JP2003243679A - Reverse-surface protection sheet for solar cell module and the solar cell module using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To stably provide a reverse-surface protection sheet for a solar cell module, which is very rich in durability, more low-cost, and safer by improving moisture resistance for preventing water, oxygen, etc., from entering and suppressing long-period performance deterioration and, specially, preventing hydrolysis, and the solar cell module which uses the reverse-surface protection sheet. <P>SOLUTION: The reverse-surface protection sheet for the solar cell module is formed of a three-layered laminated resin film formed by laminating in order a 1st heat-resisting polypropylene-based resin film of a heat-resisting polypropylene-based resin compound containing an ultraviolet-ray absorber and an optical stabilizer, a 2nd heat-resisting polypropylene-based resin film of a heat-resisting polypropylene-based resin composition containing a coloring agent, an ultraviolet-ray absorber, and an optical stabilizer, and a 3rd heat- resisting polypropylene-based resin film of a heat-resisting polypropylene-based resin composition containing an ultraviolet-ray absorber and an optical stabilizer. The solar cell modules uses the reverse-surface protection sheet. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a solar cell module.
More specifically, it relates to a backside protective sheet for solar cells and a solar cell module using the same, and more specifically, has excellent strength and weather resistance, heat resistance, water resistance, light resistance, wind pressure resistance, hail resistance, chemical resistance. , A moisture-proof, antifouling property, light-reflecting property, light-diffusing property, designability, and other properties, and is extremely durable and has excellent protective ability. And a solar cell module using the same.

[0002]

2. Description of the Related Art In recent years, attention has been paid to solar cells as a clean energy source due to increasing awareness of environmental problems, and at present, various types of solar cell modules have been developed and proposed. . Generally, the above solar cell module is, for example, a crystalline silicon solar cell element or an amorphous silicon solar cell element is manufactured, and using such a solar cell element, a surface protection sheet layer, a filler layer, It is manufactured by using a lamination method or the like in which a solar cell element as a photovoltaic element, a filler layer, a back surface protection sheet layer, and the like are laminated in this order, and vacuum suction is performed and thermocompression bonding is performed. Specifically, a glass plate as a surface protection sheet layer, an ethylene-vinyl acetate copolymer sheet as a filler layer, a solar cell element as a photovoltaic element, ethylene-acetic acid as a filler layer. Vinyl copolymer sheet, and
A solar cell module is manufactured by sequentially laminating a fluororesin sheet as a back surface protection sheet layer, and integrally molding them by using a lamination method in which vacuum suction and heating and pressure bonding are performed. is doing. Thus, the above-mentioned solar cell module was initially applied to a calculator, and then applied to various electronic devices, etc., for consumer use, its application range is rapidly expanding, Furthermore, it is said that the realization of large-scale concentrated solar cell power generation will be the most important issue in the future. By the way, generally, as a solar cell module solar cell module, for example, excellent in strength, and
Excellent weather resistance, heat resistance, water resistance, light resistance, wind pressure resistance, hail resistance, chemical resistance, light reflectivity, light diffusivity, design, etc. It is necessary to satisfy conditions such as excellent moisture resistance to prevent, high surface hardness, excellent antifouling property to prevent accumulation of dirt and dust on the surface, extremely durable, and other conditions. It is said that.

[0003]

However, in the solar cell module as described above, for example, as the back surface protective sheet layer, the fluorine resin sheet which is most commonly used at present and has excellent strength is used. -If you use
It is rich in plasticity, lightness, workability, workability, etc., but strength, weather resistance, heat resistance, water resistance, light resistance, chemical resistance, light reflection, light diffusion, impact resistance, etc. Is inferior in various fastness properties, and particularly lacks in moisture resistance, stain resistance, and designability. Further, in the above solar cell module, the fluororesin sheet used as the back surface protection sheet layer is extremely high in cost as compared with a normal polyolefin resin sheet, and the solar cell There is a problem that it is not suitable for mass-producing a module at low cost. Furthermore, when a solar cell module using a fluororesin sheet is installed on the roof or the like as the back surface protection sheet layer, for example, a fire occurs in the house or the like, and the solar cell module is exposed. If the fire spreads, it will generate toxic gases such as hydrofluoric acid, which will affect human life and so on.
There is also the problem that it becomes extremely dangerous. Therefore, the present invention is excellent in strength, and weather resistance, heat resistance, water resistance,
Excellent in light resistance, wind pressure resistance, hail resistance, chemical resistance, moisture resistance, antifouling property, light reflection property, light diffusivity, designability, and other properties, and especially prevents entry of moisture, oxygen, etc. The moisture resistance is significantly improved and its long-term performance deterioration is minimized.
Especially, it prevents hydrolysis and deterioration, and is extremely durable.
In addition, it is to provide a lower cost and safer back surface protection sheet for a solar cell module and a solar cell module using the same in a stable manner.

[0004]

Means for Solving the Problems As a result of various studies to solve the above problems of a solar cell module, the present inventor firstly prepared a heat-resistant polypropylene resin film for the solar cell module. Focusing on its use in a back surface protection sheet, first, a first heat-resistant polypropylene resin film made of a heat-resistant polypropylene resin composition containing an ultraviolet absorber and a light stabilizer, a coloring agent and ultraviolet rays. A second heat-resistant colored polypropylene-based resin film made of a heat-resistant polypropylene-based resin composition containing an absorber and a light stabilizer, and a second heat-resistant polypropylene-based resin composition made of an ultraviolet absorber and a light stabilizer. The heat-resistant polypropylene resin film of No. 3 is sequentially laminated to manufacture a back surface protection sheet for a solar cell module, which is made of a three-layer laminated resin film, and then Solar cell module consisting of the three-layered laminate resin film - for the backside Le protective sheet - using preparative, for example,
Ordinary solar cell module surface protection sheet consisting of glass plate, filler layer such as ethylene-vinyl acetate copolymer sheet, solar cell element as photovoltaic element, ethylene-vinyl acetate copolymer A first heat-resistant polypropylene-based resin film, a coloring agent, and a UV-absorbing agent, which is a filler layer of a polymer sheet or the like, and a heat-resistant polypropylene-based resin composition containing the above-mentioned UV absorber and a light stabilizer. Of a heat-resistant polypropylene resin composition containing a stabilizer and a light stabilizer
A heat-resistant colored polypropylene resin film, and a third heat-resistant polypropylene resin film containing a heat-resistant polypropylene resin composition containing an ultraviolet absorber and a light stabilizer are sequentially laminated to form a three-layer laminated resin film. The solar cell module back surface protection sheet is sequentially laminated,
Next, when a solar cell module was manufactured by using a lamination method in which these are integrally vacuum-sucked and heat-pressed, the strength is excellent, and further, the weather resistance, heat resistance, water resistance, and light resistance are excellent. , Wind pressure resistance, hail resistance, chemical resistance, stain resistance,
It has excellent properties such as other properties, especially excellent moisture resistance to prevent entry of moisture and oxygen. It also significantly improves light reflectivity, light diffusivity, designability, etc. to prevent long-term performance deterioration. The present invention was found to minimize the production of a solar cell module, which is extremely durable, and which can prevent hydrolysis and deterioration due to moisture, etc., and can be stably manufactured at a lower cost. Is completed.

That is, the present invention relates to a first heat-resistant polypropylene resin film made of a heat-resistant polypropylene resin composition containing an ultraviolet absorber and a light stabilizer, a coloring agent, an ultraviolet absorber and a light stabilizer. Heat-resistant polypropylene-based resin film containing a heat-resistant polypropylene-based resin composition containing an agent and a heat-resistant polypropylene-based resin composition containing a UV absorber and a light stabilizer The present invention relates to a back surface protection sheet for a solar cell module, which comprises a three-layer laminated resin film in which a resin film and a resin film are sequentially laminated, and a solar cell module using the same.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention described above will be described in more detail below with reference to the drawings. In the present invention, the sheet means any of a sheet-like material and a film-like material, and the film means
It means any of a film-like material and a sheet-like material. The layer structure of the back surface protection sheet for a solar cell module according to the present invention and the solar cell module using the same will be described more specifically with reference to the drawings. FIG. 1 shows the present invention. FIG. 2 is a schematic cross-sectional view illustrating an example of the layer structure of the back surface protection sheet for a solar cell module, and FIG. 2 is a back surface protection sheet for a solar cell module according to the present invention shown in FIG. It is a schematic sectional drawing which illustrates an example about the layer structure of the solar cell module manufactured using.

First, as shown in FIG. 1, a back surface protection sheet A for a solar cell module according to the present invention comprises a heat-resistant polypropylene resin composition containing an ultraviolet absorber and a light stabilizer. 1. A heat-resistant polypropylene-based resin film 1, a second heat-resistant colored polypropylene-based resin film 2 made of a heat-resistant polypropylene-based resin composition containing a coloring agent, an ultraviolet absorber and a light stabilizer, and an ultraviolet absorber. And a third heat resistant polypropylene resin film 3 made of a heat resistant polypropylene resin composition containing a light stabilizer and a light stabilizer. The above example illustrates one example of the back surface protection sheet for a solar cell module according to the present invention, and it goes without saying that the present invention is not limited thereto.

Next, in the present invention, an example of a solar cell module manufactured by using the back surface protection sheet for a solar cell module according to the present invention will be exemplified below. The solar cell module according to the present invention shown
As shown in FIG. 2, a back surface protection sheet A for a solar cell is first used, and a surface protection sheet 11a for an ordinary solar cell module such as a glass plate 11 and an ethylene-vinyl acetate copolymer sheet are first prepared.
A filler layer 12a such as a solar cell 12, a solar cell element 13 as a photovoltaic element, an ethylene-vinyl acetate copolymer sheet 1
First heat-resistant polypropylene-based resin film 1 made of a heat-resistant polypropylene-based resin composition containing the above-mentioned ultraviolet absorber and light stabilizer
And a second heat-resistant colored polypropylene-based resin film 2 made of a heat-resistant polypropylene-based resin composition containing a coloring agent, an ultraviolet absorber and a light stabilizer, and a heat-resistant material containing an ultraviolet absorber and a light stabilizer. Back surface protection sheet 15a for a solar cell module, which is composed of a three-layer laminated resin film 4 in which a third heat-resistant polypropylene resin film 3 made of a heat-resistant polypropylene resin composition is sequentially laminated,
Then, the solar cell module T can be manufactured by integrating these with one another and using a normal molding method such as a lamination method in which vacuum suction is performed and thermocompression bonding is performed, by using each of the above layers as an integrally molded body. The above example illustrates one example of a solar cell module manufactured using the back surface protection sheet for a solar cell module according to the present invention, and the present invention is limited thereby. is not. For example, although not shown, in the above solar cell module, for the purpose of absorption of sunlight, reinforcement, etc.,
Further, other layers can be optionally added and laminated.

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.
First, in the present invention, the solar cell module according to the present invention will be described.
A method for producing a back surface protection sheet for a solar cell will be described. Such a back surface protection sheet for a solar cell module is not shown, but first, for example, heat resistance containing an ultraviolet absorber and a light stabilizer. Polypropylene resin composition, and
A heat-resistant polypropylene-based resin composition containing a colorant, an ultraviolet absorber and a light stabilizer is prepared, and these are then treated with, for example, an extruder, a T-die extruder, a cast molding machine,
Using an extrusion molding machine, etc., an extrusion method,
T-die extrusion method, cast molding method, inflation method,
A first heat-resistant polypropylene-based resin composition containing an ultraviolet absorber and a light stabilizer, which is formed by a film forming method such as the above, and is further uniaxially or biaxially stretched, if necessary, or Second non-stretched or stretched heat-resistant coloring with a third non-stretched or stretched heat-resistant polypropylene-based resin film and a heat-resistant polypropylene-based resin composition containing a coloring agent, an ultraviolet absorber and a light stabilizer A polypropylene resin film is manufactured. Next, in the present invention, the first, the second, and the third manufactured as described above are used.
The non-stretched or stretched heat-resistant or heat-resistant colored polypropylene resin film is used, and these are laminated, for example, by dry lamination through an adhesive layer for lamination, which is laminated. Laminating method, or an adhesion aid layer using an anchor coating agent,
A first heat-resistant polypropylene-based resin film, a second heat-resistant colored polypropylene-based resin film, a third heat-resistant polypropylene resin film, and a third heat-resistant polypropylene resin film, which are laminated by a melt-extrusion laminating method of melt-extruding and laminating via a melt-extruded resin layer or the like. The back protective sheet for a solar cell module according to the present invention can be manufactured by manufacturing a three-layer laminated resin film comprising a transparent polypropylene resin film.

Alternatively, in the present invention, the back surface protection sheet for a solar cell module according to the present invention, which is not shown, is a heat-resistant polypropylene resin containing the ultraviolet absorber and the light stabilizer prepared above. A heat-resistant polypropylene-based resin composition containing a composition, a colorant, an ultraviolet absorber and a light stabilizer is used, and then these are used, for example, T
Using a die co-extrusion machine or an inflation co-extrusion machine, three-layer co-extrusion molding is carried out, and further, if necessary, uniaxial or biaxial stretching processing is carried out to obtain an ultraviolet absorber and a light stabilizer. A first non-stretched or stretched heat-resistant polypropylene-based resin film containing a heat-resistant polypropylene-based resin composition, and a heat-resistant polypropylene-based resin composition containing a coloring agent, an ultraviolet absorber and a light stabilizer. A second non-stretched or stretched heat-resistant polypropylene-based resin film 3 made of a heat-resistant polypropylene-based resin composition containing a non-stretched or stretched heat-resistant colored polypropylene-based resin film 2 and an ultraviolet absorber and a light stabilizer 3 By producing a three-layer coextrusion laminated resin film consisting of and, the back surface protection sheet for a solar cell module according to the present invention can be produced.

Further, in the present invention, the back surface protection sheet for a solar cell module according to the present invention is not shown,
First, heat-resistant polypropylene-based resin as the main component of the vehicle, to which the ultraviolet absorber and light stabilizer are added,
Furthermore, other additives are optionally added to prepare a heat-resistant polypropylene-based resin-containing paint or ink composition,
Then, using this, a second unstretched or stretched heat-resistant colored polypropylene-based resin film made of the heat-resistant polypropylene-based resin composition containing the coloring agent, the ultraviolet absorber and the light stabilizer produced above was used. By applying or printing on both surfaces using a usual coating method or printing method, a coating film or a printing film made of a heat-resistant polypropylene resin containing an ultraviolet absorber and a light stabilizer is formed. A coating film or a printing film made of a first heat-resistant polypropylene resin, a second heat-resistant colored polypropylene resin film, and a coating film or a printing film made of a third heat-resistant polypropylene resin. By manufacturing the layer-laminated resin film, the back surface protection sheet for a solar cell module according to the present invention can be manufactured. The above examples illustrate a few examples of the method for producing the back surface protection sheet for a solar cell module according to the present invention, and the present invention is not limited thereto. Of course.

In the back surface protection sheet for a solar cell module according to the present invention, a first heat-resistant polypropylene resin composition containing an ultraviolet absorber and a light stabilizer is used.
And as the film thickness of the second heat resistant polypropylene resin film, the film thickness is about 2 μm to 100 μm, preferably,
A preferable range is 6 μm to 30 μm. In the above, if the film thickness is too thin, it is difficult to control the film thickness during film formation, and there is a tendency for lack of light resistance. If the film thickness is too thick, handling and film thickness control become difficult. It is not preferable. Further, in the back surface protection sheet for a solar cell module according to the present invention, the second heat-resistant colored polypropylene-based resin composition comprising a heat-resistant polypropylene-based resin composition containing a colorant, an ultraviolet absorber and a light stabilizer. The film thickness of the resin film 2 is preferably about 12 μm to 400 μm, more preferably about 36 μm to 120 μm. In the above, if the film thickness is too thin, the light resistance tends to be poor, and if it is too thick, the material cost is unnecessarily high, and handling and film thickness control become difficult, which is not preferable. Thus, in the present invention, the thickness of the back surface protective sheet for a solar cell module according to the present invention is about 20 μm to 500 μm, preferably 60 μm.
The range of m to 150 μm is desirable. In the above, those having a thickness of less than 20 μm, and further less than 60 μm are not preferable because they lack light resistance and the like, and those having a thickness of more than 500 μm and more than 150 μm lack cost reduction. This is not preferable.

