invention was manufactured in the same manner as in Example 2 using the surface protection sheet manufactured as described above.

Embodiment 6 (1). As a substrate, a thickness of 5 kneaded with an ultraviolet absorber
A biaxially stretched polyethylene terephthalate film of 0 μm was used and the thickness was 30
A 0 ° aluminum oxide deposited thin film was formed, and a plasma treatment was performed on the aluminum oxide deposited thin film surface. Next, in the same manner as in Example 2 described above, the plasma-treated surface of the biaxially stretched polyethylene terephthalate film with the deposited aluminum oxide thin film having a thickness of 300 mm was applied.
The vapor-deposited thin film of silicon oxide was formed, and corona discharge treatment was further performed on the vapor-deposited thin film surface of silicon oxide. (2). Next, a surface protection sheet for a solar cell module according to the present invention was manufactured on the corona-treated surface of the silicon oxide vapor-deposited thin film in the same manner as in Example 2 above. Further, a solar cell module according to the present invention was manufactured in exactly the same manner as in Example 2 above, using the surface protection sheet manufactured as described above.

Embodiment 7 (1). As a substrate, a biaxially oriented polyethylene terephthalate film having a thickness of 50 μm was used, and
In the same manner as described above, a 300-mm-thick aluminum oxide deposited thin film was formed on the easily-adhesive treated surface, and a plasma-treated surface was further formed on the aluminum oxide deposited thin-film surface. (2). Next, a coating cured film was formed on the plasma-treated surface of the deposited aluminum oxide thin film in the same manner as in Example 1. Further, a coating film was formed on the surface of the cured coating film produced in the same manner as in Example 1 to produce a laminate. Next, a particle diameter of 0.03 μm
m of titanium oxide ultrafine particles and 90 parts by weight of a tetraethoxysilane solution (solid content: 20%) was applied by a gravure roll coating method to form a photocatalyst coating solution.
A surface protection sheet according to the present invention was manufactured by forming an antifouling layer consisting of a coating film of g / m ² (dry state). next,
The solar cell module according to the present invention was produced using the surface protection sheet manufactured as described above and in exactly the same manner as in Example 3 above.
Manufactured.

Embodiment 8 (1). As a substrate, a biaxially oriented polyethylene terephthalate film having a thickness of 50 μm was used.
In the same manner as described above, a 300-mm-thick silicon oxide vapor-deposited thin film was formed on the easily-adhesive treated surface, and a corona-treated surface was further formed on the silicon oxide vapor-deposited thin film. (2). Next, a coating cured film was formed on the corona-treated surface of the silicon oxide vapor-deposited thin film in the same manner as in Example 5 described above. Further, a coating film was formed on the surface of the cured coating film produced in the same manner as in Example 2 to produce a laminate. Next, 10 parts by weight of ultrafine titanium oxide particles having a particle diameter of 0.03 μm and 90 parts by weight of a tetraethoxysilane liquid (solid content: 20%) are formed on the surface (outermost surface) of the coating film of the laminate produced above. The photocatalyst coating liquid is applied by a gravure roll coating method, and the film thickness is 1 g / m2.
² (dry state) of an antifouling layer was formed to produce a surface protection sheet according to the present invention. (3). Next, a 38 μm-thick biaxially stretched polyethylene terephthalate film (light-receiving) in which solar cell elements made of amorphous silicon were arranged in parallel on the biaxially stretched polyethylene terephthalate film surface of the surface protection sheet produced above. The photovoltaic module according to the present invention was manufactured by laminating the photovoltaic module of the present invention with the photovoltaic cell face facing the photovoltaic cell element face and an adhesive layer of an acrylic resin.

