JP2012222188A - Solar cell module with protective film and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a protective film having wear resistance, steam barrier property and high light transmissivity, as the surface protective member of a solar cell, inexpensively.SOLUTION: In the solar cell module having a protective film on the surface, the protective film is formed by laminating a hard coat layer and an abrasion resistance layer on one side of a substrate in this order, and has a barrier layer on the side of the substrate opposite from the side where the abrasion resistance layer is formed. Resin is used in the substrate, both the abrasion resistance layer and the barrier layer contain silicon, oxygen, and nitrogen, and the content of oxygen in the abrasion resistance layer is higher than that in the barrier layer.

Description

  The present invention relates to a solar cell module having a protective film that is used on a light-receiving surface side surface and can be made flexible.

  At present, a wide variety of solar cells such as a thin film silicon type, a spherical silicon type, an organic compound type, a CdTe type, a CIGS type, a dye sensitized type, and an organic thin film type have been developed in addition to a crystalline solar cell. . In recent years, environmental awareness has been improved, and governments have been spreading in various countries.

As a surface protection member that is a component of these solar cell modules, a glass substrate that can satisfy all of translucency, hardness, and water vapor barrier properties is often used.
However, glass is heavy, and the weight ratio in a crystalline silicon solar cell accounts for about 70% of all modules.

Furthermore, when the surface protection member is glass, the module once created cannot be bent. Therefore, in order to create a structure having a curved surface, it is necessary to shape the glass so as to be a curved surface in advance. Therefore, it was difficult to create a solar cell having a curved surface.
However, in recent years, a film type solar cell that can be made flexible by a thin film solar cell or the like has come out.

Since the film-type solar cell can be bent after the module is formed, it can be used for a building material having a curved surface in addition to a portable charger.
As a result, the number of places where the solar cell module can be installed has increased, and as a result, it has been put into practical use in applications such as building material integrated solar cell modules (BIPV).

However, since a fluorine-based resin is mainly used as the protective film used in the film type solar cell, when the resin alone is used as the protective film, it is vulnerable to scratches such as scratches. Moreover, since the water vapor barrier property is several g / (m ² · day) with a fluorine-based resin film alone, the water vapor barrier property of 1 g / (m ² · day) or less required for solar cells cannot be obtained. There is a problem.

In order to cope with this, in the fluororesin, for example, as in Patent Document 1, a fluororesin sheet and a resin film having a vapor-deposited thin film of an inorganic oxide are laminated, and any one of the laminates is further provided. A surface protection sheet for a solar cell module, which is provided with an antifouling layer or an ultraviolet absorber layer on one side or both sides, has been considered.
Moreover, like patent document 2, the protective film which has a weather resistance and water vapor | steam barrier property is considered by bonding together a film with a weather resistance and the film coated with the inorganic oxide through the adhesive agent.

  Thus, in order to create a film that satisfies translucency, abrasion resistance, and water vapor barrier properties, a film that provides abrasion resistance and antifouling properties to a weather resistant substrate is required, and further, water vapor barrier properties. It was necessary to laminate another film having

JP 2000-208797 A Japanese Patent No. 3978912

  However, since two or more films are necessary as the protective film and different materials are used, the number of processes is increased, resulting in an expensive film.

By the way, in order to provide wear resistance, a hard material is used. In order to form a water vapor barrier film, a film having a dense defect is obtained. It is generally said that it is necessary to make the surface hydrophilic so that the action can work.
And, as a material used to give wear resistance, water vapor barrier properties, and antifouling performance, many inorganic materials are used, and in fact, glass is used as a transparent protective material in the present situation. Just as you did.

  This invention is made | formed in view of said subject, Comprising: It aims at providing cheaply the protective film which has abrasion resistance and water vapor | steam barrier property, and high light transmittance.

  As a means for solving the above-mentioned problems, the invention according to claim 1 is directed to a solar cell module having a protective film on the surface, wherein the protective film has a hard coat layer and an abrasion-resistant layer on one side of the substrate. Are laminated in this order, and a film having a barrier layer on the side opposite to the side on which the wear-resistant layer of the substrate is applied, the substrate uses a resin, and the wear-resistant layer and the barrier layer The solar cell module has a protective film characterized in that both contain silicon, oxygen, and nitrogen, and the content of oxygen contained in the wear-resistant layer is higher than that of the barrier layer.

