JP2014112643A - Solar cell encapsulation film and solar cell using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solar cell encapsulation film capable of sufficiently maintaining an effect that generating efficiency is improved, even when utilizing a solar cell over a long period.SOLUTION: Solar cell encapsulation films 13A, 13B contain a resin material containing olefin (co)polymer, and a wavelength conversion material. The wavelength conversion material is europium complex represented by a specific structure formula.

Description

  TECHNICAL FIELD The present invention relates to a solar cell sealing film containing an olefin (co) polymer, and in particular, by including a wavelength conversion material, it increases the light rays contributing to the power generation of the solar cell and can improve the power generation efficiency. Concerning the stop film.

  In recent years, solar cells that directly convert sunlight into electrical energy have been widely used from the viewpoint of effective use of resources and prevention of environmental pollution, and further development has been promoted in terms of durability and power generation efficiency.

  As shown in FIG. 1, a solar cell generally has a surface-side transparent protective member 11 made of a glass substrate or the like, a surface-side sealing film 13A, a solar cell 14 such as a silicon crystal power generation element, a back-side sealing film. 13B and the back side protection member (back cover) 12 are laminated in this order, and after deaeration under reduced pressure, the surface side sealing film 13A and the back side sealing film 13B are crosslinked and cured to be bonded by heating and pressurization. Manufactured by integrating.

  By the way, in general, any type of solar cell, such as a silicon crystal power generation element, has a problem that the spectral sensitivity is low for light in the ultraviolet region, and solar energy cannot be used effectively. It has been. In order to solve this problem, there is a technique for improving the power generation efficiency of solar cells by using a material (wavelength conversion material) that converts light in the ultraviolet region into light having a wavelength in the visible region or near infrared region. Proposed. Specifically, by providing a layer containing a fluorescent material on the light-receiving surface side of the solar battery cell, the wavelength of ultraviolet light in the solar spectrum is converted to a wavelength that greatly contributes to power generation of the solar battery cell. A method of emitting light (for example, Patent Document 1), a method of including a fluorescent material (for example, a rare earth complex emitting fluorescence of 500 to 1000 nm) in a sealing material (sealing film) of a solar cell module (for example, Patent Document) 2, 3) etc. are proposed.

JP 2003-243682 A JP 2006-303033 A JP 2011-210891 A

  However, when the present inventor examined the wavelength conversion materials in the technologies proposed so far in the solar cell sealing film as described above, these wavelength conversion materials are greatly deteriorated by ultraviolet rays and are outdoors. It has been found that when used in a solar cell that is used for a long period of time, the effect of wavelength conversion is reduced, and the effect of improving power generation efficiency is likely to be reduced.

  Therefore, an object of the present invention is a solar cell sealing film that can improve the power generation efficiency of a solar battery cell by including a wavelength conversion material, even when the solar battery is used over a long period of time. An object of the present invention is to provide a solar cell sealing film that can sufficiently maintain the effect of improving power generation efficiency.

  Moreover, the objective of this invention is providing the solar cell which can maintain high electric power generation efficiency over a long period of time using the sealing film for solar cells.

The above object is a solar cell sealing film including a resin material containing an olefin (co) polymer (referring to an olefin polymer or a copolymer), and a wavelength conversion material,
The wavelength conversion material has the following formula (I):

[Wherein, R independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, and n is an integer of 1 to 4. ]
It is achieved by a solar cell sealing film characterized by being a europium complex represented by the formula:

  As a result of studying a large number of wavelength converting materials, it was found that the europium complex wavelength converting material is extremely unlikely to be deteriorated by ultraviolet rays in the solar cell sealing film. Therefore, by using the wavelength conversion material, it is possible to obtain a solar cell sealing film in which the effect of improving the power generation efficiency of the solar cell is unlikely to decrease even when used outdoors for a long period of time.

  Preferred embodiments of the solar cell sealing film according to the present invention are as follows.

(1) In the formula (I), all R are hydrogen atoms and n is 1.
(2) Content of the said wavelength conversion material is 0.000001-1 mass part with respect to 100 mass parts of said resin materials. A sufficient wavelength conversion effect can be obtained, and the transparency necessary for the sealing film can be ensured.
(3) Content of the said wavelength conversion material is 0.0001-0.01 mass part with respect to 100 mass parts of said resin materials.
(4) The ethylene / α-olefin copolymer (m-LLDPE), low density polyethylene (LDPE), and linear low density polyethylene (LLDPE) polymerized using a metallocene catalyst. , Polypropylene, polybutene, and at least one polymer selected from the group consisting of ethylene-polar monomer copolymers.
(5) The olefin (co) polymer is an ethylene / α-olefin copolymer (m-LLDPE) and / or an ethylene-polar monomer copolymer polymerized using a metallocene catalyst. It is excellent in processability, can form a crosslinked structure with a crosslinking agent, and can be a sealing film with high adhesiveness.
(6) The ethylene-polar monomer copolymer is an ethylene-vinyl acetate copolymer or an ethylene-methyl methacrylate copolymer. It can be set as the sealing film which was more excellent in transparency and excellent in the softness | flexibility.

