JP2001196618A - Back face protecting sheet for solar battery module and solar battery module using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To stably provide a back face protecting sheet constituting an inexpensive and safe solar battery module for realizing excellent strength and excellent weather resistance, heat resistance, water resistance, light resistance, wind pressure resistance, hail resistance, chemical resistance, moisture resistance, dirt resistance, light reflectivity, light diffusion, and design or the like, and for sharply improving moisture proofing for preventing intrusion of moisture or oxygen; for minimizing long term deterioration; and for realizing extremely high durability and excellent protecting capabilities and a solar battery module using the back protecting sheet. SOLUTION: The sputtered film of an inorganic oxide is arranged on one face of a base material film, and polyolefin system resin and annular polyolefin system resin are used and extruded so that an extruded layer constituted of a polyolefin system resin layer and an annular polyolefin system resin layer can be arranged on the face of the evaporated film of the non-organic oxide.

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 backside protective sheet layer constituting the solar cell module in order to solve the above-mentioned problems. On one surface, 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, and the like, and further provided above. On the surface of the inorganic oxide deposited film,
Using a polyolefin-based resin and a cyclic polyolefin-based resin, coextruding them, and laminating a co-extruded resin layer composed of the polyolefin-based resin layer and the cyclic polyolefin-based resin layer with the polyolefin-based resin layer surfaces facing each other. To manufacture a backside protection sheet for a solar cell module, and using the backside protection sheet for a solar cell module, for example, a normal solar cell module made of a glass plate or the like. Surface protection sheet, filler layer, solar cell element as photovoltaic element, filler layer, and back surface protection sheet for solar cell module described above, the polyolefin resin layer and the cyclic polyolefin A lamination method in which the surfaces of a co-extruded resin layer composed of a base resin layer and a co-extruded resin layer are sequentially laminated, and then these are integrally vacuum-evacuated and heated and pressed together to utilize a lamination method or the like When the solar cell module is manufactured by integral molding, the strength is excellent, and the weather resistance, heat resistance, water resistance, light resistance, wind pressure resistance, hail resistance, chemical resistance, stain resistance, etc. Excellent in various properties such as moisture, oxygen, etc.
It also significantly improves light diffusion, design, etc., minimizes long-term performance degradation, and is extremely durable.
The present invention has been completed by finding that a safe solar cell module having excellent protection ability and lower cost can be stably manufactured.

That is, in the present invention, an inorganic oxide vapor-deposited film is provided on one surface of a substrate film, and a polyolefin resin and a cyclic polyolefin resin are further coated on the surface of the inorganic oxide vapor-deposited film. And a coextruded resin layer comprising a polyolefin-based resin layer and a cyclic polyolefin-based resin layer. The present invention relates to a solar cell module as described above.

[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
1, 2, 3, 4, 5, and 5, the layer structure of the solar cell backsheet and the solar cell module using the same will be described more specifically with reference to the drawings. 6 is a schematic cross-sectional view illustrating a few examples of the layer configuration of the back surface protection sheet for a solar cell module according to the present invention, and FIGS. 7 and 8 are solar cell modules according to the present invention. FIG. 9 is a schematic cross-sectional view illustrating another example of the layer configuration of the inorganic oxide vapor-deposited film constituting the back protection sheet for a solar cell module. It is a schematic sectional drawing which illustrates an example about the layer structure of the solar cell module manufactured using the back surface protection sheet for solar cells.

First, a backside protection sheet A for a solar cell module according to the present invention, as shown in FIG. Further, a polyolefin-based resin and a cyclic polyolefin-based resin are used on the surface of the inorganic oxide vapor-deposited film 2 provided above, and they are co-extruded to form the polyolefin-based resin layer 3 and the cyclic polyolefin-based resin layer 4. The basic structure is that a co-extruded resin layer 5 made of is laminated with the surface of the polyolefin-based resin layer 3 facing the same. As a specific example of the back surface protection sheet for a solar cell module according to the present invention, as shown in FIG. 2, an inorganic oxide vapor-deposited film 2 is provided on one surface of a base film 1, , The inorganic oxide deposited film 2 provided above
A polyolefin-based resin and a cyclic polyolefin-based resin are coextruded through a laminating adhesive layer 6 on the side of the surface, and are extruded from the polyolefin-based resin layer 3 and the cyclic polyolefin-based resin layer 4. the coextruded resin layer 5 of the surface of the polyolefin resin layer 3 is opposed to Dorairamine - be exemplified bets a ₁ - for the backside Le protective sheet - solar cell module comprising a stacked structure using a preparative method it can. Further, another 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. Further, a polyolefin resin and a cyclic polyolefin resin are used on the surface of the inorganic oxide vapor deposition film 2 provided above via the primer agent layer 7 and the laminating adhesive layer 6. And a co-extruded resin layer 5 composed of the polyolefin-based resin layer 3 and the cyclic polyolefin-based resin layer 4 laminated by a dry laminating method with the surfaces of the polyolefin-based resin layer 3 facing each other. solar cell module consisting of the structure - le for the back protective sheet - can be exemplified preparative a _2.

Further, another specific example of the back surface protection sheet for a solar cell module according to the present invention is illustrated. As shown in FIG. The vapor-deposited film 2 is provided, and the surface of the vapor-deposited film 2 of inorganic oxide provided above is interposed via an anchor coat agent layer 8.
A polyolefin resin and a cyclic polyolefin resin are melted and co-extruded using a polyolefin resin layer 3 and a cyclic polyolefin resin layer 4.
The coextruded resin layer 5 consisting of, the polyolefin melt to the surface of the resin layer 3 is opposed extrusion laminating - the door A ₃ - Solar consisting laminated structure by using a preparative method battery module - for the backside Le protective sheet Examples can be given. Furthermore,
As another specific example of the back surface protection sheet for a solar cell module according to the present invention, as shown in FIG. 5, a deposited film 2 of an inorganic oxide is provided on one surface of a base film 1. Further, on the surface of the inorganic oxide deposited film 2 provided above,
A polyolefin resin and a cyclic polyolefin resin are used via a primer agent layer 7 and an anchor coat agent layer 8 while the polyolefin resin and the cyclic polyolefin resin are melted and coextruded. Back protection sheet A for a solar cell module having a configuration in which a co-extruded resin layer 5 composed of a layer 4 and a polyolefin resin layer 3 are laminated with the surfaces of the polyolefin resin layer 3 facing each other by a melt extrusion lamination method. ₄ can be exemplified. Next, another specific example of the backside protection sheet for a solar cell module according to the present invention will be exemplified. As shown in FIG. 6, the backside protection sheet for a solar cell module shown in FIG. In the sheet A, the other surface of the co-extruded resin layer 5 composed of the polyolefin-based resin layer 3 and the cyclic polyolefin-based resin layer 4 constituting the back protection sheet A for the solar cell module,
Furthermore, the solar cell module consisting of configuration in which the vapor-deposited film 2 of an inorganic oxide - can be exemplified bets A ₅ - for the backside Le protective sheet. In FIG. 6, reference numerals 1 and 2 in the figure have the same meaning as described above. In the present invention, though not shown, the solar cell module back surface protection sheet shown in FIGS. 2 to 5 also has the same structure as the example shown in FIG. An inorganic oxide vapor-deposited film is further provided on the other surface of the co-extruded resin layer comprising a polyolefin-based resin layer and a cyclic polyolefin-based resin layer constituting a back protection sheet for use in a solar cell having various configurations. It is possible to manufacture a back protection sheet for a battery module.

