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WO2012118195A1 - Feuille de protection pour cellule solaire, son procédé de fabrication, feuille de support pour cellule solaire et module de cellule solaire - Google Patents

Feuille de protection pour cellule solaire, son procédé de fabrication, feuille de support pour cellule solaire et module de cellule solaire Download PDF

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Publication number
WO2012118195A1
WO2012118195A1 PCT/JP2012/055431 JP2012055431W WO2012118195A1 WO 2012118195 A1 WO2012118195 A1 WO 2012118195A1 JP 2012055431 W JP2012055431 W JP 2012055431W WO 2012118195 A1 WO2012118195 A1 WO 2012118195A1
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WIPO (PCT)
Prior art keywords
polymer
layer
polymer layer
solar cell
lubricant
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PCT/JP2012/055431
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English (en)
Japanese (ja)
Inventor
伊藤　維成
畠山　晶
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Fujifilm Corp
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Fujifilm Corp
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Publication of WO2012118195A1 publication Critical patent/WO2012118195A1/fr
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/12—Photovoltaic modules
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to a protective sheet for a solar cell and a manufacturing method thereof, a back sheet for a solar cell, and a solar cell module.
  • Solar cells are a power generation system that emits no carbon dioxide during power generation and has a low environmental load, and has been rapidly spreading in recent years.
  • a solar cell module generally includes a front base material disposed on the front surface side on which sunlight is incident and a back surface protection sheet (so-called back surface) disposed on the opposite side (rear surface side) to the front surface side on which sunlight is incident.
  • a solar battery cell in which a solar cell element is sealed with a sealing agent is sandwiched between the sheet and a sheet.
  • the space between the front substrate and the solar cell element (cell) and the space between the solar cell element (cell) and the back sheet are respectively sealed with ethylene-vinyl acetate (EVA) resin or the like. .
  • EVA ethylene-vinyl acetate
  • the back sheet has a function of preventing moisture from entering from the back surface of the solar cell module.
  • glass or fluororesin has been used, but in recent years, polyester is applied from the viewpoint of cost reduction and the like. Has reached.
  • a glass substrate is generally used for the front substrate from the viewpoint of high light transmittance and maintaining a certain level of strength, but attempts have been made to use polyester instead of the glass substrate. Yes.
  • polyester has been widely studied for various uses such as a solar cell application such as a back sheet, an electrical insulation application, and an optical application.
  • Polyester usually has many carboxyl groups and hydroxyl groups on its surface, and tends to undergo a hydrolysis reaction under environmental conditions where moisture exists, and tends to deteriorate over time.
  • Solar cell modules are often used in environments that are constantly exposed to wind and rain, such as outdoors, and are exposed to conditions where hydrolysis reactions are likely to proceed over a long period of time. Therefore, when applying polyester to a solar cell use, it is important that the hydrolyzability of polyester is suppressed.
  • pebbles and the like are affected by wind or the like and collide with the module surface, for example, scratches or the like enter the backsheet surface. When scratches or the like are formed, hydrolysis proceeds from that portion, and the weather resistance of the entire module can be lowered.
  • a laminate for a solar battery backsheet in which a silicone-modified acrylic resin layer is provided on a vinylidene chloride resin layer is disclosed (see, for example, JP 2009-290201 A). It is said to exhibit excellent weather resistance and moisture resistance by expressing and maintaining water vapor barrier properties.
  • a back surface protection sheet for a solar cell module provided with a weather resistant outermost layer by a curable resin composition using an acrylate copolymer and an organohydrodiene polysiloxane is disclosed (for example, JP-A-2002-83988). No. publication), and is said to be excellent in weather resistance. Furthermore, a technique using an organic fine powder such as wax as an anti-blocking agent has also been disclosed (see, for example, JP 2010-287661 A).
  • silicone resins often contain a low molecular silicone component in the resin.
  • the low molecular silicone component is advantageous in terms of slipperiness, in the production mode in which a layer is formed by coating, the low molecular silicone component in the coating film is unwound on the reverse side (that is, in the process of winding after coating) It may be transferred to the surface on the side opposite to the side on which the coating film of the polymer substrate is applied and adversely affected in the subsequent process.
  • the present invention has been made in view of the above, and has no adverse effects on the manufacturing process by transferring the components to the non-coated surface after coating, etc., and against external forces such as scratching, rubbing, and collision of flying objects (pebbles, etc.). It is possible to provide a solar cell protective sheet excellent in scratch resistance, a method for producing the same, a solar cell backsheet, and a solar cell module that exhibits stable power generation performance over a long period of time.
  • a solar cell protective sheet comprising a polymer substrate and a polymer layer that is an outermost layer disposed on one surface of the polymer substrate,
  • the polymer layer contains a polymer and a lubricant;
  • the polymer molecule has a structure containing a siloxane bond,
  • the content of the polymer in the polymer layer is more than 0.2 g and 15 g or less per 1 m 2 of the polymer layer, and the content of the lubricant in the polymer layer is 0.2 mg or more and 200 mg or less per 1 m 2 of the polymer layer.
  • ⁇ 2> The solar cell protective sheet according to ⁇ 1>, wherein the lubricant is at least one selected from a synthetic wax compound, a natural wax compound, and a surfactant compound.
  • the polymer layer has a surface dynamic friction coefficient of 0.4 or less.
  • the polymer layer contains a matting agent having an average secondary particle size of 0.3 ⁇ m to 10 ⁇ m in a range of 0.3 mg to 30 mg per 1 m 2 of the polymer layer. It is the protection sheet for solar cells as described in any one.
  • ⁇ 5> The solar cell protective sheet according to any one of ⁇ 1> to ⁇ 4>, wherein the polymer layer further contains colloidal silica and an alkoxysilane compound.
  • ⁇ 6> The solar cell protective sheet according to any one of ⁇ 1> to ⁇ 5>, wherein the polymer substrate is subjected to corona treatment on a surface on which the polymer layer is disposed.
  • the lubricant is selected from the group consisting of polyolefin waxes, fatty acid metal salts, natural fatty acid ester compounds, synthetic fatty acid ester compounds, alkyl sulfate surfactants, and polyoxyethylene alkyl sulfate surfactants.
  • the protective sheet according to any one of ⁇ 1> to ⁇ 6>.
  • a polymer having a structure containing a siloxane bond in a molecule, a lubricant, and an aqueous coating solution containing water are applied, and more than 0.2 g and 15 g or less of the polymer per m 2
  • It is a manufacturing method of the protection sheet for solar cells including forming the polymer layer containing the said lubricant of 0.2 mg or more and 200 mg or less.
  • the polymer layer is formed by mixing at least an aqueous dispersion of the polymer and an aqueous dispersion of the lubricant to prepare the aqueous coating liquid, and the prepared aqueous coating liquid is used as the polymer.
  • a solar cell having excellent scratch resistance against external forces such as scratching, rubbing, and collision of flying objects (pebbles, etc.) without adversely affecting the manufacturing process by transferring components to a non-coated surface after coating.
  • Protective sheet, method for producing the same, and back sheet for solar cell can be provided.
  • ADVANTAGE OF THE INVENTION According to this invention, the solar cell module which exhibits the stable electric power generation performance over a long term can be provided.
  • the numerical range display (“m or more and n or less” or “m to n”) includes the numerical value (m) displayed as the lower limit value of the numerical value range as the minimum value, and is displayed as the upper limit value of the numerical value range.
  • the range including the numerical value (n) as the maximum value is shown.
  • the protective sheet of the present disclosure is formed as a polymer substrate and an outermost layer on one surface of the polymer substrate, and at least a polymer having a (poly) siloxane structure in a molecule is more than 0.2 g / m 2 and more than 15 g / m 2. m 2 or less and a polymer layer containing a lubricant of 0.2 mg / m 2 or more and 200 mg / m 2 or less.
  • the protective sheet may further include a colored layer colored with a colorant (including a light reflecting layer that reflects sunlight) and a constituent substrate of the battery side substrate (for example, a sealing material such as EVA).
  • Other layers such as an easy-adhesive layer that increases the adhesion between the two and the like (for example, the adhesive force to the sealing material is 10 N / cm or more) may or may not be provided.
  • the protective sheet includes a transparent base material (a front base material such as a glass substrate) disposed on the side on which sunlight is incident, and an element structure part (including a solar cell element and a sealant that seals it). And a solar cell having a laminated structure of “transparent front substrate / element structure portion / back sheet”, which is applied to either the front substrate or the back sheet.
  • the back sheet is a back surface protection sheet disposed on the side where the front base material is not located when viewed from the element structure portion of the battery side substrate.
