Title of Invention

FLUORESCENT RESIN COMPOSITION AND SOLAR BATTERY MODULE USING THE SAME

Abstract

This invention provides an organic rare earth metal complex, which emits fluorescence with a wavelength in the range of 550 to 900 nm, particularly a fluorescent resin composition comprising an ethylene-vinyl acetate copolymer containing 0.01 to 10% by mass of an organic rare earth metal complex represented by general formula wherein R represents an aliphatic or aromatic hydrocarbon group; Ln represents a rare earth metal; A represents group -CH=CH-; and n is 0 or 1. There are also provided a solar battery module using the fluorescent resin composition as a sealing material between a front cover and a crystalline silicon cell, and a solar battery with high conversion efficiency.

Full Text

FORM THE PATENT ACT 1970 {39 Of 1970 The Patents Rules,|2003 COMPLETE SPECIFICATION (See Section 10, and rule 13) TITLE OF INVENTION FLUORESCENT RESIN COMPOSITION AND SOLAK BATTERY MODULE USING THE SAME APPLICANT(S) a) Name b) Nationality c) Address SANVIC INC. JAPANESE Company 30-8, HORIKIRI l-CHOMg, KATSUSHIKA-KU, TOKYO 1240006, JAPAN PREAMBLE TO THE DESCRIPTION The following specification particul and the manner in which it is to be jarly describes the invention performed : - Technical Field The present invention relates to a novel fluorescent resin composition suitable as a solar cell or battery module-sealing material and a solar cell module using the same. Background Art A solar cell that converts sun light directly into electrical energy has been attracting attention as a means of supplying clean and inexhaustible energy and has been studied in various fields. Generally, the performance of a solar cell is evaluated by conversion efficiency that is a percentage of electrical energy converted from incident light energy of the sun. The incident light energy is light energy that has been absorbed into a cell (photovoltaic element) inside a solar cell, and thus the conversion efficiency depends on the ability (absorption ability) of a cell to absorb light energy incident on the cell, and the absorption ability varies significantly depending on the performance of the cell used. For example, sun light has a broad wavelength range including ultraviolet light, visible light and infrared light, but not all these lights upon incident on a solar cell are converted into electrical energy, and only light in the wavelength range which can be adsorbed by the cell can be converted. Light in the wavelength range adsorbed by a cell is determined by physical properties inherent in the cell, where the peak wavelength in spectral irradiance distribution of sun light is in the vicinity of 500 nm, while when a crystalline silicon cell is used, the peak wavelength of spectral sensitivity thereof is in the range of 600 to 1000 nm, and thus sun light cannot be sufficiently adsorbed and the efficiency of conversion of sun light into electrical energy is inevitably lowered. Accordingly, it is an important task for the solar cell to improve conversion efficiency by absorbing as much sun light as possible. A solar cell using a crystalline silicon cell is known which includes a module structured such that a front cover is arranged at the side of a light-receiving surface and a back cover at the other side, and a crystalline silicon cell is sealed with a sealing material between the covers (JP 6-177412 A). A fluorescent film-forming ink composition is proposed in which an inorganic 2 14 MAY2009' fluorescent material and an ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVA) have been dissolved in a solvent (JP 8-102257 A), and a composite panel is proposed in which EVA has been compounded with a luminescent pigment and an inorganic light-accumulating fluorescent material (JP 2004-249644 A), but as a solar cell module-sealing material, there is not known a combination of a fluorescent material and EVA. In these fluorescent materials, however, when a rare earth metal inorganic material is used as a fluorescent substance, the transparency of EVA is significantly inhibited, while when an organic material is used as a fluorescent substance, thermal deterioration is significant with insufficient durability, and thus the combination of the fluorescent substance and EVA has been disadvantageous and practically problematic. Disclosure of the Invention The present invention was completed for the purpose of providing a rare earth metal complex-containing fluorescent resin composition preferable as a solar cell module-sealing material, which exhibits excellent durability to ultraviolet light etc. without deteriorating the transparency of EVA. The present inventors have made extensive studies on a sealing material for a solar cell module, and as a result, found that when an EVA-based resin composition obtained by