The above examples illustrate only a few examples of the backside protection sheet for a solar cell module according to the present invention, and the present invention is of course not limited thereto. It is. For example, in the back surface protection sheet for a solar cell module shown in FIGS. 1 to 6 above, as a vapor deposition film of an inorganic oxide, as shown in FIGS. Two or more layers of inorganic oxide vapor deposited films 2 and 2 were laminated as in the case of two or more layers of inorganic oxide vapor deposited films by the above method or two or more layers of inorganic oxide vapor deposited films by the chemical vapor deposition method. A multilayer film 2a (FIG. 7) or an inorganic oxide deposited film 2b formed by a physical vapor deposition method described later and an inorganic oxide deposited film 2c formed by a chemical vapor deposition method
And a composite film 2d (FIG. 8) in which two or more layers of inorganic oxide vapor deposition films 2b and 2c of different types are laminated. Also, in the present invention, for example, although not shown, the lamination by the dry lamination method and the lamination by the melt extrusion lamination method are combined to produce a back surface protection sheet for a solar cell module. It can also be.

Next, in the present invention, an example of a solar cell module manufactured by using the above-mentioned back surface protection sheet for a solar cell module according to the present invention will be described with reference to FIG. The solar cell module according to the present invention shown
FIG. 9 shows an example in which a 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. The backing protective sheet 15 (A) is sequentially laminated with the surfaces of the co-extruded resin layer 5 composed of the polyolefin resin layer 3 and the cyclic polyolefin resin layer 4 facing each other. A solar cell module T can be manufactured by integrally forming using a normal forming method such as a lamination method in which vacuum suction is performed and heat-compression bonding is performed, and each of the above-described layers is formed into an integrally formed body. is there. 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, solar cell modules having various forms are manufactured in the same manner as described above using the solar cell module back surface protection sheets shown in FIGS. In addition, in the above solar cell module, the solar cell module can absorb, reinforce,
For other purposes, any other layers can be further added and laminated.

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 surface protection sheet for a solar cell module, a solar cell module and the like according to the present invention, a base film for forming a vapor-deposited film of an inorganic oxide or the like is used. Withstand conditions, others, etc., and have excellent tight adhesion with a vapor-deposited film of those inorganic oxides, etc., can be held well without impairing the properties of those films, and also 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.

Furthermore, in the present invention, among the various resin films or sheets described above, particularly, for example, polytetrafluoroethylene (PTFE), tetrafluoroethylene and perfluoroalkyl vinyl ether are preferable.
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 as 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 are extruded, cast-molded, T-die-processed, and cut. A method of forming the above various resins alone using a film forming method such as an inflation method, an inflation method, or the like, 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-mentioned additives, it is particularly preferable to use films or sheets of various resins obtained by kneading and processing an ultraviolet absorber or an antioxidant.

The above-mentioned ultraviolet absorber absorbs harmful ultraviolet rays in sunlight and has harmless heat energy in the molecule.
To prevent excitation of the active species that initiates photodegradation in the polymer, for example, benzophenone, benzotriazole, saltyl, acrylonitrile, metal complex salts, One or more inorganic UV absorbers such as hindered amine-based, ultra-fine titanium oxide (particle size, 0.01 to 0.06 μm) or ultra-fine zinc oxide (0.01 to 0.04 μm) Can be used. Further, as the above antioxidant, it is one that prevents light deterioration or heat deterioration 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 benzophenone-based ultraviolet absorber or the above-mentioned phenol
A polymer-type ultraviolet absorber or an antioxidant obtained by chemically bonding an antioxidant such as toluene or the like can 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 the inorganic oxide vapor-deposited film and 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 films or sheets of various resins and a deposited film of an inorganic oxide. As a method for improving the properties, for example, a primer coat agent layer, an undercoat agent layer, an anchor coat layer, etc. may be previously provided on the surface of various resin films or sheets.
A coating layer, an adhesive layer, a vapor-deposited anchor coating agent layer, or the like may be arbitrarily formed to form a surface treatment layer.
As the coating agent layer of the above pretreatment, for example, polyester-based resin, polyamide-based resin, polyurethane-based resin,
Epoxy resin, phenol resin, (meth) acrylic resin, polyvinyl acetate resin, polyolefin resin such as polyethylene aliha polypropylene or copolymers or modified resins thereof, cellulose resin, etc. A resin composition containing the main component of the vehicle can be used.

The above resin composition may contain an epoxy-based silane coupling agent for improving the tight adhesion, an anti-blocking agent for preventing blocking of the substrate 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. As the above-mentioned ultraviolet absorber, one or more of the above-described ultraviolet absorbers can be used, and as the antioxidant, the above-described antioxidants and the like can be used similarly. Can be. 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 above, as a method for forming the coating agent layer, for example, a coating agent such as a solvent type, an aqueous type, or an emulsion type is used, and a roll coating method, a gravure roll coating is used. The coating can be performed using a coating method such as a method, a kiss coating method, or the like.
It can be carried out after the film formation of the fluororesin sheet or as a post-process after the biaxial stretching treatment, or by film formation or in-line treatment of the biaxial stretching treatment.