In the above, the polypropylene resin constituting the back surface protection sheet for a solar cell module according to the present invention is, for example, a by-product produced when ethylene is produced by thermal decomposition of petroleum hydrocarbons. Which is a homopolymer of propylene, or an ethylene-propylene random or block copolymer such as propylene and α-
Copolymers with other monomers such as olefins and the like, as well as recycled polypropylene and the like can be used. Thus, in the present invention, as the polypropylene resin, when a cation polymerization catalyst or the like is used in the case of polymerizing propylene, a low molecular weight polymer can be obtained. , Tealer
When a Natta catalyst is used, an isotactic polymer having a high molecular weight and a high crystallinity can be obtained, and this isotactic polymer is used. In the above isotactic polymer, the melting point is 164 ° C to 1
It is about 70 ° C., the specific gravity is about 0.90 to 0.91, the molecular weight is about 100,000 to 200,000, and the properties are largely controlled by its crystallinity, but a polymer with high isotacticity is used. -Is excellent in tensile strength, impact strength, heat resistance, moisture resistance, water resistance, water vapor resistance, and other toughness, and also has good bending fatigue strength and workability. It is extremely good, and is excellent in cost reduction as compared with a fluororesin sheet or the like. Further, in the present invention, the use of recycled polypropylene has advantages of low cost and excellent environmental adaptability.

In the present invention, it is preferable to use a mixture of a propylene homopolymer (homo) and an ethylene-propylene random copolymer as the polypropylene resin. In the present invention, basically, as the propylene homopolymer, one having a relatively high melting point and a rigid rigidity is used, whereas, as a random copolymer of ethylene-propylene, it is used. Uses a material having a low melting point and a softness in terms of rigidity. Therefore, in the present invention, by mixing both of them, a material having a low melting point and a material having a high melting point are used, It is intended to widen the processing temperature range to improve processing suitability, and by mixing and using soft and hard hardness materials, it improves bending suitability and prevents its whitening. That is, the so-called waist and shape retention are maintained.
In the above, as the mixing ratio of the propylene homopolymer (homo) and the ethylene-propylene random copolymer, the former, the compounding ratio of the latter 5 to 60% by weight to 40 to 90% by weight, and further, The former is 60 to 90% by weight, and the latter is preferably 10 to 40% by weight.

Generally, a polypropylene resin used as a heat-sealable resin layer (sealant layer) of a packaging material for packing foods and the like is heated in a low temperature range of about 100 ° C. for several seconds. Since the heat-sealing property is required, the low temperature processability is required, and the one having a considerably lowered melting point is applied, but in the present invention,
It is unsuitable to use such a polypropylene resin having low heat resistance. In the present invention,
As the back surface protection sheet for solar cell modules, there are mainly two types, a non-stretched (unstretched) type and a stretched type. It is better than the unstretched type, but when producing a solar cell module, the lamination is usually performed by heat and pressure at 150 to 170 ° C. for 20 to 30 minutes. Because it goes through the process,
At that time, the stretched type shrinks violently, and it is difficult to produce a preferable solar cell module. Therefore, as a back surface protection sheet for a solar cell module,
It is preferable to use a non-stretched (unstretched) type. Further, in the present invention, it is desirable to use a polypropylene resin having a composition having a relatively high melting point as the above polypropylene resin, and thus, in general, 150 to 170 ° C., 20
When a solar cell module is manufactured through a lamination process of thermocompression bonding for about 30 minutes, heat shrinkage is small and stable, and hydrolysis of polypropylene resin does not occur. It has an advantage that it is also excellent in durability during a test.

In the present invention, a heat-resistant polypropylene resin film containing a colorant, an ultraviolet absorber and a light stabilizer, or a heat-resistant polypropylene resin film containing a colorant, an ultraviolet absorber and a light stabilizer. When the resin film is laminated by dry lamination, the surface thereof may be optionally subjected to surface modification pretreatment such as corona discharge treatment, ozone treatment, or plasma discharge treatment in advance. In addition, in the present invention, in addition to the above polypropylene-based resin, if necessary, for example, a polyethylene-based resin, a resin compatible with the polypropylene-based resin such as others, may be optionally added for modification. Is something that can be done. Thus, in the present invention, by using the polypropylene resin as described above, when a solar cell module is manufactured, it is excellent in tight adhesion with a filler layer and the like, and further, water, oxygen, etc. The moisture-proof property to prevent the invasion of water is remarkably improved, its long-term performance deterioration is minimized, and in particular, hydrolysis deterioration is prevented, and it is extremely durable and has excellent protection ability, and more A low-cost and safe solar cell module can be constructed.

Next, as the ultraviolet absorber constituting the back surface protection sheet for solar cell module according to the present invention, a heat energy which is harmless in the molecule by absorbing harmful ultraviolet rays in the sunlight. To prevent the active species of photodegradation initiation in the polymer from being excited, for example, benzophenone-based, benzotriazole-based, sulphate-based, acrylonitrile-based, metal complex salt-based, Hindered amine type,
Ultra fine particle titanium oxide (particle size, 0.01-0.06μ
m) or ultrafine zinc oxide (0.01 to 0.04μ)
One or more inorganic UV absorbers such as m) can be used. It is desirable that the polypropylene resin composition be used by adding about 0.1% to 10% by weight, preferably about 0.3% to 10% by weight, in the polypropylene resin composition.

Further, as the light stabilizer constituting the back surface protection sheet for solar cell module according to the present invention, the excited active species which is the photodegradation initiation source in the polymer is trapped,
It prevents light deterioration, and for example, one or more light stabilizers such as hindered amine compounds, hindered piperidine compounds, and the like can be used. It is desirable that the polypropylene resin composition be used by adding about 0.1% to 10% by weight, preferably about 0.3% to 10% by weight, in the polypropylene resin composition.

Further, as the coloring agent constituting the back surface protection sheet for solar cell module according to the present invention, for example, the sunlight transmitted through the solar cell module is reflected or diffused. Light reflective, for reuse
It is added for the purpose of imparting light diffusivity and the like, and further imparting designability, for example, various inorganic or organic dyes, pigments such as white, black, blue, red, etc. It is possible to use one kind or a mixture of two or more kinds of colorants such as. Thus, in the present invention, as the coloring agent, for example, basic lead carbonate, basic lead sulfate,
White pigments such as basic lead silicate, zinc white, zinc sulfide, lithopone, antimony trioxide, anatas type titanium oxide, rutile type titanium oxide, etc., or carbon black (channel or furnace), etc. It is particularly preferable to use one or more of the above black pigments. The amount used is about 0.1 to 30% by weight, preferably 0.5 to 10% by weight, based on the resin.
It is desirable to use by adding about wt%.

Thus, in the present invention, the heat-resistant polypropylene-based resin composition containing the ultraviolet absorber and the light stabilizer first comprises a heat-resistant polypropylene-based resin as a main component, and the One or more of the agents,
Also, one or more light stabilizers are added, and if necessary, a plasticizer, an antioxidant, an antistatic agent, a crosslinking agent, a curing agent, a filler, a lubricant, a reinforcing agent, and a reinforcing agent. , Flame retardant, flameproofing agent, foaming agent, antifungal agent, coloring agent such as pigments and dyes, and one or more kinds of other additives, and further, if necessary, a solvent or a diluent. Etc. are added and sufficiently kneaded to prepare a heat resistant polypropylene resin composition. Further, in the present invention, the heat-resistant polypropylene-based resin composition containing a coloring agent, an ultraviolet absorber, and a light stabilizer includes, first, a heat-resistant polypropylene-based resin as a main component, and a coloring agent 1 or 2 or more, 1 or 2 or more of an ultraviolet absorber, and 1 or 2 or more of a light stabilizer are added, and further, if necessary, a plasticizer, an antioxidant, an electrostatic charge. Inhibitor, cross-linking agent, curing agent, filler, lubricant, reinforcing agent, reinforcing agent, flame retardant, flame retardant, foaming agent,
One or more kinds of additives such as antifungal agent and others are optionally added, and further, if necessary, a solvent, a diluent and the like are added and sufficiently kneaded to form a heat resistant polypropylene resin composition. Prepare. Furthermore, in the present invention, as a heat-resistant polypropylene resin-containing paint or ink composition containing an ultraviolet absorber and a light stabilizer, first, a heat-resistant polypropylene is used as a main component of a vehicle for paint or ink. 1 type or 2 types or more of the system resin is used, 1 type or 2 types or more of the ultraviolet absorber and 1 type or 2 types or more of the light stabilizer are added thereto, and further, if necessary, Plasticizer, antioxidant, antistatic agent, crosslinking agent, curing agent, filler, lubricant, reinforcing agent, reinforcing agent, flame retardant, flameproofing agent, foaming agent,
One or more kinds of additives such as antifungal agent and other additives are optionally added, and further, a solvent, a diluent and the like are added and sufficiently kneaded to prepare a coating material or an ink composition.

Next, in the present invention, the surface protection sheet for a solar cell module, such as a glass plate, which constitutes the solar cell module according to the present invention, has solar light transmittance, insulation, etc. Furthermore, it has weather resistance, heat resistance, light resistance, water resistance, wind pressure resistance, hail resistance, chemical resistance, moisture resistance, stain resistance,
It has various characteristics such as other properties, is excellent in physical or chemical strength, toughness, etc., is extremely rich in durability, and is said to protect solar cell elements as photovoltaic elements.
It is necessary to have excellent scratch resistance and shock absorption. Specific examples of the surface protection sheet for the solar cell module include, for example, well-known glass plates, and further, for example, polyamide-based resins (various nylons), polyester-based resins, Polyethylene resin, polypropylene resin, cyclic polyolefin resin, polystyrene resin, (meth) acrylic resin, polycarbonate resin, acetal resin, cellulose resin,
Various other resin films or sheets can be used. As the resin film or sheet, for example, a biaxially stretched resin film or sheet can also be used. In addition, in the above-mentioned resin film or sheet, the film thickness is 12 to
It is preferably about 200 μm, more preferably about 25 to 150 μm.

Next, in the present invention, a solar cell module
As the filler layer such as ethylene-vinyl acetate copolymer sheet constituting the polymer, sunlight is required to be incident, and it is necessary to have transparency because it transmits and absorbs the sunlight. It is also necessary to have a surface protection sheet for a battery module and an adhesive property with a solar cell element or the like as a photovoltaic element, and further to improve the surface smoothness of the solar cell element as a photovoltaic element. It is necessary to have excellent scratch resistance, shock absorption and the like, since it has thermoplasticity to fulfill the function of holding it, and further it protects the solar cell element as a photovoltaic element. Specifically, examples of the filler layer include ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid, or methacrylic acid copolymer, polyethylene resin, polypropylene resin, polyethylene or polypropylene. Acid-modified polyolefin resin, polyvinyl butyral resin, silicone resin, epoxy resin, which is obtained by modifying the above polyolefin resin of acrylic acid, itaconic acid, maleic acid, fumaric acid, etc. It is possible to use one kind or a mixture of two or more kinds of resins such as resins, (meth) acrylic resins and the like. In the present invention, the resin constituting the filler layer, in order to improve the heat resistance, light resistance, weather resistance such as water resistance, etc., within the range not impairing its transparency, for example, cross-linked. Additives such as agents, thermal antioxidants, light stabilizers, ultraviolet absorbers, photooxidants, and the like can be arbitrarily added and mixed. Therefore, in the present invention, considering the weather resistance such as light resistance, heat resistance, and water resistance, the filler on the incident side of sunlight is preferably a silicone resin or an ethylene-vinyl acetate resin. It is a material. The thickness of the filler layer is about 200 to 1000 μm, preferably 3
About 50 to 600 μm is desirable.

Next, in the present invention, the solar cell module
As a solar cell element as a photovoltaic element that constitutes a module, a conventionally known one, for example, a single crystal silicon solar cell element, a crystalline silicon solar electronic element such as a polycrystalline silicon solar cell element, a single junction type or Amorphous silicon solar cell elements of tandem structure type, gallium arsenide (GaAs) and indium phosphide (InP) II
I-V group compound semiconductor solar electronic device, cadmium tellurium (CdTe) and copper indium selenide (CuInSe)
II-VI group compound semiconductor solar electronic devices such as ₂ ) and others can be used. Furthermore, 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, the solar cell element is formed of, for example, a glass substrate, a plastic substrate, a metal substrate, or another substrate on which crystalline silicon such as a pn junction structure or p-
Amorphous silicon having an in junction structure or the like and an electromotive force portion such as a compound semiconductor are formed to form a solar cell element.

In the present invention, the solar cell element as a photovoltaic element constituting the above-mentioned solar cell module has at least water vapor, oxygen gas, decomposition products, on the surface of the solar cell element. Alternatively, a solar cell element with a protective layer provided with a barrier layer that blocks the permeation of one or more additives can be used. The above-mentioned solar cell element with a protective layer will be described in more detail. As the solar cell element that constitutes the solar cell element with a protective layer, each of the above-exemplified solar cell elements can be similarly used. Thus, in the present invention, the solar cell element is formed on the substrate such as a glass substrate, a plastic substrate, a metal substrate, etc. by pn
A solar cell element is formed by forming crystalline silicon having a junction structure, amorphous silicon having a pin junction structure, or an electromotive force portion such as a compound semiconductor. And
In the present invention, the surface opposite to the substrate constituting the solar cell element, that is, the surface constituting the solar cell element,
Alternatively, a barrier layer or the like is formed on the surface of the transparent conductive film. Of course, in the present invention, the barrier layer can be provided on the other surface, and two layers can be provided on both sides of the barrier layer.

Next, the barrier layer constituting the above-mentioned solar cell element with a protective layer will be described. As the barrier layer, for example, at least water vapor, oxygen gas, and deterioration or decomposition of the filler constituting the filler layer are described. Or one or more substances such as additives that elute from the filler layer, a surface protection sheet for a solar cell module, a back surface protection sheet for a solar cell module, or a filler layer. It is intended to prevent the solar cell element itself from being adversely affected by penetrating the above. Therefore, in the present invention, as the above-mentioned barrier layer,
It can be directly or directly provided on the surface of the solar cell element and has the property of transmitting sunlight, and further, at least water vapor, oxygen gas, and a degradation or decomposition product of the filler constituting the filler layer Alternatively, it is possible to use a coating having a property capable of preventing the permeation of one or more substances such as additives eluted from the filler layer. Specifically, in the present invention, as the barrier layer, for example,
A resin film made of various resins, a barrier resin film made of a barrier resin, a vapor deposition film of an inorganic oxide, a resin film provided with a vapor deposition film of an inorganic oxide, and a composition made of a polycondensate obtained by hydrolysis of a silicon compound. A coating film composed of a coating film, a metal-containing gas barrier coating film, or a composite film composed of two or more of them can be used.

First, in the present invention, the resin film constituting the above barrier layer will be described. Examples of the resin film include polyethylene resin, polypropylene resin, cyclic polyolefin resin, fluorine resin and polystyrene resin. , Acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyvinyl chloride resin,
Polyvinylidene chloride resin, polyvinyl acetate resin, polyvinyl alcohol resin, ethylene-vinyl alcohol copolymer, poly (meth) acrylic resin, polycarbonate resin, polyethylene terephthalate, Polyester resins such as polyethylene naphthalate, polyamide resins such as various nylons, polyimide resins, polyamide imide resins, polyaryl phthalate resins, silicone resins, polysulfone resins, polyphenylene sulfide resins. Resin, polyethersulfone resin, polyurethane resin, phenol resin, aminoplast resin such as melamine resin or urea resin, xylene resin, epoxy resin, acetal resin, cellulose resin Resin films made of various resins such as, and the like can be used. In the present invention, as a method of forming the resin film as the barrier layer, for example, one or more kinds of the above resins are used, and a film or sheet of the resin is prepared by a conventional method. Then, a film or sheet of the resin is laminated on the surface of the solar cell element, for example, via a laminate adhesive layer or the like, or a dry laminate lamination method, or an anchor coat. It can be formed by a melt-extrusion laminating method in which the resin is laminated through a melt-extruded resin layer or the like through a coating agent layer or the like.
Alternatively, in the present invention, one or more of the above resins are used to prepare a resin composition containing this as a main component, and then the above resin composition is applied to the surface of the solar cell element, The resin film can be formed by using an ordinary coating method or printing method, or by using a melt extrusion coating method. In the present invention, the thickness of the resin film forming the barrier layer is preferably about 1 to 100 μm, more preferably about 5 to 50 μm.

