 Polymer electrolyte composition and fuel cell
专利摘要:
PURPOSE: Provided are a polyelectrolyte composition excellent in radical resistance property, a polyelectrolyte membrane comprising the composition, and a fuel cell comprising the polyelectrolyte membrane. CONSTITUTION: The polymer electrolyte composition comprises a polyelectrolyte and at least one of antioxidant selected from the group consisting of a trivalent phosphorus-containing antioxidant and a sulfur-containing antioxidant. The fuel cell which comprises a polyelectrolyte membrane comprising the composition, is produced by joining a catalyst and an electroconductive substance as a current collector on both sides of the polyelectrolyte membrane respectively. 公开号:KR20030014621A 申请号:KR1020020046540 申请日:2002-08-07 公开日:2003-02-19 发明作者:히다까야스아끼；이와사끼가쯔히꼬 申请人:스미또모 가가꾸 고오교오 가부시끼가이샤； IPC主号:
专利说明:
POLYMER ELECTROLYTE COMPOSITION AND FUEL CELL [1] The present invention relates to a polymer electrolyte composition, and more particularly to a polymer electrolyte composition for use in fuel cells. [2] Fuel cells have recently attracted attention as high efficiency, clean energy conversion devices. In particular, a fuel cell using a polymer electrolyte composition membrane containing a polymer electrolyte having electronic conductivity as an electrolyte has a dense structure, has a high power, and can be operated in a simple system, so that the fuel cell is a mobile power source for transportation and the like. Receives attention as a circle [3] The polymer electrolyte used in a fuel cell is a polymer having electrolyte groups such as sulfone groups and carboxyl groups in a polymer chain, and is added to the polymer electrolyte composition membrane of a battery and applied to various applications such as electrodialysis and diffusion dialysis. [4] The fuel cell is provided with a pair of electrodes on both sides of the membrane of the proton conductivity polymer electrolyte composition, in which pure hydrogen gas or reformed hydrogen gas is supplied to one electrode (fuel electrode) as fuel gas, and oxygen gas or air as another oxidant. Supplied to an electrode (air electrode) to obtain an electromotive force. [5] In fuel cells containing polymers, it is known that peroxides are produced by cell reaction in a catalyst layer formed in the space between the polymer electrolyte composition membrane and the electrode. In addition, peroxides that are converted to peroxide radicals during their diffusion corrode the polymer electrolyte composition membrane. It has been proposed to contain phenolic compounds in order to provide radical resistance to the polymer electrolyte composition membrane (for example, Japanese Patent Laid-Open No. 2001-118591). [6] However, since the radical resistance is not always sufficiently satisfactory in the polymer electrolyte composition membrane containing a phenolic compound, a polymer electrolyte composition membrane showing more excellent radical resistance is desired. [7] An object of the present invention is to provide a composition of a polymer electrolyte having excellent radical resistance. The present invention also relates to a polymer electrolyte composition membrane containing the polymer electrolyte composition, and a fuel cell containing the polymer electrolyte composition membrane. [8] The present inventors show that the polymer electrolyte composition containing a special phosphorus compound containing a trivalent phosphorus containing antioxidant or a special sulfur compound including a sulfur containing antioxidant exhibits excellent radical resistance, and the polymer electrolyte composition exhibits excellent film forming properties. Has been found to be complexed to a porous support membrane. [9] The present invention provides a polymer electrolyte composition containing a polymer electrolyte and at least one antioxidant selected from the group consisting of trivalent phosphorus-containing antioxidants and sulfur-containing antioxidants. Furthermore, the present invention provides a polymer electrolyte composition membrane containing the polymer electrolyte composition and a fuel cell containing the polymer electrolyte composition membrane. [10] The trivalent phosphorus containing compound used by this invention can contain the phosphorus containing compound represented by