JP2001111077A - Backside protecting sheet for solar cell module and solar cell module using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To stably offer a backside protecting sheet constituting a solar cell module and a solar cell module using it. The solar cell module is good at strength, a weather resistance, heat resistance, water proof, light proof, wind endurance, resistance to hail, chemical proof, preventability from humidity and from contamination, light reflection performance, light diffusion performance, and design performance, especially its preventability from humidity is remarkably improved so as to prevent penetration of water, oxygen or the like, and the deterioration in its long-term performance can be restrained to the minimum, and has excellent endurance and protecting ability, and further is safe and of low cost. SOLUTION: A backside protecting sheet for a solar cell module and a solar cell module using it are provided. A vapor deposition film of inorganic oxide is arranged on one side of a substrate film, and further a resin film of a polypropylene group which includes a whitening agent and an absorbent of ultraviolet rays and has a heat resistance is laminated on both sides of the substrate film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a solar cell module.
More specifically, the present invention relates to a solar cell module using the same, and more specifically, has excellent strength, weather resistance, heat resistance, water resistance, light resistance, wind pressure resistance, and hail resistance. , Chemical resistance, moisture resistance, stain resistance, light reflection,
A backside protection sheet for a solar cell module which is excellent in various properties such as light diffusion property, design property, etc., extremely durable and excellent in protection ability, and a solar cell module using the same.
It is about the file.

[0002]

2. Description of the Related Art In recent years, attention has been paid to solar cells as a clean energy source due to increasing awareness of environmental issues. At present, solar cell modules of various forms have been developed and proposed. . In general, the above solar cell module produces, for example, a crystalline silicon solar cell element or an amorphous silicon solar cell element, and uses such a solar cell element to form a surface protective sheet layer, a filler layer, It is manufactured by laminating a solar cell element as a photovoltaic element, a filler layer, a backside protective sheet layer, and the like in that order, vacuum-sucking, and heat-compressing, for example, using a lamination method. Thus, the above-mentioned solar cell module is first applied to calculators and thereafter applied to various electronic devices and the like, and its application range is rapidly expanding for consumer use. Furthermore, it is said that the most important issue in the future is to realize large-scale centralized solar cell power generation. By the way, as a back surface protective sheet layer constituting the above-mentioned solar cell module, a plastic substrate or the like having excellent strength is most commonly used at present, and a metal plate or the like is also used. . Thus, in general, the backside protective sheet layer constituting the solar cell module has, for example, excellent strength, weather resistance, heat resistance, water resistance, light resistance, wind pressure resistance, hail resistance, Excellent in various fastnesses such as chemical resistance, light reflectivity, light diffusion, design, etc., in particular, excellent in moisture proofness to prevent the invasion of moisture, oxygen, etc., and also high in surface hardness and surface dirt It is required to satisfy conditions such as excellent antifouling property for preventing accumulation of dust and the like, extremely high durability, high protection ability, and others.

[0003]

However, for example, a plastic substrate having excellent strength, which is most commonly used at present, is used as a backside protective sheet layer constituting a solar cell module. In the case, it is rich in plasticity, lightness, workability, workability, cost reduction, etc., but strength, weather resistance, heat resistance, water resistance, light resistance, chemical resistance, light reflection, light diffusion Inferior in various fastnesses such as water resistance, impact resistance, and others, and in particular, lacks moisture resistance, stain resistance, and design. Further, when a metal plate or the like is used as the back surface protective sheet layer constituting the solar cell module, it is excellent in strength, and has weather resistance, heat resistance, water resistance, light resistance, chemical resistance, Excellent in stab resistance, impact resistance, and other robustness, and also excellent in moisture resistance, etc. In addition, the surface hardness is hard and the antifouling property to prevent the accumulation of surface dirt and dust etc. It has the advantages of excellent and extremely high protection ability, but lacks plasticity, lightness, light reflection, light diffusion, design, etc., and further has poor workability, workability, etc., and low There is a problem that the cost is low. Therefore, the present invention is excellent in strength, and weather resistance, heat resistance, water resistance, light resistance, wind pressure resistance, hail resistance, chemical resistance, moisture resistance,
Excellent in various properties such as antifouling property, light reflection property, light diffusing property, design property, etc., and in particular, significantly improves moisture resistance to prevent moisture and oxygen from entering, and minimizes long-term performance deterioration. The backside protection sheet which constitutes a solar cell module which is extremely durable, has excellent protection ability, is lower in cost and is safer, and a solar cell module using the same is stable. It is to provide.

[0004]

The present inventor has conducted various studies on the back surface protective sheet layer constituting the solar cell module in order to solve the above-mentioned problems. On one side of, silicon oxide, or, provided with a transparent, glassy, such as aluminum oxide, inorganic vapor deposited film excellent in water vapor barrier properties, oxygen barrier properties, etc., further, the inorganic oxide A heat-resistant polypropylene resin film containing a whitening agent and an ultraviolet absorber is laminated on both sides of the base film provided with the vapor-deposited film to produce a back surface protection sheet for a solar cell module. The solar cell module back surface protection sheet is used, for example, a normal solar cell module surface protection sheet made of a glass plate or the like, a filler layer, a solar cell as a photovoltaic element. Battery element,
A filler layer and the above-mentioned back surface protection sheet for a solar cell module are sequentially laminated with one polypropylene resin film facing the other, and then these are integrally vacuum-suctioned. The solar cell module was manufactured using the lamination method of thermocompression bonding. Excellent in various properties such as antifouling property, etc., especially excellent in moistureproof property to prevent invasion of moisture, oxygen, etc. In addition, light reflection property, light diffusion property, design property etc. are significantly improved, Performance degradation to a minimum,
The present invention has been completed by finding that a solar cell module which is extremely durable, has excellent protection ability, can be manufactured at low cost and is safe can be manufactured stably.

That is, according to the present invention, an inorganic oxide vapor-deposited film is provided on one side of a substrate film, and a whitening agent and an ultraviolet ray The present invention relates to a solar cell module backside protection sheet characterized by laminating a heat-resistant polypropylene resin film containing an absorbent and a solar cell module using the same.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The above-mentioned present invention will be described below in more detail with reference to the drawings and the like. In the present invention, a sheet means any of a sheet-like material and a film-like material.
This means any of a film-like material and a sheet-like material. Solar cell module according to the present invention
The layer structure of the back surface protection sheet for solar cells and the solar cell module using the same will be described more specifically with reference to the drawings and the like. FIGS. 1, 2 and 3 show the solar cell according to the present invention. FIGS. 4 and 5 are schematic cross-sectional views illustrating a few examples of the layer configuration of the back surface protection sheet for a module. FIGS. 4 and 5 show the back surface protection sheet for a solar cell module according to the present invention. FIG. 6 is a schematic cross-sectional view illustrating another example of a layer configuration of a deposited inorganic oxide film.
FIG. 2 is a schematic cross-sectional view illustrating one example of a layer configuration of a solar cell module manufactured using the solar cell module back surface protection sheet according to the present invention shown in FIG. 1.

First, as shown in FIG. 1, a backside protection sheet A for a solar cell module according to the present invention is provided with an inorganic oxide vapor-deposited film 2 on one side of a base film 1, The basic structure is such that a heat-resistant polypropylene-based resin film 3 containing a whitening agent and an ultraviolet absorber is laminated on both sides of the base film 1 provided with the above-mentioned inorganic oxide vapor-deposited film 2. It is assumed that. A specific example of the back surface protection sheet for a solar cell module according to the present invention will be described. As shown in FIG.
A vapor-deposited inorganic oxide film 2 is provided.
Heat-resistant polypropylene-based resin films 3 and 3 containing a whitening agent and an ultraviolet absorber through the adhesive layers 4 and 4, respectively.
The Dorairamine - Sorted consisting with the structures stacked solar cell module - can be exemplified bets A ₁ - for the backside Le protective sheet. Alternatively, in the present invention, as shown in FIG.
An inorganic oxide vapor-deposited film 2 is provided on one surface of the substrate film 1, and further, an adhesive coating agent or the like is attached to both surfaces of the substrate film 1 on which the inorganic oxide vapor-deposited film 2 is provided. A heat-resistant polypropylene-based resin composition containing a whitening agent and an ultraviolet absorber is extruded and laminated via the agent layers 5, 5 and the like, and a heat-resistant polypropylene-based resin film containing a whitening agent and an ultraviolet absorber extruded 3,3 laminating - Sorted consisting with the structures stacked solar cell module - can be exemplified bets a ₂ - for the backside Le protective sheet. The above examples illustrate only a few examples of the back surface protection sheet for a solar cell module according to the present invention, and the present invention is, of course, not limited thereto.

For example, in the solar cell module back surface protection sheets shown in FIGS. 1 to 3, the inorganic oxide vapor-deposited film may be a physical Two or more layers of inorganic oxide vapor-deposited films 2 and 2, such as two or more layers of inorganic oxide vapor-deposited films formed by phase growth method, or two or more layers of inorganic oxide vapor-deposited films formed by chemical vapor deposition method 2a (FIG. 4), or an inorganic oxide vapor deposition film 2b formed by a physical vapor deposition method described below and an inorganic oxide vapor deposition film 2c formed by a chemical vapor deposition method. Composite film 2d in which two or more layers of vapor-deposited films 2b and 2c are laminated
(FIG. 5). Also,
In the present invention, for example, although not shown, it is also possible to manufacture a back surface protection sheet for a solar cell module by combining the above-mentioned lamination with dry laminating and lamination with extrusion laminating. is there.

Next, in the present invention, an example of a solar cell module manufactured by using the above-described back surface protection sheet for a solar cell module according to the present invention is illustrated in FIG. The solar cell module according to the present invention shown
FIG. 6 shows an example in which the back surface protection sheet A for
As shown in FIG. 1, first, a normal surface protection sheet 11 for a solar cell module, a filler layer 12, a solar cell element 13 as a photovoltaic element, a filler layer 14, and the above-described solar cell module. Lamination is performed by successively laminating the back surface protection sheet 15 (A) for the tape with the surface of one of the polypropylene-based resin films 3 facing each other, and then vacuum-suctioning and heat-compressing them integrally. The solar cell module T can be manufactured by using a normal molding method such as a method and using each of the above layers as an integrally molded body. The above example is an example of a solar cell module manufactured using the solar cell module back surface protection sheet according to the present invention, and the present invention is not limited thereto. is not. For example, although not shown, the solar cell module having various forms is used in the same manner as described above using the solar cell module back surface protection sheet shown in FIGS.
In addition, in the above-described solar cell module, another layer is optionally added and laminated for the purpose of absorbing sunlight, reinforcing, and the like. Can be done.