Next, in the present invention, the barrier resin film constituting the above barrier layer will be described. As the barrier resin film, a resin having a property of preventing permeation of oxygen gas or water vapor, for example, Polyvinyl alcohol resin, ethylene-vinyl alcohol copolymer, M
It can be formed using a resin having a barrier property such as XD6 nylon resin, polyester resin, or the like. In the present invention, as a method for forming the above-mentioned barrier resin film, for example, one or more kinds of the above-mentioned resins are used, and a film or sheet of the resin is produced by a conventional method. And then a film or sheet of the resin
On the surface of the solar cell element in the same manner as described above, for example,
A dry laminate laminating method of laminating with an adhesive layer for laminate or a melt extrusion laminating method of laminating with a melt extruded resin layer etc. with an anchor coating agent layer etc. is used. Can be formed. Alternatively, in the present invention, one or more of the above resins are used to prepare a resin composition containing this as a main component, and then the surface of the solar cell element is subjected to a usual coating method or printing method. Etc., or by using a melt extrusion coating method or the like, the barrier resin layer can be formed. Further, in the present invention, one or more of the above resins are used to prepare a resin composition containing this as a main component, and then,
For example, the above-mentioned resin composition is applied to one surface of an ordinary resin film or sheet such as a polyester resin film or a polyamide resin film by using an ordinary coating method or printing method. Alternatively, a barrier resin film is formed using a melt extrusion coating method or the like, and then a resin film or sheet having the barrier resin film is formed on the surface of the solar cell element in the same manner as described above. It can be formed by using the dry laminate laminating method, or the melt extrusion laminating method. In the present invention, the thickness of the barrier resin film forming the barrier layer is 1 to 1
It is desirable that the particle size is about 00 μm, preferably about 5 to 30 μm.

Next, in the present invention, the vapor deposition film of the inorganic oxide which constitutes the barrier layer will be described. Examples of the vapor deposition film of the inorganic oxide include silicon oxide and
A deposited film of an inorganic oxide such as aluminum oxide, magnesium oxide, calcium oxide, potassium oxide, tin oxide, boron oxide, titanium oxide, lead oxide, zirconium oxide, yttrium oxide, or the like can be used.
Thus, in the present invention, as a method for providing a vapor deposition film of inorganic oxide as the above-mentioned barrier layer, for example, a physical vapor phase such as a vacuum vapor deposition method, a sputtering method, an ion plating method or the like is formed on the surface of the solar cell element. Growth method ((Physica
l VaporDeposition method, PVD method),
Alternatively, for example, a chemical vapor deposition method such as a plasma chemical vapor deposition method, a thermochemical vapor deposition method, a photochemical vapor deposition method (Ch
the electronic vapor deposition method,
A vapor deposition film of an inorganic oxide can be formed and provided using a CVD method or the like. In the present invention, the thickness of the vapor deposition film of the above-mentioned inorganic oxide is preferably about 50 to 5000Å, and more preferably 100 to 1000Å.

Next, in the present invention, a resin film provided with a vapor deposition film of an inorganic oxide which constitutes the above barrier layer will be described. As the resin film provided with a vapor deposition film of such an inorganic oxide, for example, Use a resin film provided with a deposited film of an inorganic oxide such as silicon oxide, aluminum oxide, magnesium oxide, calcium oxide, potassium oxide, tin oxide, boron oxide, titanium oxide, lead oxide, zirconium oxide, yttrium oxide, etc. be able to. Thus, in the present invention, as a method for producing a resin film provided with a vapor deposition film of an inorganic oxide, for example, on one surface of a resin film or a sheet, for example, in the same manner as described above, a vacuum vapor deposition method is used. , A physical vapor deposition method such as a sputtering method or an ion plating method, or a chemical vapor deposition method such as a plasma chemical vapor deposition method, a thermochemical vapor deposition method, or a photochemical vapor deposition method. A deposited film of an inorganic oxide can be formed.

Specifically, a metal oxide is used as a raw material, and a vacuum vapor deposition method in which the metal oxide is heated and vapor-deposited on a resin film or sheet is used, or a metal or a metal oxide is used as a raw material. , An oxidation reaction deposition method of introducing oxygen to oxidize and deposit on a resin film or sheet, and a plasma-assisted oxidation reaction deposition method of further assisting the oxidation reaction with plasma. A vapor-deposited thin film can be formed. In the above, as a heating method of the vapor deposition 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. Further, in the present invention, a vapor deposition monomer such as an organic silicon compound is formed on one surface of the resin film or sheet.
Using a gas as a raw material, an inert gas such as argon gas or helium gas as a carrier gas, and an oxygen gas or the like as a reaction gas with a monomer gas for vapor deposition, a low temperature plasma generator, etc. A vapor deposition film of an inorganic oxide such as silicon oxide can be formed by using the low temperature plasma chemical vapor deposition method (CVD method) used. In the above,
As the low temperature plasma generator, for example, a generator of high frequency plasma, pulse wave plasma, microwave plasma or the like may be used, and in the present invention,
In order to obtain highly active and stable plasma, it is desirable to use a high frequency plasma generator.

In the present invention, a concrete example of the method for forming a thin film of an inorganic oxide by physical vapor deposition is shown in FIG. 3. FIG. Is. As shown in FIG. 3, in the vacuum chamber 22 of the take-up type vacuum vapor deposition device 21, a resin film or sheet fed from the unwinding roll 23.
The guide 24 is guided to the cooled coating drum 27 via guide rollers 25 and 26. Then, on the resin film or sheet 24 guided on the cooled coating drum 27, a vapor deposition source 29 heated by a crucible 28, for example, metal aluminum or aluminum oxide is used. Is further evaporated, and if necessary, oxygen gas or the like is jetted from the oxygen gas outlet 30 and while supplying this, through the masks 31, 31, for example,
Form a deposited film of inorganic oxide such as aluminum oxide,
Next, in the above, for example, the resin film or sheet 24 on which the vapor deposition film of the inorganic oxide such as aluminum oxide is formed is sent out through the guide rolls 32 and 33 and wound up on the winding roll 34. As a result, a vapor deposition film of an inorganic oxide can be formed by physical vapor deposition. In addition, in the present invention, first, a vapor deposition film of the inorganic oxide of the first layer is formed by using the above-described winding type vacuum vapor deposition device, and then, the vapor deposition film of the inorganic oxide is similarly formed. An inorganic oxide vapor-deposited film is further formed on the above, or the wound-up type vacuum vapor deposition apparatus as described above is used to connect the two in series to continuously vapor-deposit the inorganic oxide. By forming the film, it is possible to form a vapor deposition film of an inorganic oxide composed of a multilayer film of two or more layers.

In the above, as the vapor deposition film of the inorganic oxide, basically any thin film obtained by vapor deposition of a metal oxide can be used. For example, silicon (Si), aluminum (Al), magnesium (Mg). , Calcium (C
a), potassium (K), tin (Sn), sodium (N
It is possible to use a vapor deposition film of an oxide of a metal such as a), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), or yttrium (Y). Thus, preferred are silicon (Si), aluminum (A
Examples thereof include vapor deposited films of metal oxides such as l).
Thus, the above-mentioned vapor-deposited film of metal oxide can be referred to as a metal oxide such as silicon oxide, aluminum oxide, and magnesium oxide, and the notation is, for example, SiO _x , AlO _x. , MO such as MgO _x
X (However, in the formula, M represents a metal element, and the value of X is
Each metal element has a different range. ). Further, the range of the value of X is silicon (S
i) is 0 to 2, aluminum (Al) is 0 to 1.
5, magnesium (Mg) is 0 to 1, calcium (C
a) is 0 to 1, potassium (K) is 0 to 0.5, tin (Sn) is 0 to 2, and sodium (Na) is 0 to 0.
5, boron (B) is 0 to 1.5, titanium (Ti) is
0-2, lead (Pb) is 0-1, zirconium (Zr)
Can range from 0 to 2 and yttrium (Y) can range from 0 to 1.5. In the above, when X = 0,
It is a perfect metal and is not transparent and cannot be used at all, and the upper limit of the range of X is a completely oxidized value. In the present invention, generally, other than silicon (Si) and aluminum (Al), there are few examples used, and silicon (Si) is 1.0 to 2.0 and aluminum (A).
As l), those having a value in the range of 0.5 to 1.5 can be used. In the present invention, the film thickness of the vapor deposition film of the inorganic oxide as described above varies depending on the metal used, the type of the metal oxide, and the like, but is, for example, 50 to 20.
It is desirable to form it by arbitrarily selecting it in the range of 00Å, preferably in the range of 100 to 1000Å. Further, in the present invention, the metal used as the vapor deposition film of the inorganic oxide, or the metal oxide to be used, is used in one kind or in a mixture of two or more kinds. It is also possible to configure a vapor deposition film.

Next, in the present invention, a method for forming a vapor deposition film of an inorganic oxide by the above-mentioned low temperature plasma chemical vapor deposition method will be specifically described by way of an example, and FIG. 4 shows the above plasma. FIG. 1 is a schematic configuration diagram of a low-temperature plasma chemical vapor deposition apparatus showing an outline of a method for forming an inorganic oxide vapor deposition film by chemical vapor deposition. In the present invention, as shown in FIG. 4 above, a resin film or sheet 44 is fed out from an unwinding roll 43 arranged in a vacuum chamber 42 of a plasma enhanced chemical vapor deposition apparatus 41. , The resin film or sheet 44 is cooled at a predetermined speed through an auxiliary roll 45, and the electrode drum 4 is cooled.
It is conveyed on the 6th circumferential surface. Thus, in the present invention, oxygen gas, inert gas, monomer gas for vapor deposition of organic silicon compounds and the like are supplied from the gas supply devices 47 and 48, the raw material volatilization supply device 49 and the like, and from these, The mixed gas composition for vapor deposition was adjusted, and then the mixed gas composition for vapor deposition was introduced into the vacuum chamber-42 through the raw material supply nozzle 50, and then was conveyed onto the peripheral surface of the cooling / electrode drum 46. Plasma is generated by the glow discharge plasma 51 on the resin film or sheet 44, and the mixed gas for vapor deposition is reacted in the plasma atmosphere to form a vapor deposited film of inorganic oxide such as silicon oxide. , To make a film. In the present invention, the cooling / electrode drum 46 is
Predetermined electric power is applied from a power source 52 arranged outside the chamber, and a magnet 53 is arranged in the vicinity of the cooling / electrode drum 46 to promote plasma generation. The resin film or sheet 44 on which a vapor deposited film of an inorganic oxide such as silicon oxide is formed by
The film can be wound on the winding roll 55 via the auxiliary roll 54 to produce a deposited film of an inorganic oxide by the plasma chemical vapor deposition method according to the present invention. In the figure, 56 represents a vacuum pump.

It is needless to say that the above-mentioned exemplification is one example, and the present invention is not limited thereby. Although not shown, in the present invention, the inorganic oxide vapor deposition film may be not only one layer of the inorganic oxide vapor deposition film but also a multi-layered film in which two or more layers are laminated and used. The materials may be used alone or as a mixture of two or more kinds, and it is also possible to form a vapor deposition film of an inorganic oxide in which different materials are mixed. Further, in the present invention, using the low temperature plasma chemical vapor deposition apparatus as described above, first, a vapor deposition film of an inorganic oxide of the first layer is formed, and then, the vapor deposition of the inorganic oxide is similarly performed. An inorganic oxide vapor-deposited film is further formed on the film, or the low temperature plasma-enhanced chemical vapor deposition apparatus as described above is used to connect the two in series to continuously form the inorganic oxide. By forming the vapor-deposited film of, it is possible to form a vapor-deposited film of an inorganic oxide composed of a multilayer film of two or more layers.

In the above, as the monomer gas for vapor deposition of an organic silicon compound or the like which forms 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, etc. can be used. In the present invention, among the above-mentioned organic silicon compounds, it is preferable to use 1.1.3.3-tetramethyldisiloxane or hexamethyldisiloxane as a raw material because of its handleability and vapor deposition film formed. It is a particularly preferable raw material in view of the characteristics and the like. Further, in the above, as the inert gas, for example, argon gas, helium gas or the like can be used.

In the present invention, in the silicon oxide vapor-deposited film formed as described above, a monomer gas such as an organic silicon compound chemically reacts with oxygen gas and the reaction product is brought into close contact with the plastic sheet. It can be applied to form a dense, flexible thin film, which is usually formed by the general formula SiO _x (however,
X represents a number of 0 to 2) and is a continuous vapor deposition film mainly composed of silicon oxide. And Thus, the deposited film of the silicon oxide, transparency, from the viewpoint of the barrier property and the like, the general formula SiO _X (provided that, X represents represents. A number of 1.3 to 1.9) are represented by It is preferable that the thin film mainly comprises a vapor-deposited film of silicon oxide. In the above, the value of X changes depending on the molar ratio of the monomer gas and the oxygen gas, the energy of plasma, etc. Generally, the smaller the value of X, the smaller the gas permeability, but It becomes yellowish and has poor transparency. Further, the above-described vapor-deposited film of silicon oxide has silicon (Si) and oxygen (O) as essential constituent elements, and further, one of carbon (C) and hydrogen (H), or both elements. Consisting of a vapor-deposited film of silicon oxide containing as a trace constituent element, and having a film thickness of 50 Å ~
It is in the range of 2000Å, and the constituent ratios of the above essential constituent elements and trace constituent elements are continuously changing in the film thickness direction. Further, the above-mentioned vapor-deposited film of silicon oxide is characterized in that, when a compound made of carbon is contained, the carbon content is reduced in the depth direction of the film thickness.

Thus, in the present invention, for the above-mentioned vapor-deposited film of silicon oxide, for example, an X-ray photoelectron spectrometer (Xr
ay Photoelectron Spectros
copy, XPS), secondary ion mass spectrometer (Sec)
onary Ion Mass Spectrosc
The above physical properties are confirmed by performing elemental analysis of the vapor-deposited film of silicon oxide by using a method of analyzing by ion etching in the depth direction using a surface analyzer such as can do. Further, in the present invention, the film thickness of the vapor-deposited film of silicon oxide is preferably about 50Å to 2000Å, and specifically, the film thickness is preferably about 100 to 1000Å. Then, in the above, 1000Å, and further 20
If it is thicker than 00Å, cracks and the like are likely to occur in the film, which is not preferable.
When it is less than 0Å, it is difficult to exert the effect of barrier property, which is not preferable. In the above, the film thickness can be measured by the fundamental parameter method using, for example, a fluorescent X-ray analyzer (model name, RIX2000 type) manufactured by Rigaku Co., Ltd. Further, in the above, as a means for changing the film thickness of the above-mentioned vapor-deposited film of silicon oxide, increasing the volumetric velocity of the vapor-deposited film, that is, a method of increasing the amount of monomer gas and oxygen gas or a vapor deposition rate is used. It can be done by a method of slowing down.

By the way, in the present invention, as the vapor deposited film of the inorganic oxide according to the present invention, for example, the vapor deposited film of different kinds of inorganic oxides is used by using both the physical vapor deposition method and the chemical vapor deposition method in combination. It is also possible to form and use a composite film composed of layers or more. Then, as a composite film composed of two or more layers of the above-mentioned vapor deposition films of different kinds of inorganic oxides,
A vapor-deposited film of an inorganic oxide, which is dense and rich in flexibility and can relatively prevent the occurrence of cracks, is provided on a resin film or sheet by a chemical vapor deposition method, and then the inorganic oxidation film is formed. It is desirable to provide a vapor deposition film of an inorganic oxide by physical vapor deposition on the vapor deposition film of a substance to form a vapor deposition film of an inorganic oxide composed of a composite film composed of two or more layers. In the present invention, of course, contrary to the above, on the resin film or sheet, a vapor deposition film of an inorganic oxide is first provided by a physical vapor deposition method, and then chemical vapor deposition is performed. By forming a dense, flexible, vapor-deposited inorganic oxide film that can relatively prevent the occurrence of cracks, a vapor-deposited inorganic oxide film composed of a composite film composed of two or more layers is formed. It is also possible. In the present invention, in order to improve the close adhesion, affinity, etc. with the filler layer described later, the vapor deposition film surface of the inorganic oxide, for example, by ionizing a gas by arc discharge, It is possible to form a plasma-treated surface by using a plasma surface treatment method or the like for surface modification using generated plasma gas, or a corona-treated surface by a corona discharge treatment method or the like.