Further, 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 deposited film is formed, for example, Its yellowing, deterioration or shrinkage, or suppresses cohesive failure or the like in the film surface layer or inner layer, and further, on one surface of the base film, a deposited film of an inorganic oxide is successfully formed into a film, and In order to improve the tight adhesion between the substrate film and the inorganic oxide vapor-deposited film, etc., in advance, on one surface of the substrate 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. Further, when the thickness is less than 10 °, 20 °, and 30 °, the protective layer as a deposition-resistant protective layer is formed. Is lost because it is 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 an inorganic oxide vapor deposition film by physical vapor deposition is shown in FIG. 10. FIG. 10 is a schematic structural 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; Then, on the base film 1 guided on the cooled coating drum 26, the evaporation source 28 heated by the crucible 27, for example, metal aluminum or aluminum oxide is evaporated. Further, if necessary, oxygen gas or the like is jetted from the oxygen gas outlet 29, and the masks 30, 30 are supplied while supplying the gas.
Then, for example, a deposited film of an inorganic oxide such as aluminum oxide is formed into a film. 25 'and 24', and wound on a take-up roll 31,
An inorganic oxide deposited film can be formed by the physical vapor deposition method according to the present invention. In the present invention,
First, using the winding type vacuum evaporation device as described above,
A first layer of an inorganic oxide deposited film is formed, and then, in the same manner, on the inorganic oxide deposited film, a further inorganic oxide deposited film is formed, or as described above. Using a roll-up type vacuum deposition apparatus, these are connected in series and an inorganic oxide deposited film is formed by continuously forming an inorganic oxide deposited film of two or more layers. can do.

In the above description, as the inorganic oxide deposited film, any thin film obtained by basically depositing a metal oxide can be used. For example, silicon (Si), aluminum (Al), magnesium (Mg) , Calcium (C
a), potassium (K), tin (Sn), sodium (N
a), a vapor-deposited 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-described chemical vapor deposition method will be further described. Chemical vapor deposition (Ch) such as vapor deposition, thermochemical vapor deposition, photochemical vapor deposition, 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. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic configuration diagram of a low-temperature plasma-enhanced chemical vapor deposition apparatus showing an outline of a method for forming a deposited oxide film. As shown in FIG. 11 described above, in the present invention, the base film 1 is unwound from an unwinding roll 43 disposed in a vacuum chamber -42 of a plasma enhanced chemical vapor deposition apparatus 41. The film 1 is cooled at a predetermined speed through an auxiliary roll 44 at a cooling / electrode drum 45.
Convey on the peripheral surface. Thus, in the present invention, oxygen gas, an inert gas, a monomer gas for vapor deposition such as an organic silicon compound, and the like are supplied from the gas supply devices 46 and 47 and the raw material volatile supply device 48 and the like. While adjusting the mixed gas composition for vapor deposition, the mixed gas composition for vapor deposition was introduced into the vacuum chamber -42 through the raw material supply nozzle 49, and was conveyed onto the peripheral surface of the cooling / electrode drum 45 described above. Glow discharge plasma 5 on base film 1
0, plasma is generated, and a vaporized monomer gas or the like in the mixed gas composition for vapor deposition is reacted in a plasma atmosphere to form a vapor-deposited film of an inorganic oxide such as silicon oxide, thereby forming a film. In the present invention, at this time, a predetermined power is applied to the cooling / electrode drum 45 from the power source 51 disposed outside the chamber.
5, the generation of plasma is promoted by disposing a magnet 52. Next, the base film 1 on which the deposited film of an inorganic oxide such as silicon oxide is formed is an auxiliary roller.
The film is wound around a take-up roll 54 via a roll 53 to produce a deposited film of an inorganic oxide by the plasma enhanced chemical vapor deposition method according to the present invention. In the figure, 55 represents a vacuum pump. The above exemplification is merely an example, and it goes without saying that the present invention is not limited thereby. 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, and then deposit the inorganic oxide in the same manner. On top of the film, further form an inorganic oxide deposited film,
Alternatively, using a low-temperature plasma chemical vapor deposition apparatus as described above, these are connected in series, and an inorganic oxide vapor deposition film is continuously formed to form an inorganic film composed of a multilayer film of two or more layers. An oxide deposited film 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 deposited film formed above, a monomer gas such as an organic silicon compound and an oxygen gas chemically react, and the reaction product is closely adhered to the substrate film. It is possible to form a dense 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.

According to the present invention, the above-mentioned silicon oxide vapor-deposited film is, for example, an X-ray photoelectron spectrometer (Xr
ay Photoelectron Spectros
copy, XPS), secondary ion mass spectrometer (Sec.)
onion Ion Mass Spectrosc
The above physical properties are confirmed by performing elemental analysis of a deposited silicon oxide film using a method of performing analysis by ion etching in the depth direction or the like using a surface analysis device such as O.I. can do. In the present invention, the thickness of the deposited silicon oxide film is preferably about 50 to 4000 °, and specifically, about 100 to 1000 °. Then, in the above, 1000 °, furthermore, 40
When the thickness is more than 00 °, cracks and the like are easily generated in the film, which is not preferable.
If it is less than 0 °, it is not preferable because it is difficult to exhibit the effect of the barrier property. In the above description, the film thickness can be measured by a fundamental parameter method using, for example, a fluorescent X-ray analyzer (model name: RIX2000) manufactured by Rigaku Corporation. Further, in the above, as 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.

In the present invention, as a backside protective sheet for a solar cell module according to the present invention, as a vapor-deposited film of an inorganic oxide constituting a solar cell module or the like, for example, a physical vapor deposition method can be used. It is also possible to form and use a composite film composed of two or more layers of vapor deposited films of different kinds of inorganic oxides by using both of the chemical vapor deposition methods. 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. In the backsheet for a solar cell module according to the present invention described above, the backsheet for a solar cell module comprises a polyolefin-based resin layer and a cyclic polyolefin-based resin layer. As a method of further providing a vapor-deposited film of an inorganic oxide on the other surface of the extruded resin layer, the above-described physical vapor deposition method, the chemical vapor deposition method, or the like is used, and the inorganic oxide film is similarly formed. It can form a deposited film of an object.

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.
The co-extruded resin layer comprising a polyolefin-based resin layer and a cyclic polyolefin-based resin layer constituting a resin or the like will be described. As the resin, those which can be co-extruded with a cyclic polyolefin-based resin described later can be used. For example, high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear (linear) low-density polyethylene, A polyethylene-based resin such as an ethylene-α-olefin copolymer polymerized using a metallocene catalyst (single-site catalyst), a propylene homopolymer, or propylene and an α-olefin;
Polypropylene resins such as copolymers with other monomers such as others, ethylene-vinyl acetate copolymer, ethylene-
Acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylate copolymer, ionomer
Resin, polymethylpentene resin, polybutene resin,
Use an acid-modified polyethylene resin or polypropylene resin obtained by modifying a polyethylene resin or polypropylene resin with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, etc. can do. In the present invention, among the above-mentioned polyolefin-based resins, particularly, ethylene-polymerized using a linear low (linear) density polyethylene (LLDPE) or a metallocene-based catalyst (single-site catalyst). It is preferable to use a polyethylene resin such as an α-olefin copolymer.