Next, in the present invention, the back 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. Basically, as a base film constituting a back protective sheet for a solar cell module, a solar cell module and the like according to the present invention, a vapor deposition for forming a vapor-deposited film of an inorganic oxide or the like is performed. Withstand conditions, others, etc., and have excellent adhesion to the inorganic oxide vapor-deposited film, etc., can be held well without impairing the properties of those films, and have excellent strength, And weather resistance,
Excellent in heat resistance, water resistance, light resistance, wind pressure resistance, hail resistance, chemical resistance, etc., especially excellent in moisture resistance to prevent intrusion of moisture, oxygen, etc., and also high surface hardness, Use of various resin films or sheets that have excellent antifouling properties to prevent accumulation of dirt and dust on the surface, are extremely durable, and have high protective ability. Can be. Specifically, as the film or sheet of the above various resins, for example, polyethylene-based resin,
Polypropylene resin, cyclic polyolefin resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyvinyl chloride resin,
Fluorine resin, poly (meth) acrylic resin, polycarbonate
Bonnet resin, polyester resin such as polyethylene terephthalate or polyethylene naphthalate, polyamide resin such as various nylons, polyimide resin,
Polyamide imide resin, polyaryl phthalate resin, silicone resin, polysulfone resin, polyphenylene sulfide resin, polyether sulfone resin, polyurethane resin, acetal resin, cellulose
Film or sheet of various resins such as
Can be used. In the present invention, among the above resin films or sheets, fluorine-based resins,
Cyclic polyolefin-based resin, polycarbonate-based resin,
It is preferable to use a film or sheet of a poly (meth) acrylic resin, a polyamide resin, or a polyester resin.

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

In the present invention, among the various resin films or sheets described above, particularly, for example, cyclopentadiene and its derivatives, dicyclopentadiene and its derivatives, cyclohexadiene and its derivatives, Norbornadiene and its derivatives,
A polymer obtained by polymerizing a cyclic diene such as another, or one or more of a cyclic diene and an olefin-based monomer such as ethylene, propylene, 4-methyl-1-pentene, styrene, butadiene, isoprene and others; It is preferred to use a cyclic polyolefin resin film or sheet made of a copolymer or the like obtained by copolymerizing the above. In the present invention,
Film or sheet of the above-mentioned cyclic polyolefin resin
Among them, in particular, cyclopentadiene and its derivatives, dicyclopentadiene and its derivatives, or
A cyclic polyolefin-based resin film or sheet made of a cyclic diene polymer or copolymer such as norbornadiene or a derivative thereof is preferred from the viewpoint of strength and the like. Thus, in the present invention, by using a film or sheet made of the above-mentioned fluorine-based resin or cyclic polyolefin-based resin, the mechanical properties and chemical properties of the fluorine-based resin or the cyclic polyolefin-based resin are improved. Utilizing excellent properties such as physical properties, physical properties, etc., specifically, various properties such as weather resistance, heat resistance, water resistance, light resistance, moisture resistance, stain resistance, chemical resistance, etc. It is a backside protection sheet that constitutes a solar cell,
Due to this, it has durability, protective function, etc., and it is light due to its flexibility, mechanical properties,
Further, it has advantages such as excellent workability and easy handling.

In the present invention, as the film or sheet of the above-mentioned various resins, for example, one or more of the above-mentioned various resins are used, and the extrusion method, the cast molding method, the T-die method, and the cutting method are used. A method of forming the above various resins alone using a film forming method such as an inflation method, an inflation method, etc., or a multi-layer coextrusion film forming using two or more kinds of various resins. A film or sheet of various resins is manufactured by a method of forming two or more resins, and a method of mixing and forming a film before forming a film. For example, various resin films or sheets stretched in a uniaxial or biaxial direction using a tenter method or a tuber method can be used. In the present invention, the film thickness of various resin films or sheets is 12 to 300 μm.
And more preferably about 20 to 200 μm.

In the above, one or more of the above-mentioned various resins are used, and when forming the film, for example, the processability, heat resistance, weather resistance, mechanical properties, dimensional stability, Antioxidant, slippery, mold release, flame retardant,
Various plastic compounding agents and additives can be added for the purpose of improving or modifying the antifungal property, electric properties, etc., and the amount of addition can be from a very small amount to several tens%. They can be arbitrarily added according to the purpose.
In the above, as a general additive, for example, a lubricant, a crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing fiber, a reinforcing agent, an antistatic agent, a flame retardant,
Flameproofing agents, foaming agents, mildewproofing agents, pigments, and the like can be used, and furthermore, modifying resins and the like can be used. In the present invention, among the above additives, it is particularly preferable to use various resin films or sheets obtained by kneading and processing an ultraviolet absorber or an antioxidant. As the above-mentioned ultraviolet absorber, it absorbs harmful ultraviolet rays in sunlight, converts it into harmless heat energy in the molecule, and prevents excitation of the active species that initiates photodegradation in the polymer. For example, benzophenone, benzotriazole, saltate, acrylonitrile, metal complex, and solder
Doamine-based, ultrafine titanium oxide (particle size, 0.01 to
0.06 μm) or ultrafine zinc oxide (0.01 to
One or more inorganic UV absorbers such as 0.04 μm) can be used. The antioxidants are those that prevent photodeterioration or thermal degradation of the polymer, and include, for example, phenol-based, amine-based,
Antioxidants such as sulfur-based, phosphoric-based, and others can be used. Further, as the above-mentioned ultraviolet absorber or antioxidant, for example, the above-mentioned ultraviolet absorber such as benzophenone or the above antioxidant such as phenol is added to the main chain or side chain constituting the polymer. A polymer-type ultraviolet absorber or an antioxidant obtained by chemically bonding may also be used. The content of the ultraviolet absorber and / or antioxidant varies depending on the particle shape, density and the like, but is preferably about 0.1 to 10% by weight.

In the present invention, the surface of various resin films or sheets may be prepared in advance, if necessary, in order to improve the tight adhesion with an inorganic oxide vapor-deposited film or the like.
A desired surface treatment layer can be provided. In the present invention, as the surface treatment layer, for example, a corona discharge treatment, an ozone treatment, a low-temperature plasma treatment using an oxygen gas or a nitrogen gas, a glow discharge treatment, an oxidation treatment using a chemical or the like, Arbitrarily perform pretreatment such as other,
For example, a corona treatment layer, an ozone treatment layer, a plasma treatment layer, an oxidation treatment layer, and the like can be formed and provided. The above-mentioned surface pretreatment may be performed in a separate step, and, for example, in the case of a surface pretreatment such as a low-temperature plasma treatment or a glow discharge treatment, before forming the above-mentioned inorganic oxide vapor-deposited film or the like. The processing can be performed in pre-processing by in-line processing, and in such a case, there is an advantage that the manufacturing cost can be reduced. The above-mentioned surface pretreatment is carried out as a method for improving the tight adhesion between the film or sheet of various resins and the deposited film of the inorganic oxide or the like. As another method, for example, a primer coat agent layer, an undercoat or the like may be previously provided on the surface of various resin films or sheets.
A coating agent layer, an anchor coating agent layer, an adhesive layer, a vapor-deposited anchor coating agent layer, or the like may be arbitrarily formed to be a surface treatment layer. Examples of the coating agent layer of the above pretreatment include polyester resin, polyamide resin, polyurethane resin, epoxy resin, and phenol resin.
Resin, (meth) acrylic resin, polyvinyl acetate resin, polyolefin resin such as polyethylene aliha polypropylene or a copolymer or modified resin thereof,
A resin composition containing a cellulose-based resin or the like as a main component of the vehicle can be used.

The above resin composition may be added with an epoxy-based silane coupling agent in order to improve the tight adhesion, an antiblocking agent in order to prevent blocking of the base film, and the like. Can be arbitrarily added. The addition amount is preferably about 0.1% by weight to 10% by weight. In the present invention, for example, an ultraviolet absorber and / or an antioxidant can be added to the resin composition in order to improve light resistance and the like. The above-mentioned ultraviolet absorber absorbs the above-mentioned harmful ultraviolet rays in sunlight, converts them into harmless heat energy in the molecule, and excites the active species that initiates photodegradation in the polymer. Is to prevent
For example, benzophenone-based, benzotriazole-based, saltylate-based, acrylonitrile-based, metal complex-based, hindered amine-based, ultrafine titanium oxide (particle diameter, 0.0
1 to 0.06 μm) or ultrafine zinc oxide (0.0
One or more UV absorbers such as inorganic UV absorbers (1 to 0.04 μm) can be used. Further, the antioxidant is one that prevents the above-mentioned photodeterioration or thermal degradation of the polymer, for example, phenol-based,
Amine-based, sulfur-based, phosphoric-based, and other antioxidants can be used. Further, as the above-mentioned ultraviolet absorber or antioxidant, for example, the above-mentioned ultraviolet absorber such as benzophenone or the above antioxidant such as phenol is added to the main chain or side chain constituting the polymer. A polymer-type ultraviolet absorber or an antioxidant obtained by chemically bonding may also be used. The content of the above ultraviolet absorber and / or antioxidant varies depending on the particle shape, density, etc., but is about 0.1 to 10% by weight.
Position is preferred. 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. Method, kiss-coat method, etc.
Coating can be carried out using a coating method, and the coating time is after the film formation of the fluororesin sheet, as a post-process after the biaxial stretching treatment, or film formation, or It can be carried out by an in-line process such as a biaxial stretching process.

Furthermore, in the present invention, the base film is protected on one side of the base film against the vapor deposition conditions when an inorganic oxide vapor deposition film is formed. Its yellowing, deterioration or shrinkage, or suppresses cohesive failure and the like in the film surface layer or inner layer, and further, on one surface of the base film, a vapor-deposited film of an inorganic oxide is successfully formed into a film, and In order to improve the tight adhesion between the base film and the inorganic oxide vapor-deposited film, etc., in advance, on one surface of the base film, as a surface pretreatment layer, for example, a plasma chemical vapor deposition method described later , Thermal chemical vapor deposition, photochemical vapor deposition, etc.
Vapor Deposition method, CVD method) or physical vapor deposition method (Physic) such as vacuum evaporation method, sputtering method, ion plating method, etc.
al Vapor Deposition method, PVD
By forming a vapor-deposited thin film of an inorganic oxide using the above method, a vapor-deposited protective film can be provided. Note that, in the present invention, the thickness of the deposition-resistant protective film made of silicon oxide or the like is a thin film, and further, a non-barrier film having no barrier property against water vapor gas, oxygen gas, or the like is sufficient. Specifically, the thickness is desirably less than 150 °, and specifically, the thickness is 10 to 100 °.
Position, preferably 20 to 80 °, and more preferably 30 to 60 °. Thus, in the above, 150 ° or more, specifically, 100 °, and further, 80 °
When the thickness is more than 60 °, it is not preferable because it becomes difficult to form a good deposition-resistant protective film. In addition, when the thickness is less than 10 °, further 30 °, and less than 60 °, the protective layer becomes a deposition-resistant protective layer. This is not preferable because the function of the above is lost and it becomes difficult to achieve the effect.