Next, in the present invention, the resin film constituting the above-mentioned resin film provided with the vapor deposition film of inorganic oxide is basically used for forming the vapor deposition film of inorganic oxide. Withstands vapor deposition conditions, etc., and has excellent close adhesion to the vapor deposited film of those inorganic oxides, and can be well retained without impairing the properties of those films, and has strength as a base material. It is possible to use various resin films or sheets having excellent durability. In particular,
Examples of the film or sheet of various resins described above include polyethylene resin, polypropylene resin, cyclic polyolefin resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene. Polyester resin such as copolymer (ABS resin), polyvinyl chloride resin, fluorine resin, poly (meth) acrylic resin, polycarbonate resin, polyethylene terephthalate, polyethylene naphthalate , Polyamide resins such as various nylons, polyimide resins, polyamide imide resins, polyaryl phthalate resins, silicone resins, polysulfone resins, polyphenylene sulfide resins, polyethylene sulfone resins, polyurethane resins Resin, acetal resin, cell B - scan resin, various resins other such film or sheet - may be used and. In the present invention, among the above-mentioned resin films or sheets, a fluorine-based resin sheet, a cyclic polyolefin-based resin sheet, a polycarbonate-based resin sheet, a poly (meth) acrylic resin Sheet, polyamide resin sheet,
Alternatively, it is preferable to use a polyester resin sheet.

In the present invention, the surface of the film or sheet of various resins is, if necessary, in advance, in order to improve the close adhesion to the vapor deposition film of the inorganic oxide and the like.
A desired surface treatment layer can be provided. In the present invention, as the surface treatment layer, for example, corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment using chemicals, Pre-treatment such as other is arbitrarily given,
For example, a corona treatment layer, an ozone treatment layer, a plasma treatment layer, an oxidation treatment layer, etc. can be formed and provided. The above surface pretreatment may be carried out in a separate step, and in the case of the surface pretreatment such as low temperature plasma treatment or glow discharge treatment, for example, before forming the above-mentioned inorganic oxide vapor deposition film or the like. As a treatment, in-line treatment can be performed as a pretreatment, 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 close adhesion between various resin films or sheets and the vapor-deposited film of the inorganic oxide. As another method, for example, a primer-coating agent layer and an undercoat are previously formed on the surface of various resin films or sheets.
A coating agent layer, an anchor coating agent layer, an adhesive layer, a vapor deposition anchor coating agent layer or the like may be optionally formed to form a surface treatment layer. Examples of the pretreatment coating agent layer include polyester resins, polyamide resins, polyurethane resins, epoxy resins, and phenol resins.
Resin, (meth) acrylic resin, polyvinyl acetate resin, polyolefin resin such as polyethylene or polypropylene, or a copolymer or modified resin thereof,
A resin composition containing a cellulosic resin or the like as a main component of the vehicle can be used.

Next, in the present invention, a resin film provided with the above-mentioned vapor deposition film of inorganic oxide is used, and this is applied to the surface of, for example, a solar cell element in the same manner as described above for the adhesive for lamination. A dry barrier lamination method of laminating via a layer or the like, or a melt extrusion laminating method of laminating using a melt extrusion resin layer or the like via an anchor coating agent layer or the like to form a barrier. A resin film provided with a vapor deposition film of an inorganic oxide as a layer can be formed on the surface of the solar cell element.

Next, in the present invention, a coating film made of a composition comprising a polycondensate obtained by hydrolysis of the silicon compound constituting the barrier layer will be described.
In order to form such a coating film, first, a silicon compound is used as a main component, and the raw material thereof is directly or dissolved in a suitable solvent such as ethanol or isopropanol, and then it is stoichiometrically. Required for the above, preferably 1 part or a few parts excess of water, to bring about hydrolysis to prepare a composition comprising a polycondensate resulting from the hydrolysis. The above hydrolysis is generally performed at -20 to 130 ° C, preferably
It is preferably carried out at a temperature of 0 ° C. to 30 ° C., or the boiling point of the solvent used selectively. Incidentally, in the above, as the best method of contacting with water,
It depends on the reactivity of the raw materials used. Therefore, for example, the dissolved raw material can be slowly dropped into excess water, or water can be added to the selectively dissolved raw material all at once or in several portions. Further, instead of adding water as it is, it is advantageous to use an organic or inorganic solvent containing water and introduce water into the reaction mixture instead. In many cases, it is particularly suitable to introduce water into the reaction mixture using adsorbents containing water, such as molecular sieves, and organic solvents containing water, such as 30% ethanol. I know it. Water can also be added by a reaction that forms water, for example, a reaction that forms an ester from an acid and an alcohol. In the case of using a solvent, in addition to the above-mentioned lower aliphatic alcohol which can be effectively used, ketones, preferably lower dialkyl ketones such as acetone and methyl isobutyl ketone, esters, preferably diethyl ether. Suitable are lower dialkyl ethers such as ter, tetrahydrofuran (THF), amides, esters, especially ethyl acetate, dimethylformamide and mixtures thereof.

The above-mentioned polycondensation by hydrolysis can be selectively carried out by adding a catalyst, for example, a compound releasing a proton or a hydroxyl ion, or amines. Suitable catalysts include organic or inorganic acids such as hydrochloric acid or acetic acid, ammonia, alkali metal hydroxides and alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide or calcium hydroxide. And organic or inorganic salts such as and amines that are soluble in the reaction medium, such as lower alkyl amines or altanol amines. Volatile acids and bases,
Particularly, hydrochloric acid, ammonia and triethylamine are particularly preferable. The total concentration of catalyst may be, for example, up to 3 mol per liter. It is not necessary that all of the starting compounds be already present at the beginning of hydrolysis (polycondensation), in fact, in certain cases, only some of these compounds are first contacted with water and the rest of the compounds are It may be advantageous to add it later. In order to avoid precipitation as much as possible during polycondensation by hydrolysis, it is preferable to add water in several steps, for example, in three steps. In the first stage, for example, one-tenth to one-twentieth of the stoichiometrically required amount of water by hydrolysis is added. After stirring for a short time, one-fifth to one-tenth of the stoichiometric amount of water is added, and after stirring for a further short time, an amount of water in a stoichiometric excess is finally present. Add water. The polycondensation time by hydrolysis depends on the specific raw material components and their quantitative ratio, the catalyst used selectively, the reaction temperature, and the like. Generally, polycondensation by hydrolysis is carried out at atmospheric pressure, but it can also be carried out under pressure or under reduced pressure. When the addition of water is complete, the mixture is stirred, preferably for a long time, for example 2-3 hours, at room temperature or slightly elevated temperature to prepare a composition consisting of the polycondensate from the hydrolysis of the silicon compound.

Next, in the present invention, the composition prepared as described above is applied to, for example, a floating knife coat method, a knife over roll coat method, an inverted knife coat method, a squeeze knife. Zlucole coat method, reversal roll coat method, roll coat method, gravure roll coat method, kiss roll coat method, air blade coat method, dip coat method Coating method, flow coating method, spin coating method, spray coating method, bar coating method, curtain coating method, etc., or gravure printing, offset printing, According to the present invention, printing or coating is applied to the surface of the solar cell element by using a printing method such as silk screen printing, transfer printing, etc., followed by drying and further aging treatment. A coating film can be formed. In the above, the thickness of the coating film is preferably 0.1 to 75 g / m ² (dry state), more preferably 1.0 to 50 g / m ² (dry state).

In the present invention, the composition of the composition comprising a polycondensate obtained by hydrolysis of the above silicon compound is used.
When the coating film is cured by irradiation with a thermal means or ionizing radiation, it is preferable to add an initiator or the like in advance to the composition consisting of a polycondensate obtained by hydrolysis of a silicon compound. Is. As the above initiator, a commercially available photopolymerization reaction initiator can be used.
Examples of these initiators include, for example, Irgacure 185 (1-hydroxycyclohexyl phenyl ketone) and Irgacure 500 manufactured by Ciba-Geigy, Switzerland.
(1-hydroxycyclohexyl phenyl ketone +
Benzophenone), and other Irgacure type photoinitiators, Glocure 1173, 1116, 139
6, 1174 and 1020 (Merck, Switzerland),
Benzophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone,
Benzoin, 4.4'-dimethoxybenzoin, benzoin ethyl ether, benzoin isopropyl
Ether, benzoin dimethyl ether, 1.1.
1-Trichloroacetophenone, diethoxyacetophenone and dibenzosuberone can be used.
Suitable thermal initiators can be used, in particular, organic peroxides in the form of diacyl peroxides, peroxydicarbonates, alkyl peresters, dialkyl peroxides, perketals, ketones and alkyl peroxides. .
Specific and preferred examples of thermal initiators can be dibenzoyl peroxide, tert-butyl perbenzoate and azobisisobutyronitrile. Of course, it is also possible to use an initiator that initiates the ionic polymerization reaction. In particular, it includes a group R'having an epoxy group (eg, glycidyloxypropyltrimethoxysilane),
It has been found that a UV initiator that initiates a cationic polymerization reaction is effective for the compound represented by the general formula (1) described below. In these cases, the cation cure results under the same conditions are often better than the free radical initiator cure results. The reaction initiator can be added to the composition in a usual amount, for example, 30 to 50% by weight.
The initiator can be added in an amount of 0.5 to 2% by weight (based on the total amount) in the composition containing the solid content of.

In the present invention, the coating film may be cured by coating, printing, drying and then curing. The coating film can then be cured by known methods, either thermally or by irradiation (eg, using a UV lamp, laser, etc.), depending on the form of initiator used. . Thermal curing is particularly advantageous in the case of coating films containing groups R'having an epoxy group, which will be described later, while coating films containing groups R'having unsaturated C--C bonds are preferred. It has been found that curing by irradiation is usually more advantageous.

In the four inventions, the above silicon is used.
The compound is represented by the general formula R'SiR ₃(However, in the formula,
R'is hydrolytically stable and can be heated and / or charged.
Represents a group which can be polymerized by irradiation with releasing radiation, and R is OH
Represents a group and / or a group susceptible to hydrolysis. )so
Use one or more of the silicon compounds represented
be able to. In the above, the general formula R'SiR₃In
R'is an epoxy group or a C-C double bond
It is desirable to consist of a group containing the atomic group
It Specific examples of the group containing the above epoxy atomic group include
Is a glycidyloxyalkyl group, especially an alkyl moiety
Is a group having 1 to 4 carbon atom groups, and is particularly preferable.
As an example, use the γ-glycidyloxypropyl group.
You can Further, in the above, the general formula R'SiR₃
R'in the group containing an atomic group having a C-C double bond
Are optionally substituted alkenyl and alkynyl
Group, for example, 2 to 20, preferably 2 to 10
Having at least one carbon atom and at least one C--C double bond
Two straight chain, side chain or cyclic groups, especially vinyl, 1- and
And 2-propenyl, butenyl, isobutenyl, styrene.
And lower alkenyl groups such as propargyl, and
, An alkynyl group, or a methacryl group or an acryl group.
It is particularly preferable to use a group containing an atomic group containing a ryl group.
It is a good one.

Next, in the above, the general formula R'SiR
Examples of R in ₃ include hydrogen, halogen, alkoxy, hydroxyl, alkynylcarbonyl and the like. In the present invention, particularly preferred specific examples include, for example, methoxy, ethoxy, n- and i-propoxy, n-, sec- and tert-butoxy, isobutoxy, β-methoxyethoxy, acetyloxy, propionyloxy, monomethylamino, Monoethylamino, dimethylamino, diethylamino, N-
Examples thereof include ethylanilino, methylcarbonyl, ethylcarbonyl, methoxycarbonyl and ethoxycarbonyl. In the present invention, the R group in the general formula R′SiR ₃ does not exist in the final product and is lost by hydrolysis, and the hydrolysis product can be obtained immediately or later by a suitable method. Since it has to be removed at a low molecular weight, it has no substituents and produces a low molecular weight hydrolyzate such as lower alcohols such as methanol, ethanol, propanol and butanol. The R group is particularly preferred.

In the present invention, the silicon compound represented by the general formula R'SiR ₃ is wholly or partly in the form of precondensation, that is, a part of the silicon compound represented by the general formula R'SiR _3. The compound produced by the hydrolyzate alone,
Alternatively, it can be used as a mixture with another hydrolyzable compound such as an organometallic compound represented by the general formula described later. Such oligomers are preferably soluble in the reaction medium and are linear or cyclic, low molecular weight, partial condensation products (polycondensates, for example about 2 to 100, in particular about 2 to 6). Preference is given to using organosiloxanes). In the present invention, the general formula R ′S effectively used
Specific examples of the silicon compound represented by iR ₃ include γ
-(Meth) acryloxypropyltrimethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane and vinyltris (β
-Methoxyethoxy) silane, γ-glycidyloxypropyltrimethoxysilane, and the like.

Next, in the present invention, the silicon compound represented by the above general formula R'SiR ₃ is preferably not used alone, but is generally used in forming glass or ceramics. MR _n (wherein, M represents an element selected from silicon, aluminum, titanium, zirconium, vanadium, boron, or tin, and R
Represents an OH group and / or a group susceptible to hydrolysis, and n represents the valence of the metal element. 1) or 2 or more of the organometallic compounds represented by the formula (1) are mixed, and these compounds can be used by being converted into corresponding oxide hydrates by hydrolysis, preferably complete hydrolysis. . In the organometallic compound represented by the above general formula MR _n ,
As the metal element, for example, silicon, aluminum, titanium, zirconium, vanadium, boron, tin and the like can be used, and of course, in the present invention, compounds of other elements not described here can also be used. You can Further, in the organometallic compound represented by the above general formula MR _n , R may be the same or different, and the silicon compound represented by the above general formula R′SiR ₃ including the meaning in a preferable form. In the case of
Can be defined as In the present invention,
The organometallic compound represented by the above general formula MR _n is preferably mixed with the silicon compound represented by the above general formula R′SiR ₃ in a molar ratio of 1:99 to 99: 1. It is possible.

Further, in the present invention, in order to form the coating film according to the present invention, the above-mentioned general formula R'Si is used.
In addition to the silicon compound represented by R ₃ and the organometallic compound represented by the general formula MR _n , one or more resins having a hydrogen bond-forming group are added as a binder component.
It can also be mixed. Examples of the resin having a hydrogen bond-forming group include polymers having a hydroxyl group and derivatives thereof, such as polyvinyl alcohol, polyvinyl acetal, ethylene-vinyl alcohol copolymer, and phenol resin. , A methyl melamine resin or the like and a derivative thereof, a polymer having a carboxyl group and a derivative thereof, such as poly (meth) acrylic acid, maleic anhydride, itaconic acid, etc. Combined with esterified products of these polymers,
For example, a vinyl ester such as vinyl acetate, a homo- or copolymer containing units such as (meth) acrylic acid ester such as methyl methacrylate, a polymer having an ether bond,
For example, in addition to polyalkylene oxide, polyoxyalkylene glycol, polyvinyl ether, etc., polymers having an amide bond such as silicon resin, for example,> N (CO
N) of polyoxazoline or polyalkyleneimine having a R) -bond (wherein R represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent). An acylated product, polyvinylpyrrolidone and a derivative thereof having a> NC (O) -bond, polyurethane having a urethane bond, a polymer having a urea bond, a polymer having an amide bond and the like can be used. Thus, in the present invention, the resin having the above hydrogen bond-forming group is
The weight ratio to the mixture of the silicon compound represented by the general formula R′SiR ₃ and the organometallic compound represented by the general formula MR _n is 1:99 to 99: 1, preferably 5 It is possible to mix and use it in the ratio of -30.

Furthermore, in the present invention, the metal-containing gas barrier coating film constituting the barrier layer will be described. Examples of such a metal-containing gas barrier coating film include, for example, at least a polyvinyl alcohol resin [hereinafter It is called A) ingredient. ], And the general formula R ¹ _m M (OR ² ) _n
... (1) (In the formula, M represents a metal atom, R
¹ is the same or different and represents an organic group having 1 to 8 carbon atoms, R ² is the same or different and represents an alkyl group having 1 to 5 carbon atoms, an acyl group having 1 to 6 carbon atoms, or a phenyl group; And n each represent an integer of 0 or more,
m + n represents the valence of M. ), A metal alcoholate, a hydrolyzate of the metal alcoholate, a condensate of the metal alcoholate, a chelate compound of the metal alcoholate, a hydrolyzate of the chelate compound, and Metal acylate
At least one kind selected from the group of G. ] A gas-barrier coating film made of a gas-barrier composition containing and can be used. In the above, it is preferable that the gas barrier composition contains a nitrogen-containing organic solvent, and inorganic fine particles [hereinafter referred to as component (C)]. ] Is also preferable. Further, in the above, as the component (B),
The component (B) can be hydrolyzed in water or a mixed solvent containing water and a hydrophilic organic solvent, and then mixed with the component (A) to prepare a gas barrier composition.

