WO2023054673A1 - 太陽電池モジュール用バリア性積層体および太陽電池モジュール - Google Patents

太陽電池モジュール用バリア性積層体および太陽電池モジュール Download PDF

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WO2023054673A1
WO2023054673A1 PCT/JP2022/036693 JP2022036693W WO2023054673A1 WO 2023054673 A1 WO2023054673 A1 WO 2023054673A1 JP 2022036693 W JP2022036693 W JP 2022036693W WO 2023054673 A1 WO2023054673 A1 WO 2023054673A1
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Prior art keywords
solar cell
cell module
barrier
layer
laminate
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English (en)
French (fr)
Japanese (ja)
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靖史 白髭
慶太 在原
敦 中原
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Dai Nippon Printing Co Ltd
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Dai Nippon Printing Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
    • H10F19/80—Encapsulations or containers for integrated devices, or assemblies of multiple devices, having photovoltaic cells
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
    • H10F19/80—Encapsulations or containers for integrated devices, or assemblies of multiple devices, having photovoltaic cells
    • H10F19/85—Protective back sheets

Definitions

  • the present disclosure relates to a barrier laminate for a solar cell module and a solar cell module.
  • a solar cell module that constitutes a solar cell has a configuration in which a transparent front plate, a front side sealing material, a solar cell, a back side sealing material, and a back protective sheet are laminated in this order from the light receiving surface side. It has the function of generating electricity when light enters the solar cell.
  • a transparent front plate a transparent glass substrate is often used, but a protective sheet similar to that used on the back side can also be used.
  • Patent Document 1 proposes, as a back protection sheet, a back protection sheet in which a metal foil such as an aluminum foil is laminated on a weather-resistant substrate.
  • the above-mentioned back surface protection sheet using metal foil such as aluminum foil may cause electric leakage due to its low insulation when used in a solar cell module. Therefore, there is a demand for a back protective sheet for a solar cell module that has a high water vapor barrier property without using a metal foil such as an aluminum foil. Also, when used as a transparent front plate, it preferably has a high water vapor barrier property.
  • the present disclosure has been made in view of the above circumstances, and a main object thereof is to provide a barrier laminate for a solar cell module having high water vapor barrier properties.
  • One embodiment of the present disclosure is a barrier laminate for a solar cell module, comprising: a base material; a first barrier layer containing an inorganic compound disposed on one side of the base material; a second barrier layer disposed on the side opposite to the substrate side of the barrier layer, wherein the second barrier layer has a melting peak temperature measured by a DSC (differential scanning calorimetry) method; The temperature is 220° C. or higher, and the barrier laminate for a solar cell module has a water vapor permeability of 5.0 ⁇ 10 ⁇ 2 g/(m 2 day) or less. do.
  • Another embodiment of the present disclosure is a solar cell module having, in this order, a transparent front plate, a front sealing material, a plurality of solar cells, a back sealing material, and a back protective sheet,
  • a solar cell module is provided in which the back protective sheet is the barrier laminate for a solar cell module described above.
  • Another embodiment of the present disclosure is a solar cell module having, in this order, a transparent front plate, a front sealing material, a plurality of solar cells, a back sealing material, and a back protective sheet,
  • a solar cell module in which the transparent front plate is the barrier laminate for a solar cell module described above.
  • the present disclosure can provide a barrier laminate for a solar cell module having high water vapor barrier properties.
  • FIG. 1 is a schematic cross-sectional view showing an example of a barrier laminate for a solar cell module of the present disclosure
  • FIG. 1 is a schematic cross-sectional view showing an example of a barrier laminate for a solar cell module of the present disclosure
  • FIG. 2 is an image diagram for explaining expansion of free volume pores due to molecular motion of a polymer compound.
  • 1A and 1B are a schematic cross-sectional view and a schematic plan view showing an example of a solar cell module of the present disclosure; FIG.
  • 2 when expressing a mode of arranging another member on top of a certain member, when simply describing “above” or “below”, unless otherwise specified, 2 includes both cases in which another member is arranged directly above or directly below, and cases in which another member is arranged above or below a certain member via another member.
  • 2 when expressing a mode in which another member is arranged on the surface of a certain member, when simply describing “on the surface side” or “on the surface”, unless otherwise specified, It includes both the case of arranging another member directly above or directly below so as to be in contact with it, and the case of arranging another member above or below a certain member via another member.
  • the inventors of the present invention conducted repeated studies to improve the water vapor barrier property of a barrier laminate that can be used as a back protective sheet or a transparent front plate for a solar cell module. A laminate was discovered and the above problems were solved.
  • the barrier laminate for solar cell module of the present disclosure will be described in detail.
  • FIG. 1 is a schematic cross-sectional view showing an example of a barrier laminate for a solar cell module in the present disclosure.
  • the barrier laminate 1 for a solar cell module of the present disclosure includes a substrate 2, a first barrier layer 3 disposed on one side of the substrate 2, and a first barrier layer 3. and a second barrier layer 4 disposed on the surface side opposite to the substrate 2 side.
  • the first barrier layer 3 contains an inorganic compound
  • the second barrier layer 4 has a melting peak temperature of 220° C. or higher as measured by the DSC method.
  • the barrier laminate 1 for a solar cell module of the present disclosure is characterized by having a water vapor permeability of 5.0 ⁇ 10 ⁇ 2 g/(m 2 ⁇ day) or less.
  • the solar cell module 10 includes a transparent front plate 14, a front-side sealing material 13, a solar cell 15, a back-side sealing material 12, and a barrier laminate 1 for a solar cell module of the present disclosure.
  • the rear surface protection sheet 11 is laminated in this order.
  • the resin layer in which the front-side sealing material 13 and the back-side sealing material 12 are combined and laminated and integrated is also simply referred to as a sealing material.
