TW201109380A - Sealing materials for solar cell - Google Patents

Abstract

Provided is a sealing materials for solar cell comprising a thermoplastic polymer having a structure unit derivated from ethylene, and a phosphite compound.

Description

201109380 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a sealing material for a solar cell. [Prior Art] The sealing material for a solar cell is obtained by processing an ethylene-vinyl acetate s-copolymer into a sheet form (Non-Patent Documents 1 and 2). [Non-Patent Document 1] Addition of Solar Cell Sealing Sheet Manufacturing Equipment (June 7, 2005) [Searched on June 30, 2009] <URL: http://jp.mitsuichem.com/release/ 2005/pdf/050 607. pdf> [Non-Patent Document 2] Fuji Electric Co., Ltd., "Current Status and Future Prospects of Solar Cell Related Technology and Markets" (July 11, 2008) P. 169-172 [Summary of the Invention] The sealing material for solar cells is required to be deteriorated or deteriorated even when exposed to light for a long period of time. Under such circumstances, the inventors of the present invention have completed the present invention as a result of review. That is, the present invention provides the following <1> to <14>. <1> A solar cell sealing material comprising: a thermoplastic polymer containing a structural unit derived from ethylene; and a sub-filler compound represented by the formula (I); 3 322169 201109380

Wherein R, R2, R4 and R5 each independently represent a hydrogen atom, an alkyl group having a carbon number of 丄 to 8, an alkyl group having 5 to 8 carbon atoms, an alkyl group having 6 to 12 carbon atoms, and a slave a 7 to 12 aralkyl group or a phenyl group, each independently representing a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and X represents a single bond, a sulfur atom, or a divalent group represented by the formula (M);

I 卞 (1-1) Η (wherein R6 represents a hydrogen atom, an alkyl group having a carbon number of 丨 to 8 or a cycloalkyl group having a carbon number of 5 to 8) Α represents a carbon number of 2 to 8 An alkyl group, or a divalent group represented by the formula (1-2); 7 R • CHO I * (1-2) (wherein R represents a single bond or an alkylene group having 1 to 8 carbon atoms, *结合, the Z-form represents a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an aralkoxy group having 7 to 12 carbon atoms, and the other represents A hydrogen atom or an alkyl group having 1 to 8 carbon atoms]. (2) The sealing material for a solar cell according to the above [1], which is contained in the formula (!) 322169 4 201109380, which is contained in an amount of 〇. 〇〇1 parts by weight to 5 parts by weight with respect to 100 parts by weight of the thermoplastic polymer. Phosphite compound. The sealing material for a solar cell according to the above-mentioned item, wherein the phosphite compound represented by the formula is 6-[3-(3-tert-butyl-4-hydroxy- 1) 5-methylphenyl)propoxy]-2, 4, 8, 10-tetra-tert-butyldibenzo[d,f][l,3,2]dioxaphospholane (6 -[3-(3-t-butyl-4-hydroxy-5-methylphenyl)pr〇p〇xy] -2, 4, 8, l〇-tetra-t-butyldibenz[d, f][1, 3, The sealing material for a solar cell according to any one of the above-mentioned, wherein the solar cell sealing material further comprises the formula (11'). a part of the structure of a piperidine compound;

(In the formula, R represents a hydrogen atom, a group having a carbon number of 1 to 20, or a methoxy group having a carbon number of i to 20, γ represents an oxygen atom or a nitrogen atom). 5. The solar cell sealing material according to <4>, wherein the gnatide compound having the partial structure of the formula (II) is a brittle compound represented by the formula (1));

[wherein R" independently represents a hydrogen atom, a carbon number of 1 to 20, 5 322169 201109380 or an alkoxy group having 1 to 20 carbon atoms, and a represents an alkyl group having a carbon number of 1 to ι〇, or a formula a divalent group as shown in (III);

(wherein R8 each independently represents a hydrogen atom, an alkyl group having a carbon number of 丨 to 2〇, or an alkoxy group having 1 to 20 carbon atoms)]. The solar cell sealing material according to any one of the above-mentioned items, wherein the solar cell sealing material contains a UV absorber. The sealing material for a solar cell according to any one of <1>, wherein the sealing material for a solar cell further contains a crosslinking agent. The sealing material for a solar cell according to the <7>, wherein the crosslinking agent is an organic peroxide. <9> The solar cell sealing material according to <7> or <8>, wherein the solar cell sealing material contains a crosslinking auxiliary agent. The solar cell sealing material according to any one of the above-mentioned items, wherein the solar cell sealing material further contains a decane coupling agent. The solar cell sealing material according to any one of the above-mentioned items, wherein the thermoplastic polymer contains (iv) a structural unit derived from ethylene and a source derived from ethylene acetate. Structure early polymer. 322169 6 201109380 &lt;1> The use of a sub-disk ester compound represented by the formula (I) for improving the durability of a solar cell sealing material;

Wherein R, R, R and R5 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, and carbon a 7 to 12 aralkyl group, or a phenyl group, and R 3 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and X represents a single bond, a sulfur atom, or a divalent group represented by the formula;

RICIH

(wherein R represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms) A represents a stretching group having a number of gorges of 2 to 8, or a formula (1-2) 2 valence; 7 RI cno I (wherein R represents a single bond or a carbon number of 1 to 8, and * represents a bond to the oxygen atom side) Y, Z represents either a hydroxyl group or a carbon number of 1 to An alkyl group of 8, an alkoxy group having a carbon number of 8 or an aralkoxy group having 7 to 12 carbon atoms, and the other represents a gas atom or an alkyl group having 1 to 8 carbon atoms. 322169 7 201109380 &lt;13&gt; - Sealing of a solar cell battery unit (ceu), which is a solar cell according to any one of &lt;1&gt; to &lt;11&gt; a step of laminating a sheet-like molded article; q% using a sealing material sheet-like molded article bonded to a battery unit for a solar cell; and the obtained step or both sides &lt;14&gt; a molded article, which is &lt;1&gt; To any of &lt;ii&gt; - the pool sealing material is heated and formed. Solar Power Planted Embodiments Hereinafter, the present invention will be described in detail. In the present invention, the term "durability" refers to a property of using a sub-filled vinegar compound represented by the above formula (1) to improve the enthalpy property even if it is deteriorated and deteriorated over a long period of time (hereinafter: 1 Niuru By the compound (1)), for example, the light-shielding-inhibiting-labeled glass-based battery system has a configuration in which a substrate is used as a surface-side edge-preserving member and a base (b: ckseat) as an inner-side member: In the meantime, the solar cell battery such as ruthenium crystal is sealed to the W seal by the sealing material. The solar cell of the present invention is used for the surface of the battery unit, and can be used as a sealing material on the surface side. In addition, it can also be used as a member constituting a base. The sealing material for solar cells of the moon contains: a thermoplastic flat containing a structure derived from ethylene, and a compound (hereinafter, sometimes It is also labeled as a vinyl polymer. The vinyl polymer can be exemplified by a structural unit derived from ethylene and derived from propylene, 1 ·~

, pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-癸, 1 I elecene, 1_12 women, 1-10 322169 201109380 Triene, 1-tetradecene, 1-pentadecene, anthracene-hexadecene, hexadecene, octadecene, 1-nonene, 1-hexene, etc. a copolymer of structural units of an α-olefin; a copolymer comprising a structural unit derived from ethylene and a structural unit derived from an epoxy group-containing monomer such as glycidyl methacrylate; and a structural unit derived from ethylene a copolymer of structural units derived from α,anthracene-unsaturated carboxylic acids; containing structural units derived from ethylene and/or propylene and derived from vinyl acetate, vinyl propionate, vinyl butyrate, vinyl versatate ( Vinyl versatate) A copolymer of structural units such as a vinyl ester of a carboxylic acid having 2 to 5 carbon atoms. Examples of the α,/3 -unsaturated hydrocarbons include α,/3-unsaturated carboxylic acids such as propyl benzoic acid and methyl acrylate; and sodium, potassium and calcium of the above α, fluorene-unsaturated carboxylic acids. a salt, such as a salt of the above α,/3-unsaturated carboxylic acid; maleic anhydride, itaconic anhydride, citraconic anhydride, nadic anhydride, guanidinic anhydride, Unsaturated carboxylic anhydride such as HIMIC Anhydride; decyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, tert-butyl acrylate, isobutyl acrylate, sulfhydryl Methyl methyl acrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, isobutyl methacrylate, etc. Acrylic or mercaptoacrylic acid with a ketone having a carbon number of 1 to 12. Specific examples of the ethylene-based polymer include linear low-density polyethylene (LLDPE, which contains a structural unit derived from 1-butene), and ethylene-propylene rubber (EPR). 9 322169 201109380 A copolymer having a structural unit derived from ethylene and a structural unit derived from an α-olefin having 3 or more carbon atoms; a copolymer of ethylene and glycidyl methacrylate containing a structural unit derived from ethylene and a copolymer derived from a structural unit of an epoxy group-containing monomer; an ethylene-methyl methacrylate copolymer (ΕΜΑ), an ethylene/ethyl acrylate copolymer (ΕΕΑ), and the like, and a structural unit derived from ethylene a copolymer of a structural unit of a β-unsaturated carboxylic acid ester; a copolymer of a structural unit derived from ethylene and a structural unit derived from a vinyl ester of a carboxylic acid, such as ethylene·vinyl acetate copolymer (EVA); • copolymers of ethylene and unsaturated carboxylic anhydride such as maleic anhydride copolymer; ethylene/acrylic acid copolymer (EAA), ethylene/methacrylic acid copolymer (EMMA), etc. a copolymer of a structural unit derived from an unsaturated acid; an ionomer resin belonging to a resin obtained by crosslinking a molecule of an ethylene-mercaptoacrylic acid copolymer with a metal ion; The copolymer of a dilute structural unit and a structural unit derived from an unsaturated carboxylic acid further contains a metal salt or the like. Preferred examples of the vinyl polymer include a copolymer containing a structural unit derived from ethylene and a structural unit derived from an α,β-unsaturated carboxylic acid ester, a structural unit derived from ethylene and a carboxylic acid-derived compound. The copolymer of the structural unit of the vinyl ester may, for example, be a copolymer containing a structural unit derived from the acetyl group and a structural unit derived from the ethical group. a copolymer of a structural unit and a structural unit derived from ethyl acetate. The content of the structural unit derived from ethylene in the ethylene-based polymer is preferably in the range of 50 to 95% by weight, more preferably in the range of 55 to 90% by weight. 10 322169 201109380 The melt flow rate (Melt fl〇wrate, ie MFR) of the vinyl polymer is preferably in the range of 4 to 10 g/10 min, in the range of 5 to 5 g/i min. Preferably, the range of 6 to 2 〇 § / 1 〇 minutes is more preferably, and the range of 6 to 10 g / l 〇 minutes is particularly preferred. Further, the MFR is determined by the eight method under the conditions of temperature 19 (rc and load 21 (10) according to K7210-1995'. The vinyl polymer is derived from the structural unit derived from ethylene and derived from other orders.

The structure of the body is preferably a block polymer or a recording polymer, and a random polymer is more preferable. The method for producing the ethylene-based polymer is, for example, a method in which ethylene is brought into contact with another monomer in the presence of a catalyst such as a radical polymerization catalyst or a polymerization catalyst, and the polymerization is carried out. The catalyst may, for example, be a peroxide catalyst, a Ziegler-Natta catalyst, a metallocene catalyst, etc., and the polymerization method may be, for example, a solution polymerization method or a slurry ( Slurry) polymerization, high pressure ion polymerization, high pressure radical polymerization, and gas phase polymerization. The sealing material for a solar cell of the present invention contains the compound (I). In the above formula (1), the carbon number shown by Rm R5! The alkyl group to 8 may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl first butyl group, a second butyl group, a third fluorenyl group, an isooctyl group or the like. Trioctyl, 2-ethylhexyl. The cycloalkyl group having 5 to 8 carbon atoms may, for example, be a cyclopentyl group, a cyclohexyl group, a cycloheptyl group or a % octyl group. The alkylcycloalkyl group having 6 to 12 carbon atoms may, for example, be a pentyl group, a benzylcyclohexyl group or a benzyl-4-isopropylcyclohexyl group. Carbon number 7 322169 11 201109380 to 12; the base group can be exemplified by benzyl (benZyi), α-mercaptobenzyl, "α-dimercaptobenzyl. 