Next, in the present invention, the cyclic polyolefin resin constituting the co-extruded resin layer composed of the polyolefin resin layer and the cyclic polyolefin resin layer can be co-extruded with the above-mentioned polyolefin resin. What can be used, for example, the above-mentioned cyclopentadiene and its derivatives, dicyclopentadiene and its derivatives, cyclohexadiene and its derivatives, norbornadiene and its derivatives, polymers obtained by polymerizing cyclic dienes such as others, or ,
The cyclic diene and ethylene, propylene, 4-methyl-1
-A cyclic polyolefin-based resin comprising a copolymer obtained by copolymerizing one or more olefin-based monomers such as pentene, styrene, butadiene, isoprene and others, and the like can be used. In addition,
In the present invention, among the above-mentioned cyclic polyolefin-based resins, in particular, cyclopentadiene and its derivatives,
It is preferable to use a cyclic polyolefin-based resin comprising a cyclic diene polymer or copolymer such as dicyclopentadiene and a derivative thereof, or norbornadiene and a derivative thereof.

Next, in the present invention, the above-mentioned polyolefin resin and cyclic polyolefin resin are used, and they are co-extruded to form a co-extrusion comprising the polyolefin resin layer and the cyclic polyolefin resin layer. The method for forming the resin layer will be described. First, one or two or more of the above-mentioned polyolefin-based resins are used as main components, and if necessary, a whitening agent as a light reflecting agent or a light diffusing agent, and ultraviolet light. One or more absorbers are added, and if necessary, a plasticizer, a light stabilizer,
Addition of antioxidants, antistatic agents, crosslinkers, 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 kinds of agents are optionally added, and if necessary, a solvent,
A polyolefin resin composition is prepared by adding a diluent and kneading sufficiently. In the same manner as above, one or more of the above-mentioned cyclic polyolefin-based resins are further used as a main component, and if necessary, a whitening agent and a UV absorber as a light reflecting agent or a light diffusing agent. 1 or 2
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.
A cyclic polyolefin resin composition is prepared by adding a solvent, a diluent, and the like, and kneading the mixture sufficiently.

In the present invention, the polyolefin-based resin composition and the cyclic polyolefin-based resin composition prepared as described above are used.
T-die co-extrusion machine, co-extrusion inflation molding machine,
Using other materials, co-extrusion, co-extrusion inflation method, co-extrusion by other film forming methods such as others, and a film or sheet of a co-extruded resin comprising a polyolefin resin layer and a cyclic polyolefin resin layer. The polyolefin resin layer and the cyclic polyolefin resin layer are stretched in a uniaxial or biaxial direction using, for example, a tenter method or a tuber method, if necessary. A film or sheet of a co-extruded resin comprising: Next, in the present invention, for example, a laminating adhesive layer, or a primer agent layer and a laminating layer are formed on the surface of the inorganic oxide vapor-deposited film provided on one side of the base film. Using a dry laminating method or the like, a dry extruded resin film or sheet composed of the polyolefin-based resin layer and the cyclic polyolefin-based resin layer is laminated by dry lamination via an adhesive layer or the like. Thereby, the back surface protection sheet for a solar cell module according to the present invention can be manufactured.

Alternatively, in the present invention, the polyolefin-based resin composition and the cyclic polyolefin-based resin composition prepared above are used, and these are used, for example, by using a co-extruder, a T-die co-extruder, or the like. Then, melt co-extrusion is performed by a molding method such as a co-extrusion method or the like, and is adhered to a surface of the inorganic oxide vapor-deposited film provided on one surface of the base film by, for example, an anchor coating agent. A polyolefin-based resin layer and a cyclic polyolefin-based resin are formed by a melt extrusion laminating method via an anchor coating agent layer such as an auxiliary agent, or a primer agent layer and an anchor coating agent layer. By subjecting the co-extruded resin layer composed of the layers to melt extrusion and lamination, the back surface protection sheet for a solar cell module according to the present invention can be manufactured. In the above, the film or sheet of a co-extruded resin composed of a polyolefin-based resin layer and a cyclic polyolefin-based resin layer, or the thickness of a co-extruded resin layer composed of a polyolefin-based resin layer and a cyclic polyolefin-based resin layer, And about 10 μm to 500 μm, preferably about 25 μm to 300 μm. In the present invention, when laminating a co-extruded resin layer composed of a polyolefin-based resin layer and a cyclic polyolefin-based resin layer on the surface of the inorganic oxide vapor-deposited film provided on one surface of the base film, Any surface of the polyolefin-based resin layer or the cyclic polyolefin-based resin layer constituting the co-extruded resin layer may be laminated with the surfaces facing each other.

In the above, as a whitening agent as an additive, light reflecting or light diffusing properties are provided to reuse the solar light transmitted through the solar cell module after the light is reflected or diffused. It is added for the purpose of, for example, basic lead carbonate, basic lead sulfate, basic lead silicate, zinc white, zinc sulfide, lithopone, antimony trioxide, anatas titanium oxide, rutile titanium oxide, One or more kinds of other white pigments can be used. It is desirable to use about 0.1% to 30% by weight, preferably about 0.5% to 10% by weight, of the polypropylene-based resin composition.

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.

In the dry laminating method, the adhesive constituting the laminating adhesive layer may be, for example, a polyvinyl acetate-based adhesive, ethyl, butyl, 2-ethylhexyl ester of acrylic acid. Or a polyacrylate adhesive comprising a copolymer thereof with methyl methacrylate, acrylonitrile, styrene, etc., a cyanoacrylate adhesive, ethylene and vinyl acetate, ethyl acrylate, acrylic Acid, an ethylene copolymer adhesive comprising a copolymer with a monomer such as methacrylic acid, a cellulose adhesive,
Polyester adhesives, polyamide adhesives, polyimide adhesives, amino resin adhesives made of urea resin or melamine resin, phenolic resin adhesives, epoxy adhesives, polyurethane adhesives, reactive type ( (Meth) acrylic adhesives, rubber adhesives composed of chloroprene rubber, nitrile rubber, styrene-butadiene rubber, etc., silicone adhesives, inorganic adhesives composed of alkali metal silicate, low melting point glass, etc. And the like. The composition system of the above-mentioned adhesive may be any composition form such as an aqueous type, a solution type, an emulsion type, and a dispersion type, and the properties thereof include a film sheet, a powder, and a solid. Any form may be used, and the bonding mechanism may be any form such as a chemical reaction type, a solvent volatilization type, a heat melting type, and a heat pressure type. The above adhesive can be applied by a coating method such as a roll coating method, a gravure roll coating method, a kiss coating method, or the like, or a printing method. The coating amount is desirably about 0.1 to 10 g / m ² (dry state).