compounding an EVA-based resin composition, which has conventionally been used to merely fulfill a role as a sealing binder, with a rare earth metal complex emitting fluo :escence with a wavelength in the range of 550 to 900 nm is used as a sealing material for a crystalline silicon cell, the sealing material absorbs sun light with a wavelength in the range of 500 nm or less and emits fluorescent light with a wavelength in the range of 550 to 900 nm, which light is to be adsorbed by the crystalline silicon cell, thereby achieving a solar cell module having high conversion efficiency and being excellent in transparency and durability, the present invention has been achieved. On the basis of this finding, That is, the present invention provides a fluorescent resin composition comprising EVA containing 0.01 to 10% by mass of an organic rare earth metal complex emitting fluorescence with a waveleng h in the range of 550 to 900 nm, as well as a solar cell module having a structure comprising a front cover, a 3 14MAY2009 back cover and a number of units each having a crystalline silicon cell which are integrated between the covers as sealed with a sealing material, wherein the sealing material between the front cover and the crystalline silicon cell contains the fluorescent resin composition described above. The fluorescent resin composition of the present invention comprises an organic rare earth metal complex and EVA. The rare earth metal as a central metal in the complex is not particularly limited and can be selected arbitrarily from among scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium, among which europium and samarium are preferable, and europium is more preferable. The ligand in the rare earth metal complex is not particularly limited and may be any organic compound having a site to be coordinated in the rare earth metal ion, and examples include a carboxylic acid, a p-diketone, and a nitrogen-containing organic compound. This carboxylic acid may be either an aliphatic carboxylic acid or an aromatic carboxylic acid. To minimize deterioration in the transparency of EVA, the aliphatic carboxylic acid is preferably one whose hydrocarbon group bound to atoms or more, particularly a a carboxyl group is a group having 3 carbon higher alkyl or alkenyl group having 8 carbon atoms or more or a bulky branched alkyl group such as t-butyl group. Examples of such aliphatic carboxylic acids include butyric acid, stearic acid, oleic acid, coconut oil fatty acid, t-butyl carboxylic acid and succinic acid. The aromatic carboxylic acid includes carboxyli: acids having an aromatic ring or aromatic heterocycle, for example benzoic acid, naphthoic acid, quinoline carboxylic acid, etc. The aromatic rings in these aromatic carboxylic acids may be substituted with an alkyl group such as a methyl group or an ethyl group, an alkenyl group such as an ethenyl group or a propenyl group, an alkoxy group such as a methoxy group or an ethoxy group, and a halogen atom such as a chlorine atom or a bromine atom. Particularly preferable among these aromatic carboxylic acids are 1-naphthoic acid and 2-naphthoic acid. 14 MAY 2009, These carboxylic acids may be used alone or in combination of two or more thereof. The p-diketone is not particularly limited, but is preferably a compound represented by the general formula I Ri-COCHR2COR3 (I), wherein R1 and R3 each represent an aliphatic, alicyclic or aromatic :om or an aliphatic, alicyclic or hydrocarbon group, R2 represents a hydrogen a aromatic hydrocarbon group. R3 include an alkyl group, a In this general formula, examples of R1 and cycloalkyl group, a cycloalkyl-substituted alkyl group, an aryl group and an aralkyl group, and examples of R2 include a hydrogen atom, an alkyl group, a cycloalkyl group, a cycloalkyl-substituted alky group, an aryl group and an aralkyl group. The cyclic groups in these groups may further be substituted with a lower alkyl group, a lower alkoxyl group or a halogen atom. Such p-diketone includes, for example, l,3-diphenyl-l,3-propanedione, acetylacetone, benzoylacetone, dibenzoylacetone, diisobutyloylmethane, dibivaloylmethane, 3-methylpentane-2,4-dione, ^-dimethylpentane-S/S-dione, 2-methyl-l,3-butanedione, 1,3-butanedione, 3-phenyl-2,4-pentanedione, 1,1,1-trifloro-2,4-pentanedione, l,l,l-tnfloro-5,5-dimethyl-2,4-hexanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 3-methyl-2,4-pentanedione, 2-acetylcyclopentanone, 2-acetylcyclohexanone, l-heptafloropropyl-3-t-butyl-1,3-propanedione, l,3-diphenyl-2-methyl-l,3-propanedione (diphenylacetylacetone), and l-ethoxy-l,3-butanedione, among which 1,3-diphenyl-l,3-propanedione, acetylacetone and benzoylacetone are preferable. These p-diketones may be used alone or in combination of two or more thereof. described above includes and a nitrogen-containing The nitrogen-containing