(7) An emission peak area of a wavelength of 580 to 640 nm in a fluorescence emission spectrum obtained when a solar cell sealing film is irradiated with a light beam of 325 nm corresponding to the excitation wavelength of the wavelength conversion material is defined as 1000 W / When the solar cell sealing film is disposed at a distance of 235 mm from an ultraviolet lamp having an irradiation intensity of cm ^2, the irradiation is continuously performed at a temperature of 63 ° C., and the fluorescence intensity is measured over time. The time required for the fluorescence intensity of the sealing film to decrease to 30% of the fluorescence intensity before irradiation is 10 hours or more.

  Moreover, the said objective is achieved by the solar cell characterized by sealing a solar cell element with the sealing film for solar cells of this invention. Since the solar cell sealing film of the present invention is used in the solar cell of the present invention, the power generation efficiency of the solar cell element is improved by the wavelength conversion material, and the solar in which high power generation efficiency is maintained over a long period of time. It can be said that it is a battery.

  Since the solar cell sealing film of the present invention contains a specific europium complex as a wavelength conversion material having an effect of improving the power generation efficiency, the wavelength conversion material is hardly deteriorated by the influence of ultraviolet rays or the like, and the power generation efficiency is improved. The effect is maintained for a long time. Therefore, it can be said that the solar cell of the present invention is a solar cell in which high power generation efficiency is maintained for a long time.

It is a schematic sectional drawing which shows the structure of a general solar cell.

  As described above, the solar cell sealing film of the present invention has the following formula (I) as a wavelength conversion material.

[Wherein, each R independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, and n is an integer of 1 to 4, preferably 1. . ]
The europium complex represented by these is included.

  The europium complex represented by the above formula (I) is extremely excellent in weather resistance (particularly, UV resistance) as compared with other wavelength conversion materials, and is therefore installed outdoors and exposed to sunlight for a long time. Even when used as a sealing film for solar cells, the wavelength conversion effect can be maintained at a high level. Moreover, since it is excellent also in heat resistance compared with another wavelength conversion material, even if a solar cell is exposed to sunlight and becomes high temperature, the wavelength conversion effect can be maintained.

  Note that the europium complex of the formula (I) has an absorption peak near 330 nm as compared with other wavelength conversion materials having an absorption peak near 360 nm. Therefore, it is possible to convert ultraviolet light having a lower contribution rate to power generation into visible light, and exhibit an effective effect by improving power generation efficiency. In addition, polyester (particularly PET) materials often used for solar cell back surface protection members and cell stopper tapes for placing solar cells at desired positions during manufacturing tend to be particularly deteriorated by UV rays of 330 nm. Therefore, if the europium complex of the formula (I) is used, it is possible to reduce deterioration and yellowing of the back surface side protective member and the cell stopper tape.

  In the above formula (I), the hydrocarbon group having 1 to 20 carbon atoms of R may be aliphatic or aromatic, may contain an unsaturated bond or a heteroatom, and may be linear or branched. You may do it. For example, alkyl group (methyl group, ethyl group, propyl group etc.), alkenyl group (vinyl group, allyl group, butenyl group etc.), alkynyl group (ethynyl group, propynyl group, butynyl group etc.), cycloalkyl group, cycloalkenyl group Group, phenyl group, naphthyl group, biphenyl group and the like. The hydrocarbon group having 1 to 20 carbon atoms may be optionally substituted, and examples of the substituent include a halogen atom, a hydroxyl group, an amino group, a nitro group, and a sulfo group. R is preferably a hydrogen atom.

The europium complex is preferably Eu (hfa) ₃ (TPPO) ₂ in which n in the formula (I) is 1 and all R are hydrogen atoms, from the viewpoint of particularly excellent ultraviolet resistance. Eu (hfa) ₃ (TPPO) ₂ is a europium complex in which two ligands of triphenylphosphine oxide and hexafluoroacetylacetone are coordinated to a rare earth metal europium which is a central element.

  The content of the europium complex of the formula (I) is preferably blended in the range of 0.000001 to 1 part by mass with respect to 100 parts by mass of the resin material of the solar cell sealing film. When the amount is less than 0.000001 parts by mass, a sufficient wavelength conversion effect may not be obtained, and it is particularly preferably 0.00001 parts by mass or more, and more preferably 0.0001 parts by mass or more. On the other hand, when the amount exceeds 1 part by mass, it may be difficult to ensure the transparency necessary for allowing sunlight to sufficiently enter the power generation element, and the cost tends to be disadvantageous. In particular, it is preferably 0.1 parts by mass or less, more preferably 0.01 parts by mass or less.