Next, in the present invention, the back surface protection sheet for a solar cell module and the solar cell module according to the present invention.
Explained about the deposited film of the inorganic oxide constituting the metal and the like, as the deposited 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 a single layer film composed of one layer of an inorganic oxide vapor-deposited film or a multilayer film or composite film composed of two or more layers. The vapor-deposited film of an inorganic oxide formed by the above-described physical vapor deposition method will be described in more detail. Examples of the vapor-deposited film of an inorganic oxide formed by the physical vapor deposition method include, for example, a vacuum vapor deposition method, a sputtering method, an ion plating method, Physical vapor growth method such as ion cluster beam method (Physical Vapor)
A deposition film of an inorganic oxide can be formed by a deposition method (PVD method). In the present invention, specifically, a metal oxide as a raw material, a vacuum deposition method of heating and vapor deposition on a substrate film, or
Oxidation reaction deposition method of using metal or metal oxide as a raw material, introducing oxygen, oxidizing and depositing on a base film, and plasma-assisted oxidation reaction deposition method of further assisting the oxidation reaction with plasma, etc. Can be used to form a deposited film. In the above, as a heating method of the evaporation material, for example, a resistance heating method, a high-frequency induction heating method, an electron beam heating method (EB), or the like can be used.

In the present invention, a specific example of a method for forming a vapor-deposited inorganic oxide film by physical vapor deposition is shown in FIG. 7. FIG. 7 is a schematic diagram showing an example of a roll-up type vacuum vapor deposition apparatus. It is. As shown in FIG. 7, in the vacuum chamber 22 of the take-up type vacuum evaporation apparatus 21, the base film 1 unwound from the unwinding roll 23 is cooled through guide rolls 24 and 25. -Guided to the ding drum 26; Thus, on the substrate film 1 guided on the cooled coating drum 26,
The evaporation source 28 heated in the crucible 27, for example, metal aluminum or aluminum oxide is evaporated,
Further, if necessary, oxygen gas or the like is spouted from the oxygen gas outlet 29 and, while supplying the gas, a deposition film of an inorganic oxide such as aluminum oxide is formed through the masks 30 and 30 to form a film. Next, in the above, for example, the base film 1 on which a vapor-deposited film of an inorganic oxide such as aluminum oxide is formed is sent out via guide rolls 25 ′ and 24 ′ and wound up on a take-up roll 31. In addition, a deposited film of an inorganic oxide can be formed by the physical vapor deposition method according to the present invention. In the present invention, first, using the above-mentioned winding type vacuum evaporation apparatus, the first
Forming a layer of inorganic oxide on the layer, and then forming a layer of inorganic oxide on the layer of inorganic oxide, Forming an inorganic oxide vapor deposition film consisting of two or more multilayer films by connecting these in series using a vacuum evaporation system and forming an inorganic oxide vapor deposition film continuously. Can be.

In the above description, as the inorganic oxide deposited film, basically any thin film obtained by 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 film of an oxide of a metal such as boron (B), titanium (Ti), lead (Pb), zirconium (Zr), and yttrium (Y) can be used. Thus, preferred are silicon (Si), aluminum (A
1) and the like.
Thus, the above-mentioned vapor-deposited film of a metal oxide can be referred to as a metal oxide, such as silicon oxide, aluminum oxide, and magnesium oxide. The notation is, for example, SiO _x , AlO _x MO such as MgO _X
X (wherein, M represents a metal element, and the value of X is
The range differs depending on the metal element. ). The range of the value of X is silicon (S
i) is 0-2, and aluminum (Al) is 0-1.
5. Magnesium (Mg) is 0-1, calcium (C
a) is 0-1, potassium (K) is 0-0.5, tin (Sn) is 0-2, and sodium (Na) is 0-0.
5, boron (B) is 0-1,5, titanium (Ti) is
0-2, lead (Pb): 0-1, zirconium (Zr)
Can have a value in the range of 0 to 2 and yttrium (Y) can have a value in the range of 0 to 1.5. In the above, when X = 0,
It is a perfect metal, is not transparent and cannot be used at all, and the upper end of the range of X is a fully oxidized value. In the present invention, generally, except for silicon (Si) and aluminum (Al), examples used are scarce. Silicon (Si) is 1.0 to 2.0, aluminum (A)
For l), a value in the range of 0.5 to 1.5 can be used. In the present invention, the thickness of the above-mentioned inorganic oxide vapor-deposited film varies depending on the type of the metal or the metal oxide used, and is, for example, 50 to 40.
It is desirable to arbitrarily select and form it within the range of about 00 °, preferably about 100 to 1000 °. Further, in the present invention, as the deposited metal film of the inorganic oxide, the metal to be used, or as the oxide of the metal, used in one kind or a mixture of two or more kinds, and the inorganic oxide mixed with different materials is used. A vapor deposition film can also be formed.

Next, in the present invention, the vapor-deposited inorganic oxide film formed by the above-mentioned chemical vapor deposition method will be further described. Chemical vapor deposition methods (Ch, such as vapor phase epitaxy, thermochemical vapor phase epitaxy, photochemical vapor phase epitaxy, etc.)
electrical Vapor Deposition method,
A deposited film of an inorganic oxide can be formed by using a CVD method or the like. In the present invention, specifically, a monomer for vapor deposition of an organic silicon compound or the like is provided on one surface of the base film.
Gas 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 or the like is used as an oxygen supply gas. A deposition film of an inorganic oxide such as silicon oxide can be formed by a phase growth method. In the above, as the low-temperature plasma generator,
For example, it is possible to use a generator such as a high-frequency plasma, a pulsed-wave plasma, a microwave plasma, and the like. It is desirable to use

More specifically, an example of a method of forming a deposited film of an inorganic oxide by the low-temperature plasma enhanced chemical vapor deposition method will be described. FIG. FIG. 1 is a schematic configuration diagram of a low-temperature plasma chemical vapor deposition apparatus showing an outline of a method of forming an oxide deposition film. As shown in FIG. 8 described above, in the present invention, the vacuum chamber of the plasma enhanced chemical vapor deposition apparatus 41 is used.
42, the base film 1 is unwound from an unwinding roll 43, and the base film 1 is further transferred to an auxiliary roll.
The cooling / electrode drum 45 is conveyed onto the peripheral surface of the cooling / electrode drum 45 at a predetermined speed via the nozzle 44. Thus, in the present invention, a monomer for vapor deposition of an oxygen gas, an inert gas, an organic silicon compound or the like is supplied from the gas supply devices 46 and 47 and the raw material volatile supply device 48 and the like.
While supplying a gas, etc., and adjusting the mixed gas composition for vapor deposition comprising them, the mixed gas composition for vapor deposition is introduced into the vacuum chamber -42 through the raw material supply nozzle 49, and the above cooling / cooling is performed. The glow discharge plasma 50 is placed on the substrate film 1 transported on the peripheral surface of the electrode drum 45.
To generate plasma, and irradiate the plasma to form a deposited film of an inorganic oxide such as silicon oxide, thereby forming a film. In the present invention, at this time, predetermined electric power is applied to the cooling / electrode drum 45 from a power source 51 disposed outside the chamber, and a magnet 52 is provided near the cooling / electrode drum 45. The base film 1 on which the deposited film of the inorganic oxide such as silicon oxide is formed as described above, is wound up through the auxiliary roll 53 to form a roll 54. In this way, a deposited film of an inorganic oxide can be manufactured by the plasma enhanced chemical vapor deposition method according to the present invention. In the figure, 55 is
Represents a vacuum pump. The above exemplification is merely an example, and it goes without saying that the present invention is not limited thereby. Although not shown,
In the present invention, the deposited film of the inorganic oxide is not limited to one layer of the deposited film of the inorganic oxide, and may be a multilayer film in which two or more layers are laminated. Alternatively, it is also possible to use a mixture of two or more kinds and form a deposited film of an inorganic oxide mixed with different materials. In the present invention, a low-temperature plasma-enhanced chemical vapor deposition apparatus as described above is used to first form a first layer of an inorganic oxide vapor-deposited film. On the film, an inorganic oxide vapor-deposited film is further formed, or by using a low-temperature plasma-enhanced chemical vapor deposition apparatus as described above, this is connected in series, and the inorganic oxide is continuously formed. By forming a vapor deposition film of above, a vapor deposition film of an inorganic oxide composed of a multilayer film of two or more layers can be formed.

In the above description, as a monomer gas for vapor deposition of an organic silicon compound or the like for forming a vapor deposition film of an inorganic oxide such as silicon oxide, for example, 1.1.3.3-tetramethyldisiloxane, hexamethyldisiloxane Siloxane, 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 properties and the like. In the above, for example, an argon gas, a helium gas, or the like can be used as the inert gas.