  • the application of the barrier laminate 1 for a solar cell module of the present disclosure is not necessarily limited to placement on the back side of the solar cell module as described above, but is placed on the front side of the solar cell module 10 as the transparent front plate 14 . can also be used as
  • the barrier laminate for a solar cell module of the present disclosure includes a first barrier layer containing an inorganic compound, and a second barrier layer having a melting peak temperature measured by the DSC method equal to or higher than the above value. It has good water vapor permeability.
  • barrier layers with melting peak temperatures lower than 220° C. (for example, about 200° C.) measured by the DSC method have been used in some cases, but such barrier layers have sufficient water vapor barrier properties. It wasn't.
  • the present inventors have found that a barrier layer having a melting peak temperature of 220° C. or higher as measured by the DSC method improves the water vapor barrier function.
  • the barrier layer includes, for example, a hydrolytic polycondensate produced from a resin composition containing a metal alkoxide and a hydrophilic group-containing resin.
  • the hydrolysis polycondensate has a high crosslink density and the small free volume pores improve the water vapor barrier function.
  • the present inventors have found that by combining such a barrier layer (second barrier layer) and a barrier layer (first barrier layer) containing an inorganic compound, a solar cell module barrier having high water vapor barrier properties can be obtained. It was found that it becomes a flexible laminate.
  • the barrier laminate may become yellowish. This is because when attempting to form a barrier layer containing an inorganic compound with high barrier properties by chemical vapor deposition, it is necessary to reduce the amount of oxygen introduced, and the color of the source gas tends to affect the color of the barrier layer, resulting in a yellow tint. This is presumed to be due to On the other hand, since the barrier laminate for a solar cell module of the present disclosure includes the second barrier layer in addition to the first barrier layer containing an inorganic compound, it is expected to have excellent water vapor barrier properties while suppressing yellowness. Become.
  • the second barrier layer in the present disclosure has a peak melting temperature of 220° C. or higher as measured by the DSC method.
  • the melting peak temperature of the second barrier layer measured by the DSC method is preferably 230° C. or higher, particularly preferably 235° C. or higher.
  • the melting peak temperature is, for example, 270° C. or lower, preferably 260° C. or lower.
  • Fig. 3 shows an image diagram for explaining the expansion of free volume pores due to the molecular motion of the polymer compound in the barrier layer.
  • thermal motion causes the spacing between the polymer compounds to widen and the free volume pores to expand.
  • a hydrolytic polycondensate produced from a resin composition containing a metal alkoxide and a hydrophilic group-containing resin can suppress the expansion of the free volume to some extent by crosslinking, but it is measured by the DSC method. If the melting peak temperature is lower than the above value, the effect of suppressing the expansion of free volume pores is not sufficient (Fig. 3(b)).
  • the second barrier layer of the present disclosure if the melting peak temperature of the second barrier layer measured by the DSC method is equal to or higher than the above value, for example, the second barrier layer contains a metal alkoxide and a hydrophilic group.
  • the hydrolytic polycondensate When a hydrolytic polycondensate produced from a resin composition containing a resin is included, the hydrolytic polycondensate has a high crosslink density, and spread between polymer compounds due to thermal motion is suppressed ( FIG. 3(c)). Therefore, the free volume pores are reduced and the water vapor barrier function is improved.
  • the melting peak temperature of the second barrier layer is a value measured as follows according to JIS K 7121-1987.
  • a measurement sample is prepared by sampling the outermost surface of the second barrier layer from the barrier laminate by a microsampling method. Using a differential scanning calorimeter (NEXTA (registered trademark) DSC600, manufactured by Hitachi High-Tech Science), after holding the measurement sample at 20 ° C. for 30 minutes, the temperature was raised from 20 ° C. to 300 ° C. at a heating rate of 5 ° C./min. and measure the melting peak temperature. Note that the measurement is performed in a nitrogen atmosphere, and the maximum peak within the measurement temperature range (20° C. to 300° C.) is defined as the melting peak.
  • NEXTA registered trademark
  • DSC600 manufactured by Hitachi High-Tech Science
  • the material of the second barrier layer in the present disclosure is not particularly limited as long as the melting peak temperature of the second barrier layer measured by the DSC method is equal to or higher than the above value.
  • the second barrier layer contains a hydrolyzed polycondensate produced from a resin composition containing a metal alkoxide and a hydrophilic group-containing resin.
  • the metal alkoxide has the general formula R 1 n M (OR 2 ) m (wherein R 1 and R 2 represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n+m represents the valence of M.).
  • R 1 and R 2 represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n+m represents the valence of M.
  • Examples of the metal atom M of the alkoxide represented by the above general formula include silicon, zirconium, titanium, and aluminum. Among them, silicon is preferred.
  • n 0
  • specific examples of such alkoxysilanes include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and the like.
  • Tetraethoxysilane (TEOS) is preferred as the alkoxide of silicon.
  • the alkoxide represented by the general formula R 1 n M(OR 2 ) m at least one of partial hydrolysates of alkoxides and hydrolytic condensates of alkoxides can be used.
  • the partial hydrolyzate of the above alkoxide is not limited to one in which all of the alkoxide groups are hydrolyzed, and may be one in which one or more alkoxy groups are hydrolyzed, or a mixture thereof.
  • the condensate of hydrolysis dimers or higher of partially hydrolyzed alkoxides, specifically dimers to hexamers, may be used.
  • hydrophilic group-containing resins include resins containing hydrophilic groups, and specific examples include polyvinyl alcohol-based resins, ethylene-vinyl alcohol copolymers, acrylic acid-based resins, natural polymer-based methyl cellulose, carboxymethyl cellulose, Examples include cellulose nanofibers and polysaccharides.
  • polyvinyl alcohol-based resin is preferable, and polyvinyl alcohol-based resin is preferable as the polyvinyl alcohol-based resin.
  • the content of the hydrophilic group-containing resin in the resin composition is, for example, 5 parts by mass or more, preferably 7 parts by mass or more, with respect to 100 parts by mass of the metal alkoxide content.