'R1, R2 and R4 are each independently carbon Preferably, the alkyl group having 8 to 8 carbon atoms, the cycloalkyl group having 5 to 8 carbon atoms or the alkylcycloalkyl group having 6 to 12 carbon atoms, and the R1 &amp; R4 groups are independently a third butyl group, a third pentyl group, More preferably, a third alkyl group such as a third alkyl group, a cyclohexyl group or a dicyclohexyl group. The R 2 groups are independently a fluorenyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a second group. The alkyl group having 1 to 5 carbon atoms such as a butyl group, a second butyl group and a second pentyl group is preferred, and more preferably a fluorenyl group, a second butyl group or a second pentyl group. , n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, tert-butyl, third &quot;pentyl and other carbon number 1 to 5 of 6 or hydrogen atom is preferred, The base or the nitrogen atom is more preferably. The alkyl group having 1 to 8 carbon atoms represented by R3 may, for example, be an alkyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a second butyl group. , tert-butyl, third pentyl, isooctyl, third octyl, 2_B a hexyl group having a carbon number of 甲基 to 5, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-butyl, or pentyl, or The hydrogen atom is preferably a T group or a hydrogen atom. X represents a single bond, a sulfur atom or a divalent group represented by the above formula (1-1). In the formula (1-1), R6 is represented. The alkyl group having 1 to 8 carbon atoms may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a second butyl group, a third butyl group, a third fluorenyl group or an isooctyl group. Examples of the cycloalkyl group having a carbon number of 5 to 8 in the group of the third, octyl group and the 2-octyl group are, for example, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group or a cyclooctyl group. The R6 group is a methyl group, an ethyl group or a n-propyl group. Base, isopropyl, n-butyl, isobutyl 322169 12 201109380 The number of rabbits such as 1 or 5, or the nitrogen source, is preferably a single bond or a divalent group represented by the formula (i) 'It is more preferable to use a single bond. A represents a diasterium group having a carbon number of 2 to 8 or a divalent group represented by the above formula (1_2) but preferably a stretching group having a carbon number of 2 to 8. Bases such as ethylene, propyl, butyl, pentamethylene, and hexa The benzyl group, the octamethyl group, the 2,2-diyl group, the q 3 propyl group, etc. are preferably a propyl group. The divalent group represented by the formula (1 - 2) is bonded to an oxygen atom and a benzene nucleus. And * represents a combination with an oxygen atom. The alkylene group having 1 to 8 carbon atoms represented by R? may, for example, be a methylene group, an exoethyl group, a propyl group, a butyl group, a penta-indenyl group or a hexamethylene group. , octamethyl, 2 2 dimethyl _13 _ propyl, etc.. The R 7 is preferably a single bond or an ethyl group. γ, z is either a hydroxy group or an alkyl group having a carbon number of 8 to 8 The alkoxy group having a carbon number of i to 8 or an aralkyloxy group having a carbon number of 7 to 12, and the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Here, the alkyl group having a carbon number of 丨 to 8 may, for example, be a methyl 'ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a second butyl group, a third butyl group, or a third pentyl group. , isooctyl, trioctyl, 2-ethylhexyl. Examples of the alkoxy group having 1 to 8 carbon atoms include, for example, a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, a second butoxy group, and a third butoxy group. Base, third pentyloxy, isooctyloxy, third octyloxy, 2-ethylhexyloxy. Examples of the aralkyloxy group having 7 to 12 carbon atoms include a benzyloxy group, an α-methylbenzyloxy group, and an α,dimethylbenzyloxy group. In the sulphite g compound represented by the formula (I), a special example is: y and R are a second alkyl group, a cyclohexyl group or a 1-methylcyclohexyl group, and R 2 is a carbon number of 1 to 5 The base 'R5 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R3 is a hydrogen atom or 322169 13 201109380 an alkyl group having 1 to 5 carbon atoms, X is a single bond, and A is an alkyl group having 2 to 8 carbon atoms. . In the sealing material for a solar cell of the present invention, a compound may be used as the compound (anthracene), or two or more compounds may be used in combination. The compound (I) can be exemplified by 6-[3-(3-t-butyl-4-transyl-5-mercaptophenyl)propoxy]-2, 4, 8, 10-tetra- Tributyldibenzo[d,f][1,3,2]dioxane-filled hexanthene["§11111丨;1丨261*(registered trademark)〇?" by Sumitomo Chemical Sold on the market], 2, 1〇_二曱基__4, 8_二_ Third butyl-6-[3-(3,5-di-t-butyl- 4-hydroxyphenyl) Propyloxy]-12H-dibenzo[d,g][l,3,2]dioxaphospholane (2, 10-dimethyl-4, 8-di-t-butyl-6- [3-(3, 5-di-t-butyl-4-hydroxyphenyl)prop〇xy]-l2H-dibenzo[d, g][l,3,2]d ioxaphosphocine), 2,4,8, 10- Tetra-tert-butyl-6-[3_(3,5-a-''t-butyl-4-hydroxyphenyl)propoxy]dibenzo[d,f][i,3,2]dioxo Heterophosphorane, 2, 4, 8, 10-tetra-tripentyl_6_[3-(3,5-di-t-butyl-4-hydroxyphenyl)propoxy]&lt; 2 monomethyl μ2h_dibenzo[d,g] [ 1,3, 2]-oxazepine heterocyclic octyl, 2,1 fluorenyl- 4,8-di- 2nd butyl- 6-[3-(3,5-di-t-butyl-4-ylhydroxyphenyl)propenyloxy]-12H-dibenzo[d,g][l,3,2]dioxaphosphorus Heterocyclic octane, 2' 4, 8, 10-tetra-tripentyl_6_[3_(3,5-di-t-butyl-4-hydroxyphenyl)propan(4-)yl]-12-methyl -12H-dibenzo-3, 2]dioxanthene, 2,4,8,1G-tetra-tert-butyl_6_[3_(3,5-di-t-butyl-4 - minus phenyl) (tetra)oxy]-dibenzo[^[^,^dioxaphospholane, 2,10-diindenyl_4 8_di-t-butyl _6_(3 5_ Di-t-butyl-4-alkyl hydroxy)-12H_dibenzo[dg][13 2] 322169 14 201109380 &quot;f oxaweixin H 4, 8, 10-tetra- Tributyl-6-(3,5-di-first butyl 4-benzylbenzyloxy)-12-mercaptodibenzo[d,g] • [1,3'2]dioxaphosphorane Cyclooctane, 2,1〇-dimercapto- 4,8-two-third-buty-yl-j-,[3-(3-methyl-4-hydroxy-5-tert-butylphenyl) Propoxybu 12H-benzo[d,g][i,3,2]dioxaphospholane, 2, 4, 8, 1〇_tetra-tert-butyl-6-[3 -(3,5-di-t-butyl-4-hydroxyphenyl)propoxy]12H-monobenzo[tg]!^,3,2]dioxaphosphazepane, 2, 1 〇_ monoethyl-4, 8-di-t-butyl_6_[3_(3,5-di-t-butyl-4-ylhydroxy)propyloxy]- 12H-di-p-[d,g][i,3,2]dioxaphospholane, 2,4,8, 10-tetra-tert-butyl_6_[2 2-dimethyl- 3_(3_Tert-butyl-4-carbyl-5-fluorenylphenyl)propoxydibenzo[mountain fm,3,2] dioxaphosphanee, etc., to 6-[ 3-(3-Tertibutyl-4-hydroxy-5-methylphenyl)propoxy]-2, 4, 8, 10-tetra-tert-butyldibenzo[d,f] [1 '3,2] dioxaphosphanane is preferred. The compound (I) can be produced, for example, according to the method described in JP-A-H07-273494. The sealing material for a solar cell of the present invention preferably contains 0.001 to 5 parts by weight of the compound (1), more preferably 〇. 〇丨 to 3 parts by weight, based on 100 parts by weight of the ethylene-based polymer. More preferably, it contains 1 to 2 parts by weight of hydrazine, and particularly preferably contains 0.03 to 5.00 parts by weight. The content of the compound (1) tends to be suppressed in the above range, that is, the light transmittance of the obtained solar cell sealing material is suppressed. The sealing material for a solar cell of the present invention preferably comprises a ketone compound having a partial structure represented by the formula (π,) (hereinafter, it may be labeled only as 322169 15 201109380 "piperidin-based compound"):