[Resin material]
In this invention, the resin material of the sealing film for solar cells contains an olefin (co) polymer as a main component. Here, the olefin (co) polymer means an ethylene / α-olefin copolymer (for example, an ethylene / α-olefin copolymer (m-LLDPE) polymerized using a metallocene catalyst), polyethylene (for example, Olefin polymers such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), polypropylene, polybutene, and the like, and copolymers of olefins and polar monomers such as ethylene-polar monomer copolymers. It means a copolymer and has adhesiveness and transparency required for a sealing film for solar cells. As the olefin (co) polymer, one of these may be used, or two or more may be mixed and used. In the present invention, as the olefin (co) polymer, an ethylene / α-olefin copolymer (m-LLDPE) polymerized using a metallocene catalyst, a low density polyethylene (LDPE), a linear low density polyethylene (LLDPE). ), At least one polymer selected from the group consisting of polypropylene, polybutene and ethylene-polar monomer copolymers. In particular, an olefin (co) polymer can be formed using a metallocene catalyst because it is excellent in processability, can form a crosslinked structure with a crosslinking agent, and can form a solar cell sealing film with high adhesion. A polymerized ethylene / α-olefin copolymer (m-LLDPE) and / or an ethylene-polar monomer copolymer is preferred.

(Ethylene / α-olefin copolymer (m-LLDPE) polymerized using a metallocene catalyst) m-LLDPE is composed mainly of ethylene-derived structural units, and further an α-olefin having 3 to 12 carbon atoms, for example, , Propylene, 1-butene, 1-hexene, 1-octene, 4-methylpentene-1, 4-methyl-hexene-1, 4,4-dimethyl-pentene-1, etc. An ethylene / α-olefin copolymer (including a terpolymer) having a structural unit. Specific examples of the ethylene / α-olefin copolymer include an ethylene / 1-butene copolymer, an ethylene / 1-octene copolymer, an ethylene-4-methyl-pentene-1 copolymer, an ethylene / butene / hexene copolymer. Center polymers, ethylene / propylene / octene terpolymers, ethylene / butene / octene terpolymers, and the like. The content of the α-olefin in the ethylene / α-olefin copolymer is preferably 5 to 40% by mass, more preferably 10 to 35% by mass, and still more preferably 15 to 30% by mass. When the content of α-olefin is small, the flexibility and impact resistance of the solar cell sealing film may not be sufficient, and when it is too large, the heat resistance may be low.

  A known metallocene catalyst may be used as the metallocene catalyst for polymerizing m-LLPDE, and is not particularly limited. The metallocene catalyst is generally a compound having a structure in which a transition metal such as titanium, zirconium or hafnium is sandwiched between unsaturated cyclic compounds containing a π-electron cyclopentadienyl group or a substituted cyclopentadienyl group. And a promoter such as an aluminum compound such as alkylaluminoxane, alkylaluminum, aluminum halide, and alkylaluminum halide. Metallocene catalysts are characterized by a uniform active site (single site catalyst), and usually a polymer having a narrow molecular weight distribution and an approximately equal comonomer content of each molecule is obtained.

In the present invention, the density of m-LLDPE (according to JIS K 7112; the same applies hereinafter) is not particularly limited, but is preferably 0.860 to 0.930 g / cm ³ . The melt flow rate (MFR) of m-LLDPE (according to JIS-K7210) is not particularly limited, but is preferably 1.0 g / 10 min or more, more preferably 1.0 to 50.0 g / 10 min. 3.0 to 30.0 g / 10 min is more preferable. In addition, MFR is measured on condition of 190 degreeC and load 21.18N.

  In the present invention, commercially available m-LLDPE may be used. For example, Harmolex series, Kernel series manufactured by Nippon Polyethylene Co., Ltd., Evolution series manufactured by Prime Polymer Co., Ltd., Excellen GMH series, Excellen FX series manufactured by Sumitomo Chemical Co., Ltd. and the like can be mentioned.

(Ethylene-polar monomer copolymer)
Examples of the polar monomer of the ethylene-polar monomer copolymer include an unsaturated carboxylic acid, a salt thereof, an ester thereof, an amide thereof, a vinyl ester, and carbon monoxide. More specifically, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, itaconic acid, monomethyl maleate, monoethyl maleate, maleic anhydride, itaconic anhydride, lithium of these unsaturated carboxylic acids, sodium, Salts of monovalent metals such as potassium, salts of polyvalent metals such as magnesium, calcium and zinc, methyl acrylate, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, n-butyl acrylate, isooctyl acrylate, methacrylic acid Examples include unsaturated carboxylic acid esters such as methyl, ethyl methacrylate, isobutyl methacrylate, and dimethyl maleate, vinyl esters such as vinyl acetate and vinyl propionate, carbon monoxide, sulfur dioxide, etc. be able to.

