JP5638378B2 - Fluorine resin coated steel sheet and steel sheet integrated solar cell module - Google Patents

Description

  The present invention is a steel plate suitable for a substrate of a steel plate-integrated solar cell module, and is a fluorine-based resin-coated steel plate excellent in adhesion, corrosion resistance, workability, and weather resistance to the sheet type solar cell module, and an upper layer thereof. The present invention relates to a steel sheet integrated solar cell module that is excellent in insulation, corrosion resistance, workability, and weather resistance formed by disposing a sheet type solar cell module.

  In recent years, there has been a strong demand for conservation of the global environment, carbon dioxide emission regulations have been strengthened, and the use of natural energy has become active. In particular, power generation using sunlight has attracted attention, and it is also influenced by the improvement in the performance of solar cells, so that a large number of solar cells are laid on a roof or the like to perform solar power generation. Under such circumstances, for the purpose of improving workability and the like, there has been a demand for the development of a solar cell integrated roof material in which a solar cell and a roof material are integrated.

  In response to such a demand, for example, Patent Document 1 proposes a solar roof material. The technique described in Patent Document 1 is an iron system in which an intermediate flat portion that is lowered by one step is formed in the middle of the main plate via both step portions that are bent downward, and bent joint portions are formed on both sides of the main plate. It is a solar roof plate made of a thin steel plate roof plate body, a solar mounted on and attached to an intermediate flat portion, and a glass plate or hard plastic fixed on the solar. In the technique described in Patent Document 1, the solar is coated with EVA (ethylene-vinyl acetate copolymer) resin on the upper and lower sides of a crystalline solar cell, and an insulating sheet is further provided on the lower side of the EVA resin. It has a structure with EVA resin underneath. In the technique described in Patent Document 1, the solar is vacuum heated together with the roof plate body in a state where only the intermediate flat portion that is lowered through the stepped portion is formed, and solar EVA resin is applied to the intermediate flat portion. It is assumed that the solar is adhered and fixed to the roof plate body by thermocompression bonding, and then bent joints are formed at both ends of the roof plate body. As a result, it is possible to provide a solar roof plate that is excellent in strength, easy to construct, and inexpensive, and that is excellent in design and wind pressure resistance.

  Patent Document 2 proposes a roof material integrated solar cell module in which thin-film solar cells are laid across the front wall and the upper surface of the roof material. In the technique described in Patent Document 2, a solar cell module is used as a flexible substrate, and a thin solar cell or the like is sealed in a sandwich shape with a sheet-like sealing material and a weather-resistant surface protective material. It is pasted on the surface. Examples of the sealing material include EVA (ethylene-vinyl acetate copolymer) resin, and examples of the surface protection material include fluorine-based resin films such as ETFE. This makes it easy to perform roll bending and die bending. In the technique described in Patent Document 2, the solar cell module is attached to the roofing material when the roofing material is in a flat plate state and then bent.

JP 2002-194858 A Japanese Patent Laid-Open No. 2004-87769

  Recently, as a solar cell element used for a solar cell module, a sheet-type thin film amorphous solar cell is widely used from the viewpoint of lightness and workability. A solar cell module (solar) in which such a sheet-type solar cell element is sandwiched between encapsulants is a technique described in Patent Document 1, in which an EVA resin, which is a solar encapsulant, is thermocompression bonded to a roof. Affixed to the plate body. Moreover, in the technique described in Patent Document 2, a solar cell module in which a sheet-type solar cell element is sandwiched between sealing materials is attached to a roof plate body with an adhesive. In general, a silicon-based adhesive is used as the adhesive.

  However, with the above-mentioned silicon-based adhesive, there is a concern that it will be peeled off from long-term use due to intrusion of water or the like from the bonding end surfaces of the solar cell module and the roof plate main body, leaving a problem in adhesiveness. Further, in the techniques described in the cited documents 1 and 2, EVA resin (ethylene-vinyl acetate copolymer) used as a sealing material in solar cell modules has poor weather resistance and heat resistance, and is outdoors for a long time. When left alone, there is a problem that the adhesion to the steel plate for roof becomes insufficient.

  The present invention solves the problems of the prior art, and is a fluorine-based resin-coated steel sheet that is excellent in corrosion resistance (weather resistance), workability, and adhesion to a solar cell module, and a sheet type solar cell on the upper layer thereof It is an object of the present invention to provide a steel plate integrated solar cell module that is excellent in insulation, corrosion resistance, workability, and weather resistance.

  In order to achieve the above-mentioned object, the present inventors diligently studied various factors affecting the adhesion of a steel plate integrated solar cell module, particularly the adhesion between the solar cell module and a steel plate as a substrate. As a result, a fluorine resin coating layer is formed on the surface of the steel plate as a substrate, and corona discharge treatment is applied to both sides of the fluorine resin coating layer, and the solar cell module and the steel plate are bonded via the fluorine resin coating layer. It was found that this is effective for improving the adhesion.

  And based on the said knowledge, it came to the idea that the steel plate suitable for the board | substrate of a steel plate integrated solar cell module was obtained by providing a fluorine-type resin coating layer in a steel plate. Moreover, even when it is applied to a solar roof plate installed outdoors by providing a rust-preventing primer layer containing a predetermined pigment as a lower layer of a fluorine-based resin coating layer as a zinc-based plated steel plate, It was found that corrosion resistance and weather resistance that can withstand harsh environments can be obtained.