  Further, in the invention according to claim 2, the hard coat layer has an uneven shape in the solar cell module having the protective film according to claim 1, and the wear-resistant layer is in the recess along the uneven shape. A solar cell module having a protective film characterized in that the wear-resistant layer is thinner than the unevenness of the hard coat layer.

  The invention according to claim 3 is the protective film according to claim 1 or 2, wherein the contact angle between the wear-resistant layer and water is smaller than the contact angle between the barrier layer and water. This is a solar cell module having a film.

  The invention described in claim 4 is a solar cell module having a protective film, wherein the hard coat layer described in claims 1 to 3 is an ionizing radiation curable resin.

  Moreover, as a manufacturing method of the solar cell module which has the protective film of Claim 1 to 4, the abrasion-resistant layer and the barrier layer are a polysilazane solution with respect to the board | substrate with which the hard-coat layer and the base material layer were united. The protective film is characterized by drying the solvent in the polysilazane solution after the coating by the above, performing the plasma treatment only on the side that becomes the barrier layer, and then subjecting the film to an aging treatment in a water or water vapor atmosphere. It is a manufacturing method of the solar cell module which has.

  By using the present invention, it becomes possible to create a solar cell module using a protective film having wear resistance and water vapor barrier properties for one film. Moreover, it becomes possible to use a film with a high transmittance | permeability by shaping a hard-coat layer. Furthermore, since the starting materials for the two layers of the wear-resistant layer and the barrier layer are the same, the materials can be shared, so that the cost can be reduced.

It is sectional drawing (a) which shows an example of the whole solar cell structure concerning this Embodiment, and sectional drawing (b) which shows an example of the protective film structure in the solar cell. It is the schematic of plate | board creation for creating the hard-coat layer of the protective film of this implementation.

  Hereinafter, an embodiment of a solar cell module using the protective film of the present invention will be described in detail based on the drawings.

  FIG. 1 shows a sectional view of a solar cell module using a protective film in (a). Moreover, (b) is a cross-sectional view (b) of the protective film on the surface of the solar cell of the embodiment. As shown in FIG. 1B, the protective film 100 on the surface of the solar cell module includes an abrasion-resistant layer 1, a hard coat layer 2, a base material layer 3, and a barrier layer 4 from the light receiving surface side.

The wear-resistant layer 1 is disposed on the foremost surface on the light receiving surface side of the solar cell module, and light is incident on the surface. The abrasion resistant layer 1 is a layer formed by applying a polysilazane solution and then performing a treatment in a water or water vapor atmosphere.
Polysilazane is a polymer having a silicon-nitrogen bond, and is a ceramic precursor inorganic polymer such as SiO ₂ , Si ₃ N _{4 made of} Si—N, Si—H, N—H or the like, and both intermediate solid solutions SiOxNy. It is.

  Polysilazane

However, each of R1, R2, and R3 in the formula is a hydrogen atom, an alkyl group, an alkenyl (ALKENYL) group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group, an alkoxy group, etc. In particular, perhydropolysilazane in which all of R 1, R 2 and R 3 are hydrogen atoms is particularly preferred from the viewpoint of the denseness as a gas barrier film to be obtained.

Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on 6- and 8-membered rings. The molecular weight is about 600 to 2000 (polystyrene conversion) in terms of number average molecular weight (Mn), and becomes a liquid or solid substance depending on the molecular weight. These are marketed in a solution state dissolved in an organic solvent, and the commercially available product can be used as it is as a polysilazane-containing coating solution.
In addition, it is not preferable to use an organic solvent or water-containing one that easily reacts with polysilazane as an organic solvent for preparing a liquid containing polysilazane. Specifically, hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, ethers such as halogenated hydrocarbon solvents, aliphatic ethers and alicyclic ethers can be used.

Specific examples of organic solvents to be used include hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso and terpene, halogenated hydrocarbons such as methylene chloride and chloroform, and ethers such as dibutyl ether, dioxane and tetrahydrofuran. Etc. These solvents may be selected according to purposes such as the solubility of polysilazane and the evaporation rate of the solvent, and a plurality of solvents may be mixed.

  The polysilazane concentration in the polysilazane-containing solution is about 0.2 to 35% by mass, although it varies depending on the target silica film thickness and the pot life of the coating solution.