organic compound alkylamine, aromatic amine such as aniline aromatic heterocyclic compound, among which a nitrogen-containing aromatic heterocyclic compound, particularly a bidentate ligand 1,10-phenanthroline or 5 1 4 MAY 2009." bipyridyl, is preferable. Imidazole, triazole, pyrimidine, pyrazine, aminopyridine, pyridine, and derivatives thereof, nucleobases such as adenine, thymine, guanine and cytosine, and derivatives thereof can also be used. These nitrogen-containing organic compounds may be used alone or in combination of two or more thereof. The ligand in the complex may be one type or two or more types. Particularly, a ligand in which a carboxylic acid is combined with a nitrogen-containing organic compound is preferable because it exhibits high fluorescence intensity. However, the organic rare earth metal complex used in the fluorescent resin composition of the present invention is most preferably a complex represented by the following general formula 11 wherein R represents an aliphatic or aromatic hydrocarbon group, Ln represents a rare earth metal, A represents group 'CH=CH-, and n is 0 or 1, or by the following general formula III wherein R1, R2, R3, A, Ln and n have the same meanings as defined above. These complexes are soluble in an organic solvent and excellent in compatibility with EVA, and can thus be uniformly dispersed in EVA. 6 14 MAY 2009' An example of R in the general formula II can be a residue of 1-naphthoic acid or 2-naphthoic acid, and an example of -0-CHR1CHR2CHR3-0- in the general formula III can be a residue of l,3-diphenyl-l,3-propanedione, acetylacetone or benzoylacetone. of the rare earth metal complex, and high cos amount is less than 0.01% by mass, fluorescence The amount of the rare earth metal complex used shall be 0.01 to 10% by mass, preferably 0.05 to 1% by mass, based on EVA. When this amount is higher than 10% by mass, the increase in costs due to addition of the rare earth metal complex is greater than the increase in fluorescence intensity due to the effect :s may result, while when the intensity becomes insufficient. EVA used in the fluorescent resin composition of the present invention is not particularly limited and can be selected from among customarily used EVAs, and the content of its vinyl acetate unit is in the range of 10 to 40% by mass, more preferably 20 to 35% by mass. When the content of the vinyl acetate unit in EVA is less than 10% by mass, the uniform dispersibility of the rare earth metal complex in EVA is deteriorated, and transparency is lowered. When the content is higher than 40% by mass, EVA itself is softened and tends to be poor in practical utility as a sheet. In the fluorescent resin composition of the oresent invention, an organic peroxide can be previously added to EVA and thermally decomposed, thereby forming a crosslinked structure of EVA or the EVA composition. The organic peroxide used herein may be any peroxide as long as it generates a radical at 100°C or higher, but in consideration of the stability thereof in compounding, an organic peroxide whose half-life-10-hour decomposition temperature is 70°C or higher is preferable. Examples of such organic peroxides include, for example, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy) hexane-3, di-t-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy) hexane, a,a'-bis(t-butylperoxyisopropyl) benzene, n-butyl-4,4-bis(t-butylperoxy) butane, 2,2-bis(t-butylperoxy) butane, l,l-bis(t-butylperoxy) cyclohexane, l,l-bis(t-butylperoxy) 3,3,5-trimethylcyclohexane, t-butylperoxybenzoate, benzoyl peroxide, etc. 7 1.4 MAY 2009 It is sufficient for the amount of the organic peroxide incorporated to be up to 5% by mass based on EVA. added if necessary to the to further improve the the EVA composition. An accelerating crosslinking agent may be fluorescent resin composition of the present invention degree of crosslinking and durability of EVA or The accelerating crosslinking agent that can be used includes not only trifunctional accelerating crosslinking agents such as triallyl isocyanurate and triallyl isocyanate but also monofunctional accelerating crosslinking agents such as NK esters. It is sufficient for the amount of the accelerating crosslinking agent incorporated to be up to 10% by mass based on EVA. The fluorescent resin composition of the present invention may be compounded if necessary with stabilizers such as hydroquinone, hydroquinone monomethyl ether, p-benzoquinone, methyl hydroquinone, etc. in order to improve stability. It is sufficient for the amount of the stabilizer incorporated to be up to 5% by mass based on EVA. An ultraviolet absorber, an antioxidant, a discoloration inhibitor, etc. can be added to the fluorescent resin composition of the present invention. The ultraviolet absorber that can be used includes, for example, benzophenone-based