  • a battery part having a laminated structure of “transparent front base material / element structure part” in which an element structure part is arranged on a transparent base material arranged on the side where sunlight enters is referred to as “battery”. It is called “side substrate”.
  • the polymer layer formed by coating has high film strength, and scratches, scratches, flying objects ( It can exhibit excellent scratch resistance against external forces such as collisions of pebbles, etc., and can stably maintain light resistance, heat resistance, and moisture resistance for a long period when arranged as the outermost layer.
  • the said protection sheet can exhibit the outstanding weather resistance performance as a protection sheet of a solar cell, and can acquire the electric power generation performance stable for a long period of time.
  • the polymer layer can be applied to any layer constituting the back sheet as the outermost layer farthest from the polymer substrate. From the point that the polymer layer is excellent in durability under a moist heat environment such as heat and moisture, the protective sheet is the outermost layer exposed to the external environment when used in a solar cell module as a back sheet, that is, on the back side. It is particularly preferable to function as the outermost layer (back layer).
  • polymer substrate examples include polyester, polyolefin such as polypropylene and polyethylene, or fluorocarbon polymer such as polyvinyl fluoride.
  • the substrate may be a film or a sheet.
  • a polyester base material is preferable from the viewpoint of cost and mechanical strength.
  • polyester substrate used as the polymer substrate (support) examples include a linear saturated polyester substrate synthesized from an aromatic dibasic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof.
  • Specific examples of such polyester include polyethylene terephthalate, polyethylene isophthalate, polybutylene terephthalate, poly (1,4-cyclohexylenedimethylene terephthalate), polyethylene-2,6-naphthalate and the like. Of these, polyethylene terephthalate or polyethylene-2,6-naphthalate is preferable from the viewpoint of balance between mechanical properties and cost.
  • the polyester base material may be a homopolymer or a copolymer. Furthermore, the polyester base material may be made of only polyester, or may be made of a mixture obtained by blending a small amount of other types of resins, such as polyimide, with the polyester.
  • the Ti-based compound is polymerized by using it as a catalyst so that the Ti element conversion value is in the range of 1 ppm to 30 ppm, more preferably 3 ppm to 15 ppm.
  • the amount of Ti compound used is within the above range in terms of Ti element, the terminal carboxyl group of the polyester can be adjusted to the following range, and the hydrolysis resistance of the polymer substrate can be kept high.
  • Examples of the synthesis of polyester using a Ti compound include Japanese Patent Publication No. 8-301198, Japanese Patent No. 2543624, Japanese Patent No. 3335683, Japanese Patent No. 3717380, Japanese Patent No. 3897756, Japanese Patent No. 396226, and Japanese Patent No. 39786666.
  • No. 3, Patent No. 3,996,871, Patent No. 40000867, Patent No. 4053837, Patent No. 4,127,119, Patent No. 4,134,710, Patent No. 4,159,154, Patent No. 4,269,704, Patent No. 4,313,538 and the like can be applied.
  • the carboxyl group content in the polyester is preferably 55 equivalents / t (tons; hereinafter the same) or less, more preferably 35 equivalents / t or less.
  • the lower limit of the carboxyl group content is preferably 2 equivalents / t in that the adhesion between the layer formed on the polyester film (for example, a colored layer) can be maintained.
  • the carboxyl group content in the polyester can be adjusted by the polymerization catalyst species and the film forming conditions (film forming temperature and time).
  • the polyester is preferably one that is solid-phase polymerized after polymerization. Thereby, a preferable carboxyl group content can be achieved.
  • Solid-phase polymerization may be a continuous method (a method in which a tower is filled with a resin, which is slowly heated for a predetermined time and then sent out), or a batch method (a resin is charged into a container). , A method of heating for a predetermined time).
  • Japanese Patent No. 2621563, Japanese Patent No. 3121876, Japanese Patent No. 3136774, Japanese Patent No. 3603585, Japanese Patent No. 3616522, Japanese Patent No. 3617340, Japanese Patent No. 3680523, Japanese Patent No. 3717392 are disclosed. The method described in Japanese Patent No. 4167159 can be applied.
  • the temperature of the solid phase polymerization is preferably 170 ° C. or higher and 240 ° C. or lower, more preferably 180 ° C. or higher and 230 ° C. or lower, and further preferably 190 ° C. or higher and 220 ° C. or lower.
  • the solid phase polymerization time is preferably 5 hours to 100 hours, more preferably 10 hours to 75 hours, and still more preferably 15 hours to 50 hours.
  • the solid phase polymerization is preferably performed in a vacuum or in a nitrogen atmosphere.
  • the polyester base material is obtained by melt-extruding the above polyester into a film and then cooling and solidifying with a casting drum to form an unstretched film.
  • the unstretched film is once in the longitudinal direction at Tg to (Tg + 60) ° C.
  • a biaxially stretched film formed by stretching two or more times so that the total magnification is 3 to 6 times, and then stretching to a magnification of 3 to 5 times in the width direction at Tg to (Tg + 60) ° C. It is preferable that Further, heat treatment may be performed at 180 to 230 ° C. for 1 to 60 seconds as necessary, or may not be performed.
  • Tg represents a glass transition temperature and can be measured based on JIS K7121 or ASTM D3418-82. For example, it can be measured using a differential scanning calorimeter (DSC) manufactured by Shimadzu Corporation. Specifically, 10 mg of a polymer such as polyester is weighed as a sample, set in an aluminum pan, and heated at a rate of temperature increase of 10 ° C./min from room temperature to a final temperature of 300 ° C., with a DSC apparatus, the amount of heat with respect to temperature. was measured as the glass transition temperature.
  • DSC differential scanning calorimeter
  • the thickness of the polymer substrate is preferably about 25 to 300 ⁇ m. If the thickness is 25 ⁇ m or more, the mechanical strength can be good, and if it is 300 ⁇ m or less, it can be advantageous in terms of cost. In particular, the polyester base material tends to have poor hydrolysis resistance as the thickness increases, and durability during long-term use tends to decrease. In one embodiment, when the thickness is 120 ⁇ m or more and 300 ⁇ m or less and the carboxyl group content in the polyester is 2 equivalent / t to 35 equivalent / t, the effect of improving wet heat durability can be further improved.
  • the polymer substrate is preferably in a form in which surface treatment is performed by corona treatment, flame treatment, low-pressure plasma treatment, atmospheric pressure plasma treatment, or ultraviolet treatment.
  • corona treatment By applying these surface treatments, the adhesiveness when exposed to a humid heat environment can be further enhanced. In particular, by performing the corona treatment, a better adhesive improvement effect can be obtained.
  • adhesion can be enhanced by increasing carboxyl groups and hydroxyl groups on the surface of a polymer substrate (for example, polyester substrate), and a crosslinking agent (particularly an oxazoline-based or carbodiimide having a high reactivity with a carboxyl group).
  • a cross-linking agent When a cross-linking agent) is used in combination, stronger adhesiveness can be obtained. This can be more pronounced with corona treatment. Therefore, it is particularly preferable that the surface of the polymer substrate on which the polymer layer is formed is corona-treated.
  • the polymer layer is disposed in contact with the surface of the polymer substrate or through another layer.
  • the polymer layer includes at least a polymer having a (poly) siloxane structure in a molecule and a lubricant.
  • the polymer is contained in 0.2 g / m 2 Ultra 15 g / m 2 or less in the range in the polymer layer, wherein the lubricant is contained in the 0.2 mg / m 2 or more 200 mg / m 2 or less in the range in the polymer layer Yes.
  • the polymer layer contains, as a polymer component, a polymer having a (poly) siloxane structure in the molecule and a lubricant.
  • the polymer layer By providing the polymer layer, adhesion between adjacent materials such as a polymer substrate can be improved. In certain embodiments, it is preferred that the polymer layer be disposed in direct contact with the polymer substrate.
  • This polymer layer may or may not contain other components depending on the case, and its constituent components differ depending on the intended application. Since the polymer layer is provided as the outermost layer farthest from the polymer base material, it is preferable to constitute a back layer disposed on the side opposite to the side on which sunlight is incident, and the solar light reflecting function and appearance design The structure which serves also as the colored layer etc. which bear
  • the polymer layer when configured as a light reflecting layer that reflects sunlight toward the incident side, the polymer layer may further include a colorant such as a white pigment in addition to the polymer component and the lubricant.
  • a colorant such as a white pigment
  • the polymer layer contains at least one polymer having a (poly) siloxane structure in the molecule.