  In order to promote the conversion to a silicon oxide compound, an amine or metal catalyst may be added. About these, it is possible to obtain as a commercial item, specifically, AZ Electronic Materials Co., Ltd. product Aquamica NAX120, NN110, NN120, NN310, NN320, NL110A, NL120A, NP110, NP140, NP344, SP140, etc. Is mentioned.

As a method for measuring the content of oxygen contained in each of the wear-resistant layer and the barrier layer, there is a method using a Fourier transform infrared absorption method (FTIR) or an X-ray electron spectroscopy (XPS).
When the measurement is conducted by the FTIR, the peak area of the vibration of 1080 cm ^-1 respectively, for the wear layer and the barrier layer, which is attributed to the vibration and the SiO ₂ of 840～950Cm ^-1 attributed the _Si 3 _{N 4} By comparing the two, the size can be determined. Further, when measuring using XPS, the peak area of 101 to 102 eV (electron volt: ELECTRONVOLT) attributed to Si ₃ N ₄ and the peak area of 103 to 104 eV attributed to SiO ₂ are represented as an abrasion resistant layer, Each barrier layer may be compared.

Since the wear-resistant layer is present on the outermost surface on the light-receiving surface side, it is desirable to have antifouling performance in addition to wear resistance. Since the wear-resistant layer is a SiO ₂ film, the contact angle of the Si ₃ N ₄ film with water is about 60 °, whereas in SiO ₂ it is as small as 20-30 °. Thus, by making the contact angle between the wear-resistant layer and water smaller than the contact angle between the barrier layer and water, a self-cleaning effect can be expected that floats and removes dirt when wet.

The hard coat layer 2 is made of a curable resin by ionizing radiation. The ionizing radiation referred to here is, for example, ultraviolet light, visible light, infrared light, or electron beam. Among them, it is desirable that the ionizing radiation is made of an ultraviolet curable resin that is easy to produce.
As materials of these hard coat layers 2, urethane acrylate, polyether acrylate, polyester acrylate, epoxy acrylate, acrylic acrylate, those dispersed in water, epoxide, reactive monomer having a photopolymerizable unsaturated bond, and these A mixture is used.

  Examples of the acrylate monomer having at least one photopolymerizable unsaturated bond in the molecule include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, and n-pentyl acrylate. , N-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxyethylene glycol acrylate, cyclohexyl acrylate, dicyclopenta Nyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, Lysidyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobornyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, phenoxyethyl acrylate, stearyl acrylate , Ethylene glycol diacrylate, diethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexadiol diacrylate, 1,3-propanediol acrylate, 1,4-cyclohexane Diol diacrylate, 2,2-dimethylolpropane diacrylate, glycerol diacrylate, tri Lopylene glycol diacrylate, glycerol triacrylate, trimethylolpropane triacrylate, polyoxyethylene trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethylene oxide modified pentaerythritol triacrylate, ethylene oxide modified pentaerythritol tetraacrylate, Propion oxide modified pentaerythritol triacrylate, propion oxide modified pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyoxypropyltrimethylolpropane triacrylate, butylene glycol diacrylate, 1,2,4-butanetriol triacrylate, 2 , 2,4-trimethyl-1,3-pentadiol diacrylate, diallyl fumarate, 1,10-decane diol dimethyl acrylate, pentaerythritol hexaacrylate, and the above acrylate replaced with methacrylate, γ-methacryloxy Examples thereof include propyltrimethoxysilane and 1-vinyl-2-pyrrolidone.

  The hard coat layer 2 may be a smooth layer (not shown), but the light utilization efficiency can be increased by making the shape into a prism shape. In this case, it is desirable that the apex angle is small. However, since there is a problem such as bending of the convex portion of the hard coat layer during processing, specifically, it is between 30 ° and 150 °, and further between 60 ° and 90 °. Is desirable.

  The state in which the wear-resistant layer is thinner than the difference in unevenness of the hard coat layer means that the wear-resistant layer has a film thickness thinner than the step in the unevenness of the hard coat layer. In this case, it is desirable that the wear-resistant layer has a uniform film thickness, but it includes the case where the thickness of the wear-resistant layer in the concave portion is larger than that of the convex portion due to the influence of the uneven shape of the hard coat layer.