The above-mentioned adhesive may contain 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.

In the above-mentioned melt extrusion laminating method, in order to obtain a stronger adhesive strength, for example, an adhesive aid such as an anchor coat agent is used.
Lamination can be performed via a coating 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 with the inorganic oxide vapor-deposited film provided on one side of the substrate film, for example, a primer coat agent layer is further provided in advance. And the like can be arbitrarily formed to form a surface treatment layer. Examples of the above primer coating agent include polyester resin, polyamide resin, polyurethane resin, epoxy resin, phenol resin, (meth) acrylic resin, polyvinyl acetate resin, polyethylene and the like. A resin composition containing a polyolefin resin such as 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, a primer is prepared by coating using a coating method such as roll coating, gravure roll coating, kiss coating and others.
A coating agent layer can be formed, and the coating amount is desirably about 0.1 to 5 g / m ² (dry state).

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. -The backside protective sheet for the roll, the co-extruded resin layer comprising the polyolefin resin layer and the cyclic polyolefin resin layer faces each other, sequentially laminated,
If necessary, arbitrarily laminate other materials between each layer,
Then, using a normal integrated molding method such as a lamination method in which these are integrated by vacuum suction or the like and heat-compressed, the above-described layers are thermocompression-molded as an integrally molded body,
A solar cell module can be manufactured. In the above, if necessary, in order to improve the adhesiveness between the respective layers,
It is possible to use a heat-melt adhesive, a solvent adhesive, a photo-curable adhesive, or the like whose main component is a resin such as a (meth) acrylic resin, an olefin resin, a vinyl resin, and the like. it can.

In the above-mentioned lamination, each lamination facing surface may be provided with, 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, and 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, the polyolefin resin layer and the cyclic polyolefin of the back surface protection sheet for a solar cell module are 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 co-extruded resin layer composed of the base resin layer, and a laminate in which the backside protective sheet for a solar cell module and the filler layer are laminated in advance is manufactured. Thereafter, 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 filler layer constituting the laminate, Further, if necessary, other materials are arbitrarily laminated, and then, the above-mentioned layers are integrally molded using a normal molding method such as a lamination method in which they are integrated by vacuum suction or the like and heat-pressed. As heat compression molding, the sun It can be produced Le - pond module.

[0049]

EXAMPLES The present invention will be described below more specifically with reference to examples. Example 1 (1). An ethylene-tetrafluoroethylene copolymer film (ETFE) having a thickness of 25 μm was used and mounted on a delivery roll of a plasma-enhanced chemical vapor deposition apparatus, and corona treatment of the ethylene-tetrafluoroethylene copolymer film was performed. On the surface, a deposited film of silicon oxide having a thickness of 800 ° was formed under the following conditions. (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, an ethylene-α-olefin copolymer polymerized using a metallocene catalyst is added to titanium oxide (5% by weight) as a whitening agent and ultrafine titanium oxide (particle diameter, 0.01 to 0.06 μm, 3% by weight), and other necessary additives, and kneaded well to prepare a polyethylene resin composition.
Similarly to the above, titanium oxide (5% by weight) as a whitening agent and ultrafine titanium oxide (particle diameter: 0.01 to 0.0) as an ultraviolet absorber were added to the polydicyclopentadiene resin.
6 μm, 3% by weight), and other necessary additives, and kneaded well to prepare a cyclic polyethylene resin composition. Next, using the polyethylene resin composition and the cyclic polyethylene resin composition prepared above,
These are co-extruded using a T-die co-extruder,
A co-extruded film having a thickness of 50 μm comprising a polyethylene resin layer having a thickness of 20 μm and a cyclic polyethylene resin layer having a thickness of 30 μm was produced, and then the surface of the polyethylene resin layer was subjected to corona discharge treatment according to a conventional method. To form a corona treated surface. Next, on the laminating adhesive layer surface formed in the above (2), similarly to the above (3)
The co-extruded film formed in step (1) was opposed to the corona-treated surface of the polyethylene resin layer, and both were laminated by dry lamination to produce a back surface protection sheet for a solar cell module according to the present invention. (4). Next, a glass plate having a thickness of 3 mm and a thickness of 4
A biaxially stretched polyethylene terephthalate film having a thickness of 38 μm in which solar cell elements made of an amorphous silicon are arranged in parallel with a 00 μm ethylene-vinyl acetate copolymer sheet, and a 400 μm-thick ethylene-vinyl acetate copolymer sheet Bonding the acrylic resin with the backsheet for the solar cell module, with the surface of the polyethylene resin layer facing the surface, and the solar cell element surface facing upward. The solar cell module according to the present invention was manufactured by laminating through the agent layer.

Examples 2 to 7 Instead of using the ethylene-tetrafluoroethylene copolymer film (ETFE) having a thickness of 25 μm in Example 1 described above, the following base film was used.
Otherwise, the procedure was performed in exactly the same manner as in the first embodiment, and in the same manner as in the first embodiment, a similar back surface protection sheet according to the present invention.
And a solar cell module 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 having a thickness of 20 μm. Biaxially stretched polyethylene terephthalate film with a thickness of 12 μm