  • the content of the hydrophilic group-containing resin in the resin composition is, for example, 20 parts by mass or less, preferably 18 parts by mass or less, with respect to 100 parts by mass of the metal alkoxide content.
  • the hydrolytic polycondensate can be a mixed compound containing a metal atom, an oxygen atom, and a hydrophilic group-containing resin, and the carbon atom (C) in the hydrophilic group-containing resin and the metal atom (M) in the metal alkoxide ) can have a C—O—M bond via oxygen (O).
  • the hydrolytic polycondensate is preferably a polycondensate of tetraethoxysilane (TEOS) and a polyvinyl alcohol-based resin.
  • TEOS tetraethoxysilane
  • polyvinyl alcohol-based resin The polycondensate of tetraethoxysilane (TEOS) and polyvinyl alcohol resin may be the same as disclosed in Japanese Patent No. 5568897, for example.
  • the second barrier layer may contain known additives such as isocyanate compounds, silane coupling agents, or dispersants, stabilizers, viscosity modifiers, and colorants.
  • the thickness of the second barrier layer is not particularly limited, it is, for example, 100 nm or more, and may be 200 nm or more. On the other hand, it is, for example, 4 ⁇ m or less, and may be 1 ⁇ m or less.
  • the method for forming the second barrier layer containing the hydrolyzed polycondensate is not particularly limited, the following methods can be mentioned. That is, it is a method of forming from a raw material liquid that contains a metal alkoxide and a hydrophilic group-containing resin and is obtained by polycondensation by a sol-gel method. Specifically, a resin composition (coating agent) is coated on the opposite side of the substrate from the first barrier layer formed on the substrate. After that, it is dried by heating to form a precursor layer having a hydrolyzed polycondensate.
  • the precursor layer is further heat-treated to increase the crosslink density of the hydrolyzed polycondensate.
  • the heating temperature is preferably 170° C. or higher, particularly preferably 180° C. or higher. This is because the melting peak temperature of the second barrier layer can be made equal to or higher than the value described above. On the other hand, it is, for example, 250° C. or lower, and may be 220° C. or lower.
  • the heating time is preferably 10 seconds or longer, and particularly preferably 15 seconds or longer. On the other hand, for example, it is one minute or less, and may be 45 seconds or less.
  • the second barrier layer may be a single film formed by vapor deposition once, or may be a multilayer film formed by vapor deposition multiple times.
  • films of the same composition may be combined, or films of different compositions may be combined.
  • the first barrier layer in the present disclosure is arranged on one side of the substrate and contains an inorganic compound.
  • the first barrier layer is preferably an inorganic compound film containing an inorganic compound as a main component.
  • the inorganic compound forming the inorganic compound film include oxides, oxynitrides, nitrides, oxycarbides, and oxycarbonitrides of metallic elements or non-metallic elements.
  • the above metal elements include silicon, aluminum, magnesium, calcium, potassium, tin, sodium, titanium, boron, yttrium, zirconium, cerium, and zinc.
  • the above inorganic compounds include silicon oxides such as SiOx , aluminum oxides such as AlyOz , magnesium oxides, titanium oxides, tin oxides, silicon-zinc alloy oxides, and indium alloys. oxides, silicon nitrides, aluminum nitrides, titanium nitrides, silicon oxynitrides, silicon zinc oxides, and the like.
  • the metal element is preferably silicon
  • the inorganic compound is preferably silicon oxide such as SiOx .
  • the above inorganic compounds may be used alone, or may be used by mixing the above materials in an arbitrary ratio.
  • the metal element contained in the inorganic compound is preferably the same as the metal element in the metal alkoxide in the second barrier layer.
  • the adhesion between the first barrier layer and the second barrier layer is improved, and the water vapor permeability of the barrier laminate for a solar cell module is increased. It is because it becomes a favorable value.
  • both the first barrier layer and the second barrier layer preferably contain silicon.
  • the first barrier layer may be a coating film by coating or the like, or may be a vapor deposition film. Among them, a deposited film is preferable from the viewpoint of high adhesion to the resin substrate and high gas barrier performance.
  • the first barrier layer may be a single film formed by vapor deposition once, or may be a multilayer film formed by vapor deposition multiple times. When the first barrier layer is a multilayer film, films of the same composition may be combined, or films of different compositions may be combined.
  • the thickness of the first barrier layer is not particularly limited as long as the desired gas barrier performance can be exhibited.
  • the lower limit of the thickness of the first barrier layer can be appropriately set according to the type and structure of the barrier layer, and can be, for example, 5 nm or more, preferably 10 nm or more.
  • the upper limit of the thickness of the first barrier layer can be, for example, 200 nm or less, preferably 100 nm or less.
  • the first barrier layer is a multilayer film, it refers to the thickness of the entire multilayer film that constitutes the first barrier layer.
  • Substrate The substrate in the present disclosure is not particularly limited as long as it can support the first barrier layer and the second barrier layer.
  • resin substrates such as resin films and resin sheets are preferably used.
  • the resin film may be unstretched, or may be uniaxially or biaxially stretched. It is also possible to use a resin that shrinks little even at the heating temperature in the heating step, such as engineering plastics.
  • the resin used for the substrate is not particularly limited, and examples include polyolefin, polyester, polystyrene, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), poly(meth)acrylic
  • AS resin acrylonitrile-styrene copolymer
  • ABS resin acrylonitrile-butadiene-styrene copolymer
  • poly(meth)acrylic such as acid esters, polycarbonates, polyvinyl alcohol resins, polyamides, polyimides, polyurethanes, acetal resins and cellulose resins can be used.
  • Polyolefins include, for example, polyethylene and polypropylene.
  • polyester include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate (PBT).
  • Polyvinyl alcohol resins include, for example, polyvinyl alcohol (PVA) resins and ethylene-vinyl alcohol copolymer (EVOH) resins.