In the present invention, in the silicon oxide vapor-deposited film formed above, a monomer gas such as an organic silicon compound and an oxygen gas are chemically reacted, and the reaction product is closely adhered to the substrate film. In addition, it is possible to form a dense and thin film having a high flexibility and the like, and usually, a general formula SiO _x (where X is
(Representing a number from 0 to 2). Thus, from the viewpoint of transparency, barrier properties, and the like, the silicon oxide deposited film of the general formula SiO
_X (where X represents a number from 1.3 to 1.9) is preferably a thin film mainly composed of a deposited silicon oxide film. In the above, the value of X changes depending on the molar ratio of the monomer gas to the oxygen gas, the energy of the plasma, etc. In general, the gas permeability decreases as the value of X decreases, but the film itself has It has a yellow color and poor transparency. Further, the above-described deposited film of silicon oxide has silicon (Si) and oxygen (O) as essential constituent elements, and furthermore, one of carbon (C) and hydrogen (H), or
It consists of a deposited film of silicon oxide containing both of these elements as trace constituent elements, and has a thickness of 50 ° to 400 °.
It is in the range of 0 °, preferably in the range of 100 ° to 1000 °, and the composition ratio of the essential constituent elements and the trace constituent elements continuously changes in the film thickness direction. Further, when the silicon oxide vapor-deposited film contains a compound composed of carbon, the content of carbon is reduced in the depth direction of the film thickness. Thus, in the present invention, the above-mentioned deposited film of silicon oxide is, for example, an X-ray photoelectron spectrometer (Xray P
photoelectron Spectroscope
y, XPS), secondary ion mass spectrometer (Second
ary Ion Mass Spectroscop
y, SIMS), etc. to confirm the above physical properties by performing elemental analysis of the deposited silicon oxide film using a method of analyzing by ion etching in the depth direction etc. using a surface analyzer such as can do. In the present invention, the thickness of the silicon oxide vapor deposition film is 50
It is desirable to be about {4000}, and specifically,
The thickness is preferably about 100 to 1000 °,
Thus, in the above, 1000Å, further 4000
If it is thicker, cracks and the like are likely to occur in the film, which is not preferable.
If it is less than this, it is difficult to achieve the effect of the barrier property, which is not preferable. In the above description, the film thickness can be measured by a fundamental parameter method using, for example, a fluorescent X-ray analyzer (model name: RIX2000) manufactured by Rigaku Corporation. Further, in the above, as a means for changing the thickness of the deposited film of silicon oxide, 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 backside protective sheet for a solar cell module according to the present invention, as a vapor deposition film of an inorganic oxide constituting a solar cell module or the like, for example, a physical vapor deposition method can be used. By using both of the chemical vapor deposition methods together, a composite film composed of two or more vapor deposited films of different kinds of inorganic oxides can be formed and used. Thus, as a composite film composed of two or more layers of the above-mentioned vapor-deposited films of different types of inorganic oxides, first, a dense, flexible film is formed on a base film by a chemical vapor deposition method. Provision of a deposited film of an inorganic oxide capable of preventing the occurrence of cracks,
On the inorganic oxide vapor deposited film, it is desirable to provide an inorganic oxide vapor deposited film by physical vapor deposition to form an inorganic oxide vapor deposited film composed of a composite film composed of two or more layers. is there. Of course, in the present invention, contrary to the above,
First, a vapor-deposited inorganic oxide film is formed on the base film by physical vapor deposition, and then dense, flexible, and relatively cracked by chemical vapor deposition. It is also possible to provide an inorganic oxide vapor deposition film composed of a composite film composed of two or more layers by providing an inorganic oxide vapor deposition film capable of preventing the above.

Next, in the present invention, the back surface protection sheet for a solar cell module and the solar cell module according to the present invention.
When describing a heat-resistant polypropylene-based resin film containing a whitening agent and an ultraviolet absorber that constitute
As such a polypropylene resin film, first,
A polypropylene-based resin as a main component, and one or two or more of a whitening agent and an ultraviolet absorber as a light reflecting agent or a light diffusing agent are added thereto, and further, if necessary, a plasticizer and a light stabilizer , Antioxidants, antistatic agents, crosslinking agents, curing agents, fillers, lubricants, reinforcing agents, reinforcing agents, flame retardants, flame retardants, foaming agents, fungicides, coloring agents such as pigments and dyes, etc. One or more additives are arbitrarily added, and if necessary, a solvent, a diluent and the like are added, and the mixture is sufficiently kneaded to prepare a polypropylene resin composition. Thus, in the present invention, using the polypropylene resin composition prepared above, for example, an extruder, a T-die extruder,
Using a cast molding machine, inflation molding machine, etc.
An extrusion method, a T-die method, a cast molding method, an inflation method, a film forming method such as an inflation method, a polypropylene resin film or sheet is produced, and if necessary, for example, a tenter method, or A heat-resistant polypropylene resin film which is stretched in a uniaxial or biaxial direction using a tuber method or the like and kneaded with a whitening agent and an ultraviolet absorber. .

Alternatively, in the present invention, as a heat-resistant polypropylene resin film containing a whitening agent and an ultraviolet absorber, first, an ordinary paint or ink vehicle is used as a main component, One or two of a whitening agent and an ultraviolet absorber as an agent or a light diffusing agent
Seeds, if necessary, further, if necessary, plasticizers, light stabilizers, antioxidants, antistatic agents, crosslinking agents, curing agents, fillers, lubricants, reinforcing agents, reinforcing agents, flame retardants, flame retardants, Foaming agent,
A fungicide, a colorant such as a pigment or a dye, and one or more additives such as other additives are optionally added.
Solvents, diluents, etc. are added and kneaded well to prepare a paint or ink composition. Thus, in the present invention, the coating or ink composition prepared as described above is used, and is applied to the surface of a transparent heat-resistant polypropylene-based resin film by a usual coating method or printing method. It is used to produce a heat-resistant polypropylene resin film having a coating or printing film containing a whitening agent and an ultraviolet absorber on its surface by coating or printing to form a coating or printing film. is there. In the above description, when the ultraviolet absorber is previously kneaded and processed into a transparent heat-resistant polypropylene-based resin film, it is not always necessary to add the ultraviolet absorber to the paint or the ink composition. Things.

Next, in the present invention, a heat-resistant polypropylene-based resin film obtained by kneading the whitening agent and the ultraviolet absorber produced above, or a whitening agent and an ultraviolet absorber on the surface thereof. A heat-resistant polypropylene-based resin film containing a whitening agent and an ultraviolet absorber comprising a heat-resistant polypropylene-based resin film having a coating film or a printed film containing the same, and using the above-mentioned inorganic oxide On both sides of the base film with the deposited film,
For example, by laminating and laminating through a laminating adhesive layer or the like, the back protective sheet for a solar cell module according to the present invention can be manufactured. Alternatively, in the present invention, a polypropylene-based resin composition prepared to produce a heat-resistant polypropylene-based resin film obtained by kneading a whitening agent and an ultraviolet absorber as described above is used and extruded. The extruder is melt-extruded using a machine or the like, and a whitening agent is applied to both surfaces of the base film provided with the above-mentioned inorganic oxide vapor-deposited film, for example, via an adhesion aid layer made of an anchor coating agent or the like. By heat-extruding and laminating a heat-resistant polypropylene-based resin film containing a resin and an ultraviolet absorber, the backside protective sheet for a solar cell module according to the present invention can be manufactured. In the above description, the thickness of the heat-resistant polypropylene-based resin film containing a whitening agent and an ultraviolet absorber is preferably about 10 μm to 300 μm, and more preferably about 15 μm to 150 μm.

In the above description, as the polypropylene resin, a homopolymer of propylene, which is a by-product generated when ethylene is produced by pyrolysis of petroleum hydrocarbons, or propylene and α-olefin, and other materials such as Copolymers with other monomers can be used.
Thus, in the present invention, as the polypropylene-based resin, specifically, when polymerizing propylene, when a cationic polymerization catalyst or the like is used, a low-molecular-weight polymer can be obtained. When a Ziegler-Natta catalyst is used, an isotactic polymer having a high molecular weight and high crystallinity can be obtained, and this isotactic polymer is used. In the above isotactic polymer, its melting point is about 164 ° C. to 170 ° C., its specific gravity is about 0.90 to 0.91, and its molecular weight is about 100,000 to 200,000. Although properties are largely controlled by crystallinity, polymers with high isotacticity have excellent tensile strength and impact strength, good heat resistance, good bending fatigue resistance, and extremely good workability. It is. In the present invention, as a heat-resistant polypropylene-based resin film containing a whitening agent and an ultraviolet absorber, when laminated by dry laminating,
The surface can be arbitrarily subjected to a surface modification pretreatment such as a corona discharge treatment, an ozone treatment, or a plasma discharge treatment in advance. In the present invention,
In addition to the above-mentioned polypropylene-based resin, if necessary, a resin having compatibility with the polypropylene-based resin such as a polyethylene-based resin or the like can be optionally added for modification.

In the above, the whitening agent includes
It is added for the purpose of imparting light reflectivity, light diffusivity, and the like for the purpose of reusing and reflecting the light transmitted through the solar cell module by light reflection or light diffusion. For example, basic lead carbonate is added. , Basic lead sulfate, basic lead silicate,
One or more white pigments such as zinc white, zinc sulfide, lithopone, antimony trioxide, anatase-type titanium oxide, rutile-type titanium oxide and others can be used.
The amount to be used is about 0.1% to 30% by weight, preferably about 0.1% by weight in the polypropylene resin composition.
It is desirable to add about 5% by weight to 10% by weight for use.

Further, in the above, the ultraviolet absorber absorbs the above-mentioned harmful ultraviolet light in sunlight, converts it into harmless heat energy in the molecule, and activates the photodegradation initiation in the polymer. It prevents the species from being excited, for example, benzophenone-based, benzotriazole-based, saltylate-based, acrylonitrile-based, metal complex-based, hindered
Doamine-based, ultrafine titanium oxide (particle size, 0.01 to
0.06 μm) or ultrafine zinc oxide (0.01 to
One or more inorganic UV absorbers such as 0.04 μm) can be used. It is desirable to use about 0.1% by weight to 10% by weight, preferably about 0.3% by weight to 10% by weight, of the polypropylene resin composition.

Next, in the above-mentioned dry laminate laminating method, examples of the adhesive constituting the adhesive layer for the laminate include a polyvinyl acetate adhesive, ethyl, butyl, and 2-ethylhexyl acrylates. A homopolymer such as an ester, or a polyacrylate adhesive, a cyanoacrylate adhesive, a copolymer of ethylene methacrylate, acrylonitrile, styrene, etc., ethylene and vinyl acetate, ethyl acrylate, Ethylene copolymer adhesive, cellulose adhesive, polyester adhesive, polyamide adhesive, polyimide adhesive, urea resin or melamine composed of a copolymer with a monomer such as acrylic acid or methacrylic acid. Amino resin adhesive, phenol resin adhesive, epoxy adhesive, poly Urethane-based adhesives, reactive (meth)
Acrylic adhesive, chloroprene rubber, nitrile rubber,
Adhesives such as rubber-based adhesives made of styrene-butadiene rubber or the like, silicone-based adhesives, inorganic adhesives made of alkali metal silicate, low-melting glass, or the like, and the like can be used. The composition system of the above adhesive is an aqueous type,
Any composition such as a solution type, an emulsion type, and a dispersion type may be used.
Any form of powder, solid, etc., and furthermore, regarding the bonding mechanism, a chemical reaction type, a solvent evaporation type, a heat melting type,
Any form such as a heat-pressure type may be used. Thus,
The above-mentioned adhesive can be applied by a coating method such as a roll coating method, a gravure rolling method, a kiss coating method, etc., or a printing method. The amount is 0.1 to 10 g / m ² (dry state)
Position is desirable.