  • the polymer layer can improve the strength of the surface of the polymer layer, and can reduce scratches that are likely to occur due to scratches, scratches, collisions of flying objects such as pebbles and sand, etc. It can be more excellent in adhesion to adjacent materials and durability in wet heat environment.
  • the polymer is not particularly limited as long as it has a (poly) siloxane structure in the molecule.
  • the “siloxane structure” means a structure containing at least one siloxane bond.
  • Polysiloxane structure means a structure in which a plurality of siloxane bonds are continuous.
  • the term “(poly) siloxane structure” encompasses siloxane structures and polysiloxane structures within its scope.
  • the expressions “the polymer has a siloxane structure in the molecule” and “the polymer has a (poly) siloxane structure in the molecule” mean that the polymer contains a siloxane structure or a polysiloxane structure in the molecule.
  • a homopolymer (monopolymer) of a compound having a (poly) siloxane structural unit, or a copolymer of a compound having a (poly) siloxane structural unit and another compound, that is, a (poly) siloxane structure Copolymers having units and other structural units are preferred.
  • the other compound is a non-siloxane monomer or polymer, and the other structural unit is a non-siloxane structural unit.
  • the polymer has a (poly) siloxane structural unit represented by the following general formula (1) in the molecule.
  • R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, or a monovalent organic group.
  • n represents an integer of 1 or more.
  • R 1 and R 2 may be the same or different, and a plurality of R 1 and R 2 existing when n is 2 or more may be the same or different from each other. * Represents a position linked to an adjacent structural unit.
  • — (Si (R 1 ) (R 2 ) —O) n —” is a (poly) siloxane segment derived from various (poly) siloxanes having a linear, branched or cyclic structure.
  • Examples of the halogen atom represented by R 1 and R 2 include a fluorine atom, a chlorine atom, and an iodine atom.
  • the “monovalent organic group” represented by R 1 and R 2 is a group that can be covalently bonded to an Si atom, and may be unsubstituted or may have a substituent.
  • Examples of the monovalent organic group include an alkyl group (e.g., methyl group, ethyl group), an aryl group (e.g., phenyl group), an aralkyl group (e.g., benzyl group, phenylethyl group), an alkoxy group (e.g.
  • methoxy group, ethoxy group, propoxy group, etc. examples: methoxy group, ethoxy group, propoxy group, etc.), aryloxy group (eg, phenoxy group, etc.), mercapto group, amino group (eg, amino group, diethylamino group, etc.), amide group and the like.
  • R 1 and R 2 are each independently a hydrogen atom, a chlorine atom, a bromine atom, an unsubstituted or substituted, in terms of adhesion to adjacent materials such as a polymer substrate and durability in a wet and heat environment.
  • Alkyl groups having 1 to 4 carbon atoms particularly methyl group, ethyl group
  • unsubstituted or substituted phenyl group unsubstituted or substituted alkoxy group
  • mercapto group unsubstituted amino group
  • amide group More preferably an unsubstituted or substituted alkoxy group (preferably an alkoxy group having 1 to 4 carbon atoms) from the viewpoint of durability in a moist heat environment.
  • the n is preferably 1 to 5000, and more preferably 1 to 1000.
  • the content of “— (Si (R 1 ) (R 2 ) —O) n —” in the polymer depends on the total mass of the polymer. On the other hand, it is preferably 15 to 85% by mass, and among them, it is possible to improve the strength of the surface of the polymer layer, to prevent the occurrence of scratches due to scratching, scratching, etc., and to adhere to adjacent materials such as a polymer substrate.
  • the range of 20 to 80% by mass is more preferable from the viewpoint that it can be more excellent in durability under a humid heat environment.
  • the ratio of the (poly) siloxane structural unit is 15% by mass or more, the strength of the polymer layer surface is improved, and scratches caused by scratches, scratches, collisions of flying pebbles, etc. can be prevented, and the support It can be excellent in adhesiveness with adjacent materials such as a polymer substrate.
  • the weather resistance can be improved by suppressing the occurrence of scratches, and the peel resistance, shape stability, and adhesion durability when exposed to a wet and heat environment, which are likely to deteriorate when heat and moisture are applied, can be effectively enhanced.
  • the coating liquid for polymer layer formation can be kept stable as the ratio of the (poly) siloxane structural unit is 85% by mass or less.
  • the mass of the (poly) siloxane structural unit represented by the general formula (1) in the molecule is It may contain 15 to 85% by mass in proportion and 85 to 15% by mass in terms of mass ratio of non-siloxane structural units.
  • the film strength of the polymer layer can be improved, the occurrence of scratches due to scratching or scratching, etc. can be prevented, and adhesion with the polymer substrate forming the support, that is, heat and moisture can be given. If this is done, the peel resistance, shape stability, and durability in a humid heat environment, which are likely to deteriorate, can be drastically improved as compared with the prior art.
  • the copolymer is represented by the general formula (1) obtained by copolymerization of a siloxane compound (including polysiloxane) and a compound selected from a non-siloxane monomer or a non-siloxane polymer.
  • a block copolymer having a siloxane structural unit and a non-siloxane structural unit is preferred.
  • each of the siloxane compound and the non-siloxane monomer or non-siloxane polymer to be copolymerized may be one kind or two or more kinds.
  • the non-siloxane structural unit (derived from the non-siloxane monomer or non-siloxane polymer) copolymerized with the (poly) siloxane structural unit is not particularly limited except that it does not have a siloxane structure, and is arbitrary. Any of the polymer segments derived from the polymer may be used. Examples of the polymer (precursor polymer) that is a precursor of the polymer segment include various polymers such as a vinyl polymer, a polyester polymer, and a polyurethane polymer. Among these, vinyl polymers and polyurethane polymers are preferable, and vinyl polymers are particularly preferable because they are easy to prepare and have excellent hydrolysis resistance.
  • the vinyl polymer include various polymers such as an acrylic polymer, a carboxylic acid vinyl ester polymer, an aromatic vinyl polymer, and a fluoroolefin polymer.
  • acrylic polymers are particularly preferable from the viewpoint of design freedom.
  • the polymer which comprises a non-siloxane type structural unit may be single 1 type, and 2 or more types of combined use may be sufficient as it.
  • the precursor polymer forming the non-siloxane structural unit is preferably one containing at least one of an acid group and a neutralized acid group and / or a hydrolyzable silyl group.
  • the vinyl polymer includes, for example, (a) a vinyl monomer containing an acid group and a vinyl monomer containing a hydrolyzable silyl group and / or a silanol group.
  • the precursor polymer can be produced and obtained using, for example, the method described in paragraph Nos. 0021 to 0078 of JP-A-2009-52011.
  • the polymer layer may be used alone or in combination with another polymer as a binder.
  • the content of the polymer containing the (poly) siloxane structure is preferably 30% by mass or more, more preferably 60% by mass or more, based on the total amount of binder in the polymer layer.
  • the content of the polymer containing the (poly) siloxane structure is 30% by mass or more, so that the strength of the surface of the layer can be improved and the occurrence of scratches due to scratching or scratching can be prevented, and the adhesion to the polymer substrate In addition, it can be more excellent in durability under humid heat environment.
  • the molecular weight of the polymer is preferably 5,000 to 100,000, and more preferably 10,000 to 50,000.
  • a method of reacting the precursor polymer with (poly) siloxane having the structural unit represented by the general formula (1), (ii) the R 1 in the presence of the precursor polymer a method such as a method of hydrolyzing and condensing a silane compound having the structural unit represented by the general formula (1) in which R 2 is a hydrolyzable group can be used.
  • the silane compound used in the method (ii) include various silane compounds, and alkoxysilane compounds are particularly preferable.
  • the temperature is about 20 to 150 ° C. for about 30 minutes to 30 hours. It can be prepared by reacting (preferably at 50 to 130 ° C. for 1 to 20 hours).
  • various silanol condensation catalysts such as an acidic compound, a basic compound, and a metal containing compound, can be added.
  • water and a silanol condensation catalyst are added to a mixture of a precursor polymer and an alkoxysilane compound, and the temperature is about 20 to 150 ° C. for 30 minutes to 30 hours. It can be prepared by carrying out hydrolysis condensation to a degree (preferably at 50 to 130 ° C. for 1 to 20 hours).
  • polymer having a (poly) siloxane structure commercially available products may be used.
  • SERATE (registered trademark) series for example, SERATE (registered trademark) WSA-1070, SERATE (registered trademark) manufactured by DIC Corporation. (Trademark) WSA-1060, etc.
  • Polydurex (registered trademark) H7600 series H7650, H7630, H7620, etc.) manufactured by Asahi Kasei Chemicals Co., Ltd.