Embodiment 9 (1). As a substrate, a biaxially oriented polyethylene terephthalate film having a thickness of 50 μm was used.
In the same manner as above, a thickness of 300 mm
Was formed on the silicon oxide vapor-deposited thin film, and a corona-treated surface was formed on the silicon oxide vapor-deposited thin film. Next, a vapor-deposited aluminum oxide thin film having a thickness of 300 ° was formed on the corona-treated surface of the silicon oxide vapor-deposited thin film of the biaxially stretched polyethylene terephthalate film in exactly the same manner as in Example 1 described above. Then, a plasma-treated surface was formed on the aluminum oxide-deposited thin film surface. (2). Next, a coating cured film was formed on the plasma-treated surface of the deposited aluminum oxide thin film in the same manner as in Example 3. Further, a coating film was formed on the cured coating film surface produced in the same manner as in Example 1 to produce a laminate. Further, a photocatalyst comprising 10 parts by weight of ultrafine titanium oxide particles having a particle size of 0.03 μm and 90 parts by weight of a tetraethoxysilane liquid (solid content: 20%) is formed on the surface (outermost surface) of the coating film of the laminate produced above. The coating liquid was applied by using a gravure roll coating method, and a film thickness of 1 g /
An m ² (dry state) antifouling layer was formed. Also, 5 parts by weight of ultrafine titanium oxide particles having a particle size of 0.03 μm and 95 parts by weight of methyl methacrylate solution (solid content: 20%) were applied on the biaxially stretched polyethylene terephthalate film surface of the laminate produced above. An ultraviolet absorbent composition comprising
Coating and drying using a coating method, and a film thickness of 0.5 g / m ²
A (dry) ultraviolet absorber layer was formed to produce a surface protective sheet according to the present invention. (3). 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.

Comparative Example 1 A polyvinyl fluoride resin film (PVF) having a thickness of 50 μm was used as a base material, this was subjected to a surface protection sheet, and solar cell elements made of amorphous silicon were arranged in parallel on one surface. A 38 μm-thick biaxially stretched polyethylene terephthalate film (light-receiving surface) was laminated with an acrylic resin adhesive layer facing the solar cell element surface to produce a solar cell module. .

Comparative Example 2 In Example 1, a coating film was not formed using a composition containing a metal alkoxide compound and / or a hydrolyzate thereof as a main component of a vehicle.
A surface protection sheet and a solar cell module using the same were produced in exactly the same manner as in Example 1 described above.

Comparative Example 3 In Example 2 described above, a coating film was not formed using a composition containing a metal alkoxide compound and / or a hydrolyzate thereof as a main component of a vehicle.
A surface protection sheet and a solar cell module were manufactured in exactly the same manner as in Example 2 described above.

Experimental Example The total light transmittance of the surface protective sheets according to the present invention produced in Examples 1 to 9 and the surface protective sheets according to Comparative Examples 1 to 3 was measured. Examples 1 to 9
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 sheet and the color of the surface protection sheets according to the present invention manufactured in Examples 1 to 9 and the surface protection sheets according to Comparative Examples 1 to 3. -The total light transmittance (%) was measured by a computer. (2). Solar cell module evaluation test This is based on JIS standard C8917-1989.
An environmental test of the solar cell module was performed, and the output of the photovoltaic power before and after the test was measured and compared and evaluated. (3). Measurement of Water Vapor Permeability and Oxygen Permeability The water vapor permeability was determined by the surface protection sheet according to the present invention manufactured in Examples 1 to 9 and the surface protection sheet according to Comparative Examples 1 to 3.
Under the conditions of a temperature of 40 ° C. and a humidity of 90% RH, a measuring device manufactured by MOCON, USA [model name, part
MATTRAN (PERMATRAN)]
Oxygen permeability was measured at a temperature of 23
℃, humidity 90% RH, USA, Mocon (MOCO
N) Company [Model name, OXTRA
N)]. The results of the above measurements are shown in Table 1 below.

[0055] In Table 1 above, the water vapor permeability is [g / m ² / d
ay.40 ° C. · 100% RH], and the oxygen permeability is [cc / m ² / day · 23 ° C. · 90% RH].
H].

As is clear from the measurement results shown in Table 1 above, those of Examples 1 to 9 have high total light transmittance, and are excellent in water vapor barrier property and oxygen barrier property. The output reduction rate was also low. In contrast,
In Comparative Example 1, although the total light transmittance was high, the water vapor barrier property and the oxygen barrier property were inferior, and therefore, there was a problem that the output reduction rate was high.
As compared with those of Examples 1 to 9, those having no coating film were slightly inferior in water vapor barrier properties and oxygen barrier properties.