The above-mentioned adhesive may be added with the above-mentioned ultraviolet absorber and / or antioxidant in order to prevent the deterioration of ultraviolet rays and the like. The above-mentioned ultraviolet absorber absorbs the above-mentioned harmful ultraviolet rays in sunlight, converts them into harmless heat energy in the molecule, and excites the active species that initiates photodegradation in the polymer. For example, benzophenone-based, benzotriazole-based, saltylate-based, acrylonitrile-based, metal complex-based, hindered amine-based, and ultrafine titanium oxide (particle diameter: 0.01 to 0.06 μm) ) Or one or more ultraviolet absorbers such as inorganic oxides such as ultrafine zinc oxide (0.01 to 0.04 µm). Examples of the antioxidant include those which prevent the aforementioned polymer from light degradation or thermal degradation, and include, for example, phenol-based, amine-based, sulfur-based, phosphoric acid-based, and other antioxidants. Can be used. Further, as the above-mentioned ultraviolet absorber or antioxidant, for example, the above-mentioned ultraviolet absorber such as benzophenone or the above antioxidant such as phenol is added to the main chain or side chain constituting the polymer. A polymer-type ultraviolet absorber or an antioxidant obtained by chemically bonding may also be used. The content of the above ultraviolet absorber and / or antioxidant varies depending on the particle shape, density, etc., but is about 0.1%.
About 10 to about 10% by weight is preferable.

Further, in the above-mentioned melt extrusion lamination method, in order to obtain a stronger adhesive strength, for example, an adhesive aid such as an anchor coat agent is used, and the anchor coat is used.
It can be laminated via the agent layer. Examples of the above-mentioned anchor coating agent include various aqueous or oily anchor coating agents such as organotitanium, isocyanate, polyethyleneimine, polybutadiene, etc. such as alkyl titanate. Can be used. The above-mentioned anchor coating agent can be coated by using a coating method such as roll coating, gravure roll coating, kiss coating and others. The amount is desirably about 0.1 to 5 g / m ² (dry state).

In the present invention, in order to improve the tight adhesion between the base film provided with the inorganic oxide vapor-deposited film and the heat-resistant polypropylene-based resin film containing the whitening agent and the ultraviolet absorber. Further, for example, a primer-coating agent layer or the like may be arbitrarily formed in advance to form a surface-treated layer. Examples of the primer coating agent include polyester resin, polyamide resin, polyurethane resin, epoxy resin, phenol resin, (meth) acrylic resin, polyvinyl acetate resin, polyethylene alcohol, and the like. A resin composition containing a polyolefin resin such as iha polypropylene or a copolymer or modified resin thereof, a cellulose resin, or the like as a main component of the vehicle can be used. In the present invention, for example, roll coat, gravure roll coat, kiss coat
And a coating method such as coating, etc., to form a primer coating agent layer, and the coating amount is 0.1 to 5 g / m 2. ^Two
(Dry state) is desirable.

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

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

Next, in the present invention, the solar cell module
The solar cell element as a photovoltaic element constituting the solar cell element will be described. As such a solar cell element, a conventionally known one, for example, a crystalline silicon such as a single-crystal silicon-type solar cell element, a polycrystalline silicon-type solar cell element, etc. Solar electronic devices, single-junction or tandem-structure amorphous silicon solar cell devices, gallium arsenide (G
III-V compound semiconductor solar devices such as aAs) and indium phosphide (InP), cadmium telluride (CdTe)
And copper indium selenide (CuInSe ₂ )
Group VI compound semiconductor solar electronic devices and others 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 also be used. Thus, in the present invention, a solar cell element is formed, for example, on a substrate such as a glass substrate, a plastic substrate, a metal substrate, or the like, by forming crystalline silicon such as a pn junction structure or amorphous silicon such as a pin junction structure. An electromotive force portion such as silicon or a compound semiconductor is formed to constitute a solar cell element.

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 an adhesive property with a back surface protection sheet, and further, to have a function of maintaining the smoothness of the back surface of the solar cell element as a photovoltaic element, and to have thermoplasticity. In order to protect a solar cell element as a photovoltaic element, it is necessary to have excellent scratch resistance, shock absorption and the like. However, the filler layer laminated below the photovoltaic element constituting the solar cell module is different from the filler layer laminated below the surface protection sheet for the solar cell module. ,
It is not necessary to have transparency. Specifically, as the above-mentioned filler layer, for example, as in the case of the above-mentioned filler layer laminated below the surface protection sheet for a solar cell module, for example, a fluorine-based resin, ethylene-vinyl acetate copolymer may be used. A polyolefin resin such as coalesced, ionomer resin, ethylene-acrylic acid, or methacrylic acid copolymer, polyethylene resin, polypropylene resin, polyethylene or polypropylene can be mixed with acrylic acid, itaconic acid, maleic acid, fumaric acid, etc. One or more resins such as an acid-modified polyolefin resin modified with a saturated carboxylic acid, a polyvinyl butyral resin, a silicone resin, an epoxy resin, a (meth) acrylic resin, and the like. Mixtures can be used. In the present invention, in order to improve the heat resistance, light resistance, weather resistance such as water resistance, etc. of the resin constituting the above-mentioned filler layer, in a range where the transparency is not impaired, for example, crosslinking is performed. Additives such as an agent, a thermal antioxidant, a light stabilizer, an ultraviolet absorber, a photooxidant, and the like can be arbitrarily added and mixed. The thickness of the filler layer is 200 to
About 1000 μm, more preferably 350 to 600 μm
Position is desirable.

In the present invention, when the solar cell module according to the present invention is manufactured, in order to improve its various strengths such as strength, weather resistance, scratch resistance, etc. Material, for example, low density polyethylene,
Medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid or methacrylic Acid copolymer, methylpentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer, poly (meth) acrylic resin, poly Acrylic nitrile resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, polyamide resin, polycarbonate resin , Polyvinyl alcohol tree , Ethylene - saponified vinyl acetate copolymer, fluorine resin, diene resin, polyacetal - Le resins, polyurethane resins, nitrocellulose -
And any other known resin film or sheet. In the present invention, the above-mentioned film or sheet may be any of unstretched and uniaxially or biaxially stretched. The thickness is arbitrary,
It can be used by selecting from the range of several μm to 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. The manufacturing method includes a known method, for example, a solar cell according to the present invention. Backside protection sheet for module
For example, the above-mentioned surface protection sheet for a solar cell module, a filler layer, a solar cell element as a photovoltaic element, a filler layer, and the above-described solar cell module according to the present invention. -A backing protective sheet for a roll is sequentially laminated with the surface of one of the polypropylene resin films facing each other, and further, if necessary, any other material is laminated between the respective layers, Using a normal molding method such as a lamination method in which these are integrated by vacuum suction or the like and heat-pressed, etc., the above-mentioned layers are heat-pressed and formed as an integrally formed body to produce a solar cell module. Can be. 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.

In the above-mentioned lamination, each of the opposing surfaces of the laminations may be subjected to, for example, a corona discharge treatment, an ozone treatment, a low-temperature treatment using an oxygen gas or a nitrogen gas, if necessary, in order to improve the tight adhesion. A pretreatment such as a plasma treatment, a glow discharge treatment, an oxidation treatment using a chemical agent, or the like can be optionally performed. Further, in the above-mentioned lamination, a primer coat agent layer, an undercoat agent layer, an adhesive layer, an anchor coat agent layer, or the like is arbitrarily formed on each of the laminated opposing surfaces in advance. Then, surface pretreatment can be performed. Examples of the coating agent layer for the above pretreatment include polyester resin, polyamide resin, polyurethane resin, epoxy resin, phenol resin, (meth) acrylic resin, polyvinyl acetate resin, A resin composition containing, as a main component of the vehicle, a polyolefin resin such as polyethylene aliha polypropylene or a copolymer or modified resin thereof, a cellulose resin, or the like can be used. In the above, as a method 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 is used.
The coating can be performed by using a coating method such as a coating method, a gravure roll coating method, a kiss coating method and others.

Further, in the present invention, one of the polypropylene-based resins of the back surface protection sheet for a solar cell module is used as the back surface protection sheet for a solar cell module according to the invention. The above-mentioned filler layer is laminated on the surface of the film to produce a laminate in which the backside protective sheet for a solar cell module and the filler layer are laminated in advance, and then the above-mentioned laminate is laminated. A solar cell element as a photovoltaic element, a filler layer, and a surface protection sheet for a solar cell module are sequentially laminated on the surface of the constituent filler layer, and if necessary, other materials. Are laminated, and then they are integrated by vacuum suction or the like, and then heat-pressed.
The solar cell module can be manufactured by using a normal molding method such as a sealing method and heat-press-molding each of the above-mentioned layers as an integral molded body.

[0044]

EXAMPLES The present invention will be described below more specifically with reference to examples. Example 1 (1). A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used. The film was mounted on a delivery roll of a plasma-enhanced chemical vapor deposition apparatus, and the following corona-treated surface of the biaxially stretched polyethylene terephthalate film was used. Under the conditions, a deposited film of silicon oxide having a thickness of 800 ° was formed. (Evaporation conditions) Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 1: 10: 10 (unit: slm) Degree of vacuum in vacuum chamber: 5.0 × 10 ⁻⁶ mbar In evaporation chamber Degree of vacuum: 6.0 × 10 ⁻² mbar Cooling / electrode drum supply power: 20 kW Film transport speed: 80 m / min Next, immediately after forming the above-described 800 nm-thick silicon oxide deposited film, the silicon oxide Using a glow discharge plasma generator, a plasma output of 1500 W, a mixed gas consisting of oxygen gas (O ₂ ): argon gas (Ar) = 19: 1, and a mixed gas pressure of 6 × 10 ^-5 Too
r, a plasma treatment was performed with an oxygen / argon mixed gas at a treatment speed of 420 m / min to form a plasma treatment surface in which the surface tension of the vapor deposition film surface was increased from 35 dyne to 60 dyne. (2). Next, on the plasma-treated surface of the deposited silicon oxide film having a thickness of 800 ° formed above, an initial condensate of a polyurethane resin, an epoxy silane coupling agent (8.
0% by weight) and an antiblocking agent (1.0% by weight), and sufficiently kneaded to use a primer-resin composition.
g / m ² (dry state) to form a primer layer. Further, a two-part curable urethane-based laminating adhesive containing a benzophenone-based ultraviolet absorber (2.0% by weight) is used as an ultraviolet absorber on the surface of the primer layer formed above, This was gravure roll-coated in the same manner as described above to form a film having a thickness of 5.0 g.
/ M ² (dry state) to form an adhesive layer for lamination. (3). On the other hand, titanium oxide (8% by weight) as a whitening agent and ultrafine titanium oxide (particle diameter, 0.01%) as an ultraviolet absorber were added to an isotactic polypropylene resin.
To 0.06 μm, 3% by weight), and other necessary additives, kneading well to prepare a polypropylene resin composition, and then extruding the polypropylene resin composition with an extruder. A non-stretched polypropylene resin film having a thickness of 60 μm was produced, and one surface of the unstretched polypropylene resin film was subjected to a corona discharge treatment according to a conventional method to form a corona-treated surface. (4). Next, the corona-treated surface of the polypropylene resin film formed in the above (3) was likewise opposed to the surface of the adhesive layer for laminating formed in the above (2), and both were dry-laminated. Next, on the surface of the biaxially stretched polyethylene terephthalate film having the silicon oxide vapor-deposited film laminated on the dry laminate as described above, a benzophenone-based A two-component curable urethane-based laminating adhesive containing an ultraviolet absorber (2.0% by weight) was used, and this was applied to a film thickness of 5.0 g / m ² (gravure roll coating method). (Dry state) to form a laminating adhesive layer. Further, the corona-treated surface of another polypropylene resin film formed in the above (3) was opposed to the surface of the laminating adhesive layer formed above, and in the same manner as above,
Both were laminated by dry lamination to produce a backside protective sheet for a solar cell module according to the present invention. (5). Next, a glass plate having a thickness of 3 mm and a thickness of 4
A 38 μm-thick biaxially stretched polyethylene terephthalate film in which solar cell elements made of an amorphous silicon are arranged in parallel, and a 400 μm-thick ethylene-vinyl acetate copolymer sheet And the backside protection sheet for a solar cell module, the surface of one of the polypropylene resin films is opposed to each other, and further, the above-mentioned solar cell element surface is directed upward, and the acrylic resin The solar cell module according to the present invention was manufactured by laminating through an adhesive layer.