  The hard coat layer 2 has an effect of making the hardness larger than that of the base material by being laminated on the film. For example, the presence of the wear-resistant layer 1 makes it possible to obtain the resistance of steel wool, but the resistance to scratches, for example, is influenced by the underlying substrate because the wear-resistant layer is thin. As a result, scratch resistance may not be obtained as desired. Therefore, it is necessary to provide a hard coat layer. The hardness of the hard coat layer 2 itself is preferably 2H or more in terms of pencil hardness.

The hard coat layer may be blended with an ultraviolet absorber so that ultraviolet rays that cause deterioration of the base material layer do not reach.
In this case, the ultraviolet absorber is not particularly limited as long as it is an ultraviolet absorber, and salicylate-based, benzophenone-based, and benzotriazole-based ultraviolet absorbers are generally known.

  As salicylate ultraviolet absorbers, phenyl salicylate, 4-tert-butylphenyl salicylate, 4-tert-octylphenyl salicylate and the like are generally known.

Examples of benzophenone ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxybenzophenone, 2 -Hydroxy-4-n-dodecyl-oxybenzophenone, 2-hydroxy-4-benzyloxy-benzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2,2'-dihydroxy-4-methoxy Benzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, a mixture of 2,2′-dihydroxy-4,4′-dimethoxybenzophenone and other 4-substituted benzophenones (for example, trade name “UVINUL490” BASF 2,2 '4,4'-tetrahydroxy benzophenone, and the like 2-hydroxy-4-methoxy-2'-carboxy benzophenone is generally known.

  Examples of benzotriazole ultraviolet absorbers include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl) phenyl. ] -Benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butyl-phenyl) -benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methyl) Phenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5 ' -Di-t-amyl-benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, and 2,2'-methylenebis [4- (1,1,3 3-tetramethylbutyl)-6-(2N-benzotriazol-2-yl) phenol], etc. are generally known.

  Regarding the thickness of the hard coat layer, in order to provide a function of absorbing ultraviolet rays, it is desirable that the thickness between the base material and the concave portion, which is the thinnest part of the hard coat layer, is 3 μm or more. On the other hand, if the hard coat layer is too thick, there is a problem in adhesion between the base material layer 3 and the hard coat layer 2 due to curing shrinkage at the time of forming the hard coat layer. The thickness from the material to the convex portion is desirably 100 μm or less.

  As a method for forming irregularities in the hard coat layer 2, a substrate 3 coated with a resin for forming a hard coat layer is brought into close contact with a mold on which irregularities are formed in advance. Irregularities can be formed by irradiating with ionizing radiation and curing the resin.

  As a mold, for example, a diamond bit 6 is moved while rotating a roll-shaped substrate 5 as shown in FIG. 2, or an uneven shape is formed by pressing with a bit while moving a roll. .

The material of the transfer master is not limited to metal, ceramic, resin, etc., but preferably an iron alloy such as stainless steel having excellent dimensional stability and conductivity, and copper or nickel laminated with excellent workability are preferably used. preferable.
The surface of the transfer master is subjected to mechanical polishing, etching, cleaning, and the like to make a uniform surface.
Laser processing, sputtering, etching, photolithography, and the like can be used as a method for forming a concavo-convex shape on the surface. As a method for obtaining the desired surface irregularities with excellent productivity, a method of performing machining using a diamond tool or the like on the surface of the transfer master is preferable.

  In consideration of being installed outdoors, the base material layer 3 is preferably one having weather resistance against water, ultraviolet rays, and the like. For example, a polyester type such as polyethylene terephthalate resin (PET resin) or polyethylene naphthalate (PEN resin). Resin, polyethylene resin, polypropylene resin, methacrylic resin, polylactic acid resin, polymethylpentene resin, cyclic polyolefin resin, polystyrene resin, acrylonitrile- (poly) styrene copolymer (AS resin), acrylonitrile-butadiene -Styrene copolymer (ABS resin), polyvinyl chloride resin, poly (meth) acrylic resin, polycarbonate resin, polyester resin, polyamide resin, polyimide resin, polyamideimide resin, polyaryl phthalate resin ,silicone Resins, polysulfone resins, polyphenylene sulfide resins, polyether sulfone resins, polyether imide resins, epoxy resins, polyurethane resins, acetal resins, cellulose resins and the like.