[0057]

As is apparent from the above description, the present invention
Focusing on the characteristics of the glass plate used as the surface protection sheet layer constituting the solar cell module, photocatalyst powder, ultraviolet absorber, etc., first, a resin composition containing a fluorine-based resin as a main component of the vehicle And a transparent thin film of a vitreous inorganic oxide, such as silicon oxide or aluminum oxide, provided on one side thereof, and a metal alkoxide compound and / or Alternatively, a resin film provided with a coating film of a composition containing the eruption material as a main component of the vehicle is laminated, and further, the coating film, a deposited thin film of inorganic oxide and a coating film are formed. On one or both surfaces of a laminate comprising the provided resin film, a stain-proof layer comprising a coating film of a composition containing a photocatalyst powder and / or a composition containing an ultraviolet absorber. A surface protection sheet for a solar cell module is manufactured by providing an ultraviolet absorber layer made of a cloth film, and this is used as a surface protection sheet layer, and the antifouling layer is used as the outermost surface and the other surface is used. , A filler layer, a solar cell element as a photovoltaic element, a filler layer, a backside protective sheet layer, and the like are sequentially laminated, and then these are integrally vacuum-vacuated and heated and pressed. The solar cell module is manufactured by using the application method, etc., and the moisture-proof property to prevent the invasion of moisture, oxygen, etc. is remarkably improved, and the light-fastness, heat-resistance, and water-resistance are also improved. A solar cell module that is safer at a lower cost by minimizing its long-term performance deterioration and having excellent protection ability, and preventing contamination that accumulates dust and contaminates its surface. For manufacturing surface protection sheet and solar cell module using the same It is that it is Rukoto.

[Brief description of the drawings]

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

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

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

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

FIG. 5 is a solar cell module manufactured using the surface protection sheet for a solar cell module according to the present invention shown in FIG.
FIG. 3 is a schematic cross-sectional view schematically illustrating a layer configuration of an example of the structure.

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

FIG. 7 is a schematic configuration diagram of a low-temperature plasma-enhanced chemical vapor deposition apparatus showing an outline of a method for forming a vapor-deposited thin film of an inorganic oxide by a chemical vapor deposition method.

[Explanation of symbols]

A solar cell module - le for surface protective sheet - DOO A ₁ solar cell module - le for surface protective sheet - DOO A ₂ solar cell module - le for surface protective sheet - DOO A ₃ solar cell module - le surface protective sheet - (1) coating film 2 deposited thin film of inorganic oxide 2a deposited thin film of inorganic oxide 2b deposited thin film of inorganic oxide 3 coating film 4 resin film 5 laminate 6 antifouling layer 7 ultraviolet absorber layer 8 multilayer film T sun Battery module 11 Filler layer 12 Solar cell element 13 Filler layer 14 Back 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 BA17 BA18 HA19 HA20 JA03 JA04 JA05

Claims (20)