Further, in addition to the above, the solar cell module is further used as a sheet type solar cell module, and a solar cell element encapsulated with a fluorine resin film is used, or at least a fluorine resin as a protective sheet It was found that the adhesion between the solar cell module and the steel plate as the substrate was remarkably improved by bonding the end of the solar cell module by resin thermal fusion using the one covered with the film. .
The present invention has been completed based on such findings and further studies. That is, the gist of the present invention is as follows.

[1] A fluorinated resin-coated steel sheet having a rust-preventing primer layer on at least one surface of a zinc-based plated steel sheet and a fluorine-based resin coating layer on the upper layer, the rust-preventing primer layer comprising a resin component and 10 A rust-preventing primer layer comprising a rust-preventing pigment having a thickness of more than 1% and not more than 65% by weight and having a thickness of more than 1 μm and not more than 20 μm. A fluorine-based resin-coated steel sheet for adhering a sheet-type solar cell module, wherein a fluorine-based resin coating layer is formed on both sides by corona discharge treatment.

[2] A fluorine resin coating for adhering a sheet type solar cell module according to [1], wherein the resin component of the anticorrosion primer layer is an acrylic-silicon resin or a polyester-silicon resin steel sheet.

[3] In order to bond a sheet type solar cell module according to [1] or [2], wherein the rust preventive pigment of the rust preventive primer layer contains one or two of strontium-chromate and calcium phosphate. fluororesin-coated steel sheet.

[4] A fluorine-based resin-coated steel sheet for adhering a sheet-type solar cell module according to any one of [1] to [3], wherein the zinc-based plated steel sheet is subjected to a chemical conversion treatment.

[5] On at least one surface of the galvanized steel sheet, a rust preventive primer layer containing a resin component and a rust preventive pigment of 10% by mass to 65% by mass and having a thickness of more than 1 μm and not more than 20 μm, and an upper layer thereof The sheet type solar cell module is disposed on the fluorine resin-coated steel sheet having a fluorine resin coating layer having a thickness of 15 μm or more and 250 μm or less and having a corona discharge treatment on both sides on the antirust primer layer side. A steel sheet integrated solar cell module,
The surface of the fluorine resin-coated steel sheet on the sheet-type solar cell module side is subjected to corona discharge treatment, and the fluorine-based resin coating layer and the lower surface portion of the sheet-type solar cell module are bonded to each other. Steel sheet integrated solar cell module.

[6] In the steel sheet integrated solar cell module according to [5], the lower surface portion of the sheet type solar cell module is bonded to the fluorine resin coating layer via an adhesive layer.

[7] In [5] or [6], the sheet-type solar cell module is obtained by encapsulating a solar cell element of the sheet-type solar cell module in a sandwich shape with a fluorine-based resin film. Steel sheet integrated solar cell module.

[8] In the sheet-type solar cell module according to [5] or [6], at least the upper surface side of the sheet-type solar cell module is covered with a fluororesin film. .

[9] In [7] or [8], the adhesion between the fluororesin coating layer and the lower surface portion of the sheet-type solar cell module is performed through the adhesive layer in the portion where the solar cell element is present. And a solar cell module integrated with a steel sheet, wherein the portion where the solar cell element does not exist is bonded by thermal fusion of the fluororesin film.
[10] The steel sheet integrated solar cell module according to any one of [5] to [9], wherein the resin component of the antirust primer layer is an acrylic-silicone resin or a polyester-silicone resin.
[11] In any one of [5] to [10], the rust preventive pigment of the rust preventive primer layer includes one or two of strontium-chromate and calcium phosphate. .
[12] The steel sheet integrated solar cell module according to any one of [5] to [11], wherein the zinc-based plated steel sheet is subjected to a chemical conversion treatment.

  According to this invention, in addition to durability, such as a weather resistance and corrosion resistance, the steel plate excellent in the adhesiveness of a steel plate and a solar cell module is obtained. In addition, according to the present invention, an integrated solar cell module having excellent adhesion between a steel plate and a solar power generation module and having good durability and insulation can be provided, and an industrially significant effect is achieved. Moreover, the steel plate integrated solar power generation module of the present invention has an effect that it can be widely used as a roofing material, an outer wall material, and a sound insulation wall such as an expressway.

It is explanatory drawing which shows typically an example of the cross-sectional condition which formed the fluorine-type resin coating layer on the surface of the zinc-plated steel plate which is a board | substrate used by this invention. It is explanatory drawing which shows typically an example of the cross section of the steel plate integrated solar power generation module of this invention. It is explanatory drawing which shows typically an example of the cross section of the sheet type solar cell module used by this invention.

  The steel plate of the present invention is a fluorine-based resin-coated steel plate. As shown in FIG. 1, a rust-preventing primer layer 2 is provided on at least one surface of a zinc-based plated steel plate 3, and a fluorine-based resin coating layer 1 is provided thereon. It is characterized by having.

  The steel plate used as the base material for the fluororesin-coated steel plate of the present invention is a zinc-based plated steel plate. The zinc-based plating is provided on one side or both sides of the substrate for the purpose of imparting corrosion resistance and end face rust resistance to the steel plate. If a steel plate without a zinc-based plating layer is used as the base material, the corrosion resistance and weather resistance will be insufficient, and for example, it can be applied to applications in harsh environments such as solar roof plates installed outdoors. Can not. The substrate of the zinc-based plated steel sheet is preferably a cold-rolled steel sheet having a thickness of about 0.1 to 1.6 mm from the viewpoint of strength and workability. The zinc-based plating layer is preferably formed on at least one side of the substrate, but is preferably formed on both sides in consideration of further corrosion resistance and end surface rust resistance improvement.