absorbers such as 2-hydroxy-4-n-octoxybenzophenone and 2-hydroxy-4-methoxy-5-sulfobenzophenone, benzotriazole-based absorbers such as 2-(2'-hydroxy-5-methylphenyl)benzotriazole/ and hindered amine-based absorbers such as phenyl salicylate and p-t-butylphenyl salicylate. The antioxidant that can be used includes amine-based inhibitors, phenol-based inhibitors, bisphenyl-based inhibitors and hindered amine-based inhibitors, for example, di-t-butyl-p-cresol and bis(2,2,6,6-terramethyI-4-piperazyl) sebacate. I4 MAY 2009 The fluorescent resin composition of the present invention is useful as a fluorescent paint, a luminescent element, a wavelength conversion material, an is used particularly preferably optical sensor or a fluorescence indicator, and as a sealing material for a solar cell module. present invention is used as a When the fluorescent resin composition of the sealing material for a solar cell module, a silane coupling agent is preferably added to further improve the adhesion between the sealing material and the front cover, the back cover or the crystalline silicon cell. The silane coupling agent that can be used includes, for example, y-chloropropyltrimethoxysilane, vinyltrichlorosillane, vinyltriethoxysilane, vinyl-tris(p-methoxyethoxy) silane, y-methacryloxypropyltrimethoxy-silane, p-(3,4-ethoxycyclohexyl) ethyl-trimethoxysilane, y- glycidoxypropyl-trimethoxysilane, vinyltriacetoxysilane, y-merca ?topropyltrimethoxysilane, y-aminopropyltrimethoxysilane, N-p-(aminoethyl)-y-aminopropyl-trimethoxysilane etc. It is sufficient for the amount of the silane coupling agent incorporated to be up to 5% by mass based on the whole of the sealing material. The material of the front cover and back cover used in the solar cell module with the fluorescent resin composition as a sealing material includes glass, polycarbonate, acrylic resin, polyester, poly(vinyl fluoride) and polyethylene fluoride. When these materials are used particularly in the front cover, sun light is preferably not prevented from reaching the crystalline silicon cell. These materials are processed and molded in forms of a plate, sheet and film, depending on their physical properties. glass is preferably used in the glass usually used in solar cell In the solar cell module of the present invention, front cover. As this glass, not only white plate modules, but also blue float glass, figured glass and the like are used. The back cover can be laminated with a metal layer and/or a plastic film layer for imparting weather ability, high insulation properties and strength. The metal material used herein is one that can prevent penetration of water vapor from the outside and includes aluminum, stainless steel and tin, among which aluminum is preferable in terms of economic efficiency and weight. A plastic SI/4 MAY 2009 material used in the plastic film layer includes poly(vinylidene chloride), polyester, polyethylene, and fluorine-based plastics. Brief Description of the Drawing FIG. 1 is a schematic cross-sectional view showing a structure of a solar cell module using a crystalline silicon cell, wherein a front cover 1 is arranged at the side of a light-receiving surface and a back cover 4 at the other side and crystalline silicon cells 3, ... are sealed with a transparent sealing material 2 between the covers. The back cover 4 has, for example, a structure of 3 layers of (poly)vinyl fluoride/aluminum/poly(vinyl fluoride). Best Mode for Carrying Out the Invention not invention will be described with limited in any way by these Then, the best mode for carrying out the i reference to the Examples, but the invention is examples. Example 1 metal complexes, Six sheets (thickness: 0.5 mm) with the compositions shown in Table 1 were prepared by using EVA containing 28% by mass of vinyl acetate unit and having a melt index of 7 (trade name: "Evatate KA30", manufactured by Sumitomo Chemical Co., Ltd.), and as rare earth Eu[(CH3)3CCOO]3 (complex I), Eu(CH3CH2CH2COO)3 (complex II), Eu[(CH3)3CCOO]3(2,2'-bipyridyl) (complex III), Eu(l-naphthoic acid)3(l,10-phenanthroline) (complex IV) expressed by the formula and 10 14 MAY 2009 Eu(l/3-diphenyl-l/3-propanedione)3(l/10-phenanthroline) (complex V) expressed by the formula Table Then, when these sheets were visually observed for their transparency, No. 1 became milky as a whole, while Nos. 2 to 6 were all transparent. When these sheets were irradiated with ultraviolet light having a wavelength of 254 nm and with ultraviolet light having a wavelength of 365 nm, any of Nos. 1 to 6 emitted red fluorescence, and the sheets Nos. 4 to 6 showed significantly higher fluorescence intensity than the sheets Nos. 2 and 3. 