  • Polyamide resins include, for example, various nylons.
  • polyester resin films such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate (PBT) are preferred because of their good electrical insulation, heat resistance, dimensional stability and moldability.
  • PET polyethylene terephthalate
  • PET polyethylene naphthalate
  • PBT polybutylene terephthalate
  • PET film is preferable from the viewpoint of versatility.
  • the lower limit of the thickness of the substrate is not particularly limited, it is, for example, 8 ⁇ m or more, preferably 10 ⁇ m or more.
  • the upper limit of the thickness of the substrate is not particularly limited, but is 250 ⁇ m or less, preferably 10 ⁇ m or more.
  • the substrate is preferably transparent.
  • the barrier laminate for a solar cell module according to the present disclosure is suitable, for example, when it is a transparent back surface protective sheet used in a see-through type or double-sided lighting type solar cell module, or when it is a transparent front panel. Because there is Specifically, as the transparency, the substrate preferably has a total light transmittance of, for example, 80% or more, preferably 85% or more, and particularly preferably 90% or more. The total light transmittance can be measured according to JIS K7361-1:1997.
  • An anchor layer for improving adhesion of the first barrier layer may be arranged on the surface of the base material on the first barrier layer side.
  • an anchor layer one conventionally known as an anchor layer can be used.
  • the barrier laminate for a solar cell module of the present disclosure may contain layers described later in addition to the base material, the first barrier layer, and the second barrier layer.
  • FIG. 2 is a schematic cross-sectional view showing another example of the barrier laminate for a solar cell module of the present disclosure.
  • the first barrier layer 3 and the second barrier layer 4 in addition to the base material 2, the first barrier layer 3 and the second barrier layer 4, and an adhesive layer 6 disposed between the resin layer 5 and the second barrier layer 4 .
  • the barrier laminate for solar cell module in the present disclosure preferably includes a resin layer on the surface side of the second barrier layer opposite to the first barrier layer side.
  • a method for producing a barrier laminate for a solar cell module according to the present disclosure may include a heating step. In such a heating process, curling may occur due to shrinkage of the substrate. If curling occurs, cracks may occur in the first barrier layer and the second barrier layer, and the barrier properties may deteriorate.
  • the present disclosure by arranging a resin layer on the side opposite to the first barrier layer side of the second barrier layer to impart rigidity, it is possible to suppress the curling of the barrier laminate, and A decrease in barrier properties can be suppressed. Moreover, thermal shrinkage of the barrier laminate for solar cell module can be suppressed.
  • the barrier laminate for a solar cell module in the present disclosure when used in a solar cell module, it is preferable to arrange the resin layer so that the resin layer faces the atmosphere side (that is, the side opposite to the solar cell side). .
  • the resin layer By arranging the resin layer on the atmosphere side, it can function as a protective layer for the first barrier layer and the second barrier layer.
  • polyester-based resin typified by polyethylene terephthalate resin
  • polyethylene terephthalate resin typified by polyethylene terephthalate resin
  • Polyethylene terephthalate having such hydrolysis resistance maintains elongation at break in a tensile test after treatment in a 120° C. 85% RH environment for 48 hours in one direction and the other direction perpendicular to the one direction. It is polyethylene terephthalate with a rate of 20% or more compared to before treatment. Measurement of elongation at break in the tensile test shall be performed in accordance with JIS K7127:1999. Note that the one direction mentioned above may be the machine direction (MD) or the vertical direction (TD), or may be a direction different from the machine direction (MD) or the vertical direction (TD). The elongation at break of the barrier laminate for solar cell module is also in the same range as that of the polyethylene terephthalate film alone.
  • hydrolysis-resistant polyethylene terephthalate for example, it is preferable to use hydrolysis-resistant polyethylene terephthalate obtained by subjecting polyethylene terephthalate resin to hydrolysis-resistant treatment as a base resin.
  • the hydrolysis-resistant treatment is a treatment for imparting hydrolysis resistance by adding a hydrolysis-resistant agent such as carbodiimide or by adjusting the molecular weight.
  • the lower limit of the thickness of the resin layer is preferably 30 ⁇ m or more, particularly preferably 50 ⁇ m or more. This is because curling caused by shrinkage of the base material can be suppressed during the production of the barrier laminate (during the heating process).
  • the upper limit of the thickness of the resin layer is, for example, 250 ⁇ m or less, and may be 150 ⁇ m or less.
  • an adhesive layer may be provided between the resin layer and the second barrier layer. This is because the adhesive strength between the resin layer and the second barrier layer can be increased. Also, the adhesive layer functions as a stress relieving layer, and can protect the first barrier layer and the second barrier layer from external impact.
  • the adhesive for forming such an adhesive layer is not particularly limited, and various conventionally known transparent adhesives such as urethane-based adhesives and acrylic-based adhesives can be appropriately selected.
  • the lower limit of the thickness of the adhesive layer is, for example, 3 ⁇ m or more, and may be 4 ⁇ m or more. A thickness of at least the above value is preferable because it easily functions as a stress relieving layer.
  • the upper limit of the thickness of the adhesive layer is, for example, 10 ⁇ m or less, and may be 7 ⁇ m or less.
  • barrier laminate for a solar cell module in the present disclosure may be provided with an adhesive layer for increasing the adhesive strength of each layer other than between the resin layer and the second barrier layer.
  • the barrier laminate for a solar cell module according to the present disclosure includes a primer layer as the outermost layer on the side opposite to the first barrier layer side of the base material, for example, in order to improve adhesion to the back sealing material.
  • a primer layer can have
  • a base resin contained in a primer composition that is generally used to improve the adhesiveness between the back sealing material and the back protective sheet in a solar cell module can be used.
  • the barrier laminate for a solar cell module includes, for example, the outermost layer on the side opposite to the first barrier layer side of the base material, in order to improve the adhesiveness to the back sealing material.
  • a sealant layer is preferably arranged on the outer layer.