chemical formulas 1-6 described below, for example. Among these, compounds containing trivalent phosphorus represented by the following Chemical Formulas 1 to 6 (hereinafter, referred to as phosphorus-containing compounds) are preferable. Two or more of these antioxidants containing trivalent phosphorus may be used in combination. [11] [12] (In formula, R <1> , R <2> , R <4> and R <5> respectively independently represents a hydrogen atom, a C1-C20 alkyl group, or a C1-C20 alkoxy group, R <3> represents a hydrogen atom or a C1-C8 X represents an alkyl group, X represents a direct bond, a sulfur atom, a CHR a group (wherein R a represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), or an alkylene group having 2 to 8 carbon atoms, and A represents a C 2 to C An alkylene group of 8, a -CO- (carbonyl group), or a (*)-COR b -group, wherein R b represents an alkylene group having 1 to 8 carbon atoms, and (*) represents a bond to the oxygen side; , Any one of Y or Z represents a hydroxy group or an alkoxy group having 1 to 20 carbon atoms, the other represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), [13] [14] (In formula, R <6> , R <7> and R <8> respectively independently represents a hydrogen atom, a C1-C20 alkyl group, or a C1-C20 alkoxy group., [15] [16] (In formula, R <9> and R <10> respectively independently represents a hydrogen atom, a C1-C20 alkyl group, or a C1-C20 alkoxy group., [17] [18] (Wherein R 11 and R 12 each independently represent an alkyl group having 1 to 20 carbon atoms), [19] [20] (In formula, R <13> , R <14> and R <15> respectively independently represents a hydrogen atom, a C1-C20 alkyl group, or a C1-C20 alkoxy group., [21] [22] Wherein B represents a direct bond, a sulfur atom, a -CHR c -group (where R c represents an alkyl group having 1 to 8 carbon atoms), or an alkylene group having 2 to 8 carbon atoms, and R 16 and R 17 are Each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms, and E represents an alkoxy group or halogen atom having 1 to 20 carbon atoms). [23] Substituents R 1 , R 2 , R 4 and R 5 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms). [24] Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, tert-pentyl, iso-octyl, tert-octyl, 2- Ethylhexyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 1-methylcyclopentyl, 1-methylcyclohexyl, 1-methyl-4-isopropylcyclohexyl, nonyl, decyl, undecyl, dodecyl, tridecyl , Tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, aicosyl and the like. Furthermore, as the alkoxy group having 1 to 20 carbon atoms, mention is made of, for example, an alkoxy group wherein the alkyl moiety is alkyl having 1 to 20 carbon atoms mentioned above. [25] ROne, R2, R4And R5 Is preferably an alkyl group having 1 to 12 carbon atoms. Typical examples of these are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, tert-pentyl, iso-octyl, tert-octyl, 2-ethyl Hexyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 1-methylcyclopentyl, 1-methylcyclohexyl, 1-methyl-4-isopropylcyclohexyl and the like are mentioned. [26] Among them, R 1 and R 4 are preferably tert-alkyl groups such as tert-butyl, tert-pentyl, and tert-octyl; Hindered alkyl groups such as cyclohexyl and 1-methylcyclohexyl. R 2 is preferably an alkyl group having 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, tert-pentyl; Methyl, tert-butyl and tert-pentyl are more preferred. [27] R 5 is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and tert-pentyl. [28] Substituent R 3 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. As an alkyl group having 1 to 8 carbon atoms, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, tert-pentyl, iso-octyl, tert-octyl, 2-ethylhexyl , Cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 1-methylcyclopentyl and 1-methylcyclohexyl. Hydrogen atoms, alkyl groups having 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and tert-pentyl are preferred, and hydrogen atoms and methyl groups are more preferred. desirable. [29] In addition, X represents a direct bond, a sulfur atom, a methylene group, the methylene group substituted by the C1-C8 alkyl group, or a C2-C8 alkylene group. "X is a direct bond" means that the benzene ring is directly cross-linked. [30] Alkyl groups similar to those described above are mentioned as alkyl groups having 1 to 8 carbon atoms substituted