  • inorganic / acrylic composite emulsion manufactured by JSR Corporation, etc. can be used. .
  • the content of the polymer having the (poly) siloxane structure in the polymer layer may be in the range of more than 0.2 g / m 2 and 15 g / m 2 or less.
  • the content ratio of the polymer is 0.2 g / m 2 or less, the ratio of the polymer is too small, and scratches generated by external force may not be suppressed.
  • the polymer content ratio exceeds 15 g / m 2 , the polymer ratio is too large, and the curing of the polymer layer may be insufficient.
  • a range of 0.5 g / m 2 to 10.0 g / m 2 is preferable, and a range of 1.0 g / m 2 to 5.0 g / m 2 is more preferable. preferable.
  • the polymer layer contains at least one lubricant.
  • a lubricant By containing a lubricant, it is possible to suppress a decrease in slipperiness (that is, an increase in the dynamic friction coefficient) that is likely to occur when using a siloxane polymer having a siloxane structure as described above, so scratches, scratches, collisions with pebbles, etc.
  • the susceptibility to damage caused by the external force can be drastically reduced.
  • the weather resistance particularly the hydrolysis resistance that tends to deteriorate with the occurrence of scratches, can be dramatically improved while increasing the coating film strength using a siloxane-based polymer.
  • the lubricant is contained in the polymer layer in the range of 0.2 mg / m 2 to 200 mg / m 2 . If the content ratio of the lubricant is less than 0.2 mg / m 2 , the amount of the lubricant is too small, and the effect of reducing the dynamic friction coefficient due to the inclusion of the lubricant can be reduced. On the other hand, if the content ratio of the lubricant exceeds 200 mg / m 2 and increases too much, uneven coating or aggregates may occur or repelling failure may easily occur when the polymer layer is formed by coating.
  • Examples of the lubricant include synthetic wax compounds, natural wax compounds, surfactant compounds, inorganic compounds, and organic resin compounds. Among these, from the viewpoint of the surface strength of the polymer layer, a compound selected from synthetic wax compounds, natural wax compounds, and surfactant compounds is preferable.
  • Examples of the synthetic wax compounds include polyolefin waxes such as polyethylene wax and polypropylene wax, esters of fatty acids such as stearic acid, oleic acid, erucic acid, lauric acid, behenic acid, palmitic acid, and adipic acid, amides, and bisamides. , Ketones, metal salts and derivatives thereof, synthetic hydrocarbon waxes such as Fischer-Tropsch wax, phosphate esters, hydrogenated castor oil, hydrogenated waxes of hydrogenated castor oil derivatives, among which fatty acid ester compounds and fatty acid metal salts preferable.
  • polyolefin waxes such as polyethylene wax and polypropylene wax
  • esters of fatty acids such as stearic acid, oleic acid, erucic acid, lauric acid, behenic acid, palmitic acid, and adipic acid
  • amides and bisamides.
  • Ketones, metal salts and derivatives thereof synthetic hydrocarbon wax
  • the natural wax compound typically includes a natural fatty acid ester compound, for example, a plant wax such as carnauba wax, candelilla wax or wood wax, a petroleum wax such as paraffin wax or microcrystalline wax, or a montan wax.
  • a plant wax such as carnauba wax, candelilla wax or wood wax
  • a petroleum wax such as paraffin wax or microcrystalline wax
  • a montan wax examples include animal waxes such as mineral wax, beeswax, and lanolin.
  • surfactant compound examples include cationic surfactants such as alkylamine salts, alkyl sulfates (eg, alkyl sulfate salts), polyoxyethylene alkyl sulfates (eg, polyoxyethylene alkyl sulfate salts), and the like.
  • cationic surfactants such as alkylamine salts, alkyl sulfates (eg, alkyl sulfate salts), polyoxyethylene alkyl sulfates (eg, polyoxyethylene alkyl sulfate salts), and the like.
  • the lubricant is selected from the group consisting of polyolefin wax, fatty acid metal salt, natural fatty acid ester compound, synthetic fatty acid ester compound, alkyl sulfate surfactant, and polyoxyethylene alkyl sulfate surfactant. At least one selected from the group. In some embodiments, one lubricant selected from the group.
  • the fatty acid ester compound means a compound having in its molecule an ester bond formed between a hydroxyl group and a carboxyl group of a fatty acid.
  • Synthetic wax-based lubricants include, for example, Chemipearl (registered trademark) series (for example, Chemipearl (registered trademark) W700, W900, and W950) manufactured by Mitsui Chemicals Co., Ltd., Polylon P- manufactured by Chukyo Yushi Co., Ltd. 502, Hymicron L-271, Hydrin L-536 (all trade names), etc.
  • Examples of natural wax-based lubricants include Hydrin L-703-35 (trade name), Cellozol (registered trademark) 524, Cellozol (registered trademark) R-586 manufactured by Chukyo Yushi Co., Ltd.
  • surfactant-based lubricants examples include the NIKKOL series (for example, NIKKOL SCS (registered trademark), etc.) manufactured by Nikko Chemicals Co., Ltd., and the Emar (registered trademark) series (for example, EMAL 40 (registered trademark), manufactured by Kao Corporation). Trademark)).
  • NIKKOL SCS registered trademark
  • Emar registered trademark
  • EMAL 40 registered trademark
  • the polymer layer is composed of the SERATEN (registered trademark) series manufactured by DIC Corporation, the inorganic / acrylic composite emulsion manufactured by JSR Corporation as the polymer, and Chemipearl manufactured by Mitsui Chemicals, Inc. as the lubricant.
  • SERATEN registered trademark
  • JSR Corporation the inorganic / acrylic composite emulsion manufactured by JSR Corporation
  • Chemipearl manufactured by Mitsui Chemicals, Inc.
  • the form comprised using the (trademark) series is preferable.
  • the polymer layer may or may not contain a matting agent.
  • a decrease in the slipperiness that is, an increase in the dynamic friction coefficient
  • scratches caused by external forces such as scratches, scratches, and collisions with pebbles can be further alleviated, and hydrolysis resistance and, in turn, weather resistance can be improved.
  • the matting agent is preferably a particulate material, and may be either an inorganic material or an organic material.
  • inorganic particles or organic particles can be used.
  • the inorganic particles include metal oxides such as titanium oxide, silica, alumina, zirconia, and magnesia, and particles such as talc, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, kaolin, and clay.
  • particles such as an acrylic resin, a polystyrene resin, a polyurethane resin, a polyethylene resin, a benzoguanamine resin, an epoxy resin, are mentioned suitably, for example.
  • the average particle size of the matting agent is preferably 0.3 ⁇ m to 10 ⁇ m, more preferably 1 ⁇ m to 8 ⁇ m in terms of secondary particle size.
  • the average secondary particle diameter of the matting agent is 0.3 ⁇ m or more, the effect of preventing scratches due to scratching or abrasion due to the matting agent can be increased, and when the average secondary particle size is 10 ⁇ m or less, the polymer layer is applied and formed. It may be advantageous in that it is difficult to cause agglomerates and play failure, and it is easy to obtain a good coated surface.
  • the average particle diameter is an average of secondary particle diameters measured by a laser analysis / scattering particle size distribution measuring apparatus LA950 (trade name, manufactured by Horiba, Ltd.).
  • the content of the matting agent in the polymer layer is preferably in the range of 0.3 mg / m 2 to 30 mg / m 2 , more preferably in the range of 10 mg / m 2 to 25 mg / m 2 , and 15 mg / m 2 to 25 mg / m 2. A range of 2 is more preferred.
  • the content of the matting agent is 0.3 mg / m 2 or more, the effect of reducing the dynamic friction coefficient of the polymer layer is large, and the occurrence of scratches due to external forces such as scratches, scratches, and collisions with pebbles can be further alleviated.
  • it is less than / m 2 , it may be advantageous in that it is difficult to cause agglomerates and play failure when the polymer layer is applied and formed, and a good coated surface state can be easily obtained.
  • the polymer layer contains the structure part derived from the crosslinking agent which bridge
  • crosslinking agent examples include crosslinking agents such as epoxy compounds, isocyanate compounds, melamine compounds, carbodiimide compounds, and oxazoline compounds.
  • crosslinking agents such as carbodiimide compounds and oxazoline compounds are preferable.
  • oxazoline-based crosslinking agent examples include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2- Oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, 2,2'-bis- (2-oxazoline), 2,2'-methylene-bis- (2-oxazoline), 2,2′-ethylene-bis- (2-oxazoline), 2,2′-trimethylene-bis- (2-oxazoline), 2,2′-tetramethylene-bis- (2-oxazoline) ), 2,2′-hexamethylene-bis- (2-oxazoline), 2,2′-octamethylene-bis- (2-oxazoline), 2,2′-ethylene-bis- (4,4 ′) Dimethyl-2-oxazoline), 2,2'-p-pheny
  • (co) polymers of these compounds are also preferably used.