(wherein R8 represents a hydrogen atom, a carbon number of 1 to 20, or a carbon number! to 20 alkoxy group, and Y represents an oxygen atom or a nitrogen atom). R8 in the formula (1)) may, for example, be a gas atom, a methyl group, an ethyl group, an isopropyl group, a n-propyl group, a tert-butyl group, an isobutyl group, a n-butyl group, a methoxy group, an ethoxy group or an isopropoxy group. Base, n-propoxy, tert-butoxy, isobutoxy, n-butoxy and the like. The hydrogen atom, the alkyl group having 1 to 10 carbon atoms, or the alkoxy group having 1 to 10 carbon atoms is preferred, and a hydrogen atom is more preferred. The piperidine-based compound may, for example, be a compound of the formula (II) (hereinafter, (d) is also referred to as a compound (II))

Wherein R 8 each independently represents a hydrogen atom, an alkyl group having a carbon number of 丨 to 20, or an alkoxy group having a carbon number of 1 to 20, and A represents a C 1 to alkyl group, or a formula (III) 2 valence base 16 322169 201109380

Re (wherein R8 independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms)]; 2-(3,5-di-t-butyl-4) -hydroxybenzyl)-2-butylmalonic acid bis(1,2,2,6,6-pentamethyl-4-piperidyl), 2,2-bis(3, 5-di- Tributyl-4-hydroxybenzyl)-2-butylmalonic acid bis(i-acryloyl 2, 2, 6, 6-tetradecyl-4-pyridine); 2, 2, 6, 6-tetramethyl-4-0-butyl acrylate, 4-[3-(3, 5-a 2-butyl-4-phenylphenyl)propenyloxy] _丨_[2_(3_(3, Di-tert-butyl-4-hydroxyphenyl)propenyloxy)ethyl]_2,2,6,6-tetramethylpiperidine, 2-methyl- 2-(2, 2, 6, 6-tetramethyl-4-piperidinyl)amino-indole-(2,2,6,6-tetradecyl-4-0-bottomyl)propanamine;肆(1,2,2,6,6-pentamethyl-4decapine)], 2, 3, butyl sulphate, 1,2,3,4-butanetetracarboxylic acid and ^^^ Mixed esterified product of pentamethyl-piperidinol and 1-tridecanoyl, butane tetrakis and 2, 2, 6, 6-tetramethyl-4-ol and tridecyl alcohol Mixed vinegar, 1,2,3,4-butane tetracarboxylic acid with ^, ^^5-yl-piperidol and 3, 9-bis(2-carbyl-1 1 -dimethyl dimethyl ketone), a T-ethyl group 2, 4, 8, 10-tetraoxa 322169 17 201109380 snail [5. 5] eleven Mixing g, 1,2,3,4-butylidin tetracarboxylic acid with 2, 2,6,6-tetramethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1 -didecylethyl)-2, 4, 8, 10-tetraoxaspiro[5. 5]Η-mixed esterified product, dimethyl benzoate and 1-(2-hydroxyethyl)_4 Polycondensation of monohydroxy-2,2,6,6-tetradecyloxyl, poly[(6-(Ν-morpholinyl)-1,3,5-tris-2, 4-diyl) ((2, 2, 6, 6-tetramethyl-4-piperidinyl)imido)hexamethylene ((2, 2, 6, 6-tetradecyl-4-piperidinyl) Amino)], poly[(6-(1,1,3,3,4-tetradecylbutyl)-1,3, 5-trinyl-2,4-diyl) ((2, 2, 6, 6-tetramethyl-4-bryridinyl)imido)hexamethylene ((2, 2, 6, 6-tetradecyl-4-phenylpiperazinyl)imido)]; poly[{6 -(1,1,3,3-tetramethylbutyl)amino-1,3,5-trianth-2,4-diyl} {(2, 2, 6, 6-tetramethyl-4) -piperidinyl)imino}hexamethylene {(2, 2, 6, 6-tetramethyl-4-piperidinyl)imido}], dimethyl succinate-1-(2- Ethyl) 4-hydroxy-2, 2, 6, Yue-tetramethyl piperidine polycondensates and the like. As the piperidine-based compound, a single compound may be used, or two or more compounds may be used in combination. The piperidine-based compound is preferably a compound (Π). The compound (II) may, for example, be bis(2,2,6,6-tetramethyl-4-teridinyl) sebacate or bis(indenyl-octyloxy-2, 2, 6, sebacate. 6-tetradecyl-4-piperidinyl) vinegar, bis(Ν-benzyloxy-2, 2,6,6-tetradecyl-4-piperidinyl) sebacate, sebacic acid (Ν-cyclohexyloxy-2, 2, 6, 6-tetradecyl-4-piperidinyl) ester, azelaic acid bis(1,2,2,6,6-pentamethyl-4-piperidin Pyridyl) ester, bis(1-ethyl-2, 2,6,6-tetradecyl-4-piperidyl) sebacate, bis(1-n-butyl-2, 2, azelaic acid 6, 6-tetradecyl-4-piperidinyl), bis(1-octyl-2, 2,6,6-tetradecyl-4-piperidyl) sebacate, sebacic acid (1-Ethoxy 18 322169 1 i Ming 80, 2, 6, 6 ~ Tetra-~2'2, 6, 6, Tetramethyl, 嚷 ° 定) vinegar, azelaic acid bis(1-n-butoxy Base group) 1,2, 6, 6, four Ί mother bite base) vinegar, azelaic acid bis (1-(octyloxy compound; phenyl ~ piperidinyl) ester and other piperidine containing azelaic acid Double (1 2 : yl~2,2,6, '6^6', methyl-4^) vinegar, adipic acid bis (Bu~2'2,6,6, Sijiameichang 4 psi Pyridyl) ester, bis(1-n-butyl'2,6,6 adipate 4 ^ L base) ester, adipic acid bis (1 - octyl, 2, 2, 6, 6, tetracentric 4 ~ bite base) vinegar, adipic acid bis (1-ethoxy, 2, 2, 6,6, four ^ ~ Niang bite) ester, adipic acid bis(1-n-butoxy)~2, with a four-filament) vinegar, adipic acid double (b (octyloxy compound; ▲ 4 -piperidinyl) ester and the like piperidine-based pericarboxylic acid bis (1,2,2 "ethyl, 2,2,6,6, tetra-p-yl 4~ Niangniu) vinegar containing adipic acid Double (1-, 2, 2, 6, 6~ four soils... Chen gnach) vinegar, bismuth acid (1_n-butyl, 2, 2, 6, 6, four ^'chen bite) vinegar, A little bit of succinct (Buxinji ~ 2, 2, 6, 6 ~ four ^ cool, but a small acid (b ethoxy '2, 2, 6 β chen) base, amber 酴馐 η: ~ Butane tetradecanoic acid vinegar, UM-butane _ 肆〇: B. t-base) Witch AA b, 6-tetramethylpiperidinyl), hydrazine, 2'3,4-butane Barium tetracarboxylate (]__正丁美四尹基+piperidinyl) vinegar, 1,2,3,4-butane tetracarboxylic acid di-di-2, 2, 6, 6-tetramethyl- 4-piperidinyl) ester soil, 2' 3, 4-butane tetracarboxylic acid edge material ') Knows that it contains amber bite, /1.... 322169 19 201109 380 (B-methoxy-2, 2, 6, 6-tetramethyl- κ)-methyl-4-piperidinyl), 1,2,3,4-butanetetracarboxylic acid hydrazine (1-ethoxyl) Base-2 2 R m ^ 'A 6, 6-tetradecyl-4-piperidinyl), 1,2,3, 4-butanetetramine (Bu-n-butoxy-2, &amp;&amp; 6) _Tetramethyl+ 派基基)§,1,2'3,4~丁丁崎酸肆(Bu(octyloxy)_2,2,6,6_tetradecyl 4piperidinyl)酉曰, etc. A piperidine compound containing 12, 3, 4-butanetetracarboxylic acid or the like. It is preferable to use a mother bite compound containing azelaic acid, a bite line compound containing a succinic acid (10), and a bite line compound containing 1,2,3,4-butane 4, and azelaic acid double (1, 2,2,6,6-pentamethyl-4-(tetra)yl), bis(1,2,2,6' 6-pentamethyl-4-piperidinyl) sebacate and sebacic acid a mixture of (mercapto-1' 2,2' 6' 6-pentamethyl-4-piperidinyl) ester, azelaic acid (methyl-4-piperidyl) ester, and sebacic acid bis (2, 2, 6, 6_Tetramethyl_4_piperidinyl) bis[1-(octyloxy)-2, 2,6,6-tetradecyl-4-piperidinyl] phthalate And bis(1,2,2,6,6-pentamethyl-4-piperidinyl) succinate, preferably bis(1,2,2,6,6-pentalyl) -4- ketone base ester, azelaic acid bis(1,2,2,6,6-pentamethyl-4-bringe) ester and azelaic acid (mercapto-1,2, 2, 6 , 6-pentamethyl-4-β Chen gnathyl) g-mixture, succinic acid self-acid double (1,2, 2, 6, 6-pentamethyl-4-bendyl) ester, and bismuth The acid bis(2,2,6,6-tetramethyl-4-pyrimidinyl) ester is more preferred. With bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate and bis(1,2,2,6,6-pentamethyl-4-piperate a bite base) a mixture of ester and sebacic acid (methyl-1,2,2,6,6-pentamethyl-4-bunkyl) ester, azelaic acid bis (2, 2, 6, 6-four Mercapto-4-piperidinyl) ester is particularly preferred. When the sealing material for a solar cell of the present invention contains a piperidine-based compound, the content thereof is from 0. 〇〇1 to 5, 20 322169, 201109380, and the amount of damage is preferably 〇. 〇5. It is preferably from 3 parts by weight to 2 parts by weight, more preferably from 3 parts by weight to 2 parts by weight. In addition to the compound (I), when the vinylidene polymer is contained in the above-mentioned range of the piperidine-based compound, the light transmittance of the obtained solar cell sealing material is further suppressed. . The solar cell sealing material may also contain a UV absorber. The ultraviolet absorber may, for example, be an oxal ic acid diani 1 ide ultraviolet absorber as shown in the formula (IV).

(wherein R9 to R14 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having a carbon number of 1 to 10, and R1S represents a hydrogen atom, a methyl group or an ethyl group. A benzophenone-based ultraviolet absorber such as a compound represented by the formula (V) (hereinafter sometimes referred to as a compound (v))

(wherein 'Ru, heart and heart independently represent a hydrogen atom, a halogen atom, or a hydroxyl group

322169 21 201109380 A hydrogen atom of a benzyl group, an alkoxy group and a hydroxyalkyl group may be substituted by an alkyl group having 1 to 10 carbon atoms, respectively; a benzotriazole ultraviolet compound having a partial structure represented by the formula (VI); Absorbent

(wherein R19 represents a hydrogen atom or a tooth atom); a compound represented by the formula (VII) (hereinafter, sometimes also referred to as a compound (VII))