  Here, as the zinc-based plating, electrogalvanizing, zinc-nickel alloy plating, zinc-chromium alloy plating, hot-dip zinc plating plate, alloyed hot-dip zinc plating, zinc-aluminum alloy plating, etc. Is mentioned. In view of price and performance, hot dip galvanizing is preferable. In particular, preferable hot-dip galvanized steel sheets include 5% aluminum-zinc alloy plated steel sheets (Galfan, GF), 55% aluminum-zinc alloy plated steel sheets (galvalume, GL), and the like. Moreover, there is no problem even if Mg, Mn, Si, Ti, Ni, Co, Mo, Pb, Sn, Cr, La, Ce, Y, Nb, etc. are added to these zinc and aluminum-zinc alloys. .

In the present invention, a rust-preventing primer layer is provided on both surfaces of the zinc-based plated steel sheet as a base material. May be applied. The kind of chemical conversion treatment is not particularly limited, and examples thereof include known phosphate treatment, chromate treatment, and chromate-free treatment. From the viewpoint of reducing environmental burden, it is preferable to use a chromate-free treatment. Examples of the chromate-free treatment include inorganic treatments and / or organic treatments containing a phosphoric acid-based, silicone-based, silicate-based, magnesium-based, vanadium-based compound, etc., all of which are suitable in the present invention. From the viewpoint of heat resistance, an inorganic treatment is preferable. In addition, the adhesion amount (solid content) of the chemical conversion treatment layer is preferably a thin film thickness from the viewpoint of cost and productivity, and is usually preferably 3 g / m ² or less by dry weight.

The rust-preventing primer layer provided on at least one surface of the galvanized steel sheet as a base material is composed of a mixture containing a resin component and 10 to 65% by weight of a rust-preventing pigment, and the thickness is more than 1 μm and not more than 20 μm And
The kind of the resin component contained in the rust preventive primer layer is not particularly limited, but is required to have predetermined heat resistance. As will be described later, in the present invention, when the fluororesin coating layer is formed on the antirust primer layer, the fluororesin film is laminated on the steel plate provided with the antirust primer layer. It becomes hot. Therefore, the resin component needs to be a resin that does not decompose such as pulverization, weight loss, and discoloration even when heated at 250 ° C. for 30 seconds or more. A resin that does not decompose even when heated at 300 ° C. for 30 seconds or longer is preferable, and a resin that does not decompose even when heated at 350 ° C. for 30 seconds or longer is more preferable.

  Examples of the resin component include known polyester resins, epoxy resins, urethane resins, melamine resins, acrylic resins, urea resins, polyamide resins, silicon resins, polyimide resins, polysulfone resins, and polyethers. Examples of the coating resin include one or a combination of two or more selected from a sulfone resin and a polyphenyl sulfide resin.

  Further, from the viewpoint of adhesiveness, one or more resins selected from silicon resins, polyimide resins, polysulfone resins, polyether sulfone resins, polyphenyl sulfide resins, polyester resins, A mixture of one or more resins selected from epoxy resins, urethane resins, melamine resins, acrylic resins, urea resins, and polyamide resins, or a copolymer is preferable. Of these mixtures or copolymers, acrylic-silicone resins or polyester-silicone resins are particularly preferred from the viewpoint of the balance between heat resistance and adhesiveness.

  Moreover, the kind of the rust preventive pigment contained in the rust preventive primer layer is not particularly limited, and is selected from phosphate, chromic acid, silicone, silicate, magnesium, titanium, vanadium, and the like. Although a seed | species or 2 or more types of compound is illustrated, it is preferable from a corrosion-resistant viewpoint that 1 type or 2 types of strontium-chromate and a calcium phosphate is included.

  The content of the rust preventive pigment is 10% by mass or more and 65% by mass or less based on the total weight of the dry rust preventive primer layer. When the content of the rust preventive pigment is less than 10% by mass, it is not possible to obtain a steel plate having corrosion resistance and weather resistance that can be applied to a severe environment such as a solar roof plate installed outdoors. On the other hand, when the content of the rust preventive pigment exceeds 65% by mass, the rust preventive pigment and the resin component are not mixed in the paint at the time of preparing the paint, and the coating film cannot be formed. Therefore, the content of the rust preventive pigment is 10% by mass or more and 65% by mass or less. Preferably, it is 30 mass% or more and 60 mass% or less.

  The thickness of the rust preventive primer layer should be more than 1 μm and not more than 20 μm. If the thickness of the rust-preventing primer layer is 1 μm or less, a steel sheet having desired corrosion resistance cannot be obtained. On the other hand, if the thickness of the rust preventive primer layer exceeds 20 μm, the effect of improving the corrosion resistance is saturated, which is economically disadvantageous and there is a concern that the workability may be reduced. The thickness is preferably 3 μm or more and 10 μm or less.

  As long as the rust preventive primer layer of the present invention contains the above-described resin component and rust preventive pigment, the color pigment, extender pigment, surfactant, lubricant, antifoaming agent, bone agent and the like are within the range not impairing the object of the present invention. It may contain. In addition, it is preferable that these content shall be 40 mass% or less in total with respect to the total mass of a dry rust prevention primer layer.

  The method of forming a rust-preventing primer layer on the surface of galvanized steel sheet (paint preparation method / coating method) is not particularly limited, but after thinly coating on the steel sheet with a roll coater, etc., with a hot air dryer, Obtained by drying and baking.

The fluorine-based resin-coated steel sheet of the present invention has a fluorine-based resin coating layer as an upper layer of the antirust primer layer.
The fluororesin coating layer formed on the top layer of the rust-preventing primer layer is important for securing the adhesion between the base material (zinc-based plated steel plate) and the solar cell module when manufacturing the steel plate integrated solar cell module. It is a coating layer.