11 14 MAY 2009. Example 2 100 parts by mass of the same EVA as used in Example 1 were compounded with 2/5-dimethyl-2/5-di(t-butylperoxy)hexane (organic peroxide), y- methacryloxypropyltrimethoxysilane (silane coupling agent), bis(2,2,6,6- to prepare 3 sheets Nos. 7 to 9 tetramethyl-4-piperazyl) sebacate (antioxidant) and a rare earth metal complex respectively in the amounts shown in Table 2, (thickness: 0.5 mm) as sealing materials. Table 2 Then, as shown in FIG. 1, 72 crystalline silicon cells 3, ... were enclosed with a sealing material 2 consisting of the sheet No. 7, 8 or 9, then sandwiched between a white plate glass 1 of 3 mm in thickness and a back cover 4 with a 3-layer structure of polyvinyl fluoride) (thickness: 38 um)/ aluminum (thickness: 30 urn)/ poly (vinyl fluoride) (thickness: 38 jam), degassed for 3 minutes at 150°C with a laminator and then pressed for 30 minutes under atmospheric pressure, to produce solar cell modules Nos. 1 to 3. Is used therein were measured in Table 3. The solar cell modules Nos. 1 to 3 and silicon ce for conversion efficiency. The results are shown 12 14 MAY 2009 Table 3 From this table, it can be seen that the conversion efficiency of the solar cell module was significantly increased by using the sealing material to which the rare earth metal complex was added. Industrial Applicability The fluorescent resin composition of the present invention is useful as a fluorescent paint, a luminescent element, a wavelength conversion material, an optical sensor, a fluorescence indicator, anc a solar cell module-sealing material. The solar cell module of the present invention makes use, as a sealing material, of the fluorescent resin composition of the present invention which absorbs light with a wavelength in the range of 500 nm or less not absorbable by a crystalline silicon cell and emits fluorescent light with a wavelength in the as a solar cell module of high range of 550 to 900 nm, and can thus be used conversion efficiency. 13 WE CLAIM : A fluorescent resin composition comprising an ethylene-vinyl acetate copolymer containing 0.01 to 10% by mass of an organic rare earth metal complex emitting fluorescence in a wavelength range of 550 to 900 nm. The fluorescent resin composition according to claim 1, wherein the organic rare earth metal complex is a europium or samarium complex. The fluorescent resin composition according to claim 1 or 2, wherein the organic rare earth metal complex comprises at least one kind of three ligands selected from a carboxylic acid residue or a p-diketone compound and one ligand selected from nitrogen-containing heterocyclic compounds. The fluorescent resin composition according to claim 3, wherein the or aromatic dicarboxylic acid carboxylic acid residue is an aliphatic residue. according 5. The fluorescent resin composition diketone compound is represented by the R1-COCHR2COR3, to claim 3, wherein the p-general formula 7. wherein R1 and R3 each represent an aliphatic, alicyclic or aromatic hydrocarbon group, R2 represents a hydrogen atom or an aliphatic, alicyclic or aromatic hydrocarbon group. The fluorescent resin composition according to any of claims 3 to 5, wherein the nitrogen-containing heterocyclic compound is 1,10-phenanthroline or 2/2'-bipyridyl. The fluorescent resin composition according to claim 1, wherein the organic rare earth metal complex is a complex represented by the general formula wherein R represents an aliphatic or aromatic hydrocarbon group, Ln represents a rare earth metal, A represents group -CH=CH-, and n is 0 or 1. 8. The fluorescent resin composition according to claim 1, wherein the complex represented by the organic rare earth metal complex is a general formula and Ln represents a rare earth wherein R1 and R3 each represent an aliphatic, alicyclic or aromatic hydrocarbon group, R2 represents a hydrogen atom or an aliphatic, alicyclic or aromatic hydrocarbon group, metal. 9. The fluorescent resin composition according to any of claims 1 to 8, wherein the ethylene-vinyl acetate copolymer consists of 60 to 90% by mass of ethylene unit and 10 to 40% by mass of vinyl acetate unit. 10. A solar cell module having a structure comprising a front cover, a back cover and a number of units each having a crystalline silicon cell which are integrated between the covers as sealed with a sealing material, wherein the sealing material between the silicon cell contains the fluorescent resin of claims 1 to 9. front cover and the crystalline composition according to any 15 14 MAY 2009 11. The solar cell module according to claim 10, wherein the content of the rare earth metal complex in the fluorescent resin composition is 0.05 to 1% by mass. 12. The solar cell module according to claim the ethylene-vinyl acetate copolymer in mass or more. 0 or 11, wherein the content of the sealing material is 50% by 13. The solar cell module according to any of claims 10 to 12, wherein the front cover is formed of glass. Dated this 11th day of May, 2009. 16 Hi4 MAY 2009