Example 8 An ethylene-tetrafluoroethylene copolymer film (ETFE) having a thickness of 25 μm was used, mounted on a delivery roll of a take-up type vacuum evaporation apparatus, and then coated. The above-mentioned ethylene-tetrafluoroethylene copolymer was fed out by a reactive vacuum deposition method using an electron beam (EB) heating method while feeding oxygen onto the drum under the following conditions while using aluminum as a deposition source under the following conditions. A film thickness of 800 on the corona treated surface of the polymer film.
An aluminum oxide vapor-deposited film was formed. (Evaporation conditions) Evaporation source: Aluminum Degree of vacuum in vacuum chamber: 7.5 × 10 ⁻⁶ mbar Degree of vacuum in evaporation chamber: 2.1 × 10 ⁻⁶ mbar EB output: 40 KW Film transport speed: 600 m / 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, a linear (linear) low-density polyethylene resin is mixed with titanium oxide (5% by weight) as a whitening agent and ultrafine titanium oxide (particle diameter: 0.01%) as an ultraviolet absorber.
To 0.06 μm, 3% by weight), and other necessary additives, and sufficiently kneaded to prepare a polyethylene-based resin composition. , Titanium oxide (5% by weight) as a whitening agent and ultrafine titanium oxide (particle size, 0.01 to 0.06 μm, 3% by weight) as an ultraviolet absorber, and other necessary additives Was added and kneaded well to prepare a cyclic polyethylene resin composition. Next, the polyethylene-based resin composition and the cyclic polyethylene-based resin composition prepared above were melt-extruded using a T-die co-extruder to form a polyethylene resin layer having a thickness of 15 μm and a thickness of 15 μm. Producing a co-extruded film having a thickness of 40 μm and a cyclic polyethylene resin layer having a thickness of 25 μm;
Next, the surface of the polyethylene resin layer was subjected to a corona discharge treatment according to a conventional method to form a corona-treated surface.
Next, the co-extruded film formed in the above (3) was also made to face the laminating adhesive layer surface formed in the above (2) with the corona treated surface of the polyethylene resin layer. Was laminated on a dry laminate to produce a backside protective sheet for a solar cell module according to the present invention. (4). Next, a glass plate having a thickness of 3 mm and a thickness of 4
A biaxially stretched polyethylene terephthalate film having a thickness of 38 μm in which solar cell elements made of an amorphous silicon are arranged in parallel with a 00 μm ethylene-vinyl acetate copolymer sheet, and a 400 μm-thick ethylene-vinyl acetate copolymer sheet Bonding the acrylic resin with the backsheet for the solar cell module, with the surface of the polyethylene resin layer facing the surface, and the solar cell element surface facing upward. The solar cell module according to the present invention was manufactured by laminating through the agent layer.

Examples 9 to 14 In the above-mentioned Example 8, instead of using an ethylene-tetrafluoroethylene copolymer film (ETFE) having a thickness of 25 μm, the following base film was used.
Otherwise, the procedure is exactly the same as that of the above-mentioned embodiment 8, and like the above-mentioned embodiment 8, the same back surface protection seal according to the present invention.
And a solar cell module could be manufactured. Embodiment 9 FIG. 50μm thick polyvinyl fluoride resin screen
G (PVF) Embodiment 10 Polydicyclopentadiene resin sheet having a thickness of 100 μm. 50μm thick polycarbonate resin sheet
G. Embodiment 12 FIG. Example 13 Polyacrylic resin sheet having a thickness of 50 μm 13. A biaxially stretched nylon 6 film having a thickness of 25 μm. 25 μm thick biaxially oriented polyethylene terephthalate film

Embodiment 15 (1). An ethylene-tetrafluoroethylene copolymer film (ETFE) having a thickness of 25 μm was used, and this was mounted on a delivery roll of a plasma chemical vapor deposition apparatus, and was applied to the corona-treated surface of the ethylene-tetrafluoroethylene copolymer film. Then, a deposited thin film of silicon oxide having a thickness of 50 ° was formed under the following conditions to provide an anti-evaporation protective film. (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, in the same manner as in Example 1 described above, a back surface protection sheet for a solar cell module and a solar cell module according to the present invention similar to Example 1 are manufactured. We were able to.

Embodiment 16 (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 8 above. A treated surface was formed. (2). Hereinafter, the same procedure as in Example 8 described above was carried out, and a similar back surface protection sheet and a solar cell module according to the present invention were manufactured in the same manner as in Example 8 described above.

Embodiment 17 (1). Using an ethylene-tetrafluoroethylene copolymer film (ETFE) having a thickness of 25 μm, a silicon monoxide having a purity of 99.9% by a high-frequency dielectric heating method under a vacuum of 1 × 10 ⁻⁴ Torr under a corona-treated surface. (SiO) was heated and evaporated to form a 500 ° silicon oxide deposited film.
Next, immediately after forming the above-described silicon oxide deposited film having a thickness of 500 °, an output of 10 k was applied to the silicon oxide deposited film surface.
W, a corona discharge treatment is performed at a treatment speed of 100 m / min, and the surface tension of the vapor-deposited film surface is increased from 35 dyne to 60 dyn.
The corona-treated surface improved to e was formed. (2). Hereinafter, in the same manner as in Example 1 described above, a back surface protection sheet for a solar cell module and a solar cell module according to the present invention similar to Example 1 are manufactured. We were able to.

Embodiment 18 (1). Using a 25 μm-thick ethylene-tetrafluoroethylene copolymer film (ETFE), 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 film surface. Next, on the plasma-treated surface of the silicon oxide vapor-deposited film formed above, an aluminum oxide vapor-deposited film having a thickness of 500 ° was formed in the same manner as in Example 8 above. A plasma treated surface was formed on the film surface. (2). Hereinafter, in the same manner as in Example 8, the same back surface protection sheet for solar cell modules and solar cell modules according to the present invention as in Example 8 are manufactured. We were able to.

Embodiment 19 (1). An ethylene-tetrafluoroethylene copolymer film (ETFE) having a thickness of 25 μm was used and mounted on a delivery roll of a plasma-enhanced chemical vapor deposition apparatus, and corona treatment of the ethylene-tetrafluoroethylene copolymer film was performed. On the surface, a deposited film of silicon oxide having a thickness of 800 ° was formed under the following conditions. (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, an ethylene-α-olefin copolymer polymerized using a metallocene catalyst is added to titanium oxide (5% by weight) as a whitening agent and ultrafine titanium oxide (particle diameter, 0.01 to 0.06 μm, 3% by weight), and other necessary additives, and kneaded well to prepare a polyethylene resin composition.
Similarly to the above, titanium oxide (5% by weight) as a whitening agent and ultrafine titanium oxide (particle diameter: 0.01 to 0.0) as an ultraviolet absorber were added to the polydicyclopentadiene resin.
6 μm, 3% by weight), and other necessary additives, and kneaded well to prepare a cyclic polyethylene resin composition. Next, using the polyethylene resin composition and the cyclic polyethylene resin composition prepared above,
These were melt-extruded using a T-die co-extruder on the plasma-treated surface of the deposited silicon oxide film having a thickness of 800 ° formed in the above (1) to form a polyethylene-based resin layer having a thickness of 20 μm. A co-extruded resin layer having a thickness of 30 μm and a 50 μm-thick co-extruded resin layer was melt-extruded and laminated to produce a backside protection sheet for a solar cell module according to the present invention. (4). Next, a glass plate having a thickness of 3 mm and a thickness of 4
A biaxially stretched polyethylene terephthalate film having a thickness of 38 μm in which solar cell elements made of an amorphous silicon are arranged in parallel with a 00 μm ethylene-vinyl acetate copolymer sheet, and a 400 μm-thick ethylene-vinyl acetate copolymer sheet Bonding the acrylic resin with the backsheet for the solar cell module, with the surface of the polyethylene resin layer facing the surface, and the solar cell element surface facing upward. The solar cell module according to the present invention was manufactured by laminating through the agent layer.