  Since the fluorine-based resin is superior in weather resistance and heat resistance compared to the EVA resin, it is effective in suppressing deterioration of the adhesion between the base material and the solar cell module. In particular, if the sealing material of the solar cell module and the fluororesin coating layer of the uppermost layer of the base material (zinc-based plated steel sheet) are heat-sealed, the adhesion between the base material and the solar cell module can be further strengthened. . As mentioned above, when pasting the base material and the solar cell module, the EVA resin, which is the sealing material of the solar cell module, is thermocompression bonded and fixed to the base material. Is insufficient, the adhesion between the substrate and the solar cell module deteriorates when left outdoors for a long time.

  The type of the fluororesin used in the present invention is not particularly limited. Polyvinyl fluoride resin (PVF), ethylene-tetrafluoroethylene resin (ETFE), or a copolymer thereof, polyvinylidene fluoride resin (PVDF), Fluorine resins such as tetrafluoroethylene-hexafluoropropylene copolymer resin (FEP) and tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin (PFA) can be exemplified, and any of them can be applied. From the viewpoint of adhesion, weather resistance, and hydrolysis resistance, it is preferable to use ETFE resin or a copolymer thereof.

  The fluororesin coating layer of the present invention is formed using a fluororesin film. In addition, as a fluorine-type resin film, what is widely used for the protection sheet and back sheet | seat of a well-known solar cell module using ETFE resin, a building material, etc. is applicable.

  The thickness of the fluororesin coating layer (ETFE film) is 15 μm or more and 250 μm or less from the viewpoint of adhesion to the solar cell module, insulation, weather resistance, and corrosion resistance. If the thickness of the fluororesin coating layer is less than 15 μm, the adhesive strength with the solar cell module, insulation, weather resistance, and corrosion resistance will be insufficient. On the other hand, when the thickness of the fluororesin coating layer exceeds 250 μm, workability such as roll forming deteriorates and nonflammability decreases. The thickness is preferably 20 μm or more and 150 μm or less.

  The fluororesin coating layer of the steel sheet of the present invention is characterized in that both surfaces are subjected to corona discharge treatment. Thereby, adhesion | attachment with a fluorine resin coating layer and a solar cell module and adhesion | attachment with the zinc-based plated steel plate in which the fluorine resin coating layer and the antirust primer layer were formed can be strengthened. In the fluororesin coating layer that has not been subjected to corona discharge treatment, the adhesive strength between the galvanized steel sheet on which the antirust primer layer is formed and the solar cell module becomes insufficient.

The corona discharge treatment is preferably performed using an ordinary corona discharge treatment apparatus under an appropriate treatment condition so that a desired surface tension can be maintained on the bonded surface. For example, when the ETFE film is subjected to corona discharge treatment, the treatment condition (discharge amount) is preferably 300 to 3000 W · min / m ² .

In order to improve the adhesive strength of the fluororesin coating layer, the fluororesin may be copolymerized or modified within a range not impairing the object of the present invention. For the copolymerization of the fluororesin, for example, aliphatic polyvalent carboxylic acids such as maleic acid, adipic acid, and sebacic acid, and aliphatic polyvalent hydroxy compounds such as ethylene glycol and propylene glycol may be used.
Moreover, you may add a rust preventive pigment and a coloring pigment to the fluororesin in the range which does not impair the objective of this invention for the purpose of coloring or rust prevention. Examples of the rust preventive pigment include one or more of chromate-based, phosphate-based, magnesium-based and vanadium-based compounds. Examples of the color pigment include titanium oxide and carbon black. The addition amount of the rust preventive pigment and the color pigment is preferably 30% or less in terms of mass% with respect to the total amount of the fluororesin (solid content) from the viewpoints of film production, insulation, and corrosion resistance. . More preferably, it is 20% or less.

  The fluororesin coating layer of the steel sheet of the present invention can be obtained by laminating a fluororesin film having corona discharge on both sides to a zinc-based plated steel sheet that is a base material on which a rust preventive primer layer is formed. The laminating method is not particularly limited, but an adhesive method or a heat fusion method is preferable. In particular, the heat fusion method is preferable because it is economical and has little deterioration in characteristics. When applying the adhesive method, it is necessary to consider the aging of the adhesive.

Specific examples of the adhesive method will be described below.
A predetermined amount of adhesive is applied to a steel plate (zinc-based plated steel plate on which a rust-preventing primer layer is formed) as a base material. The coating method is preferably performed using a roll coater, spray coater, flow coater, bar coater, die coater or the like. After applying the adhesive, after drying and baking, the fluororesin film is pressure-bonded with a laminating roll, etc., and the steel sheet is cooled with water or cold air to form the above-mentioned fluororesin coating layer on the steel sheet surface. . In addition, it is preferable that the application quantity of an adhesive agent shall be 3-10 g / m < ² > by solid content. Moreover, as an adhesive agent, the adhesive agent which consists of 1 type, or 2 or more types of combinations among a polyester-type resin, a polyurethane-type resin, a polyamide-type resin, a melamine-type resin, an epoxy-type resin, a urea-type resin, and a phenol-type resin. It can be illustrated. Especially, it is preferable to set it as the adhesive agent of a polyurethane-type resin from a film adhesive viewpoint.