  • a compound having an oxazoline group Epocros K2010E, K2020E, K2030E, WS-500, WS-700 (registered trademark, all manufactured by Nippon Shokubai Chemical Co., Ltd.) and the like can be used.
  • carbodiimide-based crosslinking agent examples include dicyclohexylmethane carbodiimide, tetramethylxylylene carbodiimide, dicyclohexylmethane carbodiimide, and the like.
  • a carbodiimide compound described in JP-A-2009-235278 is also preferable.
  • carbodiimide-based crosslinking agents Carbodilite SV-02, Carbodilite V-02, Carbodilite V-02-L2, Carbodilite V-04, Carbodilite E-01, Carbodilite E-02 (all trade names, Nisshinbo Chemical (Commercially available) and the like can also be used.
  • the mass of the structure part derived from the crosslinking agent with respect to the total mass of the polymer is preferably 1 to 30% by mass, more preferably 5% to 20% by mass.
  • the content ratio of the crosslinking agent is 1% by mass or more, the strength of the polymer layer and the adhesiveness after wet heat aging can be excellent, and when it is 30% by mass or less, the pot life of the coating liquid can be kept long.
  • the polymer layer includes a polymer having a (poly) siloxane structure and a lubricant as described above, so that the strength of the polymer layer surface is improved, and scratches, scratches, collisions of flying pebbles, etc. Can be prevented, and can be excellent in adhesion to adjacent materials such as a polymer substrate forming a support. Suppressing the occurrence of scratches can improve the weather resistance, and can be excellent in peeling resistance, shape stability, and adhesion durability when exposed to a humid heat environment, which easily deteriorate when given heat and moisture.
  • the protective sheet is arranged as the outermost layer arranged at the position farthest from the polymer base material, so that it does not easily cause a phenomenon of peeling from an adjacent material, and has excellent weather resistance, so that it can be stably stably for a long time. The desired properties can be maintained.
  • the thickness of one layer of the polymer layer is usually preferably from 0.3 ⁇ m to 22 ⁇ m, more preferably from 0.5 ⁇ m to 15 ⁇ m, still more preferably from 0.8 ⁇ m to 12 ⁇ m, particularly preferably from 1.0 ⁇ m to 8 ⁇ m, The range of 2 ⁇ m to 6 ⁇ m is most preferable.
  • the thickness of the polymer layer is 0.3 ⁇ m, it is difficult for moisture to penetrate from the surface of the polymer layer to the inside when exposed to a humid heat environment, and moisture hardly reaches the interface between the polymer layer and the polymer substrate.
  • the adhesiveness can be remarkably improved, and these effects can be particularly remarkable when the thickness of the polymer layer is 0.8 ⁇ m or more.
  • the thickness of the polymer layer is 22 ⁇ m or less, the polymer layer itself is not easily fragile, and the adhesiveness can be improved because the polymer layer is not easily broken when exposed to a wet heat environment. Can be particularly prominent when the thickness of the polymer layer is 12 ⁇ m or less.
  • the polymer layer has a crosslinked structure in which the polymer and the polymer molecules of the polymer are crosslinked with a crosslinking agent, and the ratio of the structural portion derived from the crosslinking agent to the polymer is 1 to 30% by mass, and the polymer layer
  • the thickness is from 0.8 ⁇ m to 12 ⁇ m, the effect of improving the adhesion particularly after wet heat aging can be excellent.
  • the polymer layer preferably has a dynamic friction coefficient of 0.4 or less on the layer surface.
  • the dynamic friction coefficient is preferably as small as possible from the viewpoint of preventing scratches due to scratches or the like, but is preferably in the range of 0.1 to 0.3 from the viewpoint of handleability.
  • the polymer layer may further contain other components such as various additives, if necessary, in addition to the polymer and the lubricant.
  • a structure in which a battery-side substrate and a back sheet are laminated, that is, a transparent base material (such as a glass substrate) on the side where sunlight enters, an element structure portion including a solar cell element, and a back sheet are laminated in this order.
  • the back layer is a back surface protective layer disposed on the side opposite to the side facing the battery side substrate of the polymer base material which is a support, and may have a single layer structure.
  • stacked the layer or more may be sufficient.
  • the adhesion to the polymer substrate and the adhesion between layers when the back layer is composed of two or more layers is the polymer layer can be improved, and further, the deterioration resistance in a humid heat environment Can be obtained.
  • the polymer layer is preferably disposed in the outermost layer farthest from the polymer base material as a back layer located on the back surface side when viewed from the solar cell element.
  • both layers may be a polymer layer and a lubricant having the (poly) siloxane structure, or a polymer layer containing the polymer and the lubricant and the crosslinking agent.
  • only one of the layers may be the polymer and the lubricant, or the polymer layer containing the polymer and the lubricant and the crosslinking agent.
  • the back layer (second back layer) on the side farther from the polymer substrate that does not contact the polymer substrate is the polymer and the lubricant, or the It is preferable to be composed of a polymer layer containing a polymer and a lubricant and the crosslinking agent.
  • the first back layer close to the polymer substrate provided as the lower layer of the second back layer on the polymer substrate has a (poly) siloxane structure (preferably, the general formula (1)
  • the polymer having (poly) siloxane structural unit and non- (poly) siloxane structural unit represented by the following formula may not be included.
  • ком ⁇ онент that can be included in the back layer include surfactants, fillers, and the like, as will be described later. Moreover, you may include the pigment used for a colored layer.
  • the polymer layer may be substantially uncolored or a colored layer.
  • the polymer layer also serves as a colored layer (preferably a light reflecting layer), it further contains a pigment in addition to the polymer and the lubricant.
  • the colored layer may further contain other components such as various additives as necessary.
  • the colored layer As a function of the colored layer, first, by reflecting the light that has passed through the solar cells and reaches the back sheet without being used for power generation out of the incident light, and returns the solar cells to the solar cells, Increasing the power generation efficiency, secondly, improving the decorativeness of the appearance when the solar cell module is viewed from the side on which sunlight enters (front side), and the like.
  • a back sheet can be seen around the solar cell, and by providing a colored layer on the back sheet, the decorativeness can be improved and the appearance can be improved.
  • the colored layer can contain at least one pigment.
  • the pigment include inorganic pigments such as titanium dioxide, barium sulfate, silicon oxide, aluminum oxide, magnesium oxide, calcium carbonate, kaolin, talc, ultramarine blue, bitumen, and carbon black, and organic pigments such as phthalocyanine blue and phthalocyanine green. It can be appropriately selected and contained.
  • the polymer layer is a light reflecting layer that reflects light that has entered the solar cell and passed through the solar cell and returns it to the solar cell
  • a white pigment is preferable.
  • titanium dioxide, barium sulfate, silicon oxide, aluminum oxide, magnesium oxide, calcium carbonate, kaolin, talc and the like are preferable.
  • the content of the pigment in the colored layer is preferably in the range of 2.5 g / m 2 to 8.5 g / m 2 .
  • the pigment content is 2.5 g / m 2 or more, necessary coloring can be obtained, and reflectance and decorative properties can be effectively provided.
  • the content of the pigment in the colored layer is 8.5 g / m 2 or less, the surface state of the colored layer can be easily maintained and the film strength can be improved.
  • the pigment content is more preferably in the range of 4.5 g / m 2 to 8.0 g / m 2 .
  • the average particle diameter of the pigment is preferably 0.03 ⁇ m to 0.8 ⁇ m in volume average particle diameter, more preferably about 0.15 ⁇ m to 0.5 ⁇ m. When the average particle size is within the above range, the light reflection efficiency can be increased.
  • the average particle size is a value measured by a laser analysis / scattering particle size distribution measuring apparatus LA950 [trade name, manufactured by Horiba, Ltd.].
  • the content of the binder component (including the polymer) in the polymer layer is preferably in the range of 15% by mass to 200% by mass with respect to the content of the pigment in the polymer layer. A range of 17% by mass to 100% by mass is more preferable.
  • the binder content is 15% by mass or more, the strength of the colored layer can be sufficiently obtained.
  • a reflectance and decorativeness can be kept favorable as it is 200 mass% or less.
  • surfactant a filler, etc.
  • a known surfactant such as an anionic surfactant or a nonionic surfactant can be used.