  • a polyethylene film is preferred as the sealant layer.
  • the polyethylene film is not particularly limited as long as it is generally used for improving the adhesiveness between the back sealing material and the back protective sheet in the solar cell module.
  • a topcoat layer may be arranged as the outermost layer on the first barrier layer side of the base material. The topcoat layer preferably has weather resistance.
  • the barrier laminate for a solar cell module of the present disclosure has a water vapor permeability of 5.0 ⁇ 10 ⁇ 2 g/(m 2 ⁇ day) or less, which is 3.5 ⁇ 10 ⁇ 2 . It is preferably less than g/(m 2 ⁇ day). If the water vapor transmission rate is equal to or less than the above value, the solar electronic cell can be protected from water vapor when the barrier laminate for solar cell module is used in the solar cell module.
  • the water vapor transmission rate can be measured using a water vapor transmission rate measuring device under the conditions of a temperature of 40°C and a relative humidity difference of 90% RH in accordance with ISO 15106-5:2015 (differential pressure method). can.
  • a water vapor transmission rate measuring device for example, DELTAPERM manufactured by Technolox, UK can be used. The measurement was carried out so that, of the surfaces of the barrier laminate, the surface located on the second barrier layer side with respect to the substrate in the thickness direction of the barrier laminate was on the high humidity side (water vapor supply side). , is installed between the upper chamber and the lower chamber of the apparatus, and the transmission area is 50.24 cm 2 (transmission area: circular with a diameter of 8 cm). At least three samples are measured under one condition, and the average of these measurements is taken as the value of water vapor transmission rate under that condition.
  • the water vapor transmission rate described herein can be measured using the same method as described above.
  • the barrier laminate for a solar cell module of the present disclosure has a dimensional change of 1.0% or less at 150°C for 30 minutes in accordance with JIS C2151:1999 from the viewpoint of heat resistance. is preferred, and 0.5% or less is more preferred.
  • the dimensional change is equal to or less than the above value, it is possible to suppress the occurrence of cracks in the first barrier layer and the second barrier layer in the manufacturing process of the barrier laminate and the solar cell module.
  • the reliability of the solar cell module is improved.
  • the dimensional change is measured, for example, in one direction and another direction orthogonal to the one direction.
  • One direction may be the machine direction (MD) or the vertical direction (TD) or may be a different direction than the machine direction (MD) or the vertical direction (TD).
  • the tensile stress in the tensile test of the barrier laminate for solar cell module of the present disclosure is, for example, 130 MPa or more, and may be 140 MPa or more. On the other hand, for example, it is 210 MPa or less, and may be 200 MPa or less.
  • the elongation at break of the barrier laminate for solar cell module of the present disclosure is, for example, 180% or less, and may be 170% or less. On the other hand, for example, it is 60% or more, and may be 80% or more.
  • Tensile stress and elongation at break can be measured according to JIS K7127.
  • a tensile tester STA-1150 manufactured by Orientec Co., Ltd. can be used as a measuring instrument, and the measurement environment is 23 ⁇ 2° C. and a relative humidity of 50 ⁇ 5%.
  • the tensile strength and the tensile elongation are measured, for example, in one direction and another direction orthogonal to the one direction.
  • One direction may be the machine direction (MD) or the vertical direction (TD) or may be a different direction than the machine direction (MD) or the vertical direction (TD).
  • the barrier laminate for solar cell modules of the present disclosure can be used as both a backside protective sheet and a transparent front plate for solar cell modules.
  • two or more layers of the barrier laminate for solar cell module of the present disclosure can be used as a back surface protective sheet and a transparent front panel.
  • the barrier laminate for a solar cell module of the present disclosure is used for the applications described above, for example, it is preferably arranged so that the substrate 2 faces the solar cell 15 side, as shown in FIG. This is because deterioration of the base material can be suppressed by the first barrier layer 3 and the second barrier layer 4 when the base material 2 does not have hydrolysis resistance.
  • the barrier laminate for a solar cell module in the present disclosure is, for example, a back protective sheet used in a see-through type or double-sided lighting type solar cell module
  • the barrier laminate is Has transparency.
  • the barrier laminate also has transparency when used as a transparent front plate of a solar cell module. Conventionally, transparency could not be obtained when aluminum foil was used to provide water vapor barrier properties.
  • the barrier laminate for a solar cell module in the present disclosure has high water vapor barrier properties while maintaining transparency.
  • having transparency means having an average spectral transmittance of 80% or more at wavelengths of 400 nm or more and 800 nm or less.
  • the average spectral transmittance may be 85% or more, or 90% or more.
  • the average spectral transmittance at wavelengths of 400 nm or more and 800 nm or less is the average value of spectral transmittances at wavelengths of 400 nm or more and 800 nm or less.
  • the average spectral transmittance can be measured by a method conforming to JIS K 7361-1:1997.
  • the barrier laminate for solar cell module transmits light in the visible light region and the near-infrared region.
  • the average spectral transmittance at wavelengths of 400 nm to 1200 nm is preferably 80% or more, more preferably 85% or more, and even more preferably 90% or more.
  • the average spectral transmittance is within the above range, when the barrier laminate for a solar cell module according to the present disclosure is used in a solar cell module, not only the visible light region but also the near-infrared region light can be used for power generation. , can increase the power generation efficiency. In addition, it is possible to prevent the temperature of the solar cell module from rising due to the absorption of near-infrared rays by the barrier laminate for solar cell module, resulting in a decrease in the power generation efficiency of the solar cell module.
  • the average spectral transmittance at wavelengths of 400 nm or more and 1200 nm or less is the average value of spectral transmittances at wavelengths of 400 nm or more and 1200 nm or less.
  • the average spectral transmittance can be measured by a method conforming to JIS K 7361-1:1997.
  • the barrier laminate for a solar cell module of the present disclosure has its yellowness suppressed.