In the above gas barrier composition, as the polyvinyl alcohol-based resin constituting the component (A), at least one selected from the group of polyvinyl alcohol and ethylene / vinyl alcohol-based copolymer is used. be able to. Further, in the above gas barrier composition, as the component (B), a metal alcoholate represented by the general formula (1), a hydrolyzate of the metal alcoholate, a condensate of the metal alcoholate, At least one selected from the group consisting of the chelate compound of the metal alcoholate, the hydrolyzate of the chelate compound and the metal acylate can be used, and thus, as the component (B), only one kind thereof can be used. It may be a mixture of any two or more kinds. As the hydrolyzate of the metal alcoholate, O contained in the metal alcoholate is used.
It is not necessary that all R ² be hydrolyzed, for example
Only one of them may be hydrolyzed, two or more of them may be hydrolyzed, or a mixture thereof. Further, the above-mentioned metal alcoholate condensate is one in which M-OH groups of the hydrolyzate of metal alcoholate are condensed to form an M-O-M bond, but in the present invention, the M-OH group is used. Does not need to be all condensed, and is a concept including a mixture of a small part of M-OH groups, a mixture of those having different degrees of condensation, and the like. Furthermore, the chelate compound of the metal alcoholate is a metal alcoholate, β-diketones, β-ketoesters, hydroxycarboxylic acid, hydroxycarboxylic acid salt,
It is obtained by reaction with at least one compound selected from hydroxycarboxylic acid esters, keto alcohols and amino alcohols. Further, the hydrolyzate of the chelate compound does not need to have all the OR ² groups contained in the chelate compound hydrolyzed, as in the case of the hydrolyzate of the metal alcoholate described above. May be hydrolyzed, two or more may be hydrolyzed, or a mixture thereof. In the present invention, the component (B) is considered to function to form a cocondensate with the component (A).

Further, in the above gas barrier composition, as the metal atom represented by M in the above general formula (1), zirconium, titanium and aluminum can be mentioned as preferable ones, and titanium is particularly preferable. Is. Next, in the present invention, the purpose of curing the metal-containing gas barrier coating film by the above gas barrier composition faster, the component (A) and the component (B).
(D) a curing accelerator may be used for the purpose of facilitating formation of a cocondensate with the component, and curing at a relatively low temperature,
In order to obtain a more dense coating film, it is more effective to use this (D) curing accelerator together. The above gas barrier composition is usually obtained by dissolving and dispersing the above components (A) to (D) and optionally the above optional components in water and / or a hydrophilic organic solvent. Thus, in the present invention, the metal-containing gas barrier coating film can be formed by using the gas barrier composition prepared above and applying the composition by a usual coating method. Examples of the method for applying the gas barrier composition of the present invention include, for example, a roll coater such as a gravure coater, a spray coater, a spin coater, a dipping brush, a bar code, and a coating means such as an applicator, once or a plurality of times. Dry film thickness of 0.01 ~ 30μ
m, preferably 0.1 to 10 μm, to form the gas-barrier coating film of the present invention.
~ 300 ° C, preferably 70-200 ° C, at 0.
005 to 60 minutes, preferably 0.01 to 10 minutes,
By heating and drying, condensation is performed and the metal-containing gas barrier coating film of the present invention can be formed. Also, if necessary, a primer agent or the like may be applied on the vapor-deposited film of an inorganic oxide in advance when applying the gas barrier composition of the present invention in order to enhance the adhesion and the like. Is.

Furthermore, in the present invention, as the above-mentioned barrier layer, a resin film made of the above-mentioned various resins, a barrier resin film, a vapor deposition film of an inorganic oxide, a resin film provided with a vapor deposition film of an inorganic oxide, A coating film composed of a composition composed of a polycondensate obtained by hydrolysis of a silicon compound, or a coating film composed of a composite film composed of two or more kinds of metal-containing gas barrier coating films can be used. Specifically, for example, resin films made of various resins, barrier resin films made of barrier resins, vapor deposited films of inorganic oxides, or vapor deposited films of inorganic oxides of resin films provided with vapor deposited films of inorganic oxides. It is possible to use a coating film composed of two or more kinds in which a coating film or a metal-containing gas barrier coating film is provided on the above with a composition composed of a polycondensate obtained by hydrolysis of a silicon compound. In the present invention, the resin film or the like provided with the inorganic oxide vapor deposition film can be regarded as a coating film composed of two or more kinds of a composite film of the inorganic oxide vapor deposition film and the resin film. . Further, in the present invention, the above barrier layer may, of course, be provided on the element surface side of the solar cell element as the photovoltaic element, but may also be provided on the other surface side, whereby both sides are provided. It can also be provided.

Next, in the method for producing the back surface protective sheet for a solar cell module according to the present invention, or the method for providing a barrier layer, the laminate for laminating in the above dry laminating lamination method is used. Examples of the laminate adhesive constituting the adhesive layer include, for example, polyvinyl acetate-based adhesive, ethyl acrylate, butyl, homopolymers such as 2-ethylhexyl ester, or these and methyl methacrylate, acrylonitrile, Polyacrylic ester adhesives made of copolymers with styrene, etc.,
Cyanacrylate adhesive, ethylene and vinyl acetate,
Ethyl acrylate, acrylic acid, ethylene copolymer adhesive consisting of copolymers with monomers such as methacrylic acid, cellulose adhesive, polyester adhesive, polyamide adhesive, polyimide adhesive, Amino resin adhesives such as urea resin or melamine resin, phenol
Resin adhesive, epoxy adhesive, polyurethane adhesive, reactive (meth) acrylic adhesive, chloroprene rubber, nitrile rubber, rubber adhesive such as styrene-butadiene rubber, silicone adhesive Inorganic adhesives such as alkali metal silicates and low melting point glass, and other adhesives can be used. 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 its properties are:
It may be in any form such as a film sheet, a powder, a solid, etc., and the adhesive mechanism may be in any form such as a chemical reaction type, a solvent volatilization type, a heat melting type and a heat pressure type. is there. The adhesive may 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 0.1 to 10
About g / m ² (dry state) is desirable.

In the above adhesive for laminate,
UV absorbers and / or
Alternatively, an antioxidant can be added. As the above-mentioned ultraviolet absorber, it absorbs harmful ultraviolet rays in sunlight and converts them into harmless thermal energy in the molecule, and prevents excitation of photodegradation initiation active species in the polymer. For example, benzophenone-based, benzotriazole-based, sulphate-based, acrylonitrile-based, metal complex salt-based, hindered amine-based, ultrafine particle titanium oxide (particle diameter, 0.01 to 0.06 μm) or It is possible to use one or more kinds of ultraviolet absorbers such as ultrafine zinc oxide (0.01 to 0.04 μm) and the like such as inorganic type ultraviolet absorbers. Further, the above-mentioned antioxidant is for preventing photo-deterioration or thermal deterioration of the above-mentioned polymer, and examples thereof include 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 benzophenone-based ultraviolet absorber or the above-mentioned phenol-based antioxidant is added to the main chain or side chain constituting the polymer. Polymer-type UV absorbers or antioxidants chemically bonded can 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% by weight is preferable.

In order to obtain a stronger adhesive strength in the method for producing the back surface protective sheet for a solar cell module according to the present invention or the melt extrusion lamination method in the method for providing the barrier layer. For example, using an adhesion aid such as an anchor coating agent,
It can be laminated via a coating agent layer. Examples of the anchor coating agent include various organic or water-based anchor coating agents such as organic titanium-based agents such as alkyl titanate, isocyanate-based, polyethyleneimine-based, polyptadiene-based, etc. Can be used. The above anchor coating agent can be coated using a coating method such as roll coating, gravure roll coating, kiss coating, etc., and the coating thereof can be performed. The amount is preferably about 0.1 to 5 g / m ² (dry state).

In the present invention, in order to improve the dense adhesion property when the method for producing the back surface protective sheet for a solar cell module according to the present invention or the barrier layer is provided, Further, for example, a primer-coating agent layer or the like may be optionally formed in advance to form the surface-treated layer. Examples of the above-mentioned primer coating agent include polyester resins, polyamide resins, polyurethane resins, epoxy resins, phenol resins, (meth) acrylic resins, polyvinyl acetate resins, polyethylene or 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 vehicle main component can be used. In the present invention, the primer is coated by using a coating method such as roll coating, gravure roll coating, kiss coating, etc.
The coating agent layer can be formed, and the coating amount is preferably about 0.1 to 5 g / m ² (dry state).

Next, in the present invention, the solar cell module
As the filler layer laminated under the photovoltaic element constituting the solar cell module, a solar cell module is formed in the same manner as the filler layer laminated under the surface protection sheet for a solar cell module described above. Photovoltaic device constituting the solar cell module according to the present invention
It is also necessary to have adhesiveness with the back surface protection sheet for a sheet, etc., and further, having thermoplasticity to perform the function of maintaining the smoothness of the back surface of the solar cell element as a photovoltaic element, Further, it is necessary to have excellent scratch resistance, shock absorption and the like, because it is intended to protect a solar cell element as a photovoltaic element. However, the filler layer laminated under the solar cell element as the photovoltaic element constituting the solar cell module is laminated under the surface protection sheet for the solar cell module. Unlike the filler layer, it does not necessarily need to have transparency. Specifically, the above-mentioned filler layer may be, for example, an ethylene-vinyl acetate copolymer or an ionomer, similar to the above-mentioned filler layer laminated under the surface protection sheet for a solar cell module. Resin, ethylene-acrylic acid, or methacrylic acid copolymer, polyethylene resin, polypropylene resin, polyolefin resin such as polyethylene or polypropylene with acrylic acid, itaconic acid, maleic acid, unsaturated carboxylic acid such as fumaric acid A mixture of one or more kinds of modified acid-modified polyolefin-based resins, polyvinyl butyral resins, silicone-based resins, epoxy-based resins, (meth) acrylic-based resins, etc. is used. be able to. In the present invention, the resin constituting the filler layer, in order to improve the heat resistance, light resistance, weather resistance such as water resistance, etc., within the range not impairing its transparency, for example, cross-linked. Additives such as agents, thermal antioxidants, light stabilizers, ultraviolet absorbers, photooxidants, 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
Rank is desirable.

In the present invention, when manufacturing the solar cell module according to the present invention, in order to improve various strengths such as strength, weather resistance, scratch resistance, etc. Material, eg 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. Acid copolymer, methyl pentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer, poly (meth) acrylic resin, poly Acrylonitrile resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, polyamide resin, polycarbonate resin , Polyvinyl alcohol type tree , Ethylene - saponified vinyl acetate copolymer, fluorine resin, diene resin, polyacetal - Le resins, polyurethane resins, nitrocellulose -
It can be used by arbitrarily selecting from known film or sheet of resin such as cloth and the like. In the present invention, the film or sheet may be unstretched, uniaxially or biaxially stretched, or the like. The thickness is arbitrary,
It can be selected and used 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 extrusion film, an inflation film, and a coating film.

Next, in the present invention, a method for producing a solar cell module using the above-mentioned materials will be described. As such a production method, a known method, for example, the above-mentioned glass plate is used. Surface protection sheet for solar cell module, etc., filler layer such as ethylene-vinyl acetate copolymer sheet, solar cell element as photovoltaic element, ethylene-vinyl acetate copolymer sheet And the like, and a back surface protection sheet for a solar cell module according to the present invention.
Ordinary molding such as the lamination method in which other materials are optionally laminated between each layer, if necessary, and then these are integrated by heat suction bonding such as vacuum suction. A solar cell module according to the present invention can be manufactured by thermocompression-molding each of the above layers as an integrally molded body using the method. In the above, if necessary,
In order to improve the adhesiveness between each layer, (meth) acrylic resin, olefin resin, vinyl resin, and other resins whose main component is a heat-melting adhesive, solvent adhesive, photocuring Mold adhesives, etc. can be used.

Further, in the above-mentioned lamination, in order to improve the close adhesion property, for example, corona discharge treatment, ozone treatment, oxygen gas or nitrogen gas at a low temperature is used on each of the lamination-opposing surfaces, if necessary. Pretreatments such as plasma treatment, glow discharge treatment, oxidation treatment using chemicals, and the like can be optionally performed. Further, in the above-mentioned lamination, a primer-coating agent layer, an under-coating agent layer, an adhesive layer, an anchor-coating agent layer, or the like is optionally formed in advance on each layer-opposing surface. Then, the surface pretreatment can be performed. Examples of the pretreatment coating agent layer include polyester resin, polyamide resin, polyurethane resin, epoxy resin, phenol resin, (meth) acrylic resin, polyvinyl acetate resin, A resin composition containing a polyolefin resin such as polyethylene or polypropylene, a copolymer or modified resin thereof, a cellulose resin, or the like as a main component of the vehicle can be used. Further, in the above, as a method for forming the coating agent layer, for example, a solvent type, an aqueous type or an emulsion type coating agent is used, and a roll coater 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, or the like.

Furthermore, in the present invention, the solar cell module according to the present invention is manufactured by laminating a surface protection sheet for a solar cell module and a filler layer in advance to produce a laminate,
On the other hand, similarly, in advance, the solar cell module according to the present invention
To produce a laminated body in which a backside protective sheet for a resin and a filler layer are laminated, and thereafter, a solar cell element as a photovoltaic element is laminated between the filler layers constituting the both laminated bodies. In addition, if necessary, other materials may be laminated as desired, and then the above layers may be integrated by using a normal molding method such as a lamination method in which they are integrated by vacuum suction and thermocompression bonded. A solar cell module can also be manufactured by thermocompression molding as a molded body.

[0065]

EXAMPLES The present invention will be described in more detail below with reference to examples. Example 1 (1). First, a benzophenone-based UV absorber (1% by weight) as a UV absorber and a hindered amine-based light stabilizer (1% by weight) as a light stabilizer are added to a polypropylene resin, and other necessary additives. Was added and kneaded sufficiently to prepare a first heat resistant polypropylene resin composition. In addition, a polypropylene resin containing titanium oxide (5% by weight) as a whitening agent, a benzophenone-based ultraviolet absorber (1% by weight) as an ultraviolet absorber, and a hindered amine-based light stabilizer (1% by weight) as a light stabilizer. ) And, in addition to the other required additives, knead thoroughly,
A second heat resistant colored polypropylene resin composition was prepared. Furthermore, to the polypropylene resin, a benzophenone-based UV absorber (1% by weight) as an UV absorber and a hindered amine-based light stabilizer (1% by weight) as a light stabilizer are added, and other necessary additives. Was added and kneaded sufficiently to prepare a third heat resistant polypropylene resin composition. Then, the first, second and third prepared above
The heat-resistant or heat-resistant colored polypropylene resin composition of 1) is melt-extruded using a T-die co-extruder, and the first heat-resistant polypropylene resin composition having a film thickness of 12 μm is used. -Resistant polypropylene resin film, second heat-resistant colored polypropylene resin film having a second heat-resistant colored polypropylene resin composition having a thickness of 96 μm, and third heat-resistant polypropylene resin film having a third heat-resistant polypropylene resin composition having a thickness of 12 μm A white colored unstretched polypropylene resin film having a total film thickness of 120 μm made of a transparent polypropylene resin film is produced, and corona discharge treatment is applied to both surfaces of the white colored unstretched polypropylene resin film according to a conventional method to form a corona treated surface. Form,
A back surface protection sheet for a solar cell module according to the present invention was manufactured. (2). Next, using the white colored unstretched polypropylene resin film as the back surface protective sheet for the solar cell module produced above, a glass plate having a thickness of 3 mm and a thickness of 400
μm ethylene-vinyl acetate copolymer sheet, 38 μm-thick biaxially stretched polyethylene terephthalate film in which solar cell elements made of amorphous silicon are arranged in parallel, 400 μm-thick ethylene-vinyl acetate copolymer sheet -, And a white colored unstretched polypropylene resin film as a back surface protection sheet for the solar cell module are sequentially laminated, and further, with the solar cell element surface facing upward, an acrylic resin. Laminated through the adhesive layer of
A solar cell module according to the present invention was manufactured.