Examples 2 to 6 In the above Example 1, instead of using a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm,
Using the base film shown below, the other steps were performed in exactly the same manner as in Example 1 above, and in the same manner as in Example 1 above,
A similar backside protection sheet and solar cell module according to the present invention could be manufactured. Embodiment 2. FIG. 50μm thick polyvinyl fluoride resin screen
Example 3 (PVF) Polydicyclopentadiene resin sheet having a thickness of 100 μm. Polycarbonate resin sheet having a thickness of 50 μm. Polyacrylic resin sheet having a thickness of 50 μm. Nylon 6 film with a thickness of 20 μm

Example 7 A biaxially stretched nylon 6 film having a thickness of 15 μm was used.
This was mounted on a delivery roll of a take-up type vacuum evaporation apparatus, and then was unwound onto a coating drum. Under the following conditions, aluminum was used as an evaporation source and oxygen gas was supplied. An 800 mm-thick aluminum oxide deposited film was formed on the corona-treated surface of the biaxially stretched nylon 6 film by a reactive vacuum deposition method using an electron beam (EB) heating method. (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 / Immediately after the above-described 800-nm-thick aluminum oxide vapor-deposited film was formed, a plasma output of 1500 W and oxygen gas (O ₂₎ were applied to the aluminum oxide vapor-deposited film surface using a glow discharge plasma generator. ): Argon gas (A
r) = 19: 1, a plasma treatment was performed with an oxygen / argon mixed gas at a mixed gas pressure of 6 × 10 ⁻⁵ Tool and a processing speed of 420 m / min to form a plasma treated surface. (2). Next, an epoxy-based silane coupling agent (8.0% by weight) and an anti-blocking agent ( 1.0% by weight) and sufficiently kneaded to obtain a primer-resin composition, which is obtained by a gravure roll coating method so as to have a film thickness of 0.5 g / m ² (dry state). To form a primer layer. Further, a two-part curable urethane-based laminating adhesive containing a benzophenone-based ultraviolet absorber (2.0% by weight) is used as an ultraviolet absorber on the surface of the primer layer formed above, This was coated by a gravure roll coating method so as to have a film thickness of 5.0 g / m ² (in a dry state) in the same manner as described above to form a laminating adhesive layer. (3). On the other hand, titanium oxide (8% by weight) as a whitening agent and ultrafine titanium oxide (particle diameter, 0.01%) as an ultraviolet absorber were added to an isotactic polypropylene resin.
To 0.06 μm, 3% by weight), and other necessary additives, kneading well to prepare a polypropylene resin composition, and then extruding the polypropylene resin composition with an extruder. A non-stretched polypropylene resin film having a thickness of 60 μm was produced, and one surface of the unstretched polypropylene resin film was subjected to a corona discharge treatment according to a conventional method to form a corona-treated surface. (4). Next, the corona-treated surface of the polypropylene resin film formed in the above (3) was likewise opposed to the surface of the adhesive layer for laminating formed in the above (2), and both were dry-laminated. Next, on the surface of the biaxially stretched nylon 6 film having the vapor-deposited aluminum oxide film laminated with the dry laminate as described above, in the same manner as described above, as an ultraviolet absorber,
A two-part curable urethane-based laminating adhesive containing a benzophenone-based ultraviolet absorber (2.0% by weight) was used.
Coating was performed so as to be 0 g / m ² (dry state) to form an adhesive layer for laminating. Further, the corona-treated surface of another polypropylene resin film formed in the above (3) is opposed to the surface of the laminating adhesive layer formed as described above, and the both are dry-laminated in the same manner as above. Thus, a back surface protection sheet for a solar cell module according to the present invention was manufactured. (5). Next, a glass plate having a thickness of 3 mm and a thickness of 4
A 38 μm-thick biaxially stretched polyethylene terephthalate film in which solar cell elements made of an amorphous silicon are arranged in parallel, and a 400 μm-thick ethylene-vinyl acetate copolymer sheet And the backside protection sheet for a solar cell module, the surface of one of the polypropylene resin films is opposed to each other, and further, the above-mentioned solar cell element surface is directed upward, and the acrylic resin The solar cell module according to the present invention was manufactured by laminating through an adhesive layer.

Examples 8 to 12 Instead of using the biaxially stretched nylon 6 film having a thickness of 15 μm in Example 7 described above, the following base film was used. By carrying out in exactly the same manner, similar to the first embodiment, a similar back surface protection sheet and a solar cell module according to the present invention could be manufactured. Embodiment 8 FIG. 50μm thick polyvinyl fluoride resin screen
Example 9 (PVF) Polydicyclopentadiene resin sheet having a thickness of 100 μm. 50μm thick polycarbonate resin sheet
G. Embodiment 11 FIG. Example 12 Polyacrylic resin sheet having a thickness of 50 μm Biaxially stretched polyethylene terephthalate film with a thickness of 12 μm

Embodiment 13 (1). A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used and mounted on a delivery roll of a plasma-enhanced chemical vapor deposition apparatus. A deposited thin film of silicon oxide having a thickness of 50 ° was formed, and an anti-evaporation protective film was provided. (Evaporation conditions) Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 5: 5: 5 (unit: slm) Degree of vacuum in vacuum chamber: 7.0 × 10 ⁻⁶ mbar In evaporation chamber Vacuum degree: 3.8 × 10 ^-2 mbar Cooling / electrode drum supply power: 15 kW Sheet transfer speed: 100 m / min Next, the above-mentioned Example 1 Similarly, an evaporated silicon oxide film having a thickness of 800 ° was formed, and a plasma-treated surface was formed on the deposited silicon oxide film. (2). Hereinafter, the same procedure as in Example 1 described above was carried out, and a similar back surface protection sheet and solar cell module according to the present invention could be manufactured in the same manner as in Example 1 above.

Embodiment 14 (1). A biaxially stretched nylon 6 film having a thickness of 15 μm was used, and this was fed out of a take-up vacuum evaporation apparatus.
A reaction vacuum deposition method using an electron beam (EB) heating method while supplying oxygen gas under the following conditions using aluminum as a deposition source under the following conditions: Thus, a vapor-deposited thin film of aluminum oxide having a thickness of 50 ° was formed on the corona-treated surface of the above-mentioned biaxially stretched nylon film, and a vapor deposition-resistant protective film was provided. (Evaporation conditions) Evaporation source: Aluminum Degree of vacuum in vacuum chamber: 7.5 × 10 ⁻⁶ mbar Degree of vacuum in evaporation chamber: 2.1 × 10 ⁻⁶ mbar EB output: 20 KW Film transport speed: 500 m / Further, an aluminum oxide deposited film having a film thickness of 800 ° was formed on the above deposited anti-evaporation protective film in the same manner as in Example 7 above. A treated surface was formed. (2). Hereinafter, the same procedure as in the above-mentioned Example 7 was carried out, and the same back surface protection sheet and solar cell module according to the present invention as in the above-mentioned Example 7 could be produced.

Embodiment 15 (1). A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used.
Purity 9 by high frequency induction heating under vacuum of 0 ^-4 Torr
9.9% of silicon monoxide (SiO) is heated and evaporated to 50%.
A 0 ° silicon oxide deposited film was formed. Next, immediately after forming the above-described silicon oxide deposited film having a thickness of 500 °, the output of 10 kW and the processing speed of 100
Corona discharge treatment was performed at m / min to form a corona treated surface in which the surface tension of the vapor-deposited film surface was increased from 35 dyne to 60 dyne. (2). Hereinafter, the same procedure as in Example 1 described above was carried out, and a similar back surface protection sheet and solar cell module according to the present invention could be manufactured in the same manner as in Example 1 above.

Embodiment 16 (1). Using a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, a vapor-deposited silicon oxide film having a thickness of 500 ° was formed in the same manner as in Example 1 above.
A plasma treated surface was formed on the silicon oxide deposited film surface.
Next, on the plasma-treated surface of the silicon oxide vapor-deposited film formed as described above, a film thickness of 500 .ANG.
Was formed, and a plasma-treated surface was formed on the surface of the aluminum oxide film. (2). Hereinafter, the same procedure as in the above-mentioned Example 7 was carried out, and the same back surface protection sheet and solar cell module according to the present invention as in the above-mentioned Example 7 could be produced.