(VII) (wherein R20 represents a hydroxyl group, 1^21 represents a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms or a hydroxyalkyl group having 1 to 10 carbon atoms, and R22 to R23 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, a phenyl group, a benzyl group, an alkoxy group having 1 to 10 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, etc. an alkyl group, a phenyl group, a benzyl group, an alkoxy group And the hydrogen atom of the hydroxyalkyl group may also be substituted by an alkyl group having 1 to 10 carbon atoms; salic acid (sal icy lie acid) is a UV absorber; cyanopropionate 22 322169 201109380 ultraviolet absorber or the like. Specific examples of the ethylenediamine-based ultraviolet absorber include, for example, N-(2-methylphenyl)-N'-(2-methoxyphenyl)ethylenediamine, N_(2-ethylbenzene). ))-Ν'-(2-ethoxyphenyl)ethylenediamine, N_(2_t-butylphenyl)-N-(2-t-butoxyphenyl)glyoxime, 1^_(5_Tertiary-2-_2-methoxyphenyl)-N'-(4-t-butyl-2-methylphenyl)ethylenediamine, N-(5-Third 2-ylethoxyphenyl)-N,-(4-t-butyl-2-(ethylphenyl)glyoxime, N-(5-t-butyl-2-butadiene oxide Phenyl)-N-(2,4-di-t-butylphenyl)glyoxime, N,N,_bis(2-methylphenyl)glyoxime, N,Ν' - Bis(2-ethylphenyl)glyoxime, N,N,-bis(2-t-butylthene; p-phenyl)glyoxime, anthracene, Ν' _bis(2_decyloxy Phenyl) ethanediamine, hydrazine, Ν' _ bis (2-ethoxy phenyl) ethanediamine, hydrazine, Ν' _ bis (2-tert-butoxyphenyl) ethanediamine Ν_(2_ethylphenyl)-indole,-(2-ethoxyphenyl)glyoxime and ν-(5-t-butyl-2-ethoxyphenyl)-oxime -(4- Tributyl-2-ethylphenyl) Amides preferably ethylene. Specific examples of the dimercaptoketone-based ultraviolet absorber include, for example, 2, 2,-dihydroxy~4,4'-di(hydroxyindenyl)dibenzophenone, 2, 2, _dihydroxy-4, 4' 1-(2-hydroxyethyl)dibenzophenone, 2, 2, _dihydroxy-3,3,-dimethoxy~5' 5'-di(hydroxyindenyl)benzophenone, 2, 2,-Dihydroxy-3,3,-dimethoxyoxy~5' 5'-bis(2-hydroxyethyl)dibenzophenone, 2, 2, __dihydroxy_3, 3, _ Hydroxymethyl)-5,5'-dimethoxy benzophenone, 2, 2'-dihydroxy~3,3'-bis(2-hydroxyethyl)_5,5,-dimethoxy 2 Phenyl fluorenone, 2,2-dierythryl~4,4-didecyloxydibenzophenone, 2-hydroxy-4-n-octyloxydibenzopyrene, 2~-based 4-anthracene Dibenzophenone, 2-hydroxy-4-methoxy-2,-carboxy 23 322169 201109380 base dibenzophenone, 2-hydroxy-4-n-dodecyl alkoxybenzophenone (2-hydroxy -4-n-dodecyloxy benzophenone), 2-hydroxy-4-n-octadecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone' 2-hydroxy-5-chlorodiphenyl Anthrone and the like. Specific examples of the stray triazole-based ultraviolet absorber include, for example, 2-[2,-hydroxy-5'-(hydroxymethyl)phenyl]-2H-benzotriazole, 2-[2,-hydroxy-5. '-(2-Hydroxyethyl) phenyl]-211-benzotriazole, 2-[2'-hydroxy-(3-propylpropyl)phenyl]-2H- benzotrim», 2 -[2'-carbamic-3'-methyl-5'-(hydroxyindenyl)phenyl]-2H-benzotriazole, 2-[2,-hydroxy-3'-mercapto-5'- (2-hydroxyethyl)phenyl]-211-benzotriazole, 2-[2,-hydroxy-3'-mercapto-5'-(3-hydroxypropyl)phenyl]-2H-benzo Triazole, 2-[2,-hydroxy-3'-tert-butyl-5'-(hydroxyindenyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-3'- Tributyl-5'-(2-hydroxyethyl)phenyl]-2H- benzotriazole, 2-[2'-hydroxy-3'-tert-butyl-5,-(2-hydroxyethyl )]-5-gas-2H-benzotriazole, 2-[2'-hydroxy-3'-tert-butyl_5, _(3_propylidene)phenyl]-2H-benzo Tris-β, 2-[2'-trans-yl-3'-t-octyl-5'-(hydroxymethyl)phenyl]-2indole-benzotriazole, 2-[2,-trans-base-3 ,_Third-octyl-5-(2-transethylethyl)phenyl]-2Η-benzotriazine, 2-[2'- -3'-Third-octyl-5'-(3-hydroxypropyl)phenyl]-2-indole-benzotriazole, etc., or 2,2'-methylenebis[6-(211-benzo) Triazol-2_yl)_4-(hydroxyindenyl)phenol], 2,2'-methylenebis[6-(211-benzotriazol-2-yl)_4_(2_hydroxy^ethyl) Phenol], 2, 2'-fluorenylene bis[6-(5-chloro-2indole-benzotriazol-2-yl)-4-(2-hydroxyethyl)phenol], 2,2'- Methyl bis[6-(5-bromo-211-benzotriazol-2-yl)-4-(2-hydroxyethyl)phenol], 2, 2,-fluorenylene double 322169 24 201109380 [6- (2H-benzotriazol-2-yl)-4-(3-hydroxypropyl)phenol], 2, 2'-methylenebis[6-(5-chloro-2}]-benzotrisene -2-yl)-4-(3-propylpropyl)-, 2, 2'-methylenebis[6-(5-bromo-2H-benzotriazol-2-yl)-4 -(3-hydroxypropyl)phenol], 2, 2'-fluorenylene bis[6-(2H-benzotriazol-2-yl)-4-(4-hydroxybutyl)phenol], 2, 2'-Amidino bis[6-(5-Gas-2H-benzotriazol-2-yl)-4-(4-hydroxybutyl)phenol], 2, 2'-Amidinoyl double [6 -(5-bromo-2H- benzotriazol-2-yl)-4-(4-hydroxybutyl)phenol], 3, 3-{2, 2,-bis[6-(2H- stupid Salhr-2-yl)-1-yl-4-yl-2-(2-ylethylethyl)phenyl]} Propylene, 2, 2-{2, 2'-bis[6-(2H-benzotrien. Sodium-2-yl)-1-yl-4-(2-ylethylethyl)phenyl]}butane, 2,2,-oxybis[6-(2Η-benzotriazole-2- 4-(2-hydroxyethyl)phenol], 2, 2'-bis[6-(2Η-benzotriazol-2-yl)-4-(2-hydroxyethyl)phenol]thioether , 2, 2,-bis[6-(2Η-benzotriazol-2-yl)-4-(2-hydroxyethyl)phenol] sulfoxide, 2, 2,-bis[6-(2Η-benzene) And triazol-2-yl)-4-(2-hydroxyethyl)phenol]sulfone, 2, 2,-bis[6-(2Η- benzotris-2-yl)-4-(2-hydroxyl Ethyl)phenol]amine and the like. Specific examples of the three-pigmented ultraviolet absorber include, for example, 2-(2-hydroxy 4 via hydrazinyl)-4,6-diphenyl-S-tri[I, 2-(2-amino-4) -transmethylmethylphenyl)-4,6-bis(2,4-dimethylphenyl)-s-trin, 2-[2-hydroxy-4-(2-hydroxyethyl)phenyl] -4,6-diphenyl-s-triphthyl, 2-[2-hydroxy-4-(2-hydroxyethyl)phenyl]-4,6-bis(2,4-didecyl) -s-triterpene, 2-[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-4,6-diphenyl-s_trimorphine, 2-[2-hydroxy-4-(2 -hydroxyethoxy)phenyl]-4,6-bis(2,4-dimercaptophenyl)-s-triphthyl, 2-[2-hydroxy-4-(3-hydroxypropyl)phenyl ]-4,6-diphenyl-S-triazine, 2-[2-hydroxy-4-(3-hydroxypropyl) stupid 322169 25 201109380 base]~4, 6-bis (2, 4-di Phenyl)-s-triterpene, 2-[2-hydroxy-4-yl-(3-hydroxypropyloxy)phenyl]-4,6-diphenyl-s-triterpene, 2-[2-hydroxy-4 -(3-hydroxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)s-triazine, 2-[2-hydroxy-4-(4-hydroxybutyl) Phenyl]-4,6-diphenyl-s-trisole, 2-[2-hydroxy-4-(4-hydroxybutyl)phenyl]-4,6-bis(2,4-didecyl) Stupid base)- S-trimorphine, 2-[2-hydroxy-4-(4-hydroxybutoxy)phenyl]-4,6-diphenyl-s~trisole, 2-[2-hydroxy-4-(4) -hydroxybutoxy)phenyl]_4,6-bis(2,4-diphenylphenyl)-s-trin, 2-(2-hydroxy-4-hydroxyindolyl)-4,6 - bis(2-hydroxy-4-methylphenyl)-s-three tillage, 2-mono[2-hydroxy-4-(2-hydroxyethyl)phenyl]-4,6-bis(2-hydroxy- 4-methylphenyl)-s-triphthyl, 2-[2-hydroxy-4-(2-hydroxyethoxy)phenyl]_4,6-bis(2-hydroxy-4-methylphenyl) -S-triterpene, 2-[2-hydroxy-4-(3-hydroxypropyl)phenyl]-4,6-bis(2-hydroxy-4-methylphenyl)-s-triterpene, 2 —[2-hydroxy~4-(3-pyridyloxy)phenyl]-4,6-bis(2-pyridyl-4-indolylphenyl)-s-triterpene, 2-[4, 6-bis(2,4-didecylphenyl)-5-(octyloxy)phenol, 2-(4,6-diphenyl-1,3,5-trian-2-yl)- 5-[(hexyl)oxy]- aliquot. Specific examples of the salicylic acid-based ultraviolet absorber include phenyl sulphate, p-t-butylphenyl sulphate, p-octyl phenyl sulphate Specific examples of the lanthanum cyanoacrylate ultraviolet absorber include, for example, 2-ethylhexyl-2-cyano-3, 