with methylene groups. Furthermore, as the alkylene group having 2 to 8 carbon atoms, for example, ethylene, propylene, butylene, pentamethylene, hexamethylene, octamethylene, 2,2'-dimethyl-1,3-propylene and the like are mentioned. [31] X is preferably a direct bond, a methylene group or a methylene group substituted with an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl; Direct bonding is more preferred. [32] In formula (1), A represents an alkylene group having 2 to 8 carbon atoms, a -CO- (carbonyl group), or a (*)-COR b -group (R b represents an alkylene group having 1 to 8 carbon atoms, and (*) is on the oxygen side) It is combined). [33] As alkylene groups having 2 to 8 carbon atoms, alkylene groups similar to those described above are represented. [34] Moreover, (*) in the (*)-COR b -group indicates that carbon of carbonyl is bonded to oxygen of phosphite. As the alkylene group having 1 to 8 carbon atoms in R b , for example, methylene, ethylene, propylene, butylene, pentamethylene, hexamethylene, octamethylene, 2,2′-dimethyl-1,3-propylene and the like are mentioned. [35] As A, an alkylene group having 2 to 8 carbon atoms, a carbonyl group, and a (*)-COR b -group in which R b is ethylene are preferable, and alkylene having 2 to 8 carbon atoms is more preferable. [36] Any one of Y or Z represents a hydroxy group or an alkoxy group having 1 to 20 carbon atoms, and the other represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. [37] As the alkyl group having 1 to 20 carbon atoms and the alkoxy group having 1 to 20 carbon atoms, for example, alkyl groups and alkoxy groups similar to those described above are mentioned. [38] Examples of the phosphorus-containing compound represented by the formula (1) include 2,4,8,10-tetramethyl-6- [3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propoxy] dibenzo [ d, f] [1,3,2] dioxaphosphine; 2,4,8,10-tetraethyl-6- [3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propoxy] dibenzo [d, f] [1,3,2] Dioxaphosphine; 2,4,8,10-tetra-n-propyl-6- [3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propoxy] dibenzo [d, f] [1,3 , 2] dioxaphosphine; 2,4,8,10-tetra-isopropyl-6- [3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propoxy] dibenzo [d, f] [1,3, 2] dioxaphosphine; 2,4,8,10-tetra-n-butyl-6- [3- (3-methyl-4--hydroxy-5-tert-butylphenyl) propoxy] benzo [d, f] [1,3 , 2] dioxaphosphine; 2,4,8,10-tetra-isobutyl-6- [3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propoxy] dibenzo [d, f] [1,3, 2] dioxaphosphine; 2,4,8,10-tetra-sec-butyl-6- [3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propoxy] dibenzo [d, f] [1,3 , 2] dioxaphosphine; 2,4,8,10-tetra-tert-butyl-6- [3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propoxy] dibenzo [d, f] [1,3 , 2] dioxaphosphine; 2,4,8,10-tetra-tert-pentyl-6- [3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propoxy] dibenzo [d, f] [1,3 , 2] dioxaphosphine; 2,4,8,10-tetra-iso-octyl-6- [3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propoxy] dibenzo [d, f] [1,3 , 2] dioxaphosphine; 2,4,8,10-tetra-tert-octyl-6- [3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propoxy] dibenzo [d, f] [1,3 , 2] dioxaphosphine; 2,4,8,10-tetrakis (2-ethylhexyl) -6- [3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propoxy] dibenzo [d, f] [ 1,3,2] dioxaphosphine and the like. [39] Among them, 2,4,8,10-tetra-tert-butyl-6- [3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propoxy] dibenzo [d, f] [ 1,3,2] dioxaphosphine; 2,4,8,10-tetra-tert-pentyl-6- [3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propoxy] dibenzo [d, f] [1,3 , 2] dioxaphosphine; 2,4,8,10-tetra-tert-octyl-6- [3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propoxy] dibenzo [d, f] [1,3 , 2] dioxaphosphine, etc. are preferable. [40] R 6 , R 7 and R 8 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. [41] As examples of alkyl groups having 1 to 20 carbon atoms and alkoxy groups having 1 to 20 carbon atoms, for example, alkyl groups and alkoxy groups similar to those described above are mentioned. [42] R 6 , R 7 and R 8 are preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. As an alkyl group having 1 to 8 carbon atoms, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, tert-pentyl, iso-octyl, tert-octyl, 2 Ethylhexyl and the like. Hydrogen atoms or methyl, tert-butyl, and