[Claims] 1. A coating film of a resin composition containing a fluorine-based resin as a main component of a vehicle, and a vapor-deposited thin film of an inorganic oxide are provided, and a metal alkoxide compound and / or Alternatively, a resin film provided with a coating film of a composition containing the hydrolyzate as a main component of the vehicle is laminated, and further, the coating film, a vapor-deposited thin film of inorganic oxide and a coating film are provided. A surface protection sheet for a solar cell module, wherein an antifouling layer and / or an ultraviolet absorber layer is provided on one or both surfaces of a laminate made of a resin film. 2. A coating film of a resin composition containing a fluorine-based resin as a main component of a vehicle, and a vapor-deposited thin film of an inorganic oxide are provided, and a metal alkoxide compound and / or Alternatively, a resin film provided with a coating film of a composition containing the hydrolyzate as a main component of the vehicle is laminated, and further, the coating film, a vapor-deposited thin film of inorganic oxide and a coating film are provided. For a solar cell module, wherein an antifouling layer and an ultraviolet absorber layer are provided on a coating film surface constituting a laminate comprising a cured resin film, and the antifouling layer is the outermost surface. Surface protection sheet. 3. A coating film made of a resin composition containing a fluorine-based resin as a main component of a vehicle, and a vapor-deposited thin film of an inorganic oxide. Further, a metal alkoxide compound and / or Alternatively, a resin film provided with a coating film of a composition containing the hydrolyzate as a main component of the vehicle is laminated, and further, the coating film, a vapor-deposited thin film of inorganic oxide and a coating film are provided. An antifouling layer is provided on the coating film surface constituting the laminate composed of the resin film,
Further, a core and a vapor-deposited thin film of an inorganic oxide constituting the laminate are used.
A surface protection sheet for a solar cell module, characterized in that an ultraviolet absorbent layer is provided on the surface of the resin film provided with the coating film and the antifouling layer is the outermost surface. 4. A coating film made of a resin composition containing a fluorine-based resin as a main component of a vehicle, and a vapor-deposited thin film of an inorganic oxide are provided. Further, a metal alkoxide compound and / or Alternatively, a resin film provided with a coating film of a composition containing the hydrolyzate as a main component of the vehicle is laminated, and further, the coating film, a vapor-deposited thin film of inorganic oxide and a coating film are provided. An antifouling layer is provided on the coating film surface constituting the laminate composed of the resin film,
A surface for a solar cell module, wherein an ultraviolet absorber layer is provided between the coating film and the coating film constituting the laminate, and the antifouling layer is the outermost surface. Protection sheet. 5. The coating film according to claim 1, wherein the coating film is made of a resin composition containing a transparent fluororesin having a visible light transmittance of 90% or more as a main component of the vehicle. Surface protection sheet for solar cell module. 6. The coating film is composed of a resin composition containing a transparent fluororesin made of CYTOP (trade name) or Lumiflon (trade name, both manufactured by Asahi Glass Co., Ltd.) as a main component of the vehicle. The surface protection sheet for a solar cell module according to any one of claims 1 to 5,
G. 7. The method according to claim 1, wherein the inorganic oxide vapor-deposited thin film comprises a multilayer film of one or more layers 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. 8. The method according to claim 1, wherein the inorganic oxide vapor-deposited thin film comprises a multilayer of one or more layers of the inorganic oxide vapor-deposited thin film formed by a chemical vapor deposition method. A surface protection sheet for a solar cell module to be described. 9. The method according to claim 1, wherein the inorganic oxide vapor-deposited thin film is composed of two or more multilayer films of the inorganic oxide vapor-deposited thin film formed by physical vapor deposition and chemical vapor deposition. Surface protectors for solar cell modules as described in the above items 6 to 6
G. 10. A vapor-deposited thin film of an inorganic oxide, a vapor-deposited thin film of an inorganic oxide formed by a chemical vapor deposition method, and then an inorganic oxide deposited by a physical vapor deposition method on the vapor-deposited thin film of the inorganic oxide. 10. The surface protection sheet for a solar cell module according to claim 9, comprising a multilayer film of two or more layers provided with a vapor-deposited thin film of an object. 11. The surface protection for a solar cell module according to claim 1, wherein the vapor-deposited thin film of an inorganic oxide has a plasma-treated surface or a corona-treated surface. Sheet. 12. The surface protection sheet for a solar cell module according to claim 1, wherein the composition contains a resin component. 13. The surface protection sheet for a solar cell module according to claim 12, wherein the resin component is a water-soluble or hydrophilic resin. 14. The surface protection sheet for a solar cell module according to claim 1, wherein the composition contains a curing catalyst for a metal alkoxide compound and / or a hydrolyzate thereof. . 15. The surface protection sheet for a solar cell module according to claim 1, wherein the composition contains inorganic oxide fine particles. 16. The solar cell module according to claim 1, wherein the composition contains a crosslinking agent.
Surface protection sheet for 17. The resin film comprises a biaxially stretched polyester resin film, a biaxially stretched polyamide resin film, a biaxially stretched polypropylene resin film, a cyclic polyolefin resin film, or a (meth) acrylic resin film. The surface protection seal for a solar cell module according to any one of claims 1 to 16, wherein:
G. 18. The method according to claim 1, wherein the antifouling layer comprises a coating film made 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
G. 19. 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. 20. A coating film made of a resin composition containing a fluorine-based resin as a main component of a vehicle, and a vapor-deposited thin film of an inorganic oxide. Further, a metal alkoxide compound and / or Alternatively, a resin film provided with a coating film of a composition containing the hydrolyzate as a main component of the vehicle is laminated, and further, the coating film, a vapor-deposited thin film of inorganic oxide and a coating film are provided. On either one or both sides of the laminate comprising the resin film,
A filler layer is provided on one surface of the solar cell module surface protection sheet provided with an antifouling layer and / or an ultraviolet absorber layer.
A solar cell element as a photovoltaic element, a filler layer, and a backside protective sheet layer are sequentially laminated, and these are vacuum-suctioned to form an integrally formed body by a heat-compression lamination method or the like. Solar cell module.