Documents:

960-MUMNP-2009-ABSTRACT(2-4-2012).pdf

960-mumnp-2009-abstract.doc

960-mumnp-2009-abstract.pdf

960-MUMNP-2009-CANCELLED PAGES(2-4-2012).pdf

960-MUMNP-2009-CLAIMS(AMENDED)-(2-4-2012).pdf

960-mumnp-2009-claims.doc

960-mumnp-2009-claims.pdf

960-MUMNP-2009-CORRESPONDENCE(15-6-2009).pdf

960-MUMNP-2009-CORRESPONDENCE(18-11-2009).pdf

960-MUMNP-2009-CORRESPONDENCE(22-2-2010).pdf

960-MUMNP-2009-CORRESPONDENCE(3-12-2009).pdf

960-mumnp-2009-correspondence(8-6-2009).pdf

960-mumnp-2009-correspondence.pdf

960-mumnp-2009-description(complete).doc

960-mumnp-2009-description(complete).pdf

960-mumnp-2009-drawing.pdf

960-mumnp-2009-english translation.pdf

960-MUMNP-2009-EP DOCUMENT(2-4-2012).pdf

960-mumnp-2009-form 1(9-6-2009).pdf

960-mumnp-2009-form 1.pdf

960-mumnp-2009-form 18.pdf

960-mumnp-2009-form 2(title page).pdf

960-mumnp-2009-form 2.doc

960-mumnp-2009-form 2.pdf

960-mumnp-2009-form 3(14-5-2009).pdf

960-MUMNP-2009-FORM 3(18-11-2009).pdf

960-MUMNP-2009-FORM 3(2-4-2012).pdf

960-mumnp-2009-form 3.pdf

960-mumnp-2009-form 5.pdf

960-MUMNP-2009-FORM-PCT-IB-338(3-12-2009).pdf

960-MUMNP-2009-FORM-PCT-IPEA-409(3-12-2009).pdf

960-MUMNP-2009-GENERAL POWER OF ATTORNEY(15-6-2009).pdf

960-mumnp-2009-other.pdf

960-mumnp-2009-pct-ib-306.pdf

960-mumnp-2009-pct-ib-308.pdf

960-mumnp-2009-pct-ib-332.pdf

960-mumnp-2009-pct-isa-210.pdf

960-MUMNP-2009-REPLY TO EXAMINATION REPORT(2-4-2012).pdf

960-MUMNP-2009-SPECIFICATION(AMENDED)-(2-4-2012).pdf

960-MUMNP-2009-SPECIFICATION(MARKED COPY)-(2-4-2012).pdf

960-mumnp-2009-wo international publication report a1.pdf

abstract1.jpg