Next, a specific example of the heat fusion method will be described.
Heat the base steel sheet (zinc-plated steel sheet with a rust-preventive primer layer) to a temperature equal to or higher than the melting point (Tm) of the fluororesin used, and crimp the fluororesin film to the steel sheet with a laminate roll Then, after the fluororesin is melted, the steel sheet is rapidly cooled to form a fluororesin coating layer having a predetermined thickness. In the above, the preferable heating temperature of the steel sheet is in the temperature range of Tm or more (Tm + 150 ° C.), more preferably Tm or more (Tm + 120 ° C.). Further, it is known that the melting point of the fluororesin is lowered by copolymerization. Therefore, when the fluorinated resin used in the present invention is an ETFE resin, the melting point is 220 to 270 ° C., and therefore the heating temperature of the steel sheet is preferably in the range of 220 to 420 ° C. The steel plate (coated steel plate) after the formation of the fluororesin coating layer is preferably quenched using water, air, a cooling roll or the like for the purpose of preventing recrystallization of the fluorinated resin.

  By the above, the fluorine resin-coated steel sheet of the present invention having a desired rust preventive primer layer and fluorine resin coating layer on at least one surface of the zinc-based plated steel sheet is obtained. And in addition to durability, such as a weather resistance and corrosion resistance, the fluorine resin-coated steel plate of this invention turns into a steel plate excellent in the adhesiveness of a steel plate and a solar cell module.

Next, the steel plate integrated solar cell module of the present invention will be described.
The integrated solar cell module of the present invention is a module in which a sheet-type solar cell module is disposed on the upper layer of the above-described fluorine-based resin-coated steel plate,
The surface of the fluorine resin-coated steel sheet on the sheet-type solar cell module side is subjected to corona discharge treatment, and the fluorine-based resin coating layer and the lower surface portion of the sheet-type solar cell module are bonded to each other. And

In this invention, the lower surface part of a sheet type solar cell module is adhere | attached on the fluorine resin coating layer formed as the uppermost layer of a fluorine resin coating steel plate.
The fluorine-based resin coating layer is excellent in durability and has excellent adhesiveness with the solar cell module. For this reason, the fluororesin coating layer and the lower surface portion (back sheet) of the sheet type solar cell module can be firmly bonded by a simple bonding method and can be easily formed into a steel plate integrated type solar cell module. As a simple bonding method, for example, there is a method of bonding via an adhesive layer using an adhesive. Examples of preferable adhesives include silicon-based adhesives, urethane-based adhesives, acrylic adhesives, and the like. Among these, silicon-based adhesives that are excellent in adhesiveness to fluororesins are preferable. In addition, when the lower surface part (back sheet | seat) of a solar cell module is a special material, it is preferable to form an adhesive bond layer using the adhesive suitable for adhesion | attachment with a lower surface part (back sheet | seat).

  In the solar cell module to be used, a single crystal type, a polycrystalline type, a thin film amorphous type, a spherical silicon type, an organic thin film type, a dye sensitized type, or the like can be used as a solar cell element. However, in the steel plate integrated solar cell module of the present invention, after integration, it is required to be processed into a roof shape or the like, so the solar cell module to be used is a sheet-like thin film amorphous type that can be processed, A spherical silicon type, an organic thin film type, and a dye-sensitized type are preferable.

  Moreover, it is preferable that the sheet type solar cell module used in the present invention has a solar cell element 6 encapsulated in a sandwich shape as shown in FIG. 3, for example, using a fluorine resin film. In the figure, 4 is a protective sheet, 5 is a back sheet, and 6 is a solar cell element. In FIG. 3, the protective sheet 4 and the back sheet 5 are made of the same material (fluorine resin film), but it is not necessary to limit to this. The protective sheet 4 and the back sheet 5 may be formed of different materials, but from the viewpoint of adhesion to the fluorine resin coating layer, the back sheet (lower surface side) 5 of the sheet type solar cell module is made of a fluorine resin. It is preferable to make it. Thereby, since adhesion | attachment with a fluorine resin coating layer and a sheet type solar cell module turns into adhesion between fluorine resin, it becomes easy to ensure high adhesive strength.

  Further, the same effect can be expected even when the upper surface side of the sheet type solar cell module is covered with a fluororesin film. In this case, adhesion (thermal fusion) is performed for integration between the fluororesin film covering the upper surface side and the coated steel plate without considering the material of the protective seal and back seal of the sheet type solar cell module. be able to. In this case, the protective sheet 4 and the back sheet 5 may use a polyester (PET) resin film, a polyvinylidene fluoride (PVDF) resin, or a polyvinyl fluoride (PVF) resin film.

  In FIG. 3, the protective sheet 4 and the back sheet 5 are formed so as to wrap (enclose) the solar cell element 6 in a sandwich shape and cover the area where the solar cell element 6 does not exist. It is not limited to. By making the protective sheet 4 and the back sheet 5 larger than the size of the solar cell element 6, as shown in FIG. 2, the end portion of the protective sheet 4 where the solar cell element 6 does not exist is used. If the back sheet 5 is a fluororesin, and the back sheet 5 is a fluororesin, a heat-sealed portion 8 is formed at the end by thermal fusion of the fluororesin, and the sheet type solar cell module and the fluororesin coating Adhesion with the layer and further with the base material (galvanized steel sheet) can be strengthened. In addition, if the ends of the protective sheet 4 of the sheet type solar cell module are bonded using heat-sealing of fluororesin, the adhesive strength is increased and the sealing performance of the solar cell module is improved. is there. In this case, the adhesion between the region where the solar cell element 6 of the sheet type solar cell module is present and the fluorine-based resin coating layer 1 may be an adhesive bond from the viewpoint of preventing deterioration of the solar cell element. preferable.