  More specifically, as the ethylene-polar monomer copolymer, ethylene-acrylic acid copolymer, ethylene-unsaturated carboxylic acid copolymer such as ethylene-methacrylic acid copolymer, the ethylene-unsaturated carboxylic acid Ionomer in which some or all of carboxyl groups of copolymer are neutralized with the above metal, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene- Isobutyl acrylate copolymer, ethylene-unsaturated carboxylic acid ester copolymer such as ethylene-n-butyl acrylate copolymer, ethylene-isobutyl acrylate-methacrylic acid copolymer, ethylene-n-butyl acrylate -Ethylene-unsaturated carboxylic acid ester-unsaturated carboxylic acid such as methacrylic acid copolymer Some or all of the copolymer and its carboxyl group ionomer neutralized with the metal, ethylene - can be exemplified vinyl ester copolymer as a typical example - ethylene such as vinyl acetate copolymer.

  As the ethylene-polar monomer copolymer, it is preferable to use a copolymer having a melt flow rate defined by JIS K7210 of 35 g / 10 min or less, particularly 3 to 6 g / 10 min. By using an ethylene-polar monomer copolymer having such a melt flow rate, a solar cell sealing film having excellent processability can be obtained. In the present invention, the value of the melt flow rate (MFR) is measured based on conditions of 190 ° C. and a load of 21.18 N according to JIS K7210.

  Examples of the ethylene-polar monomer copolymer include ethylene-vinyl acetate copolymer (EVA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-ethyl methacrylate copolymer, and ethylene-methyl acrylate copolymer. , Ethylene-ethyl acrylate copolymer is preferable, and EVA and EMMA are particularly preferable. Thereby, the sealing film for solar cells which is extremely excellent in transparency can be formed.

  When EVA is used as the resin material, the content of vinyl acetate in EVA is preferably 20 to 35% by mass, more preferably 22 to 32% by mass, and particularly preferably 26 to 32% by mass. If the vinyl acetate content is less than 20% by mass, the sealing film may not be sufficiently transparent. If it exceeds 35% by mass, carboxylic acid, alcohol, amine, etc. are generated, and the sealing film and the protective member. There is a risk that foaming is likely to occur at the interface.

  When using EMMA as the resin material, the content of methyl methacrylate in EMMA is 20 to 30% by mass, preferably 22 to 28% by mass. Within this range, a highly transparent sealing film can be obtained, and a large amount of ultraviolet light can be converted into visible light and incident on the solar cell element.

  In addition, in this invention, in addition to the above-mentioned olefin (co) polymer, resin such as polyvinyl acetal resin (for example, polyvinyl formal, polyvinyl butyral (PVB resin), modified PVB) is added to the resin material. You may mix.

[Crosslinking agent]
The solar cell sealing film of the present invention preferably contains a crosslinking agent to form a crosslinked structure of an ethylene-polar monomer copolymer. As the crosslinking agent, an organic peroxide or a photopolymerization initiator is preferably used. Among these, it is preferable to use an organic peroxide because a sealing film with improved temperature dependency of adhesive strength, moisture resistance, and penetration resistance can be obtained.

  Any organic peroxide can be used as long as it decomposes at a temperature of 100 ° C. or higher to generate radicals. The organic peroxide is generally selected in consideration of the film formation temperature, the adjustment conditions of the composition, the curing temperature, the heat resistance of the adherend, and the storage stability. In particular, the one having a decomposition temperature of 70 ° C. or more with a half-life of 10 hours is preferable.

  Examples of the organic peroxide include, from the viewpoint of resin processing temperature and storage stability, for example, benzoyl peroxide curing agent, tert-hexyl peroxypivalate, tert-butyl peroxypivalate, 3, 5, 5- Trimethylhexanoyl peroxide, di-n-octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, succinic acid peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethyl Peroxy-2-ethylhexanoate, tert-hexyl par Xyl-2-ethylhexanoate, 4-methylbenzoyl peroxide, tert-butylperoxy-2-ethylhexanoate, m-toluoyl + benzoyl peroxide, benzoyl peroxide, 1,1-bis (tert-butyl Peroxy) -2-methylcyclohexanate, 1,1-bis (tert-hexylperoxy) -3,3,5-trimethylcyclohexanate, 1,1-bis (tert-hexylperoxy) cyclohexanate 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, 1,1-bis (tert-hexylperoxy)- 3,3,5-trimethylcyclohexane, 2,2-bis (4,4-di tert-butylperoxycyclohexyl) propane, 1,1-bis (tert-butylperoxy) cyclododecane, tert-hexylperoxyisopropyl monocarbonate, tert-butylperoxymaleic acid, tert-butylperoxy-3, 3,5-trimethylhexane, tert-butylperoxylaurate, 2,5-dimethyl-2,5-di (methylbenzoylperoxy) hexane, tert-butylperoxyisopropylmonocarbonate, tert-butylperoxy-2 -Ethylhexyl monocarbonate, tert-hexyl peroxybenzoate, 2,5-di-methyl-2,5-di (benzoylperoxy) hexane, and the like.