Example 2 (1). First, a benzophenone-based UV absorber (1% by weight) as a UV absorber and a hindered amine-based light stabilizer (1% by weight) as a light stabilizer are added to a polypropylene resin, and other necessary additives. Was added and kneaded sufficiently to prepare a first heat resistant polypropylene resin composition. In addition, carbon black (5% by weight) as a blackening agent, benzophenone-based ultraviolet absorber (1% by weight) as a UV absorber, and hindered amine-based light stabilizer (1% by weight) as a light stabilizer are added to polypropylene resin. %) And other necessary additives and kneaded sufficiently to prepare a second heat resistant colored polypropylene resin composition. Furthermore, to the polypropylene resin, a benzophenone-based UV absorber (1% by weight) as an UV absorber and a hindered amine-based light stabilizer (1% by weight) as a light stabilizer are added, and other necessary additives. Was added and kneaded sufficiently to prepare a third heat resistant polypropylene resin composition. Next, the first, second, and third heat-resistant or heat-resistant colored polypropylene resin compositions prepared above are used, and these are melt-extruded and molded using a T-die co-extruder. A heat-resistant polypropylene resin composition having a thickness of 12 μm, a first heat-resistant polypropylene resin film, a second heat-resistant colored polypropylene resin composition having a thickness of 96 μm, a second heat-resistant colored polypropylene resin film, and a third A black colored unstretched polypropylene resin film having a total film thickness of 120 μm, which is composed of a third heat resistant polypropylene resin film having a film thickness of 12 μm, produced by the heat resistant polypropylene resin composition In accordance with a conventional method, a corona-treated surface is formed by a corona discharge treatment to form a solar cell according to the present invention. Ju - Le for the back protective sheet - were prepared and. (2). Next, using the black colored unstretched polypropylene resin film as the back surface protective sheet for the solar cell module manufactured as described above, a glass plate having a thickness of 3 mm and a thickness of 400
38 μm thick biaxially stretched polyethylene terephthalate film in which solar cell elements made of amorphous silicon are arranged in parallel, and 400 μm thick ethylene-vinyl acetate copolymer sheet. And a black colored unstretched polypropylene resin film as a back surface protective sheet for the solar cell module, which are sequentially laminated, and further, with the solar cell element surface facing upward, an acrylic resin. Laminated through the adhesive layer of
A solar cell module according to the present invention was manufactured.

Example 3 (1). First, a benzophenone-based UV absorber (1% by weight) as a UV absorber and a hindered amine-based light stabilizer (1% by weight) as a UV stabilizer are added to recycled polypropylene resin, and other necessary additions are made. The agent was added and sufficiently kneaded to prepare a first heat resistant polypropylene resin composition. In addition, recycled polypropylene resin, titanium oxide (5 wt%) as a whitening agent, benzophenone-based UV absorber (1 wt%) as a UV absorber, and hindered amine-based light stabilizer (1 wt%) as a light stabilizer. %) And other necessary additives and kneaded sufficiently to prepare a second heat resistant colored polypropylene resin composition. Further, to the recycled polypropylene resin, a benzophenone-based UV absorber (1% by weight) as a UV absorber and a hindered amine-based light stabilizer (1% by weight) as a light stabilizer are added, and other necessary additions are made. The agent was added and sufficiently kneaded to prepare a third heat resistant polypropylene resin composition. Next, the first, second, and third heat-resistant or heat-resistant colored polypropylene resin compositions prepared above are used, and these are melt-extruded and molded using a T-die co-extruder. A heat-resistant polypropylene resin composition having a thickness of 12 μm, a first heat-resistant polypropylene resin film, a second heat-resistant colored polypropylene resin composition having a thickness of 96 μm, a second heat-resistant colored polypropylene resin film, and a third A white colored unstretched polypropylene resin film having a total film thickness of 120 μm, which is composed of a third heat resistant polypropylene resin film having a film thickness of 12 μm by the heat resistant polypropylene resin composition of In accordance with a conventional method, a corona-treated surface is formed by a corona discharge treatment to form a solar cell according to the present invention. Ju - Le for the back protective sheet - were prepared and. (2). Next, using the white colored unstretched polypropylene resin film as the back surface protective sheet for the solar cell module produced above, a glass plate having a thickness of 3 mm and a thickness of 400
μm ethylene-vinyl acetate copolymer sheet, 38 μm-thick biaxially stretched polyethylene terephthalate film in which solar cell elements made of amorphous silicon are arranged in parallel, 400 μm-thick ethylene-vinyl acetate copolymer sheet -, And a white colored unstretched polypropylene resin film as a back surface protection sheet for the solar cell module are sequentially laminated, and further, with the solar cell element surface facing upward, an acrylic resin. Laminated through the adhesive layer of
A solar cell module according to the present invention was manufactured.

Example 4 (1). First, a polyaramid film having a thickness of 50 μm in which solar cell elements made of amorphous silicon are arranged in parallel is used. 8.0% by weight) and an antiblocking agent (1.0
(% By weight) and sufficiently kneaded to form a primer resin composition, which is coated by a gravure roll coat method so as to give a film thickness of 0.5 g / m ² (dry state).
To form a primer layer. Further, on the surface of the primer layer formed as described above, a two-component curing type urethane adhesive for laminating containing a benzophenone ultraviolet absorbent (2.0% by weight) as an ultraviolet absorbent is used,
This was coated in the same manner as above by a gravure roll coat method so that the film thickness became 5.0 g / m ² (dry state).
To form an adhesive layer for laminate. next,
The thickness of the adhesive layer for laminate formed above is 12 μm.
The biaxially-stretched polyethylene terephthalate films of m were laminated so as to face each other, and then both of them were dry-laminated to form a barrier layer. (2). Next, using the solar cell element having a barrier layer formed as described above, a glass plate having a thickness of 3 mm, an ethylene-vinyl acetate copolymer sheet having a thickness of 400 μm, and the biaxially stretched polyethylene terephthalate film described above were used. Cell having the following barrier layer, an ethylene-vinyl acetate copolymer sheet having a thickness of 400 μm, and a white coloring-free sheet as a back surface protective sheet for the solar cell module produced in Example 1 above. Stretched polypropylene resin film is sequentially laminated, further, the barrier layer surface of the solar cell element is sequentially laminated upward, and, and laminated via an acrylic resin adhesive layer between each layer, then, These were thermocompression bonded and integrated to manufacture a solar cell module according to the present invention.

Example 5 (1). A MXD6 nylon resin film was used as a material for forming the barrier layer, and a 50 μm-thick polyaramid film in which solar cell elements made of amorphous silicon were arranged in parallel was used in the same manner as in Example 4 above. A barrier layer was formed by laminating dry laminate on the surface of the above solar cell element. (2). Next, using the solar cell element having the barrier layer formed above, a glass plate having a thickness of 3 mm, an ethylene-vinyl acetate copolymer sheet having a thickness of 400 μm, and a barrier layer made of the MXD6 nylon resin film described above were used. A solar cell element having the same, an ethylene-vinyl acetate copolymer sheet having a thickness of 400 μm, and a white colored unstretched polypropylene resin film as a back surface protective sheet for the solar cell module produced in Example 1 above. Are sequentially laminated, and further, the barrier layer surface of the solar cell element is sequentially laminated upward, and,
A solar cell module according to the present invention was manufactured by laminating each layer via an acrylic resin adhesive layer, and then thermocompression-bonding and integrating them.

Example 6 (1). First, a 50 μm-thick polyaramid film in which solar cell elements made of amorphous silicon are arranged in parallel is used, and the polyaramid film is attached to a delivery roll of a roll-up type vacuum vapor deposition device, and then this is coated drum. The film thickness was measured by the reaction vacuum deposition method using an electron beam (EB) heating method while supplying oxygen gas to the surface of the solar cell element under the following conditions using aluminum as a deposition source. A barrier layer consisting of a 500Å aluminum oxide thin film was formed. (Deposition conditions) Deposition source: aluminum vacuum chamber-vacuum degree: 7.5 × 10 ^-6 mbar Deposition degree-vacuum degree: 2.1 × 10 ^-6 mbar EB output: 40 KW Film transfer speed: 600 m / Next, after forming a vapor-deposited thin film of aluminum oxide having a film thickness of 500 Å as described above, immediately after the vapor deposition, a glow discharge plasma generator was used on the vapor-deposited thin film surface of aluminum oxide to produce a plasma output of 1500 W and oxygen. Gas (O ₂ ): Argon gas (Ar) = 19: 1 is used as a mixed gas, mixed gas pressure is 6 × 10 ⁻⁵ Torr, and processing speed is 420 m.
/ Min to perform plasma treatment with an oxygen / argon mixed gas to form a plasma-treated surface. (2). Next, using the solar cell element in which the barrier layer made of the vapor deposition film of aluminum oxide is formed, the thickness is 3 mm.
Glass plate, a 400 μm thick ethylene-vinyl acetate copolymer sheet, a solar cell element having a barrier layer consisting of the above-mentioned vapor-deposited thin film of aluminum oxide, a 400 μm thick ethylene-vinyl acetate copolymer sheet. , And a white colored unstretched polypropylene resin film as a back surface protective sheet for a solar cell module produced in the above Example 1 are sequentially laminated, and the barrier layer surface of the solar cell element is placed on top. To the solar cell module according to the present invention by sequentially laminating the layers toward each other with an acrylic resin adhesive layer interposed therebetween, and then thermocompression-bonding and integrating the layers.

Example 7 (1). First, a 50 μm-thick polyaramid film in which solar cell elements made of amorphous silicon are arranged in parallel is used, and the polyaramid film is attached to a delivery roll of a plasma enhanced chemical vapor deposition apparatus. The film was fed onto a coating drum, and a film was formed on the surface of the solar cell element under the following vapor deposition conditions to form a barrier layer made of a vapor-deposited thin film of silicon oxide having a film thickness of 1000Å. (Deposition conditions) Reaction gas mixing ratio: Hexamethyldisiloxane: Oxygen gas: Helium = 1:10:10 (unit: slm) Degree of vacuum in vacuum chamber: 5.0 x 10 ^-6 mbar Deposition chamber Degree of vacuum: 6.0 × 10 ^-2 mbar Cooling / electrode drum power supply: 20 kW Film transport speed: 80 m / min Deposition surface: Corona treated surface Next, a vapor deposition thin film of silicon oxide having a film thickness of 1000 Å was formed as described above. Immediately after the vapor deposition, plasma treatment was performed on the vapor-deposited thin film surface of silicon oxide in the same manner as in Example 6 to form a plasma-treated surface. (2). Next, using a solar cell element having a barrier layer formed of the vapor-deposited thin film of silicon oxide formed above, a thickness of 3 mm
Glass plate, an ethylene-vinyl acetate copolymer sheet having a thickness of 400 μm, a solar cell element having a barrier layer formed of the above vapor-deposited thin film of silicon oxide, and an ethylene layer having a thickness of 400 μm
A vinyl acetate copolymer sheet and a black colored unstretched polypropylene resin film as a back surface protective sheet for a solar cell module produced in the above Example 2 were sequentially laminated, and the above-mentioned solar cell The solar cell according to the present invention is formed by sequentially laminating the barrier layer surface of the battery element facing upward and laminating each layer via an acrylic resin adhesive layer, and then thermocompressing and integrating them. A battery module was manufactured.

Example 8 (1). First, a 50 μm-thick polyaramid film in which solar cell elements made of amorphous silicon are arranged in parallel is used, and a sol-gel composition containing the following metal alkoxide compound is used on the surface of the solar cell element. -Coating using the rukot method,
Then, it is dried at 120 ° C. for 1 hour, and the coating amount is 2.
A coating film of 0 g / m ² (dry state) was formed to produce a barrier layer. (Sol-gel composition containing metal alkoxide compound) 45
To a mixture of mol% methacryloxypropyltrimethoxysilane and 30 mol% methyltrimethoxysilane, at room temperature 25 mol% aluminum sec-butyla
The mixture was slowly added dropwise with stirring. After the addition, the mixture was stirred for a further 5 minutes and then cooled to 15 ° C. One-fifteenth of the amount of water required for complete hydrolysis was gradually added dropwise with stirring. After stirring for another 5 minutes, it was cooled to 8 ° C. Next, 2/16 of the amount of water required for complete hydrolysis was gradually added dropwise with stirring. 15 more
Stir for minutes. Finally, hydrolysis was completed and a sol-gel composition for coating was prepared. (2). Next, using a solar cell element having a barrier layer made of the coating film formed as described above, a glass plate having a thickness of 3 mm, an ethylene-vinyl acetate copolymer sheet having a thickness of 400 μm, and the above-mentioned coating were used. A solar cell element having a barrier layer made of a coating film, an ethylene-vinyl acetate copolymer sheet having a thickness of 400 μm, and a back surface protection sheet for a solar cell module produced in Example 1 above. White-colored unstretched polypropylene resin film is sequentially laminated, and further, the barrier layer surface of the solar cell element is sequentially laminated upward, and each layer is laminated with an acrylic resin adhesive layer interposed therebetween. Then, they were thermocompression bonded and integrated to manufacture a solar cell module according to the present invention.

Example 9 (1). First, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used, and this was mounted on a delivery roll of a roll-up type vacuum vapor deposition device, and then it was fed out onto a coating drum, On the corona-treated surface, aluminum was used as a vapor deposition source under the following conditions, and while supplying oxygen gas, a vapor deposition thin film of aluminum oxide having a film thickness of 500 Å was formed by a reaction vacuum vapor deposition method using an electron beam (EB) heating system. Formed. (Deposition conditions) Deposition source: aluminum vacuum chamber-vacuum degree: 7.5 × 10 ^-6 mbar Deposition degree-vacuum degree: 2.1 × 10 ^-6 mbar EB output: 40 KW Film transfer speed: 600 m / Next, after forming a vapor-deposited thin film of aluminum oxide having a film thickness of 500 Å as described above, immediately after the vapor deposition, a glow discharge plasma generator was used on the vapor-deposited thin film surface of aluminum oxide to produce a plasma output of 1500 W and oxygen. Gas (O ₂ ): Argon gas (Ar) = 19: 1 is used as a mixed gas, mixed gas pressure is 6 × 10 ⁻⁵ Torr, and processing speed is 420 m.
/ Min to perform plasma treatment with an oxygen / argon mixed gas to form a plasma-treated surface. (2). On the other hand, on the surface (solar cell element surface) of a polyaramid film having a thickness of 50 μm in which solar cell elements made of amorphous silicon are arranged in parallel, an initial condensate of a two-component curing type polyurethane resin and an epoxy silane cup are used. A primer-resin composition obtained by adding a ring agent (8.0% by weight) and an antiblocking agent (1.0% by weight) and thoroughly kneading was used. The primer resin composition was used to form a film by a gravure roll coat method. A primer layer was formed by coating so as to have a thickness of 0.5 g / m ² (dry state). Further, on the surface of the primer layer formed as described above, a two-component curing type urethane adhesive for laminating containing a benzophenone ultraviolet absorbent (2.0% by weight) as an ultraviolet absorbent is used, In the same manner as above, this was coated by a gravure roll coat method to a film thickness of 5.0 g / m ² (dry state) to form an adhesive layer for laminate.
Then, the plasma-treated surface of the biaxially stretched polyethylene terephthalate film having the vapor-deposited thin film of aluminum oxide having a film thickness of 500 Å produced above was superposed on the surface of the adhesive layer for laminate formed above, After that, both were laminated by dry lamination to form a barrier layer. (3). Next, using the solar cell element having a barrier layer formed above, a glass plate having a thickness of 3 mm, an ethylene-vinyl acetate copolymer sheet having a thickness of 400 μm, a solar cell element having a barrier layer formed above, An ethylene-vinyl acetate copolymer sheet having a thickness of 400 μm and a white colored unstretched polypropylene resin film as a back surface protective sheet for a solar cell module produced in the above Example 1 were sequentially laminated. In addition, the barrier layer surface of the above solar cell element is sequentially laminated with the surface facing upward, and the acrylic resin adhesive layer is laminated between the layers, and then they are heat-pressed to form one body. To produce a solar cell module according to the present invention.