  Among the above-mentioned resins, polyester resins and cyclic polyolefin resins are preferably used as those having a good balance of high heat resistance, strength, weather resistance, durability, water vapor barrier properties, and the like. Further, since it is necessary to transmit light, the transmittance of the base material alone is desirably 80% or more, particularly desirably 90% or more, in the total light transmittance defined in JIS K7361.

  Examples of the polyester-based resin include polyethylene terephthalate and polyethylene naphthalate. Among these polyester-based resins, polyethylene terephthalate is particularly preferable because it has a good balance between various functions such as heat resistance and weather resistance, and price.

  Examples of the cyclic polyolefin-based resin described above include polymerization of cyclic dienes such as cyclopentadiene (and derivatives thereof), dicyclopentadiene (and derivatives thereof), cyclohexadiene (and derivatives thereof), norbornadiene (and derivatives thereof), and the like. And a copolymer obtained by copolymerizing the cyclic diene with one or more olefinic monomers such as ethylene, propylene, 4-methyl-1-pentene, styrene, butadiene, and isoprene. Among these cyclic polyolefin resins, cyclopentadiene (and derivatives thereof), dicyclopentadiene (and derivatives thereof) or norbornadiene (and derivatives thereof) such as polymers having excellent strength, heat resistance, and weather resistance are particularly preferred. preferable.

  In addition, as a forming material of the base material 3, the above-mentioned synthetic resins can be used alone or in combination. In addition, various additives and the like can be mixed in the forming material of the base material 3 for the purpose of improving and modifying processability, heat resistance, weather resistance, mechanical properties, dimensional stability, and the like. Examples of the additive include a lubricant, a crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing fiber, a reinforcing agent, an antistatic agent, a flame retardant, a flame retardant, a foaming agent, and an antifungal agent. And pigments. The base material 3 may or may not be stretched.

The barrier layer 4 is coated with a polysilazane solution in the same manner as the wear-resistant layer 1, dried and then plasma treated to form a film mainly composed of silicon nitride.
For the barrier layer 4, polysilazane may be applied directly to the base material, but after providing an anchor layer for filling the unevenness of the base material itself, the polysilazane for creating the barrier layer 4 is applied. Also good.

  The barrier layer 4 is inorganic, and when the film thickness is increased, cracks occur and the barrier layer 4 does not function as a barrier layer, so the film thickness is preferably 2 μm or less. When the film thickness is thin, the influence of pinholes due to the unevenness of the substrate itself cannot be ignored, so that the thickness is preferably 0.01 μm or more.

  As a coating method for the wear-resistant layer 1 and the barrier layer 4, any appropriate method can be adopted as a coating method. As specific examples, coating can be performed by gravure coating, micro gravure coating, reverse gravure coating, comma coating, bar coating, spin coating, roll coating, flow coating, ink jet, spray coating, dip coating, and the like.

  The protective film in the solar cell module of the present invention will be described as Example 1 in FIG.

Preparation of protective film First, dilute with 1,6-hexanediol diacrylate so that the viscosity is 1500 mPa · S on the surface of 50 μm of weather resistant PET (HB, Teijin DuPont Films) which is the base material. Further, an ultraviolet curable resin (EBECRYL 800 Daicel Cytec Co., Ltd.) to which only 2% by weight of an ultraviolet absorber (UVINUL490, BASF) was added was applied. Thereafter, exposure is performed at 1000 mJ / cm ² using a UV lamp while pressing a plate having an apex angle of 60 ° and a pitch of 50 μm on the side coated with the UV curable resin at a linear pressure of 0.4 kgf / cm. To create a 60 [deg.] Prism shape.
Next, a polysilazane solution (NAX120-20) that serves as a precursor for the wear-resistant layer and the barrier layer.
AZ Electronics Co., Ltd.) was applied to both surfaces of the substrate by dipping (pulling speed 0.5 m / min) so as to be 0.4 μm, and dried by heating at 50 ° C. for 1 minute. Thereafter, on the barrier layer side, atmospheric pressure plasma is used, a mixed gas having a nitrogen flow rate of 400 L / min and an oxygen flow rate of 1.69 × 10 ⁻¹ Pa · m ³ / sec (100 SCCM) is used, and the distance between the substrate and the electrode Was 3 mm, and the treatment was performed for 30 seconds.