3 - diphenylacrylate, ethyl cyano _3, stupid 3'_ two acrylate groups. As the external absorbent, a single compound may be used, or two or more compounds may be used in combination. The UV absorber is 2-hydroxy-4-in-octyloxydiphenyl 322169 26 201109380 anthrone, 2-(3-tert-butyl-2-hydroxy-5-mercaptophenyl)-5-gas benzo The triazole is preferred, and 2-carbyl-4-n-octyloxydibenzophenone is more preferred. The sealing material for a solar cell of the present invention preferably contains 0 to 5 parts by weight of the ultraviolet absorber, and more preferably 0.005 to 3 parts by weight, based on 100 parts by weight of the acetonitrile polymer. Q5 to 3 parts by weight are particularly preferred. The sealing material for a solar cell of the present invention may further contain a crosslinking agent. Examples of the crosslinking agent include those which decompose at a temperature higher than i 〇〇 °c to generate a radical. The decomposition temperature at which the half-life of the crosslinking agent becomes 10 hours is preferably 7 or more. When the solar cell is produced, the crosslinking agent can be crosslinked to seal the battery cells in the solar cell. The organic peroxide is preferably, for example, 2, 5-dihydroperoxide, 2, 5-dimercapto-2, 5-di(t-butylperoxy) Alkane, 3-di-tert-butyl peroxide; t-dicumyl peroxide, 2, 5-dimercapto-2, 5-bis(t-butyl Peroxidation) hexane, 2,5-dimercapto-2, 5-di(t-butylperoxy)hexyne, 3,5-dimethyl-2, 5-(t-butylperoxy) Hexane, 2,5-dimercapto-2, 5-di-(t-butylperoxy)hexane-3,4,4'-bis(t-butylperoxy)-isopropylbenzene, Dicumyl peroxide, tert-butyl cumyl peroxide, α, α'-bis(t-butylperoxyisopropyl)benzene, α,α,-double (t-butyl peroxy) diisopropylbenzene, n-butyl-4,4-bis(t-butylperoxy)butane, 2,2-double Tertiary butyl peroxy)butane, hydrazine, bismidine, tert-butylperoxy)cyclohexane, 1,1-bis(t-butylperoxylated) 3,3,5-trimethylcyclo己27 322169 201109380 Burnt, tert-butyl peroxybenzoate, benzhydrin peroxide, tert-butyl 2-ethylhexyl carbonate. These may be used alone or in combination of two or more. 1,1-bis(t-butylperoxy)cyclohexane, 35-dimethyl-2'5-(t-butylperoxy)hexane, 2,5-dimethyl-2, 5_bis(t-butylperoxy)hexane, 2,5-dimethyl-2, 5-bis(t-butylperoxy)hexyne, bis(t-butylperoxy)diisopropyl Pept, dicumyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide, and tert-butyl peroxy-2-ethylhexyl carbonate are preferred.丨b double (t-butyl peroxy) cyclohexane, 2,5-dimethyl-2,5-di (t-butyl peroxy) hexane, peroxy-2-ethylhexyl carbonate Tributyl vinegar is better. When the sealing material for a solar cell of the present invention contains a crosslinking agent, the content thereof is preferably from 1 to 5 parts by weight, more preferably from 0.3 to 3 parts by weight, per 100 parts by weight of the ethylene-based polymer. The sealing material for a solar cell of the present invention may further contain a crosslinking assistant. Examples of the crosslinking auxiliary agent include ethylene glycol bis(methyl acetoacetate), trimethyl methacrylate (methacrylic acid methacrylate), polyol methacrylate, and acrylic acid, hydrazine, hydrazine: - phenyl dimaleimide, tnallyl iSOcyanurate, cyanuric acid vinegar (6), w _Urate), zinc methyl acrylate, di (methyl) Acrylic acid, town, tris(tetra)propylpropane tris (acrylic acid), trimethylmethylpropane K methyl __). These (4) auxiliaries may be used singly or in combination of two or more kinds, and may be used in combination with trimeric isomeric acetophenone, acetophenone, acetophenone, acetoacetate, acetoacetate, and triacetin. Methyl propyl __ is preferred. Tris ( III ) is preferred. When the sealing material for solar cells of Tanimoto Maoyue contains a crosslinking aid, it is 322169 28 201109380 to 100 parts by weight of the vinyl polymer. 5至2重量份为特别优选。 Preferably, the content is preferably 0. 5 to 2 parts by weight, more preferably 0.5 to 2 parts by weight. The cerium coupling agent may be further contained in the sealing material for a solar cell of the present invention. Examples of the decane coupling agent include bis(3-triethoxydecylpropyl)tetrasulfide and 3-mercaptopropyltrimethoxyl.矽, 3-glycidoxypropyltrimethoxy zeoxime, 3-glycidoxypropyl fluorenyl ruthenium oxide, ethylene dimethoxy oxime, ethylene triethoxy Crushed, ethylene ginseng (2_decyloxyethoxy)decane, 3-methylpropenyloxypropyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriazine Oxydecane, N-(2- Ethyl ethyl) 3-aminopropylmethyl dimethyl oxalate, N-(2-aminoethyl)-3-aminopropyltrimethoxy sulfonate, 3-aminopropyltriethyl Oxylate calcined, 3-aminopropyltrimethoxy decane. These decane coupling agents may be used singly or in combination of two or more, especially 3-mercapto propyleneoxypropyl fluorenyl diethoxy至至重量重量为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为More preferably, it is particularly preferably 0.1 to 1 part by weight. The sealing material for a solar cell of the present invention may further contain a polyvinyl acetal resin (for example, polyvinyl formal, Polyvinyl butyral (PVB resin), modified PVB), vinyl chloride resin, preferably PVB resin. Within the scope of not affecting the characteristics of the solar cell sealing material, the present invention 29 322169 The solar cell sealing material of 201109380 can further contain the additives described in the following additive groups. [Additive Group: Medium Agent, phenol antioxidant, phosphorus antioxidant, metal soap, fatty acid, anti-blocking agent, pigment, fiame retardant, nucleating agent, filler, Blowing Agent and Foaming Aid] The above additives may be exemplified by the following additives. The neutralizing agent may, for example, be hydrotalcite, natural hydrotalcite or calcium hydroxide. These neutralizing agents may be used alone. Further, two or more kinds may be used in combination. Examples of various antioxidants include neopentyl pentoxide [3-(3, 5-di-t-butyl-4-hydroxyphenyl) propionate, octadecyl propionate. _3_(3,5_di-t-butyl-4-phenylphenyl)ester, 3,9-bis[2_丨3_(3_t-butyl-4-hydroxy-5-fluorenyl) Phenyl)propenyloxy}di-diylethyl]u, 8, 1 〇_tetraoxaspiro[5. 5]undecene. These phenolic antioxidants may be used singly or in combination of two or more. The dish antioxidant may be exemplified by ginseng (2,4-di-tert-butylphenyl), 4,8 fluorene, bis(2,4-di-t-butylphenyl)neopentanol. Bismuth phosphite, bis(2,6-di-t-butyl-4-indolylphenyl) pentaerythritol diphosphite, bis(2,4-di-isopropylphenylphenyl) Neopentyl alcohol diphosphite, bismuth (2'4-mono-butylphenyl)_4,4,_biphenyl diphosphonate. These disc-based antioxidants may be used singly or in combination of two or more. The metal soap may, for example, be a Li salt of stearic acid, a Na salt of stearic acid, a Mg salt of hard moon, a κ salt of stearic acid, a salt of stearic acid or a stearic acid 30 322169 201109380