Embodiment 17 (1). A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used. The film was mounted on a delivery roll of a plasma-enhanced chemical vapor deposition apparatus, and the following corona-treated surface of the biaxially stretched polyethylene terephthalate film was used. Under the conditions, a deposited film of silicon oxide having a thickness of 800 ° was formed. (Evaporation conditions) Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 1: 10: 10 (unit: slm) Degree of vacuum in vacuum chamber: 5.0 × 10 ⁻⁶ mbar In evaporation chamber Degree of vacuum: 6.0 × 10 ⁻² mbar Cooling / electrode drum supply power: 20 kW Film transport speed: 80 m / min Next, immediately after forming the above-described 800 nm-thick silicon oxide deposited film, the silicon oxide Using a glow discharge plasma generator, a plasma output of 1500 W, a mixed gas consisting of oxygen gas (O ₂ ): argon gas (Ar) = 19: 1, and a mixed gas pressure of 6 × 10 ^-5 Tor
r, plasma treatment was performed with an oxygen / argon mixed gas at a treatment speed of 420 m / min to form a plasma treated surface in which the surface tension of the vapor-deposited film surface was improved from 35 dyne to 60 dyne. (2). Next, on the plasma-treated surface of the deposited silicon oxide film having a thickness of 800 ° formed above, an initial condensate of a two-component curing type polyurethane resin was added, and an epoxy silane coupling agent (8.0% by weight). And an antiblocking agent (1.0
% By weight) and kneaded sufficiently to obtain a primer-resin composition, which is coated by a gravure roll coating method so as to have a film thickness of 0.5 g / m ² (dry state).
To form a primer layer. Further, a two-part curable urethane-based anchor coating agent was used on the surface of the primer layer formed as described above, and was coated with a gravure roll coating method to form a film having a film thickness of 0.1%. Coating was performed so as to be 1 g / m ² (dry state) to form an anchor coating agent layer. (3). On the other hand, a masterbatch (15% by weight) made of a polyethylene resin containing titanium oxide (25% by weight) as a whitening agent in an isotactic polypropylene resin and ultrafine titanium oxide (particle size: 0.1%) as an ultraviolet absorber.
0.01 to 0.06 μm, 5% by weight), and
The required additives were added and kneaded well to prepare a polypropylene resin composition. (4). Next, the polypropylene resin composition formed in the above (3) is used on the surface of the anchor coating agent layer formed in the above (2), and this is melt-extruded using an extruder to obtain a thickness. A 60 μm polypropylene film was extruded and laminated by lamination. Next, the extruded lamine
In the same manner as described above, a two-component curable urethane-based anchor coating agent is applied to the surface of a biaxially stretched polyethylene terephthalate film having a silicon oxide deposited film laminated thereon. Using a gravure roll coating method to form a film having a thickness of 0.1 g / m 2.
² Anchor by coating so that it is (dry)
A coating agent layer was formed. Further, the anchor formed above
On the coating agent layer surface, the polypropylene resin composition formed in the above (3) was used, and in the same manner as described above, this was melt-extruded using an extruder, and a polypropylene film having a thickness of 60 μm was extruded. To form a back surface protection sheet for a solar cell module according to the present invention. (5). Next, a glass plate having a thickness of 3 mm and a thickness of 4
A 38 μm-thick biaxially stretched polyethylene terephthalate film in which solar cell elements made of an amorphous silicon are arranged in parallel, and a 400 μm-thick ethylene-vinyl acetate copolymer sheet And the backside protection sheet for a solar cell module, the surface of one of the polypropylene resin films is opposed to each other, and further, the above-mentioned solar cell element surface is directed upward, and the acrylic resin The solar cell module according to the present invention was manufactured by laminating through an adhesive layer.

Example 18 Using a biaxially stretched nylon 6 film having a thickness of 15 μm,
This was mounted on a delivery roll of a take-up type vacuum evaporation apparatus, and then was unwound onto a coating drum. Under the following conditions, aluminum was used as an evaporation source and oxygen gas was supplied. An 800 mm-thick aluminum oxide deposited film was formed on the corona-treated surface of the biaxially stretched nylon 6 film by a reactive vacuum deposition method using an electron beam (EB) heating method. (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 / Immediately after the above-described 800-nm-thick aluminum oxide vapor-deposited film was formed, a plasma output of 1500 W and oxygen gas (O ₂₎ were applied to the aluminum oxide vapor-deposited film surface using a glow discharge plasma generator. ): Argon gas (A
r) = 19: 1, using a mixed gas pressure of 6 × 10 ⁻⁵ Torr and a processing speed of 420 m / min to perform a plasma treatment with an oxygen / argon mixed gas to form a plasma treated surface. (2). Next, on the plasma-treated surface of the deposited aluminum oxide film having a thickness of 800 ° formed above, an initial condensate of a two-component curable polyurethane-based resin, an epoxy-based silane coupling agent (8.0% by weight). And an anti-blocking agent (1.0% by weight), and kneaded well to use a primer-resin composition, which was dried by a gravure coating method to a film thickness of 0.5 g / m ² (dry To form a primer layer. Further, on the surface of the primer layer formed as described above, a two-part curable urethane-based anchor coating agent was used. 1g / m
² Anchor by coating so that it is (dry)
A coating agent layer was formed. (3). On the other hand, a masterbatch (15% by weight) made of a polyethylene resin containing titanium oxide (25% by weight) as a whitening agent in an isotactic polypropylene resin and ultrafine titanium oxide (particle size: 0.1%) as an ultraviolet absorber.
0.01 to 0.06 μm, 5% by weight), and
The required additives were added and kneaded well to prepare a polypropylene resin composition. (4). Next, the polypropylene resin composition formed in the above (3) is used on the surface of the anchor coating agent layer formed in the above (2), and this is melt-extruded using an extruder to obtain a thickness. A 60 μm polypropylene film was extruded and laminated by lamination. Next, the extruded lamine
On the surface of the biaxially stretched nylon 6 film having the laminated aluminum oxide vapor-deposited film, a two-component curable urethane anchor coating agent is used in the same manner as described above, This was coated by a gravure coating method so as to have a thickness of 0.1 g / m ² (dry state) to form an anchor coating agent layer. Further, using the polypropylene resin composition formed in the above (3) on the surface of the anchor coating agent layer formed above,
In the same manner as described above, this is melt-extruded using an extruder, and a polypropylene film having a thickness of 60 μm is extruded and laminated to produce a backside protection sheet for a solar cell module according to the present invention. did. (5). Next, a glass plate having a thickness of 3 mm and a thickness of 4
A 38 μm-thick biaxially stretched polyethylene terephthalate film in which solar cell elements made of an amorphous silicon are arranged in parallel, and a 400 μm-thick ethylene-vinyl acetate copolymer sheet And the backside protection sheet for a solar cell module, the surface of one of the polypropylene resin films is opposed to each other, and further, the above-mentioned solar cell element surface is directed upward, and the acrylic resin The solar cell module according to the present invention was manufactured by laminating through an adhesive layer.

Embodiment 19 (1). A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used and mounted on a delivery roll of a plasma-enhanced chemical vapor deposition apparatus. A deposited thin film of silicon oxide having a thickness of 50 ° was formed, and an anti-evaporation protective film was provided. (Evaporation conditions) Reaction gas mixture ratio: hexamethyldisiloxane: oxygen gas: helium = 5: 5: 5 (unit: slm) Degree of vacuum in vacuum chamber: 7.0 × 10 ⁻⁶ mbar In evaporation chamber Degree of vacuum: 3.8 × 10 ⁻² mbar Cooling / electrode drum supply power: 15 kW Sheet conveyance speed: 100 m / min Next, the above Example 17 Similarly, an evaporated silicon oxide film having a thickness of 800 ° was formed, and a plasma-treated surface was formed on the deposited silicon oxide film. (2). Hereinafter, the same procedure as in Example 17 was performed,
In the same manner as in Example 17 above, similar back surface protection sheets and solar cell modules according to the present invention could be manufactured.

Embodiment 20 (1). A biaxially stretched nylon 6 film having a thickness of 15 μm was used, and this was fed out of a take-up vacuum evaporation apparatus.
A reaction vacuum deposition method using an electron beam (EB) heating method while supplying oxygen gas under the following conditions using aluminum as a deposition source under the following conditions: Thus, a vapor-deposited thin film of aluminum oxide having a thickness of 50 ° was formed on the corona-treated surface of the above-mentioned biaxially stretched nylon film, and a vapor deposition-resistant protective film was provided. (Evaporation conditions) Evaporation source: Aluminum Degree of vacuum in vacuum chamber: 7.5 × 10 ⁻⁶ mbar Degree of vacuum in evaporation chamber: 2.1 × 10 ⁻⁶ mbar EB output: 20 KW Film transport speed: 500 m / Further, an aluminum oxide deposited film having a film thickness of 800 ° was formed on the deposited anti-evaporation protective film in the same manner as in Example 18 above. A treated surface was formed. (2). Hereinafter, the same procedure as in Example 18 was performed,
In the same manner as in Example 18, the same back surface protection sheet and solar cell module according to the present invention could be manufactured.

Embodiment 21 (1). A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used.
Purity 9 by high frequency induction heating under vacuum of 0 ^-4 Torr
9.9% of silicon monoxide (SiO) is heated and evaporated to 50%.
A 0 ° silicon oxide deposited film was formed. Next, immediately after forming the above-described silicon oxide deposited film having a thickness of 500 °, the output of 10 kW and the processing speed of 100
Corona discharge treatment was performed at m / min to form a corona treated surface in which the surface tension of the vapor-deposited film surface was increased from 35 dyne to 60 dyne. (2). Hereinafter, the same procedure as in Example 17 was performed,
In the same manner as in Example 17 above, similar back surface protection sheets and solar cell modules according to the present invention could be manufactured.

Embodiment 22 (1). Using a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, a vapor-deposited silicon oxide film having a thickness of 500 ° was formed in the same manner as in Example 17 above.
A plasma treated surface was formed on the silicon oxide deposited film surface.
Next, on the plasma-treated surface of the deposited silicon oxide film formed above, a film thickness of 500
The aluminum oxide vapor deposition film was formed, and a plasma treated surface was formed on the aluminum oxide vapor deposition film surface. (2). Hereinafter, the same procedure as in Example 18 was performed,
In the same manner as in Example 18, the same back surface protection sheet and solar cell module according to the present invention could be manufactured.

COMPARATIVE EXAMPLE 1 A 38 μm-thick biaxially stretched polyethylene terephthalate having a 3 mm-thick glass plate, 400 μm-thick ethylene-vinyl acetate copolymer sheet, and solar cell elements made of amorphous silicon arranged in parallel. -Film, thickness 400μ
m-ethylene-vinyl acetate copolymer sheet and 50 μm thick white biaxially stretched polyethylene terephthalate
The solar cell module was manufactured by laminating a photo film with the solar cell element surface facing upward through an adhesive layer of an acrylic resin.