tert-pentyl are preferred. [43] Examples of the phosphorus-containing compound represented by the formula (2), [44] Tris (2,4-dimethylphenyl) phosphite, [45] Tris (2,4-diethylphenyl) phosphite, [46] Tris (2,4-di-n-propylphenyl) phosphite, [47] Tris (2,4-di-isopropylphenyl) phosphite, [48] Tris (2,4-di-n-butylphenyl) phosphite, [49] Tris (2,4-di-isobutylphenyl) phosphite, [50] Tris (2,4-di-sec-butylphenyl) phosphite, [51] Tris (2,4-di-tert-butylphenyl) phosphite, [52] Tris (2,4-di-tert-pentylphenyl) phosphite, [53] Tris (2,4-di-iso-octylphenyl) phosphite, [54] Tris (2,4-di-tert-octylphenyl) phosphite, [55] Tris (2,4-bis (2-ethylhexyl) phenyl) phosphite, [56] Tris (2,4,6-trimethylphenyl) phosphite, [57] Tris (2,4,6-triethylphenyl) phosphite, [58] Tris (2,4,6-tri-n-propylphenyl) phosphite, [59] Tris (2,4,6-tri-iso-propylphenyl) phosphite, [60] Tris (2,4,6-tri-iso-butylphenyl) phosphite, [61] Tris (2,4,6-tri-sec-butylphenyl) phosphite, [62] Tris (2,4,6-tri-tert-butylphenyl) phosphite, [63] Tris (2,4,6-tri-tert-pentylphenyl) phosphite, [64] Tris (2,4,6-tri-iso-octylphenyl) phosphite, [65] Tris (2,4, 6-tri-tert-octylphenyl) phosphite, [66] Tris (2,4,6-tris (2-ethylhexyl) phenyl) phosphite and the like. [67] Among these, tris (2,4-di-n-butylphenyl) phosphite, tris (2,4-di-isobutylphenyl) phosphite, tris (2,4-di-sec-butylphenyl) phosphite, Tris (2,4-di-tert-butylphenyl) phosphite, tris (2,4-dimethylphenyl) phosphite, tris (2,4-di-tert-pentylphenyl) phosphite and the like are preferable. [68] In formula (3), R 9 and R 10 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. [69] R 9 and R 10 preferably represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. As an alkyl group having 1 to 8 carbon atoms, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, tert-pentyl, iso-octyl, tert-octyl, 2 Ethylhexyl and the like. Hydrogen atoms or methyl, tert-butyl and tert-pentyl are preferred. [70] Examples of the phosphorus-containing compound represented by the formula (3), [71] Tetrakis (2,4-dimethylphenyl) -4,4'-biphenylene-di-phosphonite, [72] Tetrakis (2,4-diethylphenyl) -4,4'-biphenylene-di-phosphonite, [73] Tetrakis (2,4-di-n-propylphenyl) -4,4'-biphenylene-di-phosphonite, [74] Tetrakis (2,4-di-iso-propylphenyl) -4,4'-biphenylene-di-phosphonite, [75] Tetrakis (2,4-di-n-butylphenyl) -4,4'-biphenylene-di-phosphonite, [76] Tetrakis (2,4-di-iso-butylphenyl) -4,4'-biphenylene-di-phosphonite, [77] Tetrakis (2,4-di-sec-butylphenyl) -4,4'-biphenylene-di-phosphonite, [78] Tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene-di-phosphonite, [79] Tetrakis (2,4-di-tert-pentylphenyl) -4,4'-biphenylene-di-phosphonite, [80] Tetrakis (2,4-di-iso-octylphenyl) -4,4'-biphenylene-di-phosphonite, [81] Tetrakis (2,4-di-tert-octylphenyl) -4,4'-biphenylene-di-phosphonite, [82] Tetrakis (2,4-bis (2-ethylhexyl) phenyl) -4,4'-biphenylene-di-phosphonite, [83] Tetrakis (2,4,5-trimethylphenyl) -4,4'-biphenylene-di-phosphonite, [84] Tetrakis (2,4-diethyl-5-methylphenyl) -4,4'-biphenylene-di-phosphonite, [85] Tetrakis (2,4-di-n-propyl-5-methylphenyl) -4,4'-biphenylene-di-phosphonite, [86] Tetrakis (2,4-di-isopropyl-5-methylphenyl) -4,4'-biphenylene-di-phosphonite, [87] Tetrakis (2,4-di-n-butyl-5-methylphenyl) -4,4'-biphenylene-di-phosphonite, [88] Tetrakis (2,4-di-iso-butyl-5-methylphenyl) -4,4'-biphenylene-di-phosphonite, [89] Tetrakis (2,4-di-sec-butyl-5-methylphenyl) -4,4'-biphenylene-di-phosphonite, [90] Tetrakis (2,4-di-tert-butyl-5-methylphenyl) -4,4'-biphenylene-di-phosphonite, [91] Tetrakis (2,4-di-tert-pentyl-5-methylphenyl) -4,4'-biphenylene-di-phosphonite, [92] Tetrakis (2,4-di-iso-octyl-5-methylphenyl) -4,4'-biphenylene-di-phosphonite, [93] Tetrakis (2,4-di-tert-octyl-5-methylphenyl) -4,4'-biphenylene-di-phosphonite, [94] Tetrakis (2,4-bis (2-ethylhexyl) -5-methylphenyl) -4,4'-biphenylene-di-phosphonite, [95] Tetrakis (2,4-dimethyl-5-ethylphenyl) -4,4'-biphenylene-di-phosphonite, [96] Tetrakis (2,4,5-triethylphenyl) -4,4'-biphenylene-di-phosphonite, [97] Tetrakis (2,4-di-n-propyl-5-ethylphenyl) -4,4'-biphenylenedi-phosphonite, [98] Tetrakis (2,4-di-iso-propyl-5-ethylphenyl) -4,4'-biphenylene-di-phosphonite, [99] Tetrakis (2,4-di-n-butyl-5-ethylphenyl) -4,4'-biphenylene-di-phosphonite, [100] Tetrakis (2,4-di-iso-butyl-5-ethylphenyl) -4,4'-biphenylene-di-phosphonite, [101] Tetrakis (2,4-di-sec-butyl-5-ethylphenyl) -4,4'-biphenylene-di-phosphonite, [102] Tetrakis (2,4-di-tert-butyl-5-ethylphenyl) -4,4'-biphenylene-di-phosphonite, [103] Tetrakis (2,4-di-tert-pentyl-5-ethylphenyl) -4,4'-biphenylene-di-phosphonite, [104] Tetrakis (2,4-di-iso-octyl-5-ethylphenyl) -4,4'-biphenylene-di-phosphonite, [105] Tetrakis (2,4-di-tert-octyl-5-ethylphenyl) -4,4'-biphenylene-di-phosphonite, [106] Tetrakis (2,4-bis (2-ethylhexyl) -5-ethylphenyl) -4,4'-biphenylene-di-phosphonite and the like. [107] Among the above, [108] Tetrakis (2,4-di-n-butylphenyl) -4,4'-biphenylene-di-phosphonite, [109] Tetrakis (2,4-di-iso-butylphenyl) -4,4'-biphenylene-di-phosphonite, [110] Tetrakis (2,4-di-sec-butylphenyl) -4,4'-biphenylene-di-phosphonite, [111] Tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene-di-phosphonite, [112] Tetrakis (2,4-di-tert-pentylphenyl) -4,4'-biphenylene-di-phosphonite, [113] Tetrakis (2,4-di-iso-octylphenyl) -4,4'-biphenylene-di-phosphonite, [114] Tetrakis (2,4-di-tert-octylphenyl) -4,4'-biphenylene-di-phosphonite, [115] Tetrakis (2,4-di-n-butyl-5-methylphenyl) -4,4'-biphenylene-di-phosphonite, [116] Tetrakis (2,4-di-iso-butyl-5-methylphenyl) -4,4'-biphenylene-di-phosphonite, [117] Tetrakis (2,4-di-sec-butyl-5-methylphenyl) -4,4'-biphenylene-di-phosphonite, [118] Tetrakis (2,4-di-tert-butyl-5-methylphenyl) -4,4'-biphenylene-di-phosphonite, [119] Tetrakis (2,4-di-tert-pentyl-5-methylphenyl) -4,4'-biphenylene-di-phosphonite, [120] Tetrakis (2,4-di-iso-octyl-5-methylphenyl) -4,4'-biphenylene-di-phosphonite and tetrakis (2,4-di-tert-octyl-5-methylphenyl) -4,4'-biphenylene-di-phosphonite is preferred. [121] In Formula 4, R 11 and R 12 each independently represent an alkyl group having 1 to 20 carbon atoms. [122] As typical examples of alkyl groups having 1 to 20 carbon atoms, for example, alkyl groups similar to those described above may be mentioned. [123] Among the above, tert-octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and icosyl are preferred. [124] Examples of the phosphorus-containing compound represented by the formula (4) include di-methylpentaerythritol diphosphite, [125] Di-ethylpentaerythritol diphosphite, [126] Di-n-propylpentaerythritol diphosphite, [127] Di-iso-propylpentaerythritol diphosphite, [128] Di-n-butylpentaerythritol diphosphite, [129] Di-iso-butylpentaerythritol diphosphite, [130] Di-sec-butylpentaerythritol diphosphite, [131] Di-tert-butylpentaerythritol diphosphite, [132] Di-tert-pentylpentaerythritol diphosphite, [133] Di-iso-octylpentaerythritol diphosphite, [134] Di-tert-octylpentaerythritol diphosphite, [135] Bis (2-ethylhexyl) pentaerythritol diphosphite, [136] Di-nonylpentaerythritol diphosphite, [137] Di-decylpentaerythritol diphosphite, [138] Di-undecylpentaerythritol diphosphite, [139] Di-dodecylpentaerythritol diphosphite, [140] Di-tridecylpentaerythritol diphosphite, [141] Di-tetradecylpentaerythritol diphosphite, [142] Di-pentadecylpentaerythritol diphosphite, [143] Di-hexadecylpentaerythritol diphosphite, [144] Di-heptadecylpentaerythritol diphosphite, [145] Di-octadecylpentaerythritol diphosphite, [146] Di-nonadecylpentaerythritol diphosphite, [147] Di-icosylpentaerythritol diphosphite, [148] Di-cyclopentylpentaerythritol diphosphite, [149] Di-cyclohexylpentaerythritol diphosphite, [150] Di-cycloheptylpentaerythritol diphosphite, [151] Di-cyclooctylpentaerythritol diphosphite and the like. [152] among them, [153] Di-tetradecylpentaerythritol diphosphite, [154] Di-pentadecylpentaerythritol diphosphite, [155] Di-hexadecylpentaerythritol diphosphite, [156] Di-heptadecylpentaerythritol diphosphite, [157] Di-octadecylpentaerythritol diphosphite, [158] Di-nonadecylpentaerythritol diphosphite, [159] Di-icosylpentaerythritol diphosphite and the like are preferred. [160] R <13> , R <14> and R <15> in general formula (5) represent a hydrogen atom, a C1-C20 alkyl group, or a C1-C20 alkoxy group each independently. [161] As typical examples of the alkyl group having 1 to 20 carbon atoms and the alkoxy group having 1 to 20 carbon atoms, for example, those similar to the alkyl group and alkoxy group described above are included. [162] R 13 , R 14 and R 15 are preferably a hydrogen atom or an alkyl group having 1 to 13 carbon atoms. Examples of alkyl groups having 1 to 8 carbon atoms