  As the benzoyl peroxide-based curing agent, any can be used as long as it decomposes at a temperature of 70 ° C. or higher to generate radicals, and those having a decomposition temperature of 50 hours or higher with a half-life of 10 hours are preferable, It can be appropriately selected in consideration of preparation conditions, film formation temperature, curing (bonding) temperature, heat resistance of the adherend, and storage stability. Usable benzoyl peroxide curing agents include, for example, benzoyl peroxide, 2,5-dimethylhexyl-2,5-bisperoxybenzoate, p-chlorobenzoyl peroxide, m-toluoyl peroxide, 2, Examples include 4-dichlorobenzoyl peroxide and t-butyl peroxybenzoate. The benzoyl peroxide curing agent may be used alone or in combination of two or more.

  As the organic peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane or tert-butylperoxy-2-ethylhexyl monocarbonate is particularly preferable. Thereby, the sealing film for solar cells which is bridge | crosslinked favorably and has the outstanding transparency is obtained.

  The content of the organic peroxide used for the solar cell sealing film is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 3 parts by mass with respect to 100 parts by mass of the resin material. Is preferred. If the content of the organic peroxide is small, the crosslinking speed may be lowered during the crosslinking and curing, and if the content is large, the compatibility with the copolymer may be deteriorated.

  As the photopolymerization initiator, any known photopolymerization initiator can be used, but a photopolymerization initiator having good storage stability after blending is desirable. Examples of such a photopolymerization initiator include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, and 2-methyl-1- (4- (methylthio) phenyl). Acetophenones such as -2-morpholinopropane-1, benzoins such as benzyldimethylketal, benzophenones such as benzophenone, 4-phenylbenzophenone and hydroxybenzophenone, thioxanthones such as isopropylthioxanthone and 2-4-diethylthioxanthone, As other special ones, methylphenylglyoxylate can be used. Particularly preferably, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1, Examples include benzophenone. These photopolymerization initiators may contain one or two or more kinds of known and commonly used photopolymerization accelerators such as benzoic acid-based or tertiary amine-based compounds such as 4-dimethylaminobenzoic acid as required. Can be mixed and used. Moreover, it can be used individually by 1 type of only a photoinitiator, or 2 or more types of mixture.

  Content of the said photoinitiator is 0.1-5 mass parts with respect to 100 mass parts of resin materials, Preferably it is 0.2-3 mass parts.

[Crosslinking aid]
It is preferable that the sealing film for solar cells of the present invention further contains a crosslinking aid. The crosslinking aid can improve the gel fraction of the olefin (co) polymer and improve the adhesion and weather resistance of the solar cell sealing film.

  The content of the crosslinking aid is usually 0.1 to 5 parts by mass, preferably 0.1 to 3 parts by mass, particularly preferably 0.5 to 2.5 parts by mass with respect to 100 parts by mass of the resin material. Is done. Thereby, the sealing film which the hardness after bridge | crosslinking improved further is obtained.

  Examples of the crosslinking aid (compound having a radical polymerizable group as a functional group) include trifunctional crosslinking aids such as triallyl cyanurate and triallyl isocyanurate, and (meth) acrylic esters (eg, NK ester) ) Monofunctional or bifunctional crosslinking aids. Of these, triallyl cyanurate and triallyl isocyanurate are preferable, and triallyl isocyanurate is particularly preferable.

[Adhesion improver]
The solar cell sealing film of the present invention may further contain an adhesion improver. As the adhesion improver, a silane coupling agent can be used. Thereby, it can be set as the sealing film for solar cells which has the further outstanding adhesive force. Examples of the silane coupling agent include γ-chloropropyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, and γ-glycidoxypropyl. Trimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltrichlorosilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N Mention may be made of -β- (aminoethyl) -γ-aminopropyltrimethoxysilane. These silane coupling agents may be used alone or in combination of two or more. Of these, γ-methacryloxypropyltrimethoxysilane is particularly preferred.

  The content of the silane coupling agent in the solar cell sealing film of the present invention is 5 parts by mass or less, preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the resin material.

[Others]
The sealing film for solar cells of the present invention improves or adjusts various physical properties of the film (optical properties such as mechanical strength and transparency, heat resistance, light resistance, crosslinking speed, etc.), especially improvement of mechanical strength. Therefore, if necessary, various additives such as a plasticizer, an acryloxy group-containing compound, a methacryloxy group-containing compound and / or an epoxy group-containing compound may further be included.

[Seal film for solar cell]
As described above, the solar cell sealing film of the present invention includes the wavelength conversion material, thereby improving the power generation efficiency and maintaining the effect of improving the power generation efficiency even when the solar cell is used over a long period of time. It is something that can be done. As the evaluation, for example, the wavelength of 580 to 640 nm in the fluorescence emission spectrum obtained when the solar cell sealing film is irradiated with a light beam of 325 nm corresponding to the excitation wavelength of the wavelength conversion material (the europium complex of formula (I)). The solar cell sealing film is disposed at a distance of 235 mm from an ultraviolet lamp having an irradiation intensity of 1000 W / cm ² with the emission peak area of When the fluorescence intensity is measured, the time required for the fluorescence intensity of the solar cell sealing film to decrease to 30% of the fluorescence intensity before irradiation is preferably 10 hours or more.