Comparative Example 2 A 38 μm-thick biaxially stretched polyethylene terephthalate having a 3 mm-thick glass plate, a 400 μm-thick ethylene-vinyl acetate copolymer sheet, and a solar cell element made of amorphous silicon arranged in parallel. -Film, thickness 400μ
m of an ethylene-vinyl acetate copolymer sheet and a 50 μm-thick white polyvinyl fluoride resin sheet are opposed to each other, and the solar cell element surface thereof faces upward. The solar cell module was manufactured by laminating through an adhesive layer.

EXPERIMENTAL EXAMPLES The reflectances of the backside protection sheets for solar cell modules according to the present invention manufactured in Examples 1 to 22 and the backside protection sheets according to Comparative Examples 1 and 2 were measured. Further, a solar cell module evaluation test was performed on the solar cell modules manufactured in Examples 1 to 22 and the solar cell modules manufactured in Comparative Examples 1 and 2. (1). Measurement of reflectivity This is based on the base film, which is the back protection sheet for solar cell module according to the present invention manufactured in Examples 1 to 22 and the back protection sheet according to Comparative Examples 1 and 2. about,
The reflectance (%) with respect to a light having a wavelength of 550 nm was measured with a spectrophotometer. (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 comparing the backside protection sheet for solar cell module according to the present invention manufactured in Examples 1 to 22 and the comparative examples 1 to
2 under a condition of a temperature of 40 ° C. and a humidity of 90% RH under the conditions of a temperature of 40 ° C. and a humidity of 90% [model name, PERMATRA (PERMATRA)]
N)], and the oxygen permeability was measured using the same object as described above under the conditions of a temperature of 23 ° C. and a humidity of 90% RH. OXTRAN]. (4). Measurement of Lamination Strength In this method, the protective sheet is cut into a width of 15 mm, and a protective sheet is formed using a tensile tester (Model name: Tensilon manufactured by A & D (A & D) Co., Ltd.). The peel strength of the laminate was measured. The results of the above measurements are shown in Table 1 below.

[0061] In Table 1 above, the unit of the light reflectance is [%], and the unit of the water vapor barrier property is [g / m ² / day · 4.
0 ° C./100% RH], and the oxygen barrier unit is
[Cc / m ² / day · 23 ° C. · 90% RH]
The unit of the output reduction rate is [%], and the unit of the lamination strength is [kg / 15 mm width].

As is clear from the measurement results shown in Table 1 above, the back protective sheets for solar cell modules according to Examples 1 to 22 have a high reflectance, a water vapor barrier property and an oxygen barrier property. Excellent in properties and lamination strength. Furthermore, the solar cell module using the back surface protection sheet for a solar cell module according to Examples 1 to 22 described above had a low output reduction rate. On the other hand, Comparative Examples 1 and 2
Although the solar cell module protection sheet according to the present invention has a high reflectance, it has low water vapor barrier properties and oxygen barrier properties. Is high.

[0063]

As is apparent from the above description, the present invention provides:
On one side of the substrate film, a silicon oxide, or a transparent glassy material such as aluminum oxide, and provided with a vapor-deposited film of an inorganic oxide excellent in water vapor barrier properties, oxygen barrier properties, etc. A heat-resistant polypropylene-based resin film containing a whitening agent and an ultraviolet absorber is laminated on both sides of a substrate film provided with a vapor-deposited oxide film to produce a backside protection sheet for a solar cell module. Thus, using the back surface protection sheet for a solar cell module, for example, a normal surface protection sheet for a solar cell module made of a glass plate or the like, a filler layer, a photovoltaic element A solar cell element, a filler layer, and the above-mentioned back surface protection sheet for a solar cell module are sequentially laminated with one polypropylene resin film facing the other, and then these are integrated. Vacuum suction The solar cell module is manufactured using the lamination method of thermocompression bonding, etc., and has excellent strength, and furthermore, weather resistance, heat resistance, water resistance, light resistance, wind pressure resistance, hail resistance, chemical resistance Excellent in various properties such as antifouling property, etc., especially excellent in moistureproof property to prevent invasion of moisture, oxygen, etc. In addition, light reflection property, light diffusion property, design property etc. are significantly improved, Performance degradation to a minimum,
It is possible to stably produce a safe solar cell module which is extremely durable, has excellent protection ability, and is lower in cost.

[Brief description of the drawings]

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

FIG. 4 is a schematic cross-sectional view schematically illustrating a layer configuration of another example of a deposited film of an inorganic oxide.

FIG. 5 is a schematic cross-sectional view schematically showing a layer configuration of another example of a deposited film of an inorganic oxide.

FIG. 6 shows a solar cell module manufactured by using the solar cell module back surface protection sheet according to the present invention shown in FIG.
FIG. 2 is a schematic cross-sectional view schematically showing a layer configuration of an example of the structure.

FIG. 7 is a schematic configuration diagram showing an example of a take-up type vacuum evaporation apparatus.

FIG. 8 is a schematic configuration diagram illustrating an example of a plasma chemical vapor deposition apparatus.

[Explanation of symbols]

A solar cell module - Le for the back protective sheet - DOO A ₁ to A ₂ solar cell module - for the backside Le protective sheet - deposition of the deposited film 2a multilayer film 2b inorganic oxide sheet 1 substrate film 2 inorganic oxide film 2c Inorganic oxide deposited film 2d Composite film 3 Polypropylene resin film 4 Dry laminating adhesive layer 5 Anchor coating agent layer T Solar cell module 11 Solar cell module surface protection sheet 12 Filling Agent layer 13 Solar cell element 14 Filler layer 15 Backside protection sheet for solar cell module

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C08K 5/134 C08K 5/315 5/315 5/3475 5/3475 C08L 23/12 C08L 23/12 B32B 9/00 A H01L 31/042 H01L 31/04 F // B32B 9/00 R (72) Inventor Kojiro Okawa 1-1-1, Ichigaya-Kagacho, Shinjuku-ku, Tokyo Inside Dai Nippon Printing Co., Ltd. (72) Inventor Suzuki Junro 1-1-1, Ichigaya-Kagacho, Shinjuku-ku, Tokyo Dai-Nippon Printing Co., Ltd. (72) Inventor Kazuyuki Takasawa 1-1-1 Ichigaya-Kaga-cho, Shinjuku-ku, Tokyo F-term (reference) ) 4F006 AA12 AA22 AA35 AA36 AA38 AB74 BA05 DA01 4F100 AA01B AA01E AA01H AA17B AA17E AA20 AA21 AA21B AA21E AA21H AA25B AA25E AA25H AH02B AH02E AH02H AH03B AH03E AH03H AK02A AK07C AK07D AK07J AK17A AK25A AK41A AK42 AK45A AK46A AK48 AK51G AL01C AL01D AT00A BA04 BA05 BA07 BA10C BA10D BA13 CA07C CA07D CA13C CA13D CB02 DE01B DE01E DE01H EH23C EH23D EH46 EH 46C EH46D EH66 EH66B EH66E EJ55 EJ61 EJ65 GB41 HB31C HB31D JA20B JA20E JB01 JB07 JD04 JJ03C JJ03D JK01 JL00 JL02 JL06 JL09 JN06 JN30 YY00B YY00E 4J002 BB111 BB121 DE136 EE037 EJ067 ET007 EU177 FD057 FD096 GQ00 5F051 BA03 BA15 BA17 BA18 EA01 EA18 GA03 GA05 GA06 JA02 JA03 JA04 JA05

Claims (12)

[Claims] An inorganic oxide vapor-deposited film is provided on one side of a substrate film, and a whitening agent and an ultraviolet absorber are further provided on both sides of the substrate film provided with the inorganic oxide vapor-deposited film. A backside protection sheet for a solar cell module, comprising laminating a heat-resistant polypropylene-based resin film. 2. The base film is a fluororesin film, a cyclic polyolefin resin film, a polycarbonate resin film, a poly (meth) acrylic resin film, a polyamide resin film, or a polyester resin film. 2. The back surface protection sheet for a solar cell module according to claim 1, comprising: 3. The method according to claim 1, wherein the inorganic oxide vapor-deposited film is a multilayer film of one or more inorganic oxide vapor-deposited films or a composite film of two or more different inorganic oxide vapor-deposited films. The back surface protection sheet for a solar cell module according to claim 1 or 2, characterized in that: 4. The backside protection sheet for a solar cell module according to claim 1, wherein the inorganic oxide vapor-deposited film has a thickness of 50 to 4000 °.
G. 5. The heat-resistant polypropylene-based resin film containing a whitening agent and an ultraviolet absorber comprises a heat-resistant polypropylene-based resin film obtained by kneading a whitening agent and an ultraviolet absorber. Claim 1 above
4. A back surface protection sheet for a solar cell module according to any one of items 1 to 4. 6. A heat-resistant polypropylene-based resin film containing a whitening agent and an ultraviolet absorber, and a heat-resistant polypropylene-based resin film having an applied or printed film containing a whitening agent and an ultraviolet absorber on its surface. The back surface protection sheet for a solar cell module according to any one of claims 1 to 4, wherein the back surface protection sheet comprises: 7. The backsheet for a solar cell module according to claim 1, wherein the whitening agent comprises a white pigment. 8. An ultraviolet absorber comprising a benzophenone type, a benzotriazole type, a saltylate type, an acrylonitrile type, a metal complex salt type, a hindered amine type, or ultrafine titanium oxide (particle diameter: 0.01 to 10 μm). 8. The solar cell according to claim 1, comprising one or more inorganic UV absorbers composed of 0.06 [mu] m) or ultrafine zinc oxide (0.01 to 0.04 [mu] m). Back protection sheet for battery module. 9. The solar cell module according to claim 1, wherein the polypropylene resin film comprises a film of a propylene homopolymer or a copolymer of propylene and another monomer. -Back protection sheet for metal. 10. The backside protection sheet for a solar cell module according to claim 1, wherein the polypropylene-based resin film is formed by laminating with a dry laminate via an adhesive. 11. The back protection sheet for a solar cell module according to claim 1, wherein the polypropylene resin film is formed by lamination using an extruded laminate. 12. A surface protection seal for a solar cell module.
G, a filler layer, a solar cell element as a photovoltaic element, a filler layer, and, on one surface of the base film, a vapor-deposited film of an inorganic oxide, and further, a vapor-deposited film of the above-described inorganic oxide is provided. A backside protection sheet for a solar cell module comprising a heat-resistant polypropylene resin film containing a whitening agent and an ultraviolet absorber laminated on both sides of the base film,
A solar cell module characterized in that one of the polypropylene-based resin films is sequentially laminated with the surfaces thereof facing each other, and these are vacuum-suctioned to form an integrally molded body by a heat-compression lamination method or the like.