  • the spectral transmittance at a wavelength of 400 nm is preferably 75% or higher, particularly preferably 78% or higher.
  • the barrier laminate for a solar cell module of the present disclosure has transparency, it is preferable that the above-described topcoat layer and primer layer are provided within a range that does not impair the above-described transparency.
  • the top coat layer and the primer layer transmit light in the visible light region and the near infrared region.
  • the barrier laminate for a solar cell module in the present disclosure can have a dark colored layer from the viewpoint of design. Since the barrier laminate for a solar cell module of the present disclosure suppresses yellowness, it can reduce the influence on color (dark color). Further, the colored layer preferably has a high near-infrared transmittance. This is because heat generation due to absorption of near-infrared rays can be suppressed. As such a colored layer, an infrared transmitting dark layer disclosed in Japanese Patent No. 6721092 can be used.
  • the barrier laminate for a solar cell module of the present disclosure having the colored layer preferably further has a reflective layer.
  • the reflective layer is preferably a white resin layer that reflects near-infrared rays.
  • Near-infrared rays refer to electromagnetic waves in a wavelength range of 750 nm or more and 2200 nm or less. Among them, the wavelength that particularly promotes heat storage is 1000 nm or more and 1500 nm or less.
  • the barrier laminate for a solar cell module of the present disclosure preferably has an average reflectance of 40% or more at 750 nm or more and 2200 nm or less, and preferably has an average reflectance of 50% or more at 1000 nm or more and 1500 nm or less.
  • a resin sheet containing a white pigment or a resin sheet having a coating layer (coating film or printed film) containing a white pigment may be used.
  • a colored layer is formed on the surface of a reflective sheet capable of reflecting near-infrared rays, and the reflective sheet and the colored layer are arranged in this order from the side opposite to the first barrier layer side of the substrate.
  • the reflective sheet the one described in Japanese Patent No. 6721092 can be used.
  • the barrier laminate of the present disclosure includes a resin sheet containing a white pigment or a coat layer (coating film or By arranging a resin sheet or the like on which a printed film is formed, a white barrier laminate having a white appearance from the transparent front plate side can be obtained. By doing so, the power generation efficiency of the solar cell module can be improved by reflecting the light that has not been absorbed by the solar cells and has been transmitted through the transparent front panel and making the solar cells absorb the light again. can be improved.
  • the method for manufacturing the barrier laminate for a solar cell module of the present disclosure is not particularly limited, but a base material and a first barrier layer containing an inorganic compound disposed on one side of the base material are used. and a hydrolytic polycondensate produced from a resin composition containing a metal alkoxide and a hydrophilic group-containing resin on the side of the first barrier layer opposite to the base material side. and a heating step of heat-treating the precursor layer to obtain the second barrier layer.
  • This step is a step of preparing a laminated member having a substrate and a first barrier layer disposed on one side of the substrate.
  • the lamination member may be used by purchasing a commercially available product, or may be formed by the step of forming a first barrier layer on one side of a base material, as described below.
  • any method can be used as long as it is capable of forming a film with a desired thickness on one or both sides of the base material. method can be used. Vapor deposition is preferred in the present disclosure.
  • the surface of the base material may be subjected to surface modification such as corona treatment and anchor coating treatment to improve adhesion to the first barrier layer.
  • This step is a step of forming a precursor layer on the side of the first barrier layer opposite to the substrate side.
  • the precursor layer can be formed by the method described in "A. Barrier laminate for solar cell module 1. Second barrier layer”.
  • Heating step is a step of performing heat treatment in a state in which the first barrier layer and the precursor layer are formed on the substrate.
  • the heating step improves the cross-linking density of the hydrolyzed condensate in the precursor layer, thereby forming the above-described second barrier layer.
  • the heat treatment in the heating step is the same as the heat treatment conditions described in "A. Barrier laminate for solar cell module 1. Second barrier layer”.
  • a resin It is preferable to include a resin layer arranging step of arranging the layers.
  • the resin layer is preferably adhered to the precursor layer via an adhesive layer. This is because curling and shrinkage of the barrier laminate can be suppressed.
  • the resin layer and the adhesive layer those described in "A. Barrier laminate for solar cell module 4. Other layers" can be used.
  • the solar cell module in this aspect is a solar cell module having a transparent front plate, a front sealing material, a plurality of solar cells, a back sealing material, and a back protective sheet in this order, and
  • the protective sheet is the aforementioned barrier laminate for solar cell module.
  • the back protective sheet is the aforementioned "A. Barrier laminate for solar cell module”.
  • the back surface protective sheet that is, the barrier laminate for solar cell module, preferably has the base material arranged on the back surface sealing material side and the second barrier layer arranged on the outside air side. This is because, as described above, by arranging the second barrier layer on the outside air side, it is possible to prevent deterioration of the base material by blocking water from the outside air side with the second barrier layer. .
  • sealing material As the front sealing material and the back sealing material, sealing materials generally used for solar cell modules can be used. Examples of the front sealing material and the back sealing material include sealing materials containing olefin resins such as polyethylene and ethylene-vinyl acetate copolymer (EVA).
  • olefin resins such as polyethylene and ethylene-vinyl acetate copolymer (EVA).
  • Solar Battery Cell Various solar battery cells can be used as the solar battery cell.
  • Transparent Front Plate A glass substrate is usually used as the transparent front plate. Moreover, a transparent resin film having weather resistance may be used as the transparent front plate. Moreover, the barrier laminate for a solar cell module of the present disclosure can also be used as the transparent front plate.
  • the solar cell module of this aspect can be manufactured by heat-pressing the above members by, for example, a vacuum lamination method.
  • the heating temperature at this time can be, for example, 110° C. or higher and 190° C., preferably 130° C. or higher.
  • the lamination time can be, for example, 5 minutes or more and 60 minutes or less.
  • the solar cell module in this aspect is a solar cell module having a transparent front plate, a front sealing material, a plurality of solar cells, a back sealing material, and a back protective sheet in this order, and the transparent A solar cell module in which the front plate is the barrier laminate for a solar cell module described above.