Example 10 (1). First, a 12 μm-thick biaxially stretched polyethylene terephthalate film was used, and this was mounted on a delivery roll of a plasma chemical vapor deposition apparatus, and then the fluororesin film was placed on a coating drum. Then, a film was formed on the corona-treated surface under the following vapor deposition conditions to form a vapor-deposited thin film of silicon oxide having a film thickness of 1000Å to produce a barrier layer. (Deposition conditions) Reaction gas mixing ratio: Hexamethyldisiloxane: Oxygen gas: Helium = 1:10:10 (unit: slm) Degree of vacuum in vacuum chamber: 5.0 x 10 ^-6 mbar Deposition chamber Degree of vacuum: 6.0 × 10 ^-2 mbar Cooling / electrode drum power supply: 20 kW Film transport speed: 80 m / min Deposition surface: Corona treated surface Next, a vapor deposition thin film of silicon oxide having a film thickness of 1000 Å was formed as described above. Immediately after the vapor deposition, plasma treatment was performed on the vapor-deposited thin film of silicon oxide in the same manner as in Example 9 to form a plasma-treated surface. (2). On the other hand, on the surface (solar cell element surface) of a polyaramid film having a thickness of 50 μm in which solar cell elements made of amorphous silicon are arranged in parallel, an initial condensate of a two-component curing type polyurethane resin and an epoxy silane cup are used. A primer-resin composition obtained by adding a ring agent (8.0% by weight) and an antiblocking agent (1.0% by weight) and thoroughly kneading was used. The primer resin composition was used to form a film by a gravure roll coat method. A primer layer was formed by coating so as to have a thickness of 0.5 g / m ² (dry state). Further, a two-component curing type urethane anchor coating agent was used on the surface of the primer layer formed as described above, and the same was applied to the surface of the primer layer by the gravure roll coating method in the same manner as described above. 1 g / m
² Anchor by coating so that it becomes (dry state)
A coating agent layer was formed. Next, the anchor formed above
Plasma of a biaxially-stretched polyethylene terephthalate film having a 1000 Å-thick deposited thin film of silicon oxide formed by using low-density polyethylene on the surface of the coating agent layer and extruding it to a thickness of 30 μm. A barrier layer was formed by laminating extrusion laminates with the treated surfaces facing each other. (3). Next, using the solar cell element having a barrier layer formed above, a glass plate having a thickness of 3 mm, an ethylene-vinyl acetate copolymer sheet having a thickness of 400 μm, a solar cell element having a barrier layer formed above, An ethylene-vinyl acetate copolymer sheet having a thickness of 400 μm and a black colored unstretched polypropylene resin film as a back surface protective sheet for a solar cell module produced in Example 2 were sequentially laminated. , Further, the barrier layer surface of the above solar cell element is sequentially laminated, and each layer is laminated via an acrylic resin adhesive layer, and then they are heat-pressed and integrated. A solar cell module according to the present invention was manufactured.

Example 11 (1). Biaxially stretched polyethylene terephthalate with a thickness of 12 μm
Using a rate film, this is a plasma chemical vapor deposition device
It is attached to the delivery roll of and the film thickness is 200Å under the following conditions.
Was formed on the corona-treated surface. (Deposition conditions) Reaction gas mixture ratio: Hexamethyldisiloxane: Oxygen gas
Space: Helium = 1:10:10 (Unit: slm) Degree of vacuum in vacuum chamber: 5.5 × 10^-6mbar Degree of vacuum in vapor deposition chamber: 6.5 × 10^-2mbar Cooling / electrode drum power supply: 18kW Film transport speed: 80 m / min Deposition surface: Corona treated surface Next, a vapor deposition film of silicon oxide having a film thickness of 200 Å is formed as described above.
Deposition of cyclic polyolefin resin film
Immediately after that, on the surface of the deposited film of silicon oxide,
Perform plasma processing in exactly the same way to shape the plasma-treated surface.
I made it. (2). Next, 45 mol% of methacryloxypropyl
Trimethoxysilane and 30 mol% methyltrimetho
Add a mixture of xylsilane to 25 mol% aluminum at room temperature.
Slowly drop while stirring the sec-butyrate.
did. After the addition, the mixture is stirred for a further 5 minutes, then 15
Cooled to ° C. 1 amount of water required for complete hydrolysis
One-fifth was gradually added dropwise with stirring. 5 more minutes
After stirring, it was cooled to 8 ° C. Then completely hydrolyze
2/16 of the amount of water required for
Dropped. Stir for a further 15 minutes. Finally, the hydrolysis
Upon completion, the composition for coating was prepared. Then adjust the above
The composition for coating prepared is used, and this is used as described in (1) above.
The plasma-treated surface of the vapor-deposited silicon oxide film manufactured in
Coated using the vial roll coat method, then
Drying at 120 ° C for 1 hour, coating amount 2.0g / m
²A coating film composed of (dry state) was formed. (3). On the other hand, solar cells made of amorphous silicon
50 μm thick polyaramidphy in which elements are arranged in parallel
On the surface of the rum (solar cell element surface), a two-component curing type
Epoxy-based silane catalyst
Pulling agent (8.0% by weight) and antiblocking agent
(1.0 wt%) added and kneaded thoroughly
Using a resin composition, this is a gravure roll coat.
Method, film thickness 0.5g / m²To be (dry)
To form a primer layer. Furthermore, above
On the surface of the primer layer formed as described above, a two-component curing type urethane
An anchor coating agent is used, which is the same as above.
And a film thickness of 0.1 g / m 2 by a gravure roll coat method.
²Anchor by coating so that it becomes (dry state)
A coating agent layer was formed. Next, the anchor formed above
Use low density polyethylene on the surface of the coating agent layer.
Formed as above while melt extruding to a thickness of 30 μm
A vapor-deposited thin film of silicon oxide and a coating film with a film thickness of 200Å
Biaxially stretched polyethylene terephthalate film having
With the coating film surface facing each other.
A barrier layer was provided by laminating the nets. (4). Next, a solar cell element having the barrier layer provided above
3mm thick glass plate, 400μm thick
Ethylene-vinyl acetate copolymer sheet, the above barrier layer
Solar cell element having, ethylene-acetic acid having a thickness of 400 μm
Vinyl copolymer sheet and prepared in Example 1 above
White clothing as a backside protective sheet for solar cell modules
Color unstretched polypropylene resin film is laminated in sequence,
Further, with the barrier layer surface of the above solar cell element facing upward,
And an acrylic resin adhesive layer between each layer
Laminated through, then thermocompress them and unite
Then, the solar cell module according to the present invention was manufactured.

Example 12 (1). A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used, which was mounted on a delivery roll of a roll-up type vacuum vapor deposition device, which was then fed onto a coating drum under the following conditions. Then, using aluminum as a vapor deposition source and supplying oxygen gas, a reactive vacuum vapor deposition method using an electron beam (EB) heating system was used to form a film having a thickness of 220 Å on one surface of the above-mentioned biaxially stretched polyethylene terephthalate film. A deposited film of aluminum oxide was formed. (Deposition conditions) Deposition source: aluminum vacuum chamber-vacuum degree: 7.5 x 10 ^-6 mbar Deposition degree-vacuum degree: 2.1 x 10 ^-6 mbar EB output: 25 kW Film transfer speed: 480 m / Next, regarding the biaxially stretched polyethylene terephthalate film on which the vapor-deposited film of aluminum oxide having a thickness of 220 liters was formed, a glow discharge plasma generator was used on the vapor-deposited film of aluminum oxide immediately after the vapor deposition. However, a mixed gas consisting of plasma output of 1500 W, oxygen gas (O ₂ ): argon gas (Ar) = 19: 1 was used, mixed gas pressure was 6 × 10 ⁻⁵ Torr, and processing speed was 420 m / mi.
Plasma treatment with an oxygen / argon mixed gas was performed at n to form a plasma-treated surface. (2). Next, 25 g of ethyl silicate and 2 parts of ethanol
5g, 2N hydrochloric acid 1.86g and water 1.51g are mixed,
The mixture was stirred at 80 ° C for 1-2 hours. At this time, the molar ratio of ethyl silicate to water in the above mixture was 1: 1.51. Then, 2.5 g of epoxysilane (trade name, SH6040 manufactured by Toray Dow Corning Co., Ltd.) was added and stirred. To this, 1.7 g of an aqueous solution containing 10% of polyvinyl alcohol (Kuraray Co., Ltd., polymerization degree: 2000) was added, and the mixture was further stirred for 1 to 2 hours. A composition for coating was prepared by adding 0.1 g of a 32% by weight N-dimethylbenzylamine ethanol solution. Next, the composition for coating prepared above is used, and the composition is coated on the plasma-treated surface of the vapor-deposited film of aluminum oxide prepared in (1) above by using the gravure roll coating method. And then dried at 120 ° C for 1 hour,
A coating film having a coating amount of 2.0 g / m ² (dry state) was formed. (3). On the other hand, on the surface (solar cell element surface) of a polyaramid film having a thickness of 50 μm in which solar cell elements made of amorphous silicon are arranged in parallel, an initial condensate of a two-component curing type polyurethane resin and an epoxy silane cup are used. A primer-resin composition obtained by adding a ring agent (8.0% by weight) and an antiblocking agent (1.0% by weight) and thoroughly kneading was used. The primer resin composition was used to form a film by a gravure roll coat method. A primer layer was formed by coating so as to have a thickness of 0.5 g / m ² (dry state). Further, on the surface of the primer layer formed as described above, a two-component curing type urethane adhesive for laminating containing a benzophenone ultraviolet absorbent (2.0% by weight) as an ultraviolet absorbent is used, In the same manner as above, this was coated by a gravure roll coat method to a film thickness of 5.0 g / m ² (dry state) to form an adhesive layer for laminate.
Next, a coating film of a biaxially stretched polyethylene terephthalate film having a 220 Å-thickness vapor-deposited thin film of aluminum oxide prepared above and a coating film on the adhesive layer for laminate formed above. The surfaces were faced to overlap with each other, and then both were laminated by dry lamination to form a barrier layer. (4). Next, using the solar cell element having the barrier layer formed as described above, a glass plate having a thickness of 3 mm, an ethylene-vinyl acetate copolymer sheet having a thickness of 400 μm, a solar cell element having the barrier layer provided above, An ethylene-vinyl acetate copolymer sheet having a thickness of 400 μm and a black colored unstretched polypropylene resin film as a back surface protective sheet for a solar cell module produced in Example 2 were sequentially laminated. , Further, the barrier layer surface of the above solar cell element is sequentially laminated, and each layer is laminated via an acrylic resin adhesive layer, and then they are heat-pressed and integrated. A solar cell module according to the present invention was manufactured.

Example 13 (1). A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used, and this film was attached to a delivery roll of a plasma enhanced chemical vapor deposition apparatus, and then the above biaxially stretched polyethylene terephthalate film was placed under the following conditions. A 200 Å-thick vapor-deposited film of silicon oxide was formed on the corona-treated surface of the glass film. (Deposition conditions) Deposition surface; Corona-treated surface introduction gas amount; Hexamethyldisiloxane: Oxygen gas: Helium = 1.2: 5.0: 2.5 (unit: slm) Ultimate pressure: 5.0 x 10 ^-5 mbar film forming pressure; 7.0 × 10 ^-2 mbar power; 35 kW line speed; 300 m / min Next, immediately after the above-mentioned 200 Å film thickness of the silicon oxide film is formed, the silicon oxide film surface is formed. In addition, a glow discharge plasma generator was used, and a mixed gas consisting of a power of 9 kw and oxygen gas (O ₂ ): argon gas (Ar) = 7.0: 2.5 (unit: slm) was used for mixing. Gas pressure 6
Oxygen / argon mixed gas plasma treatment was carried out at × 10 ^-2 mbar, and the surface tension of the vapor-deposited silicon oxide film surface was adjusted to 54 dy.
A plasma treated surface having an improved ne / cm or more was formed. (2). On the other hand, in a reactor equipped with a reflux condenser and a stirrer,
100 parts of tetra-i-propoxy titanium and 70 parts of acetylacetone were added and stirred at 60 ° C. for 30 minutes to obtain a titanium chelate compound. The purity of this reaction product was 75%. Next, as the component (A), an ethylene / vinyl alcohol copolymer [Nippon Gosei Kagaku KK, trade name,
Soarnol D2935, saponification degree; 98% or more, ethylene content; 29 mol%, melt flow index; 35
g / 10 minutes] and polyvinylpyrrolidone [manufactured by Wako Pure Chemical Industries, Ltd., Mw = 25,000].
% Water / n-propyl alcohol solution (water / n-propyl alcohol weight ratio = 40/60), and 2 parts of the titanium chelate compound prepared above and n-
Propyl alcohol (16.8 parts) and water (11.2 parts) were mixed and hydrolyzed at 55 ° C. for 4 hours with component (B),
Furthermore, with 12.1 parts of N, N-dimethylformamide,
It mixed at 40 degreeC and stirred for 2 hours, and obtained the gas barrier composition of this invention. Next, the plasma-treated surface formed in (1) above is coated with the gas barrier composition prepared above by a gravure roll coating method, and then heat-treated at 120 ° C. for 1 minute. To form a biaxially stretched polyethylene terephthalate film having a vapor deposition film of silicon oxide and a metal-containing gas barrier coating film by forming a gas barrier coating film having a thickness of 1.0 g / m ² (dry state). . (3). On the other hand, on the surface (solar cell element surface) of a polyaramid film having a thickness of 50 μm in which solar cell elements made of amorphous silicon are arranged in parallel, an initial condensate of a two-component curing type polyurethane resin and an epoxy silane cup are used. A primer-resin composition obtained by adding a ring agent (8.0% by weight) and an antiblocking agent (1.0% by weight) and thoroughly kneading was used. The primer resin composition was used to form a film by a gravure roll coat method. A primer layer was formed by coating so as to have a thickness of 0.5 g / m ² (dry state). Further, on the surface of the primer layer formed as described above, a two-component curing type urethane adhesive for laminating containing a benzophenone ultraviolet absorbent (2.0% by weight) as an ultraviolet absorbent is used, In the same manner as above, this was coated by a gravure roll coat method to a film thickness of 5.0 g / m ² (dry state) to form an adhesive layer for laminate.
Next, a metal-containing biaxially stretched polyethylene terephthalate film having the above-prepared vapor-deposited thin film of silicon oxide having a film thickness of 200 liters and a metal-containing gas barrier coating film on the surface of the adhesive layer for lamination formed above. The surfaces of the gas-barrier coating films were made to face each other and were overlaid, and then both were laminated by dry lamination to form a barrier layer. (4). Next, using the solar cell element having the barrier layer formed as described above, a glass plate having a thickness of 3 mm, an ethylene-vinyl acetate copolymer sheet having a thickness of 400 μm, a solar cell element having the barrier layer provided above, An ethylene-vinyl acetate copolymer sheet having a thickness of 400 μm and a white colored unstretched polypropylene resin film as a back surface protective sheet for a solar cell module produced in Example 1 were sequentially laminated. , Furthermore, the barrier layer surface of the above solar cell element is sequentially laminated with the barrier layer surface facing upward, and the acrylic resin adhesive layer is laminated between the layers, and then they are heat-pressed to be integrated. A solar cell module according to the present invention was manufactured.