  The fluorescence intensity is measured as follows, for example. First, the solar cell sealing film prepared to 0.46 mm is sandwiched between 3.2 mm thick white plate glass, and is bonded by a 90 ° C. vacuum laminator with a degassing time of 2 minutes and a pressing time of 8 minutes. A crosslinked sample is prepared by crosslinking in an oven at 155 ° C. for 30 minutes. The obtained sample was irradiated with light having an excitation wavelength (325 nm for the europium complex of formula (I)) using a fluorescence spectrophotometer (for example, F-7000 (manufactured by Hitachi High-Technologies Corporation)), and each wavelength A fluorescence emission spectrum is obtained by plotting the light emission amount at. The emission peak area in this fluorescence emission spectrum (emission peak area of 580 to 640 nm for the europium complex of formula (I)) is calculated as the fluorescence intensity. Since the amount of fluorescence emission is an arbitrary unit that varies depending on the analyzer, the fluorescence intensity is a numerical value used for relative comparison in the present invention.

And in the sealing film for solar cells of this invention, the above-mentioned evaluation of the stability of the fluorescence intensity by ultraviolet rays can be tested as follows, for example. Using the environmental tester (for example, Super UV (manufactured by Iwasaki Electric Co., Ltd.)), the black panel temperature of 63 ° C. and the SUV lamp irradiation intensity of 1000 W / cm ² are used for the crosslinked sample of the solar cell sealing film prepared as described above. Then, continuous irradiation is performed at a distance of 235 mm to the light source, and the fluorescence intensity is measured over time. When the fluorescence intensity before irradiation is assumed to be 100%, the time until the fluorescence intensity decreases to 30% is measured, and if it is 10 hours or more, sufficient UV resistance is exhibited, and the solar cell is used for a long period of time. However, it can be determined that the solar cell sealing film can sufficiently maintain the effect of improving the power generation efficiency.

  What is necessary is just to perform according to a well-known method in order to form the sealing film for solar cells of this invention. For example, the composition containing each of the above-described components can be produced by a method of obtaining a sheet-like material by molding by ordinary extrusion molding, calendar molding (calendering) or the like. Although the thickness in particular of the sealing film for solar cells of this invention is not restrict | limited, It is 0.05-2 mm.

[Solar cell]
The structure of the solar cell of the present invention is not particularly limited as long as it includes a structure in which the solar cell element is sealed with the solar cell sealing film of the present invention. For example, the structure etc. which sealed the cell for solar cells by interposing the sealing film for solar cells of this invention between the surface side transparent protection member and the back surface side protection member, and making it bridge-integrate are mentioned. .

  Since the solar cell sealing film of the present invention is used in the solar cell of the present invention, the power generation efficiency of the solar cell element is improved by the wavelength conversion material, and the high power generation efficiency is maintained for a long time. It is a solar cell.

  In addition, in this invention, the side (light-receiving surface side) where the light of the solar cell is irradiated is referred to as “front surface side”, and the surface opposite to the light-receiving surface of the solar cell is referred to as “back surface side”.

  In the solar cell, in order to sufficiently seal the solar cell, for example, as shown in FIG. 1, the front surface side transparent protective member 11, the front surface side sealing film 13A, the solar cell cell 14, the back surface side sealing. The film 13B and the back surface side protection member 12 may be laminated, and the sealing film may be cross-linked and cured according to a conventional method such as heat and pressure.

In order to heat and pressurize, for example, a laminated body in which each member is laminated is heated by a vacuum laminator at a temperature of 135 to 180 ° C., further 140 to 180 ° C., particularly 155 to 180 ° C., a degassing time of 0.1 to 5 minutes, a press pressure. What is necessary is just to heat-press in 0.1-1.5 kg / cm < ² > and press time 5-15 minutes.

  By crosslinking the olefin (co) polymer contained in the front side sealing film 13A and the back side sealing film 13B during this heating and pressurization, the front side sealing film 13A and the back side sealing film 13B are interposed. The solar cell 14 can be sealed by integrating the front surface side transparent protective member 11, the back surface side transparent member 12, and the solar cell 14.

  Since the solar cell sealing film of the present invention can improve the power generation efficiency of the solar cell element by including the wavelength conversion material as described above, it is disposed on the light receiving surface side of the solar cell element in the solar cell. It is preferable to use as the sealing film 13A, that is, the sealing film 13A disposed between the surface-side transparent protective member 12 and the solar battery cell 14 in FIG.