Below, the preferable manufacturing method of this invention steel plate integrated solar cell module is demonstrated.
In this invention, the integrated formation process which integrates the above-mentioned fluorine-type resin-coated steel plate of this invention and a sheet type solar cell module is given, and it is set as a steel plate integrated type solar cell module. In the integrated formation step, the lower surface side (back sheet) of the sheet type solar cell module is bonded to the fluorine resin coating layer of the steel plate (fluorine resin coated steel plate), and the sheet type solar cell module and the steel plate are integrated.

Adhesion between the fluorine-based resin coating layer and the lower surface side (back sheet) of the sheet type solar cell module is performed through the adhesive layer 7 on the entire lower surface side (back sheet) of the sheet type solar cell element 6 as shown in FIG. It is preferable that the bonding be performed. The adhesive layer 7 is formed by applying an adhesive to the entire surface to be bonded (the lower surface side (back sheet) of the sheet type solar cell module). In this case, the adhesive to be used is preferably a silicon adhesive excellent in adhesiveness with a fluororesin.
In addition, it is preferable that the thickness (application amount) of the adhesive is ² to 10 μm (3 to 12 g / m ² in terms of solid content) in order to ensure desired adhesive strength. If it is less than ² μm (3 g / m ² ), the desired adhesive strength cannot be ensured. On the other hand, if the coating amount exceeds 10 μm (12 g / m ² ), it takes a long time to cure the adhesive.

  Further, the adhesion between the fluorine-based resin coating layer 1 and the sheet type solar cell module is performed by applying an adhesive and applying the adhesive layer 7 as described above in the region where the solar cell element 6 of the sheet type solar cell module exists. In the region where the solar cell element 6 does not exist (the end portion of the sheet type solar cell module), it is preferable to form the adhesive that forms the heat-sealing portion 8 using the heat-sealing of the fluororesin. Adhesion using heat-sealing of fluororesin has higher adhesion strength and higher reliability of adhesion than adhesion using an adhesive.

  In order to use such heat-sealing of fluororesin, as shown in FIGS. 2 and 3, the protective sheet 4 of the sheet type solar cell module or the back sheet 5 should be made of fluororesin. is necessary. In addition, the protective sheet 4 or the back sheet 5 needs to be large enough to cover the area where the solar cell element 6 does not exist.

  In heat fusion, devices such as induction heating devices, hot air welders, heat sealers, industrial irons, etc. are used, and the protective sheet or back sheet of the coated steel sheet and the sheet type solar cell module is used as the fluorine resin coating layer. It is preferable to heat to the melting point Tm or higher of the melting point of the base resin, or the melting point of the fluororesin used as the protective sheet or back sheet of the sheet type solar cell module. Further, at the time of heat fusion, it is preferable to remove air on the bonding surface as much as possible by a method such as vacuum forming. The heating temperature is preferably Tm or more (Tm + 150 ° C.), more preferably (Tm + 30 ° C.) or more (Tm + 120 ° C.).

In order to improve adhesion, the protective sheet or back sheet of the sheet type solar cell module may be subjected to a treatment such as a corona discharge treatment or copolymerization. Further, when the back sheet of the sheet type solar cell module is not a fluorine-based resin, the sheet type solar cell module is covered with a fluorine-based resin film as a protective sheet of the sheet type solar cell module in the region where the solar cell element exists. Even if the lower surface side is bonded with an adhesive suitable for the back sheet and the solar cell element does not exist, other parts (ends) are heat-sealed with the fluororesin film covered as a protective sheet, the same effect is obtained. can get.
Hereinafter, the present invention will be further described with reference to examples. In addition, this invention is not limited to this Example.

Example 1
As the zinc-based plated steel sheet used as the base material, (a) 55 mass% aluminum-zinc alloy plated steel sheet (sheet thickness: 0.50 mm; AZ-150), (b) 5 mass% aluminum-zinc alloy plated steel sheet (sheet thickness: Two kinds of 0.50 mm; Y25) were used. The surface of these zinc-based plated steel sheets was subjected to chromate treatment (ZM-1300AN manufactured by Nihon Parker Rising Co., Ltd.) or chromate-free treatment (CT-E224 manufactured by Nihon Parkerizing Co., Ltd.) as a chemical conversion treatment to form a chemical conversion treatment layer. The adhesion amount of the chemical conversion treatment layer was 30 mg / m ² in the solid content in the chromate treatment, and 0.8 g / m ² in the solid content in the chromate-free treatment. Some base materials were not subjected to chemical conversion treatment.

The rust preventive primer layer shown in Table 1 was coated on the surface of these base materials. The coating conditions and the amount of adhesion (solid content) are as shown in Table 1. The heat resistance of the obtained antirust primer layer was investigated. The survey method was as follows.
After applying a rust-preventive primer coating to the zinc-plated steel plate, heat it so that the maximum steel plate temperature (PMT) reaches 250 ° C, 300 ° C, and 350 ° C after 30 seconds in the hot air dryer. The presence or absence of discoloration and the presence or absence of decomposition were observed by the following method. For the evaluation of discoloration, the color difference (ΔE) was obtained with a color difference meter SM-5 manufactured by Suga Test Instruments. In addition, the evaluation of the presence or absence of decomposition was performed by cooling the steel plate, touching the fluororesin coating layer with a finger, and when the coating film component did not adhere to the finger. The case where the film was pulverized was marked as x (failed).