  • the addition amount is preferably 0.1 mg / m 2 to 15 mg / m 2 , more preferably 0.5 mg / m 2 to 5 mg / m 2 .
  • the addition amount of the surfactant is 0.1 mg / m 2 or more, generation of repellency can be suppressed and good layer formation can be obtained, and when it is 15 mg / m 2 or less, adhesion can be performed satisfactorily. .
  • a filler may be further added to the polymer layer.
  • the addition amount of the filler is preferably 20% by mass or less, more preferably 15% by mass or less, with respect to the total mass of the binder in the polymer layer. When the addition amount of the filler is 20% by mass or less, the planar shape of the polymer layer can be kept better.
  • an inorganic filler is preferable, and examples thereof include talc, silica, alumina, aluminum hydroxide, magnesia, titania, zirconia, aluminum nitride, boron nitride, and barium sulfate.
  • silica is preferable, and colloidal silica is particularly preferable.
  • the alkoxysilane compound include tetraalkoxysilane and trialkoxysilane. Among these, trialkoxysilane is preferable, and an alkoxysilane compound having an amino group is particularly preferable.
  • the light reflectance of 550 nm wavelength light on the surface on which the light reflection layer and the easy-adhesion layer are provided is 75% or more.
  • the light reflectance is the ratio of the amount of light incident from the surface of the easy-adhesion layer to the amount of incident light reflected from the light-reflection layer and emitted from the easy-adhesion layer again.
  • light having a wavelength of 550 nm is used as the representative wavelength light.
  • the light reflectance can be adjusted to 75% or more by controlling the content of the colorant in the range of 2.5 g / m 2 to 30 g / m 2 .
  • the protective sheet may have other functional layers in addition to the polymer substrate and the polymer layer.
  • an undercoat layer and an easily adhesive layer can be provided.
  • an undercoat layer may be provided between the polymer substrate (support) and the polymer layer.
  • the thickness of the undercoat layer is preferably in the range of 2 ⁇ m or less, more preferably 0.05 ⁇ m to 2 ⁇ m, and still more preferably 0.1 ⁇ m to 1.5 ⁇ m. When the thickness is 2 ⁇ m or less, the planar shape can be kept good. Moreover, it is easy to ensure required adhesiveness because thickness is 0.05 micrometer or more.
  • the undercoat layer can contain a binder.
  • a binder for example, polyester, polyurethane, acrylic resin, polyolefin, or the like can be used.
  • the undercoat layer includes an epoxy crosslinking agent, an isocyanate crosslinking agent, a melamine crosslinking agent, a carbodiimide crosslinking agent, a crosslinking agent such as an oxazoline crosslinking agent, an anionic surfactant, and a nonionic surfactant.
  • a surfactant such as an agent and a filler such as silica may be added.
  • the method for applying the undercoat layer and the solvent of the coating solution used there is no particular limitation on the method for applying the undercoat layer and the solvent of the coating solution used.
  • a coating method for example, a gravure coater or a bar coater can be used.
  • the solvent used for the coating solution may be water or an organic solvent such as toluene or methyl ethyl ketone.
  • a solvent may be used individually by 1 type and may be used in mixture of 2 or more types.
  • the coating solution may be applied to the polymer substrate after biaxial stretching, or the first stretching is performed after the coating solution is applied to the polymer substrate after uniaxial stretching.
  • the base material may be stretched in a different direction.
  • the substrate may be stretched in two directions after the coating solution is applied to the substrate before stretching.
  • the protective sheet is represented by the specific polymer described above (non-siloxane structural unit and general formula (1)) by bringing the solar cell element into contact with the sealing agent of the battery side substrate sealed with the sealing material.
  • Any polymer can be appropriately selected and produced as long as it can dispose a polymer layer containing (poly) siloxane structural unit). Especially, formation of a polymer layer can be most suitably performed with the manufacturing method of the protective sheet shown below.
  • the backsheet may or may not be provided with a colored layer (preferably a light reflecting layer) substantially free of a polymer having a (poly) siloxane structure.
  • a colored layer especially a light reflecting layer
  • a colored layer may be provided.
  • the colored layer in this case includes at least a polymer component other than the polymer having a (poly) siloxane structure and a pigment, and may further include other components such as various additives as necessary.
  • substantially free means that the polymer is not actively contained in the colored layer. Specifically, the polymer content in the colored layer is 15% relative to the total mass of the colored layer. It is said that it is below mass%, Preferably a colored layer does not contain a polymer (content is 0 (zero) mass%).
  • the protective sheet (especially the back sheet) has a polymer base on the side where the polymer layer is not provided (further, the colored layer (particularly the light reflecting layer) substantially not containing a polymer having a (poly) siloxane structure).
  • an easy-adhesive layer may or may not be provided.
  • the easy-adhesive layer seals a solar cell element (hereinafter also referred to as a power generation element) of a battery side substrate (battery body) when the protective sheet is used as a back sheet constituting a solar cell module, for example. It functions as a layer to adhere firmly to the material.
  • the easy-adhesion layer can be composed of a binder and inorganic fine particles, and may further contain other components such as additives as necessary.
  • the easy-adhesion layer is used for a sealing material (for example, ethylene-vinyl acetate (EVA; ethylene-vinyl acetate copolymer), polyvinyl butyral (PVB), epoxy resin, etc.) that seals the power generation element of the battery side substrate.
  • EVA ethylene-vinyl acetate
  • PVB polyvinyl butyral
  • the adhesive strength is preferably 10 N / cm or more, and more preferably 20 N / cm or more. When the adhesive force is 10 N / cm or more, it is easy to obtain wet heat resistance capable of maintaining adhesiveness.
  • the adhesive strength can be adjusted by adjusting the amount of the binder and inorganic fine particles in the easy-adhesive layer, and applying a corona treatment to the surface of the back sheet that adheres to the sealing material.
  • the easy-adhesion layer can contain at least one binder.
  • the binder suitable for the easy-adhesive layer include polyester, polyurethane, acrylic resin, polyolefin, and the like. Among these, acrylic resin and polyolefin are preferable from the viewpoint of durability. As the acrylic resin, a composite resin of acrylic and silicone is also preferable.
  • Examples of preferred binders include Chemipearl (registered trademark) S-120 and S-75N (both manufactured by Mitsui Chemicals, Inc.) as specific examples of polyolefin, and Julimer (registered trademark) ET-410, SEK as specific examples of acrylic resin. -301 (both made by Nippon Pure Chemicals Co., Ltd.), as specific examples of acrylic and silicone composite resins, Ceranate (registered trademark) WSA-1060, WSA-1070 (both manufactured by DIC Corporation) and Polydurex (registered trademark) ) H7620, H7630, H7650 (both manufactured by Asahi Kasei Chemicals Corporation) and the like.
  • the content of the binder in the easy adhesion layer is preferably in the range of 0.05g / m 2 ⁇ 5g / m 2, the range of 0.08g / m 2 ⁇ 3g / m 2 is more preferable.
  • the content of the binder, 0.05 g / m 2 or more is desired as easy adhesion obtained for that may give a better surface If it is 5 g / m 2 or less.
  • the easily adhesive layer can contain at least one kind of inorganic fine particles.
  • the inorganic fine particles include silica, calcium carbonate, magnesium oxide, magnesium carbonate, and tin oxide.
  • fine particles of tin oxide and silica are preferable in that the decrease in adhesiveness when exposed to a humid heat atmosphere is small.
  • the particle diameter of the inorganic fine particles is preferably about 10 nm to 700 nm, more preferably about 20 nm to 300 nm in terms of volume average particle diameter. When the particle size is within this range, better easy adhesion can be obtained.
  • the particle size is a value measured by a laser analysis / scattering particle size distribution measuring apparatus LA950 [trade name, manufactured by Horiba, Ltd.].
  • the shape of the inorganic fine particles is not particularly limited, and any shape such as a spherical shape, an irregular shape, or a needle shape can be used.
  • the content of the inorganic fine particles is in the range of 5% by mass to 400% by mass with respect to the total mass of the binder in the easy-adhesive layer.
  • the content of the inorganic fine particles is more preferably in the range of 50% by mass to 300% by mass with respect to the total mass of the binder in the easily adhesive layer.
  • the easily adhesive layer can contain at least one crosslinking agent.
  • Suitable crosslinking agents for the easily adhesive layer include crosslinking agents such as epoxy crosslinking agents, isocyanate crosslinking agents, melamine crosslinking agents, carbodiimide crosslinking agents, and oxazoline crosslinking agents.
  • an oxazoline-based cross-linking agent is particularly preferable from the viewpoint of ensuring adhesiveness after wet heat aging.