  The solar cell sealing film of the present invention is not limited to a solar cell using a single crystal or polycrystalline silicon crystal solar cell as shown in FIG. It can also be used for a sealing film of a thin film solar cell such as a solar cell and a copper indium selenide (CIS) solar cell. In this case, for example, the solar cell of the present invention is formed on a thin film solar cell element layer formed by a chemical vapor deposition method or the like on the surface of a surface side transparent protective member such as a glass substrate, a polyimide substrate, or a fluororesin transparent substrate. On the solar cell element formed on the surface of the back surface side protective member, the structure for laminating the battery sealing film and the back surface side protective member and adhering and integrating them, the front surface side Laminated transparent protective member, bonded and integrated structure, or front side transparent protective member, front side sealing film, thin film solar cell element, back side sealing film, and back side protective member are laminated in this order, For example, a structure that is bonded and integrated. In addition, in this invention, the cell for solar cells and a thin film solar cell element are named generically, and are called a solar cell element.

  The surface side transparent protective member 11 is usually a glass substrate such as silicate glass. As for the thickness of a glass substrate, 0.1-10 mm is common, and 0.3-5 mm is preferable. The glass substrate may generally be chemically or thermally strengthened.

  The back surface side protection member 12 is preferably a plastic film such as polyethylene terephthalate (PET) or polyamide. Further, a film obtained by laminating a fluorinated polyethylene film, particularly a fluorinated polyethylene film / Al / fluorinated polyethylene film in this order in consideration of heat resistance and wet heat resistance may be used.

  In addition, the sealing film for solar cells of this invention has the characteristics in the sealing film used for the surface side and / or back surface side of a solar cell (a thin film solar cell is included). Therefore, the members other than the sealing film such as the front surface side transparent protective member, the back surface side protective member, and the solar battery cell are not particularly limited as long as they have the same configuration as a conventionally known solar battery.

  Hereinafter, the present invention will be described in detail with reference to examples.

(Preparation of solar cell sealing film)
Each material was supplied to a roll mill with the formulation shown in the following table, and kneaded at 70 ° C. to prepare a solar cell sealing film composition. This solar cell sealing film composition was calendered at 70 ° C., allowed to cool, and then a solar cell sealing film (thickness 0.46 mm) was produced.

<Evaluation method>
(Preparation of cross-linked sample)
The solar cell sealing film was sandwiched between two pieces of white glass (thickness: 3.2 mm), and the resulting laminate was pressure-bonded at 90 ° C. with a degassing time of 2 minutes and a pressing time of 8 minutes using a vacuum laminator. Then, the sample was produced by heating for 30 minutes in an oven at 155 ° C. to cure by crosslinking.

(1) Light transmittance (%)
About the said sample, the spectrum measurement of 400-1000 nm was implemented using the spectrophotometer (the Hitachi Ltd. make, U-4100), and the average value was made into light transmittance (%).
(2) Haze (turbidity) (%)
About the said sample, haze value (%) was measured using the haze meter (Nippon Denshoku Industries Co., Ltd. NDH 2000 type | mold) according to JISK7105 (2000).
(3) Fluorescence intensity About the said sample, the fluorescence intensity was measured using the spectrophotometer (the Hitachi High-Technologies company make, F-7000). Measurement conditions: Photomultiplier voltage 400 V, excitation side slit 20 nm, fluorescence side slit 10 nm, scan speed 240 nm / min. The irradiation wavelength was 325 nm for the wavelength conversion material (1), 355 nm for the wavelength conversion materials (2) and (3), and 365 nm for (4). In addition, although the excitation peak wavelength of each wavelength conversion material itself is located on the shorter wavelength side than each of the above irradiation wavelengths, the light transmittance of white plate glass (absorption in white plate glass) exists in the ultraviolet region. The absorption of white glass tends to increase toward the short wavelength side. Accordingly, ultraviolet rays on the short wavelength side are strongly absorbed, and the peak wavelength of the apparent excitation shifts to the long wavelength side in the laminated glass structure test. Therefore, each irradiation wavelength was set as described above.

Then, a function f (x) representing the wavelength on the X-axis and the light emission amount on the Y-axis, the curve from the start wavelength to the end wavelength of the emission peak and two points X = X ₀ and X ₁ on the function f (x) The area of the region surrounded by the straight line connecting the two was calculated and used as the fluorescence intensity.
(4) UV degradation Using the ultraviolet lamp (Super UV, manufactured by Iwasaki Electric Co., Ltd.) for the above sample, facing a position of 235 mm from a light source that radiates 1000 W / cm ² of ultraviolet light under conditions of a black panel temperature of 63 ° C. When it was placed and irradiated with ultraviolet rays, the time (h) required to decrease to 30% of the emission intensity of the sample before ultraviolet irradiation was measured.

  The results are shown in the table below.