  • the transparent front plate is the aforementioned “A. Barrier laminate for solar cell module”.
  • the transparent front plate that is, the barrier laminate for a solar cell module, uses the base material as the front sealing material for the same reason as described in "B. Solar cell module (first embodiment)”. and the second barrier layer is preferably arranged on the outside air side.
  • Example 1 (Laminate A) A polyethylene terephthalate (PET) substrate having a thickness of 12 ⁇ m and a deposited silicon oxide film (first barrier layer) having a thickness of 10 nm was prepared (trade name: Techbarrier LX, manufactured by Mitsubishi Chemical Corporation). Next, the following resin composition was applied to the side of the deposited silicon oxide film opposite to the PET substrate side and dried by heating at 150° C. for 30 seconds to obtain a precursor layer. Next, a hydrolysis-resistant polyethylene terephthalate (BP manufactured by DuPont) having a thickness of 150 ⁇ m was applied as a resin layer A to the surface of the precursor layer opposite to the silicon oxide vapor deposition film side via an adhesive layer having a thickness of 4 ⁇ m. pasted together.
  • PET polyethylene terephthalate
  • first barrier layer deposited silicon oxide film having a thickness of 10 nm
  • the adhesive layer was formed by applying adhesive A prepared as follows. Then, heat treatment was performed at 200° C. for 30 seconds to obtain a laminate A having a PET base material, a first barrier layer (10 nm), a second barrier layer (0.3 ⁇ m), an adhesive layer, and hydrolysis-resistant PET in this order. Obtained.
  • Resin composition Liquid B tetraethyl orthosilicate (TEOS), isopropyl A hydrolyzate consisting of alcohol, hydrochloric acid and ion-exchanged water
  • TEOS tetraethyl orthosilicate
  • isopropyl A hydrolyzate consisting of alcohol, hydrochloric acid and ion-exchanged water
  • PVA Polyvinyl alcohol
  • TEOS Tetraethyl orthosilicate
  • ⁇ Preparation of Adhesive A 100 parts by mass of polyurethane diol and 15 parts by mass of aliphatic polycarbonate diol (manufactured by Asahi Kasei Chemicals, "Duranol T5651", number average molecular weight: 1000) are mixed to obtain a resin component. was prepared. 100 parts by mass of the resin component and 15 parts by mass of a pigment (CI Pigment Violet 23) were dispersed in a bead mill to prepare a main agent. When used, the solid content was adjusted to 33.3%.
  • Example 2 Using the laminate A produced in Example 1 as a member, the laminate A and a white polyethylene film (white PE film, TiO 2 -containing LLDPE with a thickness of 30 ⁇ m) are laminated via an adhesive layer to obtain a white barrier property. A laminate was obtained. Laminate A was arranged so that the hydrolysis-resistant PET (resin layer A) faced outward. The adhesive layer was formed using the adhesive A described above.
  • Example 3 Using the laminate A produced in Example 1 as a member, the laminate A, a 150 ⁇ m thick PET film (manufactured by DuPont BP), and a 30 ⁇ m thick white polyethylene film (manufactured by Tamapoly Co., Ltd. SE625NWT02), By laminating in this order with an adhesive layer interposed, a white barrier laminate was obtained. Laminate A was arranged so that the hydrolysis-resistant PET (resin layer A) faced outward. The adhesive layer was formed using the adhesive A described above.
  • Example 4 Using the laminate A produced in Example 1 as a member, the laminate A and a 30 ⁇ m thick polyethylene film (SE625N manufactured by Tamapoly) are laminated via the following black adhesive (colored layer) to form a black barrier. A flexible laminate was obtained. Laminate A was arranged so that the hydrolysis-resistant PET (resin layer A) faced outward. Black adhesive The following infrared-transmitting mixed dark pigment was mixed with the adhesive A so that the content ratio of the following infrared-transmitting mixed dark pigment was 25% by mass in terms of solid content. .
  • Infrared transparent mixed dark pigment A mixed pigment obtained by mixing the following "infrared-transmitting blue-based dark pigment” and “infrared-transmitting brown-based dark pigment” at a ratio of 50:50 was used.
  • Infrared transparent blue-based dark pigment A phthalocyanine pigment (amorphous phthalocyanine pigment blue (PigmentBlue 15, particle size 0.15 to 0.20 ⁇ m)) was used.
  • Infrared transparent brown-based dark pigment Benzimidazolone pigment (PigmentBrown25, particle size 0.08 ⁇ m)
  • Example 5 Using the laminate A produced in Example 1 as a member, the laminate A, an adhesive layer, a 150 ⁇ m thick PET (manufactured by DuPont BP), the colored layer, a 30 ⁇ m thick PE film (manufactured by Tamapoly SE625N), A black type barrier laminate having these order was obtained. Laminate A was arranged so that the hydrolysis-resistant PET faced outward. The adhesive layer was formed using the adhesive A described above.
  • Laminate B A laminate B was obtained in the same manner as in Example 1, except that a transparent PET (manufactured by DuPont) having a thickness of 140 ⁇ m was used as the resin layer B instead of the resin layer A.
  • Laminate B has a configuration of PET substrate/first barrier layer (10 nm)/second barrier layer (0.3 ⁇ m)/adhesive layer/transparent PET.
  • Example 7 ⁇ Coating agent 1 A coating agent 1 was prepared by stirring and mixing the following materials and solvent. Moreover, the curing agent was added at a rate of 16 parts by mass with respect to 100 parts by mass of the hydroxyl group-containing crosslinkable substituent-containing acrylic resin.
  • Hydroxyl group-containing crosslinkable substituent-containing acrylic resin Synthesized by the following method Curing agent: Desmodur N3200 (manufactured by Sumika essence Urethane Co., Ltd.)