include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, tert-pentyl, iso-octyl, tert-octyl , 2-ethylhexyl and the like are mentioned. Among these, a hydrogen atom or methyl, tert-butyl, and tert-pentyl are preferable. [163] Examples of the phosphorus-containing compound represented by the formula (5), [164] Bis (2,4,6-trimethylphenyl) pentaerythritol diphosphite, [165] Bis (2,6-diethyl-4-methylphenyl) pentaerythritol diphosphite, [166] Bis (2,6-di-n-propyl-4-methylphenyl) pentaerythritol diphosphite, [167] Bis (2,6-di-isopropyl-4-methylphenyl) pentaerythritol diphosphite, [168] Bis (2,6-di-n-butyl-4-methylphenyl) pentaerythritol diphosphite, [169] Bis (2,6-di-isobutyl-4-methylphenyl) pentaerythritol diphosphite, [170] Bis (2,6-di-sec-butyl-4-methylphenyl) pentaerythritol diphosphite, [171] Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, [172] Bis (2,6-di-tert-pentyl-4-methylphenyl) pentaerythritol diphosphite, [173] Bis (2,6-di-iso-octyl-4-methylphenyl) pentaerythritol diphosphite, [174] Bis (2,6-di-tert-octyl-4-methylphenyl) pentaerythritol diphosphite, [175] Bis (2,6-bis (2-ethylhexyl) -4-methylphenyl) pentaerythritol diphosphite, [176] Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, [177] Bis (2,4-di-methylphenyl) pentaerythritol diphosphite, [178] Bis (2,4-di-ethylphenyl) pentaerythritol diphosphite, [179] Bis (2,4-di-n-propylphenyl) pentaerythritol diphosphite, [180] Bis (2,4-di-isopropylphenyl) pentaerythritol diphosphite, [181] Bis (2,4-di-n-butylphenyl) pentaerythritol diphosphite, [182] Bis (2,4-di-isobutylphenyl) pentaerythritol diphosphite, [183] Bis (2,4-di-sec-butylphenyl) pentaerythritol diphosphite, [184] Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, [185] Bis (2,4-di-tert-pentylphenyl) pentaerythritol diphosphite, [186] Bis (2,4-di-iso-octylphenyl) pentaerythritol diphosphite, [187] Bis (2,4-di-tert-octylphenyl) pentaerythritol diphosphite, [188] Bis (2,4-bis (2-ethylhexyl) phenyl) pentaerythritol diphosphite and the like. [189] Among these, [190] Bis (2,6-di-n-butyl-4-methylphenyl) pentaerythritol diphosphite, [191] Bis (2,6-di-isobutyl-4-methylphenyl) pentaerythritol diphosphite, [192] Bis (2,6-di-sec-butyl-4-methylphenyl) pentaerythritol diphosphite, [193] Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, [194] Bis (2,6-di-tert-pentyl-4-methylphenyl) pentaerythritol diphosphite, [195] Bis (2,6-di-iso-octyl-4-methylphenyl) pentaerythritol diphosphite, [196] Bis (2,6-di-tert-octyl 4-methylphenyl) pentaerythritol diphosphite, [197] Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite and the like are preferable. [198] Furthermore, in the formula (6), B represents a direct bond, a sulfur atom, a -CHR c -group (where R c represents an alkyl group having 1 to 8 carbon atoms), or an alkylene group having 1 to 8 carbon atoms. R 16 and R 17 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms, and E represents an alkoxy group or halogen atom having 1 to 20 carbon atoms. B is a direct bond to which a benzene ring directly bonds. [199] As examples of the alkyl group having 1 to 8 carbon atoms, the alkylene group having 1 to 8 carbon atoms, the alkyl group having 1 to 20 carbon atoms and the alkoxy group having 1 to 20 carbon atoms, those similar to those described above are mentioned, for example. As the halogen atom, for example, fluorine, chlorine, bromine, iodine and the like are mentioned. [200] B is preferably methylene substituted with a direct bond, methylene or an alkyl group having 1 to 8 carbon atoms, and more preferably a methylene group. [201] R 16 and R 17 are independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. As a typical example of an alkyl group having 1 to 8 carbon atoms, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, tert-pentyl, iso-octyl, tert- Octyl, 2-ethylhexyl and the like are mentioned. Of these, tert-butyl and tert-pentyl are more preferred. [202] E is preferably an alkoxy group having 4 to 20 carbon atoms or a fluorine atom. As a typical example of an alkoxy group having 4 to 20 carbon atoms, for example, the alkyl moiety is n-butyl, isobutyl, sec-butyl, tert-butyl, tert-pentyl, iso-octyl, tert-octyl, 2-ethylhexyl, cyclo Pentyl, cyclohexyl, cycloheptyl, cyclooctyl, 1-methylcyclopentyl, 1-methylcyclohexyl, 1-methyl-4-isopropylcyclohexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, Mention is