<Evaluation results>
As shown in the above table, when the wavelength conversion material (1) (Eu (hfa) ₃ (TPPO) ₂ ) is used as the wavelength conversion material, it is compared with the case where another wavelength conversion material is used. It was confirmed that the deterioration degree due to ultraviolet rays was small and the wavelength conversion effect could be maintained. Furthermore, when the content of Eu (hfa) ₃ (TPPO) ₂ is 0.00001 to 0.1 parts by mass with respect to 100 parts by mass of each resin material (EVA, m-LLDPE, EMMA), particularly 0.0001 to In the case of 0.01 part by mass, the fluorescence intensity was high, and it was recognized that it was particularly advantageous for improving the power generation efficiency.

DESCRIPTION OF SYMBOLS 11 Surface side transparent protective member 12 Back surface side protective member 13A Surface side sealing film 13B Back surface side sealing film 14 Cell for solar cells

[Wherein, R is a hydrogen atom and n is 1 . ]
It is achieved by a solar cell sealing film characterized by being a europium complex represented by the formula:

(1) The olefin (co) polymer is an ethylene-methyl methacrylate copolymer .
(2) The sealing film for solar cells according to claim 1, wherein the olefin (co) polymer is an ethylene / α-olefin copolymer (m-LLDPE) polymerized using a metallocene catalyst .
( 3 ) The emission peak area at a wavelength of 580 to 640 nm in a fluorescence emission spectrum obtained when a solar cell sealing film is irradiated with a light beam of 325 nm corresponding to the excitation wavelength of the wavelength conversion material is defined as 1000 W / When the solar cell sealing film is disposed at a distance of 235 mm from an ultraviolet lamp having an irradiation intensity of cm ^2, the irradiation is continuously performed at a temperature of 63 ° C., and the fluorescence intensity is measured over time. The time required for the fluorescence intensity of the sealing film to decrease to 30% of the fluorescence intensity before irradiation is 10 hours or more.

[Wherein, R is a hydrogen atom and n is 1 . ]
The europium complex represented by these is included.

The europium complex is one of n in formula (I), R is Ri _{Eu (hfa) 3 (TPPO)} 2 Der all hydrogen atoms, in particular Ru excellent ultraviolet resistance. Eu (hfa) ₃ (TPPO) ₂ is a europium complex in which two ligands of triphenylphosphine oxide and hexafluoroacetylacetone are coordinated to a rare earth metal europium which is a central element.

The content of europium complexes of formula (I), Ru is blended in the range of 0.001 to 0.1 parts by weight with respect to the resin material 100 parts by weight of the sealing film for a solar cell. Generally, when the amount is less than 0.000001 parts by mass, a sufficient wavelength conversion effect may not be obtained, and it is particularly preferably 0.00001 parts by mass or more, and more preferably 0.0001 parts by mass or more. On the other hand, when the amount exceeds 1 part by mass, it may be difficult to ensure the transparency necessary for allowing sunlight to sufficiently enter the power generation element, and the cost tends to be disadvantageous. In particular, it is preferably 0.1 parts by mass or less, more preferably 0.01 parts by mass or less.

Claims (7)

A resin material containing an olefin (co) polymer, and a solar cell sealing film containing a wavelength conversion material,
The wavelength conversion material has the following formula (I):

[Wherein, R independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, and n is an integer of 1 to 4. ]
A solar cell sealing film characterized by being a europium complex represented by the formula:   2. The solar cell sealing film according to claim 1, wherein in the formula (I), R is all hydrogen atoms and n is 1. 3.   Content of the said wavelength conversion material is 0.000001-1 mass part with respect to 100 mass parts of said resin materials, The sealing film for solar cells of Claim 1 or 2 characterized by the above-mentioned.   Content for the said wavelength conversion material is 0.0001-0.01 mass part with respect to 100 mass parts of said resin materials, The solar cell for any one of Claims 1-3 characterized by the above-mentioned. Sealing film.   The ethylene / α-olefin copolymer (m-LLDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), polypropylene, polymerized using the metallocene catalyst as the olefin (co) polymer, The solar cell sealing film according to any one of claims 1 to 4, which is at least one polymer selected from the group consisting of polybutene and an ethylene-polar monomer copolymer. The fluorescence intensity is the emission peak area at a wavelength of 580 to 640 nm in the fluorescence emission spectrum obtained when the solar cell sealing film is irradiated with a light beam of 325 nm corresponding to the excitation wavelength of the wavelength conversion material,
When the solar cell sealing film is disposed at a distance of 235 mm from an ultraviolet lamp having an irradiation intensity of 1000 W / cm ² , continuously irradiated at a temperature of 63 ° C., and the fluorescence intensity is measured over time, The time required for the fluorescence intensity of the sealing film for solar cells to fall to 30% with respect to the fluorescence intensity before irradiation is 10 hours or more, The solar cell of any one of Claims 1-5 Sealing film.   A solar cell, wherein a solar cell element is sealed with the solar cell sealing film according to any one of claims 1 to 6.

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