Ba salt, A1 salt of stearic acid, zn salt of stearic acid, Fe salt of stearic acid, Ca salt of lauric acid, Ba salt of lauric acid, Zn salt of lauric acid, Behenic acid Ca salt, Ba salt of behenic acid, Zn salt of behenic acid, Ca salt of 12-base stearic acid, Mg salt of 12-hydroxystearic acid, 12-hydroxystearic acid Zn salt. These metal soaps may be used singly or in combination of two or more.

For example, lauric acid, myr丨S ti C acid, palmitic acid, margaric acid, stearic acid, oricoic acid (arachidic) can be cited. Acid), behenic acid. These higher fatty acids may be used singly or in combination of two or more. The anti-caking agent may, for example, be an inorganic or organic anti-caking agent such as aluminum silicate, synthetic cerium oxide, natural cerium oxide, zeolite, kaolin or diatomaceous earth. These anti-caking agents may be used singly or in combination of two or more. The pigment may, for example, be blackened, titanium oxide, phthalocyanine pigment, quinacridone pigment, isoindolinone pigment, perylene or purple ketone ( Perinone) is a pigment, enamel. Quin〇phthalone pigment, diketone ratio, 17 〇 〇 洛 ((111^1; 〇卩71*1: 〇1〇071'1*〇16) pigment, two ploughing (dioxazine) is a pigment, a disazo condensed pigment, and a benzimidazolone pigment. These pigments may be used singly or in combination of two or more. Examples of the flame retardant include decabromobiphenyl. , antimony trioxide, phosphorus flame retardant, aluminum hydroxide. These flame retardants may be used singly or in combination of two or more. 31 322169 201109380 The nucleating agent may, for example, be sodium benzoate or phosphoric acid 2, 2' - anthracene bis(4,6-di-t-butylphenyl) sodium or bis(p-fluorenylbenzylidene) sorbitol. These nucleating agents may be used singly or in combination of two or more. Examples of the filler include calcium carbonate, strontium silicate, glass silicate, talc, kaolin, mica, barium sulfate, carbon black, carbon fiber, zeolite, metal powder, and metal oxide. These fillers may be used singly or in combination. The foaming agent and the foaming aid may, for example, be an azocarboxylic acid derivative such as azobiscarboxyguanamine; hydrazine, Ν'-dinitroso a nitroso compound such as pentamethylenetetramine; a compound of sulfonyl hydrazide such as '-oxybisbenzene; etc. These foaming agents and foaming auxiliaries can be used separately The sealing material for a solar cell of the present invention contains a vinyl polymer and a compound (I). Examples of the production method include a Henschel mixer, a super mixer, and the like. Batch type mixer, method for dry mixing ethylene polymer and compound (I), and compound (Π), ultraviolet absorber, crosslinking agent, crosslinking assistant and additive as needed The molded article for solar cells of the invention can be obtained by heat molding, and a molded article can be obtained. For example, a molded article formed into a sheet shape can be bonded to both sides or a single surface of a battery unit for solar cells such as Shixia crystal. The battery unit is sealed. The heat forming method may be exemplified by using a uniaxial or multi-axis extruder for a solar cell sealing material of the present invention, usually at a temperature of 6 〇〇 c until the crosslinking agent is not crosslinked. a method of forming into a pellet shape by melting in a circle (preferably 6〇〇c to 2〇〇〇c, more preferably 7〇°c to 18〇32 322169 201109380); The granulated molded article is usually injected at a temperature range of 6 (rc to a degree at which the crosslinking agent is not crosslinked (preferably 6 G 〇 C to 2 () (further, catching. c) is heated) Forming method; then the above-mentioned granular forming (10) is hoisted at a temperature of 6 GC to cross (four) without cross-linking, to the extent that it is better to heat the shoe, and is heated by the τ mold (Τ-che) The green material to be extruded is dissolved in an organic solvent, and then applied to a substrate or the like, usually in a temperature range of 6 (rc to a degree at which the crosslinking agent does not crosslink) (preferably 60). 〇 to 200 C, more preferably 70 ° c to 180. A method in which the organic solvent is distilled off to obtain a flaky molded article; Further, the molded article obtained by heat-molding the sealing material for a solar cell of the present invention has a tendency to be deteriorated or deteriorated even after being exposed to light for a long period of time. (Embodiment) Hereinafter, the present invention will be described in detail based on examples. Example 1 The components shown below were mixed in a single-axis extruder (manufactured by Tanabe Plastics Co., Ltd., Model VS30-28 extruder) having a diameter of 30 Å. (: The sealing material for a solar cell of the present invention was obtained by kneading at a screw rotation number of 50 rpm. Next, the sealing material for a solar cell was pressed at 155 C for 15 minutes to obtain a sheet-like shape having a thickness of 0.5 mni. <Component> Ethylene polymer: ethylene/vinyl acetate copolymer (19〇t:, 2.16kg 33 322169 201109380, MFR is about 40 ' The Polyolefin Company (Singapore)

Pte. Ltd. MA-10) 100 parts by weight of cross-linking agent: 2, 5-dimercapto-2, 5-bis(t-butylperoxy)hexane oxime. 4 parts by weight of crosslinking aid: trimeric 6 parts by weight of the compound (I): 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2, 4, 8, 10-tetra-t-butyldibenzo[d,f][13,2]dioxaphosphanone 0.2 part by weight of compound (II): sebacic acid bis(2, 2, 6, 6-tetradecyl-4-piperidinyl) 0. 1 part by weight <Evaluation Test> The molded article obtained in Example 1 was obtained at a wavelength of 380 nm and 600 nm using a spectrophotometer ("V560" manufactured by JASCO Corporation). The penetration rate (%). Next, 'Xenon weatherometer (black disk temperature: 63 °C 'no rain) is irradiated with 氙, and the illuminating sheet is irradiated with a spectrophotometer to obtain wavelengths of 380 nm and 600 nm. The penetration rate (%). (Example 2) A molded article of a sheet for a solar cell and a sheet for a solar cell was obtained in the same manner as in Example 1 except that the amount of the compound (I) was changed to 1 part by weight. The obtained molded article was subjected to an evaluation test in the same manner as in Example 1, and the results were summarized in Table 1 together with Example 1. Comparative Example 1 The same procedure as in Example 1 was carried out except that the compound (I) was not used, and 34 322169 201109380 - a molded article of a sheet for a solar cell and a sheet for a solar cell was obtained. The obtained molded article was subjected to an evaluation test in the same manner as in Example ,, and the results were combined with Example 1 in a table. [Table 1] 务----**-~~~- Example 1 Example 2 Comparative Example 1 Additive (parts by weight) Compound ΰΤ'''' 0.2 0.1 - Compound (ιιΐ 0.1 0.1 0.1 light transmittance ( %) 600nm 380nm before irradiation 84.0 84.1 81.9 Γ 77.7 77.5 73.8 600nm After 1000 hours of irradiation 70.5 70.4 63.6 380nm 66. 1 65.1 55.5 Example 3 Mix the components shown below, using a 30 mm diameter single-axis extruder (Tianbian The VS30-28 extruder was mixed with 9 (TC, screw rotation number 50 rpm) to obtain the solar cell sealing material of the present invention. Next, the solar cell sealing material was subjected to a sealing material at 155 ° C for 15 minutes. Pressurization to obtain a sheet-like molded article having a thickness of 〇5 mm. <Component> Ethylene polymer: ethylene/vinyl acetate copolymer (MFR of about 40 at 190 ° C, 2.16 kg, The Polyolef in Company (Singapore) Pte. Ltd. MA-10) 100 parts by weight of cross-linking agent: 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane oxime. 4 parts by weight of crosslinking assistant : Triallyl isocyanate 0.6 parts by weight of compound (I) : 6-[3-(3-tert-butyl-4-hydroxy-5-fluorenyl) Propyloxy 35 322169 201109380 base]-2, 4, 8, 10-tetra-tert-butyldibenzo[d,f][i, 3, 2]dioxaphosphanee 0.1 part by weight Compound (ΠΙ) : 2-hydroxy-4-n-octyloxydibenzophenone oxime. 1 part by weight of compound (IV): azelaic acid, 2,2,6,6-pentamethyl_4_per pipe Mixture of pyridyl)ester, methyl phthalate 1,2,2,6, pentamethyl-4-pyrene (Tinuvin 292 (registered trademark of Ciba Holding Inc.)) 0.25 parts by weight <evaluation test> The both sides of the molded article obtained in Example 3 were obtained by immersing the glass of the thickness of 〇miD to obtain a battery cell. For the battery cell, a wavelength of 380 nm and 600 nm was obtained by a spectrophotometer (V560 manufactured by Sakamoto Seiko Co., Ltd.). Penetration rate (%). Secondly, the battery unit was irradiated with helium weathering apparatus (black plate temperature: 63 ° C, no rain), and the battery unit after 500 hours of irradiation was subjected to a spectrophotometer to obtain a wavelength of 380 nm. The transmittance (%) in the range of 600 nm. Comparative Example 2 The operation of the solar cell sheet and the solar cell sheet were carried out in the same manner as in Example 3 except that the compound (I) was not used. Formed product. The obtained molded article was subjected to an evaluation test in the same manner as in Example 3, and the results were summarized in Table 2 together with Example 3. 36 322169 201109380 - [Table 2] - Example 3 Comparative Example 2 Additive (parts by weight) Compound (I) 0.1 - Compound (III) 0. 1 0.1 Compound (IV) 0.25 0.25 Light transmittance (%) 600 nm Before irradiation 99.5 96.9 380nra 72.0 72.8 600nm irradiation 500 99.0 95.0 380nm after hours 71.9 71.2 Example 4 and * Straight-line low-density polyethylene Sumikathene L (registered trademark of Sumitomo I.), FS240, MFR=2.2 In the same manner as in Example 2 except that 100 parts by weight of the ethylene-vinyl acetate copolymer of the component used in Example 2 was used, the sealing material for a positive electrode of the present invention was obtained. Example 5 In addition to the use of a special ethylene copolymer Aery ft (registered trademark of Sumitomo Chemical Co., Ltd., WH 202, MFR = 2), 100 parts by weight of the ethylene-vinyl acetate copolymer 1 of the components used in the alternative examples. The solar weight of the present invention was also treated in the same manner as in Example 2, and the sealing material was also used. / Example β In addition to the use of ethylene/mercaptoacrylic acid copolymer Nucrel (EI du: nt company registered trademark 'AN42115C, MFR=35) 100 parts by weight instead of the ethylene/vinyl acetate copolymer of the components used in Example 2 The solar cell sealing material of the present invention was obtained in the same manner as in Example 2 except that the weight was 322169 37 201109380. Example 7 Except that 100 parts by weight of an ionic polymer resin Himilan (registered trademark of Mitsui DuPont Chemical Co., Ltd., 1555, MFR = 10) was used instead of 100 parts by weight of the ethylene-vinyl acetate copolymer of the component used in Example 2, The solar cell sealing material of the present invention was obtained in the same manner as in Example 2. In the reference example, the glass substrate and the base are obtained by laminating polyethylene and an adhesive with polyethylene terephthalate, and the polyethylene constituting the base contains the compound (I) described in Example 1. In the solar cell sealing material of the present invention obtained in Example 2, the solar cell battery unit was sealed to obtain a solar cell. (Industrial Applicability) The sealing material for a solar cell of the present invention is suitable for use as a sealing material for solar cells because it is less deteriorated or deteriorated even after exposure to light for a long period of time. [Simple description of the diagram] None [Key component symbol description] None 38 322169