Example 14 (1). As a base film, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is used.
The biaxially stretched polyethylene terephthalate film was mounted on a delivery roll of a roll-up type vacuum vapor deposition device, and then it was fed out, and the corona-treated surface of the biaxially stretched polyethylene terephthalate film was coated with aluminum. Was used as a vapor deposition source while supplying oxygen gas, and a vacuum vapor deposition method by an electron beam (EB) heating system was used to form a vapor deposition film of aluminum oxide having a film thickness of 200 Å under the following vapor deposition conditions. (Deposition conditions) Degree of vacuum in deposition chamber: 2 × 10 ⁻⁴ mbar Degree of vacuum in winding chamber: 2 × 10 ⁻² mbar Electron beam power: 25 kW Film transfer speed: 420 m / min Deposition surface Next, a plasma-treated surface was formed on the aluminum oxide vapor-deposited film surface in the same manner as in Example 9 immediately after the aluminum oxide vapor-deposited film having a thickness of 200 Å was formed. A barrier film was produced. (2). On the other hand, in a reactor equipped with a reflux condenser and a stirrer,
100 parts of tetra-i-propoxy titanium and 70 parts of acetylacetone were added and stirred at 60 ° C. for 30 minutes to obtain a titanium chelate compound. The purity of this reaction product was 75%. Next, as the component (A), an ethylene / vinyl alcohol copolymer [Nippon Gosei Kagaku KK, trade name,
Soarnol D2935, saponification degree; 98% or more, ethylene content; 29 mol%, melt flow index; 35
g / 10 minutes] 5% water / n-propyl alcohol solution (water / n-propyl alcohol weight ratio = 40/60) 1
A mixture of 00 parts, 2 parts of the titanium chelate compound prepared above, 16.8 parts of n-propyl alcohol and 11.2 parts of water and hydrolyzed at 55 ° C for 4 hours was added to the component (B) at 40 ° C. And mixed for 2 hours to obtain a gas barrier composition. Next, on the plasma-treated surface of the barrier film formed in (1) above, the gas barrier composition prepared above was used, and this was coated by the gravure roll coating method, and then at 120 ° C. for 2 minutes. A biaxially stretched polyethylene terephthalate film having a gas barrier coating film having a thickness of 1.0 g / m ² (dry state) formed by heat treatment and having an aluminum oxide vapor deposition film and a metal-containing gas barrier coating film. Was manufactured. (3). On the other hand, on the surface (solar cell element surface) of a polyaramid film having a thickness of 50 μm in which solar cell elements made of amorphous silicon are arranged in parallel, an initial condensate of a two-component curing type polyurethane resin and an epoxy silane cup are used. A primer-resin composition obtained by adding a ring agent (8.0% by weight) and an antiblocking agent (1.0% by weight) and thoroughly kneading was used. The primer resin composition was used to form a film by a gravure roll coat method. A primer layer was formed by coating so as to have a thickness of 0.5 g / m ² (dry state). Further, on the surface of the primer layer formed as described above, a two-component curing type urethane adhesive for laminating containing a benzophenone ultraviolet absorbent (2.0% by weight) as an ultraviolet absorbent is used, In the same manner as above, this was coated by a gravure roll coat method to a film thickness of 5.0 g / m ² (dry state) to form an adhesive layer for laminate.
Next, a metal-containing biaxially stretched polyethylene terephthalate film having the above-prepared vapor-deposited thin film of aluminum oxide having a film thickness of 200 Å and a metal-containing gas barrier coating film on the surface of the adhesive layer for laminating formed above. The surfaces of the gas-barrier coating films were made to face each other and were overlaid, and then both were laminated by dry lamination to form a barrier layer. (4). Next, using the solar cell element having the barrier layer formed as described above, a glass plate having a thickness of 3 mm, an ethylene-vinyl acetate copolymer sheet having a thickness of 400 μm, a solar cell element having the barrier layer provided above, An ethylene-vinyl acetate copolymer sheet having a thickness of 400 μm and a black colored unstretched polypropylene resin film as a back surface protective sheet for a solar cell module produced in Example 2 were sequentially laminated. , Further, the barrier layer surface of the above solar cell element is sequentially laminated, and each layer is laminated via an acrylic resin adhesive layer, and then they are heat-pressed and integrated. A solar cell module according to the present invention was manufactured.

Comparative Example 1 A biaxially stretched polyethylene terephthalate film having a thickness of 38 μm in which a glass plate having a thickness of 3 mm, an ethylene-vinyl acetate copolymer sheet having a thickness of 400 μm, and solar cell elements made of amorphous silicon were arranged in parallel. -Film, thickness 400μ
m ethylene-vinyl acetate copolymer sheet, and a transparent biaxially stretched polyethylene terephthalate film having a thickness of 100 μm, with the solar cell element surface facing upward, and an acrylic resin adhesive layer. A solar cell module was manufactured by stacking the layers.

Comparative Example 2 A biaxially stretched polyethylene terephthalate film having a thickness of 38 μm in which a glass plate having a thickness of 3 mm, an ethylene-vinyl acetate copolymer sheet having a thickness of 400 μm, and solar cell elements made of amorphous silicon were arranged in parallel. -Film, thickness 400μ
m ethylene-vinyl acetate copolymer sheet, and a white biaxially stretched polyethylene terephthalate film having a thickness of 100 μm, with the solar cell element side facing upward, and an acrylic resin adhesive layer. A solar cell module was manufactured by stacking the layers.

Comparative Example 3 A biaxially stretched polyethylene terephthalate film having a thickness of 38 μm in which a glass plate having a thickness of 3 mm, an ethylene-vinyl acetate copolymer sheet having a thickness of 400 μm, and a solar cell element made of amorphous silicon were arranged in parallel. -Film, thickness 400μ
m ethylene-vinyl acetate copolymer sheet, and a black biaxially stretched polyethylene terephthalate film having a thickness of 100 μm, with the solar cell element surface facing upward, and an acrylic resin adhesive layer. A solar cell module was manufactured by stacking the layers.

Comparative Example 4 A biaxially stretched polyethylene terephthalate film having a thickness of 38 μm in which a glass plate having a thickness of 3 mm, an ethylene-vinyl acetate copolymer sheet having a thickness of 400 μm, and a solar cell element made of amorphous silicon were arranged in parallel. -Film, thickness 400μ
m of an ethylene-vinyl acetate copolymer sheet and a 100 μm thick black polyvinyl fluoride resin sheet are opposed to each other, and the solar cell element surface of the sheet is faced up to form an acrylic resin. A solar cell module was manufactured by laminating via an adhesive layer.

Comparative Example 5 A biaxially stretched polyethylene terephthalate film having a thickness of 38 μm in which a glass plate having a thickness of 3 mm, an ethylene-vinyl acetate copolymer sheet having a thickness of 400 μm, and a solar cell element made of amorphous silicon were arranged in parallel. -Film, thickness 400μ
m ethylene-vinyl acetate copolymer sheet, and a three-layer consisting of a 38 μm thick black polyvinyl fluoride resin film, a 35 μm thick aluminum foil, and a 38 μm thick black polyvinyl fluoride resin film. Laminate
A solar cell module was manufactured by laminating the solar cell element face up with an acrylic resin adhesive layer in between.

Experimental Example The solar cell modules according to the present invention manufactured in the above Examples 1 to 14 and the solar cell modules according to Comparative Examples 1 to 5 were manufactured.
(1). Water vapor transmission rate, (2). Output reduction rate, (3). Tensile strength retention rate, and (4). The lamination strength was measured. (1). Measurement of Water Vapor Transmission Rate This is a condition of temperature 40 ° C. and humidity 90% RH for the solar cell module according to the present invention manufactured in Examples 1 to 14 and the solar cell module according to Comparative Examples 1 to 5. so,
The measurement was carried out using a measuring machine [model name, Permatran] manufactured by MOCON, USA. (2). Measurement of output reduction rate 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 to make a comparative evaluation. (3). Measurement of tensile strength maintenance rate This is a test when the environmental strength test is conducted at a temperature of 85 ° C, a humidity of 85%, and a time of 1000 hours, and the tensile strength before and after the test is compared and evaluated. The subsequent tensile strength retention rate was measured. The initial tensile strengths were all 50 N / 15 mm width or more. The measurement was carried out by cutting the solar cell module according to the present invention manufactured in Examples 1 to 14 and the solar cell module according to Comparative Examples 1 to 5 into a width of 15 mm, and using a tensile tester [A &・ Model name of De (A & D) Co., Ltd.
[Tensilon] was used for the evaluation. (4). Measurement of Lamination Strength This is for a solar cell module according to the present invention manufactured in Examples 1 to 14 and a solar cell module according to Comparative Examples 1 to 5 as a filler layer on one surface thereof. An ethylene-vinyl acetate copolymer sheet having a thickness of 400 μm is laminated, and then the laminated sheet is cut into a width of 15 mm, and a tensile tester [Model manufactured by A & D Co., Ltd. Peeling strength of the laminated surface of the laminated sheet was measured and evaluated using the name Tensilon. The above measurement results are shown in Table 1 below.

[0085] In Table 1 above, the unit of water vapor permeability is [g / m
² / day, 40 ° C., 100% RH], the unit of output reduction rate is [%] (85 ° C. 85% 1000 h), and the unit of tensile strength deterioration maintenance rate is [%] (85 ° C. 8
5% 1000 h), and the unit of lamination strength is [N / 1
5 mm width].

As is clear from the measurement results shown in Table 1 above, the solar cell modules according to Examples 1 to 14 were:
It was excellent in water vapor permeability, tensile strength retention rate, and lamination strength. Furthermore, the solar cell modules according to the above Examples 1 to 14 had a low output reduction rate. On the other hand, the solar cell modules according to Comparative Examples 1 to 5 have problems such as a low water vapor permeability, a low tensile strength maintenance rate, and a low lamination strength, and thus a high output reduction rate. It was a thing. The solar cell modules according to Comparative Examples 4 and 5 have a low tensile strength retention rate, a low lamination strength, etc., but have a configuration of a commonly used solar cell module, which is the same as that of this example. The output reduction rate was moderate. Considering this point, it was found that the solar cell module according to the present invention can be sufficiently used in place of the solar cell modules according to Comparative Examples 4 and 5.

[0087]

As is apparent from the above description, the present invention is
First, paying attention to the use of a heat-resistant polypropylene resin film for the back surface protection sheet for solar cell modules,
First, a first heat resistant polypropylene resin film made of a heat resistant polypropylene resin composition containing an ultraviolet absorber and a light stabilizer, and a heat resistant polypropylene containing a coloring agent, an ultraviolet absorber and a light stabilizer. A second heat-resistant colored polypropylene-based resin film made of a resin-based resin composition and a third heat-resistant polypropylene-based resin film made of a heat-resistant polypropylene-based resin composition containing an ultraviolet absorber and a light stabilizer are sequentially laminated. To produce a back surface protective sheet for a solar cell module comprising a three-layer laminated film, and then using the back surface protective sheet for a solar cell module comprising the three-layer laminated film, for example, glass. Ordinary solar cell module surface protection sheet consisting of plates, filler layer of ethylene-vinyl acetate copolymer sheet, etc., solar cell as photovoltaic element Element, a filler layer of ethylene-vinyl acetate copolymer sheet, and the like, and a first heat-resistant polypropylene-based resin film comprising the heat-resistant polypropylene-based resin composition containing the above-mentioned ultraviolet absorber and light stabilizer. A second heat-resistant colored polypropylene-based resin film containing a heat-resistant polypropylene-based resin composition containing a coloring agent, an ultraviolet absorber and a light stabilizer, and a heat-resistant polypropylene-based resin containing an ultraviolet absorber and a light stabilizer. A third heat resistant polypropylene resin film made of a resin composition is sequentially laminated, and a back surface protection sheet for a solar cell module composed of a three-layer laminated film is sequentially laminated, and then these are integrally formed. When a solar cell module was manufactured using a lamination method such as vacuum suction and heat compression bonding, it has excellent strength, and further has weather resistance, heat resistance, water resistance, and resistance to water. Excellent in various properties such as water resistance, wind pressure resistance, hail resistance, chemical resistance, antifouling property, etc., in particular, excellent moisture resistance to prevent intrusion of moisture, oxygen, etc., and also light reflectivity and light diffusion property. , The design, etc. are significantly improved, and the long-term deterioration of performance is minimized.
In particular, it is possible to stably produce a solar cell module that prevents hydrolysis and deterioration due to moisture and the like, has extremely high durability, and is safer at lower cost.

[Brief description of drawings]

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

FIG. 3 is a schematic configuration diagram showing an example of a winding-type vacuum vapor deposition device.

FIG. 4 is a schematic configuration diagram showing an example of a plasma chemical vapor deposition apparatus.

[Explanation of symbols]

A Back surface protection sheet for solar cell module 1 First heat-resistant polypropylene resin film 2 Second heat-resistant colored polypropylene resin film 3 Third heat-resistant polypropylene resin film 4 Three-layer laminated resin film T Solar cell module 11 (11a) Surface protection sheet 12 for solar cell module such as glass plate 12 (12a) Filler layer 13 such as ethylene-vinyl acetate copolymer sheet Solar cell element 14 (14a) ) Filler layer 15a such as ethylene-vinyl acetate copolymer sheet A back surface protection sheet for a solar cell module comprising a three-layer laminated resin film

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Kojiro Okawa             1-1-1, Ichigaya-Kagacho, Shinjuku-ku, Tokyo             Dai Nippon Printing Co., Ltd. (72) Inventor, Kuni Satoshi             1-1-1, Ichigaya-Kagacho, Shinjuku-ku, Tokyo             Dai Nippon Printing Co., Ltd. F-term (reference) 5F051 AA02 AA03 AA04 AA05 BA03                       BA18 EA18 JA03 JA04 JA05

Claims (11)

[Claims] 1. A first heat-resistant polypropylene-based resin film made of a heat-resistant polypropylene-based resin composition containing an ultraviolet absorber and a light stabilizer, a colorant, an ultraviolet absorber and a light stabilizer. A second heat resistant colored polypropylene resin film made of the heat resistant polypropylene resin composition, and a third heat resistant polypropylene resin film made of the heat resistant polypropylene resin composition containing an ultraviolet absorber and a light stabilizer. A back surface protection sheet for a solar cell module, comprising a three-layer resin film laminated in order. 2. The ultraviolet absorber is benzophenone-based, benzotriazole-based, sulphate-based, acrylonitrile-based, metal complex salt-based, or ultrafine titanium oxide (particle diameter, 0.01 to 0.06 μm) or The back surface protection for a solar cell module according to claim 1, characterized in that it comprises one or more inorganic ultraviolet absorbers composed of ultrafine zinc oxide (0.01 to 0.04 μm). Sheet. 3. The solar cell module according to claim 1, wherein the light stabilizer comprises one or more hindered amine compounds. Backside protection sheet. 4. The polypropylene-based resin comprises a homopolymer of propylene and a copolymer of propylene and another monomer, as described in any one of claims 1 to 3 above. Backside protection sheet for solar cell module
To. 5. The back surface protection sheet for a solar cell module according to claim 1, wherein the coloring agent is a white pigment or a black pigment.
To. 6. A heat-resistant polypropylene-based resin composition in which a three-layer laminated resin film contains an ultraviolet absorber and a light stabilizer, and a heat-resistant polypropylene containing a coloring agent, an ultraviolet absorber and a light stabilizer. 6. A three-layer coextrusion laminated resin film comprising a resin composition and a heat-resistant polypropylene resin composition containing an ultraviolet absorber and a light stabilizer. A back surface protection sheet for a solar cell module according to any one of items. 7. The three-layer laminated resin film has a thickness of 2 μm to
A first heat-resistant polypropylene-based resin film having a thickness of 100 μm, a second heat-resistant colored polypropylene-based resin film having a thickness of 12 μm to 400 μm, and a thickness of 2 μm
The solar cell module according to any one of claims 1 to 6, wherein the solar cell module is formed of a three-layer laminated resin film in which a third heat-resistant polypropylene-based resin film of m to 100 µm is sequentially laminated. -Back side protection sheet
To. 8. A surface protection sheet for a solar cell module,
Filler layer, solar cell element as photovoltaic element, filler layer, and first heat-resistant polypropylene-based resin film and coloring with heat-resistant polypropylene-based resin composition containing ultraviolet absorber and light stabilizer Heat-resistant polypropylene-based resin composition containing a second heat-resistant colored polypropylene-based resin film containing a heat-resistant polypropylene-based resin composition containing a photo-agent, an ultraviolet absorber and a light stabilizer, an ultraviolet absorber and a light stabilizer A back surface protection sheet for a solar cell module, which is a three-layer laminated resin film obtained by sequentially laminating a third heat-resistant polypropylene-based resin film, is laminated one by one, and these are vacuum-sucked to form a thermocompression-bonded laminator. -A solar cell module characterized by being formed as an integrally molded body by a method such as a method. 9. The solar cell module according to claim 8, wherein the solar cell element is a crystalline silicon solar cell element or an amorphous silicon solar cell element. 10. A solar cell element is provided on its surface with at least one of water vapor, oxygen gas, a decomposition product, or an additive.
The solar cell module according to any one of claims 8 to 9, further comprising a barrier layer that blocks permeation of one or more kinds. 11. A solar cell element, a resin film, a barrier resin film, a vapor deposition film of an inorganic oxide, a resin film provided with a vapor deposition film of an inorganic oxide, and a polycondensate obtained by hydrolysis of a silicon compound on a surface thereof. A coating film made of a composition comprising: a metal-containing gas barrier coating film;
The solar cell module according to any one of claims 8 to 10, wherein a barrier layer made of a composite film made of one or more kinds is provided.