  • UV absorber TInuvin429 (BASF)
  • Solvent ethyl acetate
  • the coating agent 1 was applied to the surface of the resin layer side of the laminate B so that the coating amount was 5 g / m 2 , dried, and the transparency was improved. to form a topcoat layer having
  • - Primer composition The following materials and solvent were stirred and mixed to prepare a primer composition.
  • the paraffin wax was blended so that the content in the solid content of the primer composition was 15% by mass.
  • the cross-linking agent was added in a proportion of 3 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin resin (solid content).
  • the above primer composition is applied to the surface of the laminate B opposite to the topcoat layer forming surface so that the coating amount is 1 g/m 2 and dried to form a primer layer having transparency. bottom.
  • a transparent type barrier laminate having a configuration of topcoat layer/laminate B/primer layer was obtained.
  • Example 8 Using the laminate B produced in Example 6 as a member, a transparent topcoat layer was formed on the surface of the laminate B on the resin layer side in the same manner as in Example 7. Next, on the other surface of the laminate B, an adhesive layer and a transparent PET (AP resin layer B manufactured by DuPont) having a thickness of 140 ⁇ m are laminated in this order, and a primer layer is formed in the same manner as in Example 7. Then, a transparent type barrier laminate was obtained. The adhesive layer was formed using the adhesive A described above.
  • Example 9 Using the laminate B produced in Example 6 as a member, two laminates B were prepared and laminated such that the base material of one laminate B and the resin layer of the other laminate B were in contact with each other. Next, on the side where the resin layer is exposed, a transparent topcoat layer is formed in the same manner as in Example 7, and a primer layer is formed on the other side in the same manner as in Example 7. Then, a transparent type barrier laminate was obtained.
  • Example 3 A white barrier laminate was obtained in the same manner as in Example 2, except that instead of the laminate A, a laminate A′ that had not been heat-treated at 200° C. for 30 seconds was used (Comparative Example 3). Further, a transparent type barrier laminate was obtained in the same manner as in Example 7, except that the laminate B′ which was not heat-treated at 200° C. for 30 seconds was used instead of the laminate B (comparative Example 4).
  • melting peak temperature The melting peak temperature of the second barrier layer of each laminate obtained was determined according to the method and conditions described in the section "A. Barrier laminate for solar cell module 1. Second barrier layer (2) Melting peak temperature”. ,It was measured. Table 1 shows the results of the melting peak temperatures of the second barrier layers of Examples 1, 6, Comparative Examples 1 and 2, Examples 2-5, Examples 7-9, Comparative Examples 3 and 4. Table 2 shows the results of the melting peak temperature of the second barrier layer.
  • Tables 3 to 5 show the layer structures of the barrier laminates obtained in Examples 2 to 5 and Examples 7 to 9 and the following physical properties.
  • Thermal shrinkage rate The dimensional change at 150° C. for 30 minutes of each of the obtained barrier laminates was measured according to the method and conditions described in the above section “A. Barrier laminate for solar cell module 5. Physical properties (2) Thermal shrinkage rate”. It was measured. The results are shown in Tables 3-5.
  • the tensile stress and the elongation at break in the tensile test of each of the obtained barrier laminates were measured in the above section "A. Barrier laminate for solar cell module 5. Physical properties (3) Tensile stress and elongation at break”. Measured by the methods and conditions described. The results are shown in Tables 3-5.
  • the test piece was a measurement sample having a width of 10 mm and a length of 100 mm from the barrier laminate for solar cell module. was collected so as to be
  • the average spectral transmittance in each wavelength region of each barrier laminate was measured according to JIS K 7361-1:1997.
  • a measurement sample having a width of 30 mm and a length of 30 mm was taken from the barrier laminate for solar cell module and measured using V-670 manufactured by JASCO Corporation.
  • a barrier laminate for a solar cell module a substrate; a first barrier layer containing an inorganic compound disposed on one side of the substrate; a second barrier layer disposed on the side of the first barrier layer opposite to the substrate side,
  • the second barrier layer has a melting peak temperature of 220° C. or higher as measured by a DSC (differential scanning calorimetry) method,
  • the barrier laminate for solar cell module has a water vapor permeability of 5.0 ⁇ 10 ⁇ 2 g/(m 2 ⁇ day) or less.
  • the solar cell module according to any one of [1] to [3], wherein the second barrier layer contains a hydrolyzed polycondensate produced from a resin composition containing a metal alkoxide and a hydrophilic group-containing resin. barrier laminate.
  • the barrier laminate for a solar cell module according to any one of [1] to [7], further comprising a resin layer disposed on the side of the second barrier layer opposite to the side of the first barrier layer. body.
  • barrier laminate for solar cell module according to any one of [1] to [11], wherein the barrier laminate for solar cell module has an average spectral transmittance of 80% or more at a wavelength of 400 nm or more and 800 nm or less. .
  • barrier laminate for solar cell module according to any one of [1] to [12], wherein the barrier laminate for solar cell module has a spectral transmittance of 75% or more at a wavelength of 400 nm.
  • the barrier laminate for a solar cell module according to any one of [1] to [11], which has a reflective layer and a colored layer, and has an average reflectance of 40% or more at a wavelength of 750 nm or more and 2200 nm or less.
  • a barrier laminate for solar cell modules is any one of [1] to [11], which has a reflective layer and a colored layer, and has an average reflectance of 40% or more at a wavelength of 750 nm or more and 2200 nm or less.
  • a solar cell module comprising, in this order, a transparent front plate, a front sealing material, a plurality of solar cells, a back sealing material, and a back protective sheet, A solar cell module, wherein the back surface protective sheet is the barrier laminate for a solar cell module according to any one of [1] to [14].
  • a solar cell module comprising, in this order, a transparent front plate, a front sealing material, a plurality of solar cells, a back sealing material, and a back protective sheet, A solar cell module, wherein the transparent front plate is the barrier laminate for a solar cell module according to any one of [1] to [13].

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