Example 20 An ethylene-tetrafluoroethylene copolymer film (ETFE) having a thickness of 25 μm was used, which was mounted on a delivery roll of a take-up type vacuum evaporation apparatus, and then coated. The above-mentioned ethylene-tetrafluoroethylene copolymer was fed out by a reactive vacuum deposition method using an electron beam (EB) heating method while feeding oxygen onto the drum under the following conditions while using aluminum as a deposition source under the following conditions. A film thickness of 800 on the corona treated surface of the polymer film.
An aluminum oxide vapor-deposited film was formed. (Evaporation conditions) Evaporation source: Aluminum Degree of vacuum in vacuum chamber: 7.5 × 10 ⁻⁶ mbar Degree of vacuum in evaporation chamber: 2.1 × 10 ⁻⁶ mbar EB output: 40 KW Film transport speed: 600 m / 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 linear (linear) low-density polyethylene resin is mixed with titanium oxide (5% by weight) as a whitening agent and ultrafine titanium oxide (particle diameter: 0.01%) as an ultraviolet absorber.
To 0.06 μm, 3% by weight), and other necessary additives, and sufficiently kneaded to prepare a polyethylene-based resin composition. , Titanium oxide (5% by weight) as a whitening agent and ultrafine titanium oxide (particle size, 0.01 to 0.06 μm, 3% by weight) as an ultraviolet absorber, and other necessary additives Was added and kneaded well to prepare a cyclic polyethylene resin composition. Next, the above-prepared polyethylene-based resin composition and cyclic polyethylene-based resin composition were used, and these were treated with the plasma-treated surface of the aluminum oxide vapor-deposited film having a film thickness of 800 ° formed in (1) above. And a co-extrusion using a T-die co-extruder to form a polyethylene resin layer having a thickness of 15 μm and a cyclic polyethylene resin layer having a thickness of 25 μm.
A 0 μm co-extruded resin layer was melt-extruded and laminated to produce a backside protection sheet for a solar cell module according to the present invention. (4). Next, a glass plate having a thickness of 3 mm and a thickness of 4
A biaxially stretched polyethylene terephthalate film having a thickness of 38 μm in which solar cell elements made of an amorphous silicon are arranged in parallel with a 00 μm ethylene-vinyl acetate copolymer sheet, and a 400 μm-thick ethylene-vinyl acetate copolymer sheet Bonding the acrylic resin with the backsheet for the solar cell module, with the surface of the polyethylene resin layer facing the surface, and the solar cell element surface facing upward. The solar cell module according to the present invention was manufactured by laminating through the agent layer.

Embodiment 21 (1). An ethylene-tetrafluoroethylene copolymer film (ETFE) having a thickness of 25 μm was used, and this was mounted on a delivery roll of a plasma chemical vapor deposition apparatus, and was applied to the corona-treated surface of the ethylene-tetrafluoroethylene copolymer film. Then, a deposited thin film of silicon oxide having a thickness of 50 ° was formed under the following conditions to provide an anti-evaporation protective film. (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 transfer speed: 100 m / min Next, the above Example 19 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 19 described above was performed.
In the same manner as in Example 19 above, a similar back surface protection sheet and solar cell module according to the present invention could be manufactured.

Embodiment 22 (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 ° is formed on the deposited anti-evaporation protective film in the same manner as in Example 20. Further, a plasma is deposited on the aluminum oxide deposited film surface. A treated surface was formed. (2). Hereinafter, the same procedure as in Example 20 was performed,
As in the case of Example 20, similar back surface protection sheets and solar cell modules according to the present invention could be manufactured.

Embodiment 23 (1). Using an ethylene-tetrafluoroethylene copolymer film (ETFE) having a thickness of 25 μm, a silicon monoxide having a purity of 99.9% by a high-frequency dielectric heating method under a vacuum of 1 × 10 ⁻⁴ Torr under a corona-treated surface. (SiO) was heated and evaporated to form a 500 ° silicon oxide deposited film.
Next, immediately after forming the above-described silicon oxide deposited film having a thickness of 500 °, an output of 10 k was applied to the silicon oxide deposited film surface.
W, a corona discharge treatment is performed at a treatment speed of 100 m / min, and the surface tension of the vapor-deposited film surface is increased from 35 dyne to 60 dyn.
The corona-treated surface improved to e was formed. (2). Hereinafter, the same procedure as in Example 19 described above was performed.
In the same manner as in Example 19 above, a similar back surface protection sheet and solar cell module according to the present invention could be manufactured.

Embodiment 24 (1). Using a 25 μm-thick ethylene-tetrafluoroethylene copolymer film (ETFE), a vapor-deposited silicon oxide film having a film thickness of 500 ° was formed in the same manner as in Example 19, and the silicon oxide was further vapor-deposited. A plasma treated surface was formed on the film surface. Next, on the plasma-treated surface of the silicon oxide vapor-deposited film formed above, an aluminum oxide vapor-deposited film having a thickness of 500 ° was formed in the same manner as in Example 20. A plasma treated surface was formed on the film surface. (2). Hereinafter, the same procedure as in Example 20 was performed,
As in the case of Example 20, similar back surface protection sheets and solar cell modules 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, 400 μm-thick ethylene-vinyl acetate copolymer sheet, and solar cell elements 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 reflectivities of the back protection sheets for solar cell modules according to the present invention manufactured in Examples 1 to 24 and the back 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 24 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 24 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 for the solar cell module back surface protection sheet according to the present invention manufactured in Examples 1 to 24 and Comparative Examples 1 to 4.
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 This is to cut the back protection sheet into a width of 15 mm and use a tensile tester [A & D (A & D) Co., Ltd.]
(Model name: Tensilon), the peel strength of the laminate constituting the back surface protection sheet was measured. The results of the above measurements are shown in Table 1 below.

[0066] 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 evident from the measurement results shown in Table 1 above, the back protective sheets for solar cell modules according to Examples 1 to 24 have high reflectance, and have a water vapor barrier property and an oxygen barrier property. Excellent in properties and lamination strength. Further, the solar cell modules using the back surface protection sheets for solar cell modules according to Examples 1 to 24 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.