Claims (1)

201109380 VII. Patent application scope: 1. A solar cell sealing material comprising: and a thermoplastic polymer containing a structural unit derived from ethylene; a phosphite compound represented by the formula (I); R2 R Ο R1 R R: 〇 X p-o-A R4 YR® (I) R1 [wherein R, R, R4 and R5 each independently represent a hydrogen atom to 8 alkyl group, a carbon number of 5 to 8 cycloalkyl group, and a carbon number of 6 to 12; a cycloalkyl group, an aralkyl group having 7 to 12 carbon atoms, or a phenyl group, and R3 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and X represents a single bond, an atom, or a formula (1-1) The above-mentioned divalent group R6 I (1-1) C- \ Η (wherein R 6 represents a hydrogen atom 'alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms), and Α represents carbon a 2 to 8 alkylene group, or a 2 valent 7 R face CHO I * represented by the formula (1-2) (wherein R 7 represents a single bond or an alkylene group having 1 to 8 carbon atoms, and * represents a combination On the side of the oxygen atom, either Y or Z represents a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having a carbon number of 1 39 322169 201109380 to 8, or an aralkoxy group having a carbon number of 7 to 12, One side does not represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms]. 2. The sealing material for a solar cell according to the above aspect of the invention, wherein the weight ratio of the thermoplastic polymer is 1 part by weight, and the weight of the thermoplastic polymer is 5 parts by weight of the phosphorous acid represented by the formula (I). Ester compound. 3. The solar cell sealing material according to the invention of claim 1, wherein the phosphite compound represented by the formula G) is 6-[3-(3-t-butyl~4:hydroxymethyl] Dioxy]-2,4,8, 10-tetra--: butyl-[benzopheno[d,f][l,3,2]dioxaphosphanane. The solar cell sealing material according to the invention, wherein the solar cell sealing material further comprises a mother β-based compound having a partial structure represented by the formula (II); -r8 ( r ) (wherein R8 represents a hydrogen atom, a carbon number of 1 ?? 5 9n — an alkyl group, or a carbon number of 1 to 20, and γ represents an oxygen material.) The sealing material for a solar cell according to the fourth aspect of the present invention, wherein the piperidine compound represented by the formula (4) of the formula (ΙΓ) is represented by the formula (ΙΓ); 322169 40 201109380 [In the formula, R each independently represents a hydrogen atom, an alkyl group having a carbon number of 丨 to 2〇, or an alkoxy group having an inverse number of 1 to 20, and A represents an alkylene group having a carbon number of 丨 to 1〇, Or a divalent group represented by formula (III) (wherein 'R8 each independently represents a hydrogen atom, an alkyl group having a carbon number of 〇 to 2〇, or an alkoxy group having 1 to 20 carbon atoms)]. 6. The solar cell sealing material according to the invention, wherein the solar cell sealing material further comprises an ultraviolet absorber. 7. The solar cell (4) sealing material according to the scope of the invention, wherein the sealing material for the solar cell further comprises a crosslinking agent. The sealing material for a solar cell according to the seventh aspect of the invention, wherein the crosslinking agent is an organic peroxide. The solar cell sealing material according to the seventh aspect of the invention, wherein the solar cell sealing material contains a crosslinking auxiliary agent. The solar cell sealing material according to the first aspect of the invention, wherein the solar cell sealing material further comprises a decane coupling agent. The solar cell sealing material according to the first aspect of the invention, wherein the thermoplastic polymer comprises a structural unit derived from ethylene and a polymer derived from a structural unit of ethylene 322169 41 201109380 I. 12. The use of a phosphite compound of the formula (I) for improving the durability of a solar cell sealing material; [In the formula, Κ 1,! ^,! And R5 each independently represent a hydrogen atom, an alkyl group having a carbon number of 丄8, a cycloalkyl group having 5 to 8 carbon atoms, a alkylcycloalkyl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms. Or a phenyl group, and R3 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and represents a single bond, a sulfur atom, or a divalent group represented by the formula (1-1) (wherein R6 represents hydrogen) An atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms, A represents an alkylene group having 2 to 8 carbon atoms, or a divalent 7 R group represented by the formula (1-2)隹CHO 1 * (wherein R represents a single bond or a carbon number of 1 to 8, and * represents a bond to the oxygen atom side), and any of Y and Z represents a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, An alkoxy group having a carbon number of from j to 8, or an aralkyloxy group having a carbon number of from 7 to 12, and the other table 42 322169 201109380 • a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. 13·- a solar cell μ cell unit (the sealing method of the ee (1), the package-described step: 'the step of heat-molding the sealing material for a solar cell according to claim 1 to obtain a sheet-like molded article; The step of bonding the obtained sheet-like molded article to both sides or one surface of a battery unit for a solar cell. 14· A molded article obtained by heat-forming a sealing material for a solar cell according to the above-mentioned patent application. 43 322169 201109380 IV. Designation of the representative figure: There is no drawing in this case (1) The representative drawing of the case is: () Figure (2) The symbol of the symbol of the representative figure is simple: 5. If there is a chemical formula in this case, Please reveal the chemical formula that best shows the characteristics of the invention: 2 322169