  • Specific examples of the oxazoline-based crosslinking agent include the same specific examples as described in the above-mentioned polymer layer section.
  • the content of the crosslinking agent in the easy-adhesive layer is preferably 5% by mass to 50% by mass and more preferably 20% by mass to 40% by mass with respect to the total mass of the binder in the easy-adhesive layer.
  • the content of the crosslinking agent is 5% by mass or more, a good crosslinking effect can be obtained, and the strength and adhesiveness of the colored layer can be maintained.
  • the content is 50% by mass or less, the pot life of the coating liquid is increased. Can keep.
  • the easily adhesive layer may further contain a known matting agent such as polystyrene, polymethylmethacrylate and silica, and a known surfactant such as an anionic surfactant and a nonionic surfactant. May be.
  • a known matting agent such as polystyrene, polymethylmethacrylate and silica
  • a known surfactant such as an anionic surfactant and a nonionic surfactant. May be.
  • the method for forming the easy-adhesion layer examples include a method of bonding a polymer sheet having easy adhesion to a substrate, and a method by application of a coating solution for forming an easy-adhesion layer.
  • the method by coating is preferable because it is simple and can form a uniform and thin film.
  • a coating method for example, a known coating method such as a gravure coater or a bar coater can be used.
  • the coating solvent used for preparing the coating solution may be water or an organic solvent such as toluene or methyl ethyl ketone.
  • a coating solvent may be used individually by 1 type, and may mix and use 2 or more types.
  • the thickness of the easy-adhesion layer is not particularly limited, but is usually preferably 0.05 ⁇ m to 8 ⁇ m, more preferably 0.1 ⁇ m to 5 ⁇ m.
  • the easy-adhesive layer is substantially transparent so as not to affect the effect of the colored layer.
  • the protective sheet When the protective sheet is used as a back sheet for a solar cell, the protective sheet is sealed for 48 hours in an atmosphere of 120 ° C. and 100% RH with the protective sheet adhered to the sealing material.
  • the adhesive strength is preferably 75% or more with respect to the adhesive strength of the protective sheet to the sealing material before storage.
  • the protective sheet includes a predetermined amount of binder and a predetermined amount of inorganic fine particles with respect to the binder, and an easy-adhesive layer having an adhesive force of 10 N / cm or more with respect to the EVA-based sealing material.
  • the protective sheet may be produced by any method as long as it can form a polymer layer and, if necessary, a colored layer, an easy-adhesive layer, and the like on the polymer substrate. .
  • the polymer layer can be formed by a method in which a polymer sheet is bonded to a polymer substrate, a method in which the polymer layer is coextruded when the polymer substrate is formed, a method by coating, or the like.
  • the method by coating is preferable because it is simple and can form a uniform and thin film.
  • a coating method for example, a known coating method such as a gravure coater or a bar coater can be used.
  • the coating solvent for the coating solution may be either an aqueous system using water or a solvent system using an organic solvent such as toluene or methyl ethyl ketone. From the viewpoint of reducing environmental burden, it is preferable to prepare an aqueous coating solution using water as a coating solvent.
  • a coating solvent may be used individually by 1 type, and may mix and use 2 or more types.
  • a water-based coating solution containing a polymer having a (poly) siloxane structure in the molecule, a lubricant, water, and preferably a cross-linking agent (and, if necessary, a coating solution for an easily adhesive layer) )
  • a polymer layer containing 0.2 g / m 2 to 15 g / m 2 or less polymer and 0.1 mg / m 2 to 50 mg / m 2 lubricant as the outermost layer.
  • a protective sheet can be suitably produced by a method including the layer forming step (a method for producing the protective sheet).
  • polymer particles having a (poly) siloxane structure and a lubricant are prepared by mixing an aqueous dispersion of a polymer having a (poly) siloxane structure in a molecule with an aqueous dispersion of a lubricant (for example, wax).
  • a lubricant for example, wax
  • An embodiment is preferred in which an aqueous dispersion in which particles are dispersed and contained in water is prepared, and this aqueous dispersion is applied onto a desired polymer substrate as an aqueous coating liquid in the polymer layer forming step.
  • the details of the polymer substrate and the polymer, lubricant, and other components constituting each coating solution are as described above.
  • an aqueous coating solution for forming a polymer layer is applied directly on the surface of the polymer substrate or through an undercoat layer having a thickness of 2 ⁇ m or less, and the polymer layer is formed as the outermost layer on the polymer substrate. Can be formed.
  • the coating solution is preferably an aqueous coating solution in which water is 50% by mass or more, preferably 60% by mass or more, based on the total mass of the coating solvent contained therein.
  • the aqueous coating solution is preferable from the viewpoint of reducing the environmental load, and the environmental load is particularly reduced when the ratio of water is 50% by mass or more.
  • the proportion of water in the coating solution is preferably larger from the viewpoint of reducing the environmental load, and it is particularly preferable that water accounts for 90% by mass or more of the total solvent.
  • a drying process for drying the coating film under desired conditions may be provided. What is necessary is just to select suitably about the drying temperature at the time of drying according to cases, such as a composition of a coating liquid, a coating amount.
  • the solar cell module is configured by providing the above-described protective sheet as a back sheet.
  • the solar cell module which is one Embodiment of this invention is equipped with the said protection sheet.
  • the polymer layer formed by coating has high film strength, excellent scratch resistance against scratching and scratching, and good light resistance, heat resistance, and moisture resistance. Thereby, the solar cell module exhibits excellent weather resistance and exhibits stable power generation performance over a long period of time.
  • the solar cell module is provided on a transparent base material (a front base material such as a glass substrate) on which sunlight enters and the base material, and the solar cell element and the solar cell element are sealed.
  • a transparent base material a front base material such as a glass substrate
  • a front substrate / element structure portion / back sheet a transparent base material (a front base material such as a glass substrate) on which sunlight enters and the base material, and the solar cell element and the solar cell element are sealed.
  • An element structure portion having an encapsulant to be sealed, and the above-described back sheet (including the protective sheet) disposed on the side of the element structure portion opposite to the side on which the substrate is located.
  • an element structure portion in which a solar cell element that converts light energy of sunlight into electrical energy is disposed, and a transparent front base material that is disposed on a side where sunlight directly enters
  • An element structure part for example, a solar cell
  • a solar cell element including a solar cell element is disposed between the front substrate and the back sheet using a sealing material such as an ethylene-vinyl acetate (EVA) system between the back sheet and the back sheet.
  • EVA ethylene-vinyl acetate
  • the transparent substrate only needs to have a light-transmitting property through which sunlight can be transmitted, and can be appropriately selected from substrates that transmit light. From the viewpoint of power generation efficiency, the higher the light transmittance, the better.
  • a transparent resin such as an acrylic resin, or the like can be suitably used.
  • the solar cell element examples include silicon-based materials such as single crystal silicon, polycrystalline silicon, and amorphous silicon, III-V groups such as copper-indium-gallium-selenium, copper-indium-selenium, cadmium-tellurium, and gallium-arsenide.
  • silicon-based materials such as single crystal silicon, polycrystalline silicon, and amorphous silicon
  • III-V groups such as copper-indium-gallium-selenium, copper-indium-selenium, cadmium-tellurium, and gallium-arsenide.
  • II-VI group compound semiconductor systems can be applied.
  • the esterification reaction vessel maintained at ° C. and a pressure of 1.2 ⁇ 10 5 Pa was sequentially supplied over 4 hours. After completion of the supply, the esterification reaction was further performed for 1 hour. Thereafter, 123 kg of the obtained esterification reaction product was transferred to a polycondensation reaction tank.
  • ethylene glycol was added to the polycondensation reaction tank to which the esterification reaction product had been transferred so that the amount was 0.3% by mass with respect to the obtained polymer.
  • an ethylene glycol solution of cobalt acetate and manganese acetate was added in the obtained polymer so that the cobalt element equivalent value and the manganese element equivalent value were 30 ppm and 15 ppm, respectively.
  • a 2 mass% ethylene glycol solution of a titanium alkoxide compound was added so that the titanium element conversion value was 5 ppm in the obtained polymer.
  • the thermal shrinkage rate, the elongation at break and the carboxyl group content were measured by the following methods.
  • the heat shrinkage rate was 0.4%
  • the elongation at break was 73%
  • the carboxyl group content was 17 equivalents / ton.