[0068]

As is apparent from the above description, the present invention provides:
On one surface of the base film, 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, and the like. A co-extruded resin layer comprising a polyolefin-based resin layer and a cyclic polyolefin-based resin layer, using a polyolefin-based resin and a cyclic polyolefin-based resin on the surface of the inorganic oxide vapor-deposited film provided in the above step. Are laminated with their polyolefin resin layer surfaces facing each other to produce a back protection sheet for a solar cell module, and using the back protection sheet for a solar cell module, for example, Protective sheet for solar cell module comprising glass plate, etc., filler layer, solar cell element as photovoltaic element, filler layer, and solar cell module described above Back protective sheets are sequentially laminated with the surfaces of the co-extruded resin layers comprising the polyolefin-based resin layer and the cyclic polyolefin-based resin layer facing each other. A solar cell module is manufactured by integral molding using a lamination method, etc., which has excellent strength, and furthermore, weather resistance, heat resistance, water resistance, light resistance, wind pressure resistance, hail resistance, chemical resistance,
It has excellent antifouling properties and other properties, and in particular, has excellent moisture proof properties to prevent the ingress of moisture, oxygen, etc., and also has remarkably improved light reflection, light diffusion, design, etc. It is possible to stably produce a safe solar cell module which is extremely durable, has excellent protection ability, is low in cost, and minimizes the performance deterioration.

[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 showing a layer configuration of an example of a back surface protection sheet for a solar cell module according to the present invention.

FIG. 5 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. 6 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. 7 is a schematic cross-sectional view schematically showing a layer configuration of another example of a deposited film of an inorganic oxide.

FIG. 8 is a schematic cross-sectional view schematically showing a layer configuration of another example of a deposited film of an inorganic oxide.

FIG. 9 is a photovoltaic module manufactured using the solar cell module back 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. 10 is a schematic configuration diagram showing an example of a take-up type vacuum evaporation apparatus.

FIG. 11 is a schematic configuration diagram illustrating an example of a plasma chemical vapor deposition apparatus.

[Reference Numerals] A solar cell module - for the backside Le protective sheet - DOO A ₁ to A ₅ solar cell module - for the backside Le protective sheet - deposited film 2a multilayer film 2b of sheet 1 substrate film 2 inorganic oxide inorganic oxide 2c Composite film 3 Polyethylene resin layer 4 Cyclic polyolefin resin layer 5 Co-extrusion resin layer 6 Laminate adhesive layer 7 Primer agent layer 8 Anchor coating agent Layer T Solar cell module 11 Surface protection sheet for solar cell module 12 Filler layer 13 Solar cell element 14 Filler layer 15 (A) Backside protection sheet for solar cell module

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Kojiro Okawa 1-1-1, Ichigaya-Kagacho, Shinjuku-ku, Tokyo Inside Dai Nippon Printing Co., Ltd. 1-1-1 Dai Nippon Printing Co., Ltd. (72) Inventor Kazuyuki Takazawa 1-1-1 Ichigaya Kagacho, Shinjuku-ku, Tokyo F-term in Dai Nippon Printing Co., Ltd. 4F100 AA17B AA17D AA17E AA20 AA21H AH02H AK03C AK04C AK17A AK18 AK25A AK41A AK45A AK46A AK51G AK63C AK80A AK80C AL01 AS00H AT00A BA05 BA07 BA10A BA10E CA07 CB02 CB10 EC182 EH20 EH201 EH23 EH231 EH232 EH66 EH662 EJ65 GB90 HB40 JB01 JB07 JJ03 JK01 JK12 JL06 JL09 JN06 YY00B YY00D YY00E 5F051 BA18 CB14 CB30 JA02 JA05

Claims (10)

[Claims] An inorganic oxide vapor-deposited film is provided on one surface of a substrate film, and further, the inorganic oxide vapor-deposited film is
A solar cell module comprising using a polyolefin resin and a cyclic polyolefin resin, coextruding them, and providing a coextruded resin layer comprising the polyolefin resin layer and the cyclic polyolefin resin layer.
Back protection sheet for 2. The method according to claim 1, wherein an inorganic oxide vapor-deposited film is further provided on the other surface of the co-extruded resin layer comprising the polyolefin-based resin layer and the cyclic polyolefin-based resin layer. Back protection sheet for solar cell module. 3. 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. 3. The backside protection sheet for a solar cell module according to claim 1, wherein the backside protection sheet comprises:
G. 4. 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 inorganic oxide vapor-deposited films. The back surface protection sheet for a solar cell module according to any one of claims 1 to 3, characterized in that: 5. The backside protective 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. 6. A co-extruded resin layer comprising a polyolefin resin layer and a cyclic polyolefin resin layer, wherein the co-extruded resin layer uses a polyethylene resin and a cyclic polyolefin resin,
6. The back protection sheet for a solar cell module according to claim 1, wherein the back protection sheet is made of a co-extruded resin layer comprising a polyethylene resin layer and a cyclic polyolefin resin layer. -G. 7. A co-extruded resin layer comprising a polyolefin-based resin layer and a cyclic polyolefin-based resin layer uses a linear low-density polyethylene-based resin and a cyclic polyolefin-based resin, and co-extrudes them to form a linear low-density polyethylene-based resin. 7. The back protection sheet for a solar cell module according to claim 1, comprising a co-extruded resin layer comprising a density polyethylene resin layer and a cyclic polyolefin resin layer. 8. A co-extruded resin layer comprising a polyolefin-based resin layer and a cyclic polyolefin-based resin layer, wherein a laminating adhesive layer or a primer agent layer and a laminating adhesive layer are interposed. The backside protection sheet for a solar cell module according to any one of claims 1 to 7, wherein the backside protection sheet is laminated by a dry lamination method. 9. A co-extruded resin layer comprising a polyolefin-based resin layer and a cyclic polyolefin-based resin layer comprises an anchor coating agent layer, or a primer agent layer and an anchor coating layer.
The backsheet according to any one of claims 1 to 7, wherein the backsheet is laminated by a melt-extrusion lamination method via a coating agent layer. 10. 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 a vapor-deposited film of an inorganic oxide provided on one surface of the base film, and further, on a surface of the vapor-deposited film of the inorganic oxide. For a solar cell module using a polyolefin resin and a cyclic polyolefin resin, coextruding them, and providing a coextruded resin layer composed of the polyolefin resin layer and the cyclic polyolefin resin layer. A back protective sheet is sequentially laminated with the surfaces of the co-extruded resin layer composed of the polyolefin-based resin layer and the cyclic polyolefin-based resin layer facing each other, and these are vacuum-evacuated and subjected to a heat compression lamination method or the like. A solar cell module, which is formed as an integrated molded body.