  Subsequently, the substrate subjected to the plasma treatment was then humidified at 60 ° C. and 90% for 3 hours.

  The film was obtained in the same manner as in Example 1 except that the process from application of the polysilazane solution to humidification in Example 1 was performed twice.

  The humidification treatment in Example 1 was carried out in the same manner except that the treatment was performed by dipping from distilled water to distilled water for 5 minutes.

  The same procedure as in Example 3 was performed, except that the steps from application of the polysilazane solution in Example 3 to immersion treatment in distilled water were performed twice.

<Comparative Example 1>
As Comparative Example 1, a polysilazane solution of Example 1 that was not subjected to plasma treatment on the barrier layer was prepared.

<Comparative example 2>
As Comparative Example 2, a polysilazane solution of Example 1 that was not humidified was prepared.

  The prepared protective sheet was subjected to a water vapor barrier test and an abrasion resistance test. In addition, the power generation efficiency of the prepared films was compared. The results are shown in Table 1.

As a water vapor barrier test, the water vapor transmission rate was measured. As a measuring method, a JIS standard K7129B method (isobaric method, temperature 40 ° C., humidity 90% RH) and a Mocon method (coulometric method) according to the measuring method shown in ASTM D3985-81 are used. The measurement was performed using PERMATRAN-W3 / 33 manufactured by the company. The measured water vapor permeability was less than 1 g / (m ² · day) for the plasma treated polysilazane solution, indicating that it sufficiently functions as a moisture-proof film. What was not plasma-treated with the polysilazane solution of Comparative Example 1 had water vapor transmission of 1 g / (m 2 / day) or more,
It did not have a function as a moisture-proof film.

As a steel wool test, # 0000 steel wool was subjected to 10 reciprocating frictions at a speed of 50 mm / sec while applying a load of 500 g / cm ² , and the state of the film thereafter was visually observed. In Examples 1 to 4 and Comparative Example 1 in which the polysilazane solution was humidified as the abrasion-resistant layer treatment, the surface was sufficiently scratch-resistant, but the polysilazane solution was not humidified. Comparative Example 2 is easily scratched and has a problem with suitability.

  Regarding the comparison of power generation efficiency, for the 6-inch solar cells, the films prepared in Examples and Comparative Examples were bonded to each other via glycerin, and then the efficiency was measured using a solar simulator, and there was no problem. .

  As described above, the solar cell module having the protective film of the present invention can maintain its performance for a long time.

DESCRIPTION OF SYMBOLS 1 ... Wear-resistant layer 2 ... Hard coat layer 3 ... Base material layer 4 ... Barrier layer 5 ... Roll-shaped base material 6 ... Diamond bit 11 ... -Sealing resin layer 12 ... Tab wire 13 ... Solar cell 14 ... Back sheet 100 ... Surface protection film of solar cell module

Claims (5)

  In the solar cell module having a protective film on the surface, the protective film is formed by laminating a hard coat layer and an abrasion resistant layer in this order on one side of the substrate, and the side on which the abrasion resistant layer of the substrate is applied It has a barrier layer on the opposite side, the substrate is made of resin, and both the wear resistant layer and the barrier layer contain silicon, oxygen, and nitrogen, and the oxygen content in the wear resistant layer is The solar cell module which has the protective film characterized by having more than a barrier layer.   The hard coat layer has a concavo-convex shape, and the wear-resistant layer is formed along the concavo-convex shape, and the film thickness of the wear-resistant layer in the concave portion is thinner than the difference in the concavo-convex shape of the hard coat layer. A solar cell module having a protective film.   The solar cell module having a protective film according to claim 1 or 2, wherein a contact angle between the wear-resistant layer and water is smaller than a contact angle between the barrier layer and water.   The solar cell module having a protective film according to any one of claims 1 to 3, wherein the hard coat layer is an ionizing radiation curable resin.   5. The method for producing a solar cell module having the protective film according to claim 1, wherein the wear-resistant layer and the barrier layer are formed of a polysilazane with respect to a substrate in which the hard coat layer and the base material layer are integrated. After the application with the solution, the solvent in the polysilazane solution is dried, the plasma treatment is performed only on the side that becomes the barrier layer, and then the film is subjected to an aging treatment in a water or water vapor atmosphere. A method for producing a solar cell module having a film.