  Then, the coating layer formation process which forms the fluorine-type resin coating layer of the average thickness shown in Table 2 on the upper layer of a rust prevention primer layer using the fluorine-type resin film shown in Table 2 is given, and fluorine-type A resin-coated steel sheet was obtained. In addition, the formation method of the fluororesin coating layer was the adhesive method for the heat fusion method and some steel plates (coated steel plate No. J). The fluorine resin film used was ETFE or copolymerized ETFE. The copolymerization component of the copolymerization ETFE is maleic acid, and the content is 10% (mass%). The fluororesin film was subjected to corona discharge treatment on both sides and then used for adhesion. The corona discharge treatment conditions were 14 KV-5 seconds.

The formation method of the fluororesin coating layer by the heat fusion method was as follows.
First, a steel plate (zinc-based plated steel plate on which a rust-preventing primer layer was formed) as a substrate was heated with a hot air dryer so that the maximum temperature reached (Tm + 80 ° C.) after 70 seconds. Tm is the melting point of the fluororesin film. And the fluorine-type resin film was crimped | bonded to the steel plate with the lamination roll. The laminate roll temperature was 140 ° C., the roll pressure was 2 kg / cm ² , and the laminate roll speed was 10 m / min. After crimping, the steel sheet was water cooled.

Moreover, the formation method by the adhesive method of the fluororesin coating layer was as follows.
On the surface of a steel plate (galvanized steel plate with a rust-preventive primer layer), with a bar coater, polyurethane paint ("ALFLEX-BOND AG-9014A" manufactured by Asahi Glass) as an adhesive is applied at a solid content of 8 g / m ^2. (Applied), and heated with a hot air dryer so that the maximum reached temperature of the steel sheet reached 220 ° C. after 70 seconds, and the ETFE film was pressure-bonded with a laminate roll. After crimping, the steel sheet was cooled with water. Thereby, the fluororesin coating layer was formed on the substrate surface via the adhesive layer.
Next, the adhesiveness of the coating layer of the obtained fluororesin-coated steel sheet was evaluated. Moreover, about the obtained fluorine resin-coated steel sheet, corrosion resistance, nonflammability, workability, and weather resistance were evaluated. The evaluation method was as follows.

(1) Corrosion resistance A test material (size: 75 × 150 mm) was sampled from the obtained fluororesin-coated steel sheet and subjected to a salt spray test in accordance with JIS Z 2371. The test conditions were temperature: 35 ± 1 ° C., test time: 3000 hr, spray: continuous spray. After the test, the presence or absence of rust and blisters in the flat portion of the test piece was visually observed. The occurrence length of rust and blister was measured, and the corrosion resistance of the fluororesin-coated steel sheet was evaluated with ○ (pass) as 3 mm or less and x (fail) as 3 mm or less.

(2) Nonflammability When a test material (size: 99 x 99mm) is collected from the obtained fluororesin-coated steel sheet and the test material is burned with a corn calorimeter for 20 minutes in accordance with ISO 5660 The total calorific value was determined. When the total heating value is high, non-flammable poor (flammable) for the total amount of heat generated incombustible good (pass: ○) the 8.0MJ / m ² or less and then, fluorine otherwise as × (fail) The incombustibility of the resin-coated steel sheet was evaluated.

(3) Workability A test material (size: 762 × 900 mm) was collected from the obtained fluororesin-coated steel sheet and formed into a folded plate shape by a roll forming method. Observe the surface of the test material after forming, visually observe the scratches, and mark X (fail) if any scratches occur, ○ (pass) otherwise, process the fluororesin-coated steel sheet Sex was evaluated.

(4) Weather resistance A test material (size: 65 x 150 mm) is collected from the obtained fluororesin-coated steel sheet, and a test is performed to irradiate the test material with ultraviolet rays by the sunshine carbon arc method in accordance with JIS A 1415. Carried out. Test time: After 2000 hr, the color difference (ΔE) and gloss retention (GR%) on the surface of the test material were measured. When ΔE was 1.0 or less and GR% was 80% or more, the weather resistance was evaluated with ○ (passed) and the others with × (failed). The color difference (ΔE) was obtained with a Suga Test Instruments color difference meter SM-5, and the gloss retention (GR%) was obtained with a Suga Test Instruments gloss meter SM-5.

(5) Coating layer adhesion The test material (size: 50 x 100mm) is collected from the obtained fluororesin-coated steel sheet and visually checked for peeling of the coating layer by the cross-cut tape method according to JIS K5600. Observed, the case of no peeling (no abnormality) was evaluated as ○ (passed), and the other was evaluated as x (failed), and the adhesion of the fluororesin coating layer was evaluated.
Table 4 shows the obtained results.
Each of the inventive examples is a steel sheet having excellent coating layer adhesion and excellent corrosion resistance, non-flammability, workability, and weather resistance. On the other hand, in the comparative example, any of the above characteristics is a deteriorated steel plate.

(Example 2)
Next, as shown in Table 3, a sheet-type solar cell module (Fwave (trade name) manufactured by Fuji Electric) is bonded to each of the obtained fluorine-based resin-coated steel plates, and the fluorine-based resin-coated steel plates and the solar cell modules are bonded. The integration process which integrates was given and the steel plate integrated solar cell module was produced. The solar cell elements used were thin amorphous solar cell elements, and the upper and lower surfaces of these solar cell elements were encapsulated with an ETFE (fluorine resin) film as a protective sheet and a back sheet. Yes.