  • the obtained polymer substrate S-1 was conditioned for 24 hours in an atmosphere of 25 ° C. and 60% RH. Using a sample after moisture conditioning, with a two scratches parallel at about 30cm intervals on the sample surface with a razor, and measuring the distance L 0. The scratched sample was heat treated by holding at 150 ° C. for 15 minutes. After heat-treating the sample after heat treatment in an atmosphere of 25 ° C. and 60% RH for 24 hours, an interval L 1 between two scratches was measured. The thermal contraction rate was calculated from the obtained L 0 and L 1 using the following formula.
  • Thermal shrinkage [%] ⁇ (L 0 ⁇ L 1 ) / L 0 ⁇ ⁇ 100
  • the heat shrinkage rate was measured and calculated for each of the MD direction (longitudinal direction) and the TD direction (width direction) of the polymer base material, and the average value thereof was taken as the heat shrinkage rate of the polymer sheet.
  • the unit of heat shrinkage is [%]. When the numerical value is positive, it indicates shrinkage, and when it is negative, it indicates elongation.
  • the breaking elongation retention ratio (%) was calculated from the following formula based on the measured elongation values L 0 and L 1 of the breaking elongation obtained by the following measurement method.
  • a practically acceptable range is one in which the elongation at break is 50% or more.
  • Elongation at break (%) (L 1 / L 0 ) ⁇ 100 ⁇ Measurement of elongation at break>
  • Sample pieces A and B for measurement were prepared by cutting the polymer substrate into a size of width 10 mm ⁇ length 200 mm. The sample piece A was conditioned in an atmosphere of 25 ° C.
  • the coating solution for forming the undercoat layer was applied to the corona-treated surface of the polymer substrate S-1 so that the binder amount was 0.1 g / m 2, and dried at 180 ° C. for 1 minute.
  • An undercoat layer having a thickness of about 0.1 ⁇ m was formed.
  • Titanium dioxide dispersion was prepared by mixing components in the following composition and subjecting the mixture to a dispersion treatment for 1 hour using a dynomill type disperser.
  • ⁇ Composition of titanium dioxide dispersion> ⁇ Titanium dioxide (volume average particle size 0.42 ⁇ m) 40.0 mass% [Product name: Taipei R-780-2, manufactured by Ishihara Sangyo Co., Ltd., solid content: 100% by mass] ⁇ Polyvinyl alcohol: 28.0% by mass [Product name: PVA-105, manufactured by Kuraray Co., Ltd., solid content: 10% by mass] ⁇ Surfactant ... 0.5% by mass [Product name: Demall EP, manufactured by Kao Corporation, solid content: 10% by mass] ⁇ Distilled water ... 31.5 mass%
  • composition of coating solution > ⁇ Titanium dioxide dispersion: 800.0 parts ⁇ Polyolefin binder: 108.0 parts [Product name: Arrow Base SE1010, manufactured by Unitika Ltd., solid content: 20 mass%] ⁇ Polyoxyalkylene alkyl ether 30.0 parts [Product name: NAROACTY CL-95, manufactured by Sanyo Chemical Industries, solid content: 1% by mass] Oxazoline compound 20.0 parts [Epocross (registered trademark) WS-700, manufactured by Nippon Shokubai Co., Ltd., solid content: 25%; crosslinking agent] ⁇ Distilled water ... 42.0 parts
  • Corona treatment was performed on the side opposite to the side where the light reflecting layer of the polymer substrate S-1 was formed (hereinafter also referred to as the back side) under the same conditions as described above. .
  • the coating solution for forming the polymer layer 1 is applied to the corona-treated surface on the back side of the polymer substrate S-1 so that the binder coating amount is 3.0 g / m 2 and dried at 180 ° C. for 1 minute.
  • a polymer layer 1 having a dry thickness of about 3 ⁇ m was formed.
  • Example 1 a back sheet was produced in the same manner as in Example 1 except that the amount of lubricant contained in the polymer layer 2 was changed as shown in Table 1 below.
  • Example 1 (Examples 7 to 9, Comparative Examples 3 to 4)
  • Example 1 a back sheet was produced in the same manner as in Example 1 except that the coating amount of the binder contained in the polymer layer 2 was changed as shown in Table 1 below.
  • Example 10 In Example 1, a back sheet was produced in the same manner as in Example 1 except that the type of lubricant contained in the polymer layer 2 was changed as shown in Table 1 below.
  • Example 14 In Example 1, a back sheet was produced in the same manner as in Example 1 except that the corona treatment applied to the back side of the polymer substrate was not performed.
  • Example 16 In Example 1, a back sheet was produced in the same manner as in Example 1 except that the polymer layer 2 did not contain a matting agent.
  • Example 17 Comparative Examples 5 to 6
  • the lubricant in the polymer layer 1 was changed as shown in Table 1 below, and the polymer layer 2 was not provided on the polymer layer 1 but a single polymer layer was formed on the back side.
  • Examples 23 to 25, Comparative Examples 7 to 8 A back sheet was produced in the same manner as in Example 1, except that the coating amounts of the binder and matting agent contained in the polymer layer 1 were changed as shown in Table 1 below.
  • Example 26 In the formation of the polymer layer 2 of Example 1, 362.3 parts of the acrylic / silicone binder used for the preparation of the coating solution for forming the polymer layer 2 was replaced with the following acrylic / silicone binder (Binder B-2) 414.1. A back sheet was prepared in the same manner as in Example 1 except that 575.5 parts of distilled water was replaced with 523.7 parts instead of the parts. ⁇ Acrylic / silicone binder (Binder B-2) (Ceranate (registered trademark) WSA-1060 (polysiloxane structural unit: 75 mass%, non-polysiloxane structural unit: 25 mass%), manufactured by DIC Corporation, solid content: 35 mass%)
  • Example 27 In the formation of the polymer layer 2 of Example 1, a back sheet was produced in the same manner as in Example 1 except that the coating liquid for forming the polymer layer 2 was prepared as follows.
  • the coating liquid for forming the polymer layer 2 was prepared by mixing each component in the following composition.
  • Example 28 3 mm thick tempered glass, EVA sheet 1 (trade name: SC50B, manufactured by Mitsui Chemicals Fabro Co., Ltd.), crystalline solar cell, and EVA sheet 2 (trade name: SC50B, manufactured by Mitsui Chemicals Fabro Co., Ltd.) ) And the back sheet of Example 1 in this order, and hot-pressing using a vacuum laminator (Nisshinbo Co., Ltd., vacuum laminating machine), tempered glass, EVA sheet 1, EVA sheet 2, and The back sheet was adhered. At this time, the back sheet produced in Example 1 was disposed so that the easy-adhesive layer was in contact with the EVA sheet 2. Moreover, the adhesion method is as follows.
  • ⁇ Adhesion method> Using a vacuum laminator, evacuation was performed at 128 ° C. for 3 minutes, and then pressure was applied for 2 minutes to temporarily bond. Thereafter, the main adhesion treatment was performed in a dry oven at 150 ° C. for 30 minutes. As described above, a crystalline solar cell module was produced. The produced solar cell module was allowed to stand for 70 hours under an environmental condition of 120 ° C. and 100% RH and then subjected to power generation operation. As a result, the solar cell module showed good power generation performance as a solar cell.
  • Example 29 to 54 A solar cell module was produced in the same manner as in Example 28 except that in Example 28, the back sheet was replaced with the back sheet produced in Examples 2 to 27. When the obtained solar cell module was subjected to power generation operation in the same manner as in Example 26, all showed good power generation performance as a solar cell.

Landscapes

  • Photovoltaic Devices (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne une feuille de protection, pour une cellule solaire, qui comporte un matériau de base polymère et une couche de polymère qui est la couche la plus à l'extérieur et qui est disposée sur une face du matériau de base polymère, la couche de polymère comportant un polymère et un lubrifiant, une molécule du polymère ayant une structure contenant une liaison siloxane, la teneur en polymère dans la couche de polymère étant supérieure à 0,2 g, mais pas supérieure à 15 g pour 1 m2 de la couche de polymère, et la teneur en lubrifiant dans la couche de polymère n'étant pas inférieure à 0,2 mg, mais pas supérieure à 200 mg pour 1 m2 de la couche de polymère.
PCT/JP2012/055431 2011-03-03 2012-03-02 Feuille de protection pour cellule solaire, son procédé de fabrication, feuille de support pour cellule solaire et module de cellule solaire Ceased WO2012118195A1 (fr)

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JP6204863B2 (ja) * 2014-03-28 2017-09-27 富士フイルム株式会社 太陽電池用裏面保護シート及び太陽電池モジュール
CN114023838B (zh) * 2021-11-03 2023-11-10 宁波勤邦新材料科技股份有限公司 一种高反射高阻隔太阳能电池背板膜及其制备方法

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