The method of adhering the sheet type solar cell module to the fluorine-based resin-coated steel sheet was as shown in Table 3. That is, apply a silicone adhesive (“KE-45T” manufactured by Shin-Etsu Chemical Co., Ltd.) to the lower surface side (back sheet) of the area (central substrate area) where the solar cell elements of the sheet type solar cell module exist, Crimped to a fluorine-based resin-coated steel sheet. The amount of adhesive layer applied (adhesive layer thickness) was as shown in Table 3. On the other hand, in the region (edge) where the solar cell element of the sheet type solar cell module does not exist, the back sheet made of ETFE is also used by the induction heating device (made by Brownie Co., Ltd.) on the protective sheet made of ETFE. In addition, the sheet type solar cell module was bonded to the coated steel sheet by heat fusion and integrated. The adhesion width was as shown in Table 3. The induction heating time was 7 seconds, and the heating temperature was ETFE melting point + 80 ° C.
In some modules (module No. 15), a silicone adhesive (“KE-45T” manufactured by Shin-Etsu Chemical Co., Ltd.) is applied to the entire lower surface of the sheet-type solar cell module, and a fluororesin is coated with a hand roller. Crimped to a steel plate.

  In some modules (module No. 14), a sheet-type solar cell module whose back sheet was made of polyester (PET) resin was used. In this case, the upper surface side of the sheet type solar cell module was covered with an ETFE film, and the same integration as described above was performed.

The obtained steel sheet integrated solar cell module was evaluated for adhesion and insulation. The evaluation method was as follows.
(1) Adhesion When the obtained steel sheet integrated solar cell module is exposed outdoors for 3 months and the occurrence of floating or peeling on the end face of the module is visually observed. ) Was evaluated as ○, and the others were evaluated as ×, and the adhesion of the solar cell module integrated with a steel plate was evaluated.

(2) Insulating property The obtained steel sheet integrated solar cell module is exposed to sunlight and checked for leakage on the back side of the fluorine resin-coated steel sheet with a tester. The insulation properties of the steel plate integrated solar cell module were evaluated.
The results obtained are shown in Table 5.

  In all of the examples of the present invention, the solar cell module integrated with a steel sheet satisfies the desired adhesion and insulation as a whole, and has excellent adhesion and insulation in addition to durability.

1 Fluorine resin coating layer
2 Antirust primer layer
3 Galvanized steel sheet
4 Protective sheet (fluorine resin film)
5 Back sheet (Fluorine resin film)
6 Solar cell element
7 Adhesive layer
8 Heat fusion part

Claims (12)

A fluorinated resin-coated steel sheet having a rust-preventing primer layer on at least one surface of a galvanized steel sheet, and a fluorine-based resin coating layer on the upper layer, the rust-preventing primer layer comprising 10% by mass or more of the resin component and the resin component A rust-preventing primer layer having a thickness of more than 1 μm and not more than 20 μm, the fluorinated resin coating layer having a thickness of 15 μm or more and 250 μm or less on the rust-preventing primer layer side. A fluorine-based resin-coated steel sheet for adhering a sheet-type solar cell module, characterized in that a fluorine-based resin coating layer is formed by corona discharge treatment on both sides. The fluorine resin-coated steel sheet for bonding a sheet-type solar cell module according to claim 1, wherein the resin component of the rust-preventing primer layer is an acrylic-silicon resin or a polyester-silicon resin. The fluorine resin for bonding a sheet type solar cell module according to claim 1 or 2, wherein the antirust pigment of the antirust primer layer contains one or two of strontium-chromate and calcium phosphate. Coated steel sheet. The fluorine-based resin-coated steel sheet for bonding a sheet-type solar cell module according to any one of claims 1 to 3, wherein the zinc-based plated steel sheet is subjected to a chemical conversion treatment. At least one surface of the galvanized steel sheet includes a resin component and a rust preventive pigment of 10% by mass or more and 65% by mass or less, and a rust preventive primer layer having a thickness of more than 1 μm and not more than 20 μm, and an upper layer having a thickness of A sheet type solar cell module is disposed on the upper layer of a fluororesin-coated steel sheet having a fluororesin coating layer having a corona discharge treatment on both sides of the anticorrosive primer layer at 15 μm or more and 250 μm or less. A steel sheet integrated solar cell module,
The surface of the fluorine resin-coated steel sheet on the sheet-type solar cell module side is subjected to corona discharge treatment, and the fluorine-based resin coating layer and the lower surface portion of the sheet-type solar cell module are bonded to each other. Steel sheet integrated solar cell module.   6. The steel sheet integrated solar cell module according to claim 5, wherein a lower surface portion of the sheet type solar cell module is bonded to the fluororesin coating layer via an adhesive layer.   The sheet-type solar cell module according to claim 5 or 6, wherein the sheet-type solar cell module is obtained by encapsulating solar cell elements of the sheet-type solar cell module in a sandwich shape with a fluorine-based resin film. Battery module.   The steel sheet-integrated solar cell module according to claim 5 or 6, wherein at least the upper surface side of the sheet-type solar cell module is covered with a fluororesin film.   Adhesion between the fluorine-based resin coating layer and the lower surface portion of the sheet-type solar cell module is adhesion through an adhesive layer in a portion where the solar cell element exists, and in a portion where the solar cell element does not exist The steel sheet-integrated solar cell module according to claim 7 or 8, wherein the adhesive is made by heat-sealing a fluororesin film. The steel plate integrated solar cell module according to any one of claims 5 to 9, wherein the resin component of the rust-preventing primer layer is an acrylic-silicon resin or a polyester-silicon resin. 11. The steel sheet integrated solar cell module according to claim 5, wherein the rust preventive pigment of the rust preventive primer layer contains one or two of strontium-chromate and calcium phosphate. The steel sheet integrated solar cell module according to any one of claims 5 to 11, wherein the zinc-based plated steel sheet is subjected to a chemical conversion treatment.

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