made of the above-mentioned alkoxy groups which are pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, aicosyl and the like. [203] Among them, the alkyl moiety is tert-octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, cyclo Alkoxy which is pentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like is preferred, with fluorine atoms being most preferred. [204] Examples of the phosphorus-containing compound represented by the formula (6), [205] 2,2'-methylenebis (4,6-dimethylphenyl)-(2-ethylhexyl) phosphite; [206] 2,2'-methylenebis (4,6-diethylphenyl)-(2-ethylhexyl) phosphite; [207] 2,2'-methylenebis (4,6-di-n-propylphenyl)-(2-ethylhexyl) phosphite; [208] 2,2'-methylenebis (4,6-di-isopropylphenyl)-(2-ethylhexyl) phosphite; [209] 2,2'-methylenebis (4,6-di-n-butylphenyl)-(2-ethylhexyl) phosphite; [210] 2,2'-methylenebis (4,6-di-isobutylphenyl)-(2-ethylhexyl) phosphite; [211] 2,2'-methylenebis (4,6-di-sec-butylphenyl)-(2-ethylhexyl) phosphite; [212] 2,2'-methylenebis (4,6-di-tert-butylphenyl)-(2-ethylhexyl) phosphite; [213] 2,2'-methylenebis (4,6-di-tert-pentylphenyl)-(2-ethylhexyl) phosphite; [214] 2,2'-methylenebis (4,6-di-iso-octylphenyl)-(2-ethylhexyl) ethylphosphite; [215] 2,2'-methylenebis (4,6-di-tert-octylphenyl)-(2-ethylhexyl) phosphite; [216] 2,2'-methylenebis (4,6-di-tert-butylphenyl) methylphosphite; [217] 2,2'-methylenebis (4,6-di-tert-butylphenyl) ethylphosphite; [218] 2,2'-methylenebis (4,6-di-tert-butylphenyl) -n-propylphosphite; [219] 2,2'-methylenebis (4,6-di-tert-butylphenyl) -isobutyl phosphite; [220] 2,2'-methylenebis (4,6-di-tert-butylphenyl) -sec-butylphosphite; [221] 2,2'-methylenebis (4,6-di-tert-butylphenyl) -tert-butylphosphite; [222] 2,2'-methylenebis (4,6-di-tert-butylphenyl) -tert-pentylphosphite; [223] 2,2'-methylenebis (4,6-di-tert-butylphenyl) nonylphosphite; [224] 2,2'-methylenebis (4,6--di-tert-butylphenyl) decylphosphite; [225] 2,2'-methylenebis (4,6-di-methylphenyl) fluorinated phosphinite; 2,2'-methylenebis (4,6-di-ethylphenyl) fluorinated phosphinite; [226] 2,2'-methylenebis (4,6-di-n-propylphenyl) fluorinated phosphinite; 2,2'-methylenebis (4,6-di-isopropylphenyl) fluorinated phosphinite; [227] 2,2'-methylenebis (4,6-di-n-butylphenyl) fluorinated phosphinite; 2,2'-methylenebis (4,6-di-isobutylphenyl) fluorinated phosphinite; [228] 2,2'-methylenebis (4,6-di-sec-butylphenyl) fluorinated phosphinite; [229] 2,2'-methylenebis (4,6-di-tert-butylphenyl) fluorinated phosphinite; [230] 2,2'-methylenebis (4,6-di-tert-pentylphenyl) fluorinated phosphinite; [231] 2,2'-methylenebis (4,6-di-iso-octylphenyl) fluorinated phosphinite; [232] 2,2'-methylenebis (4,6-di-tert-octylphenyl) fluorinated phosphinite and the like. [233] Among the above, [234] 2,2'-methylenebis (4,6-di-n-propylphenyl)-(2-ethylhexyl) phosphite; [235] 2,2'-methylenebis (4,6-di-isopropylphenyl)-(2-ethylhexyl) phosphite; [236] 2,2'-methylenebis (4,6-di-n-butylphenyl)-(2-ethylhexyl) phosphite; [237] 2,2'-methylenebis (4,6-di-isobutylphenyl)-(2-ethylhexyl) phosphite; [238] 2,2'-methylenebis (4,6-di-sec-butylphenyl)-(2-ethylhexyl) phosphite; [239] 2,2'-methylenebis (4,6-di-tert-butylphenyl)-(2-ethylhexyl) phosphite; [240] 2,2'-methylenebis (4,6-di-tert-pentylphenyl)-(2-ethylhexyl) phosphite; [241] 2,2'-methylenebis (4,6-di-iso-octylphenyl)-(2-ethylhexyl) phosphite; [242] 2,2'-methylenebis (4,6-di-tert-octylphenyl)-(2-ethylhexyl) phosphite; [243] 2,2'-methylenebis (4,6-di-tert-butylphenyl) -n-propylphosphite; [244] 2,2'-methylenebis (4,6-di-tert-butylphenyl) -isobutyl phosphite; [245] 2,2'-methylenebis (4,6-di-tert-butylphenyl) -sec-butylphosphite; [246] 2,2'-methylenebis (4,6-di-tert-butylphenyl) -tert-butylphosphite; [247] 2,2'-methylenebis (4,6-di-tert-butylphenyl-tert-pentylphosphite; [248] 2,2'-methylenebis (4,6-di-tert-butylphenyl) nonylphosphite; [249] 2,2'-methylenebis (4,6-di-tert-butylphenyl) decylphosphite; [250] 2,2'-methylenebis (4,6-di-n-propylphenyl) fluorinated phosphinite; [251] 2,2'-methylenebis (4,6-di-isopropylphenyl) fluorinated phosphinite; [252] 2,2'-methylenebis (4,6-di-n-butylphenyl) fluorinated phosphinite; [253] 2,2'-methylenebis (4,6-di-isobutylphenyl) fluorinated phosphinite; [254] 2,2'-methylenebis (4,6-di-sec-butylphenyl) fluorinated phosphinite; [255] 2,2'-methylenebis (4,6-di-tert-butylphenyl) fluorinated phosphinite; [256] 2,2'-methylenebis (4,6-di-tert-pentylphenyl) fluorinated phosphinite; [257] 2,2'-methylenebis (4,6-di-iso-octylphenyl) fluorinated phosphinite; [258] 2,2'-methylenebis (4,6-di-tert-octylphenyl) fluorinated phosphinite and the like are preferable. [259] Subsequently, as the sulfur-containing antioxidant used in the present invention, for example, sulfur-containing compounds represented by the following formulas (7) to (9) (hereinafter referred to as sulfur-containing compounds) are mentioned. Two or more present sulfur containing antioxidants may be used in combination. [260] [261] (Wherein, R 18 represents an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms), [262] [263] (Wherein, R 19 , R 20 and R 21 each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms), [264] [265] (In formula, R <22> represents a C1-C30 alkyl group, a C7-C30 aralkyl group, or a C6-C30 aryl group.). [266] Of these, sulfides represented by the formula (7) or (9) are preferred. [267] In formula (7), the substituent R 18 represents an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, but R 18 is preferably an alkyl group having 1 to 20 carbon atoms and 5 to 20 carbon atoms. A cycloalkyl group, an alkylcycloalkyl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and a phenyl group. [268] Typical examples of alkyl groups include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, tert-pentyl, iso-octyl, tert-octyl, 2-ethyl Hexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, iconic, etc. are mentioned. [269] Moreover, as the cycloalkyl group, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like are mentioned, and as the alkylcycloalkyl group, for example, 1-methylcyclopentyl, 1-methylcyclohexyl, 1-methyl-4-isopropyl Cyclohexyl and the like are mentioned. As the aralkyl group, benzyl, α-methylbenzyl, α, α-dimethylbenzyl and the like are mentioned, but not limited thereto. [270] Examples of the sulfide represented by the formula (7) include pentaerythritol tetrakis (3-methylthiopropionate), [271] Pentaerythryl tetrakis (3-ethylthiopropionate), [272] Pentaerythryl tetrakis (3-n-propylthiopropionate), [273] Pentaerythryl tetrakis (3-isopropylthiopropionate), [274] Pentaerythryl tetrakis (3-n-butylthiopropionate), [275] Pentaerythryl tetrakis (3-isobutylthiopropionate), [276] Pentaerythryl tetrakis (3-sec-butylthiopropionate), [277] Pentaerythryl tetrakis (3-tert-butylthiopropionate), [278] Pentaerythryl tetrakis (3-tert-pentylthiopropionate), [279] Pentaerythryl tetrakis (3-iso-octylthiopropionate), [280] Pentaerythryl tetrakis (3-tert-octylthiopropionate), [281] Pentaerythryl tetrakis (3- (2-ethylhexyl) thiopropionate), [282] Pentaerythryl tetrakis (3-nonylthiopropionate), [283] Pentaerythryl tetrakis (3-decylthiopropionate), [284] Pentaerythryl tetrakis (3-undecylthiopropionate), [285] Pentaerythryl tetrakis (3-dodecylthiopropionate), [286] Pentaerythryl tetrakis (3-tridecylthiopropionate), [287] Pentaerythryl tetrakis (3-tetradecylthiopropionate), [288] Pentaerythryl tetrakis (3-pentadedecylthiopropionate), [289] Pentaerythryl tetrakis (3-hexadecylthiopropionate), [290] Pentaerythryl tetrakis (3-heptadecylthiopropionate), [291] Pentaerythryl tetrakis (3-octadecylthiopropionate), [292] Pentaerythryl tetrakis (3-nonadecylthiopropionate), [293] Pentaerythryl tetrakis (3-icosylthiopropionate), [294] Pentaerythryl tetrakis (3-cyclopentylthiopropionate), [295] Pentaerythryl tetrakis (3-cyclohexylthiopropionate), [296] Pentaerythryl tetrakis (3-cycloheptylthiopropionate), [297] Pentaerythryl tetrakis (3-cyclooctylthiopropionate), [298] Pentaerythryl tetrakis (3- (1-methylcyclopentyl) thiopropionate), [299] Pentaerythryl tetrakis (3- (1-methylcyclohexyl) thiopropionate), [300] Pentaerythryl tetrakis (3- (1-methyl-4-isopropylcyclohexyl) thiopropionate), [301] Pentaerythryl tetrakis (3-benzylthiopropionate), [302] Pentaerythryl tetrakis (3- (α-methylbenzyl) thiopropionate), [303] Pentaerythryl tetrakis (3- (α, α-dimethylbenzyl) thiopropionate) and the like. [304] Among these, pentaerythryl tetrakis (3-n-butylthiopropionate), [305] Pentaerythryl tetrakis (3-isobutylthiopropionate), [306] Pentaerythryl tetrakis (3-sec-butylthiopropionate), [307] Pentaerythryl tetrakis (3-tert-butylthiopropionate), [308] Pentaerythryl tetrakis (3-tert-pentylthiopropionate), [309] Pentaerythryl tetrakis (3-iso-octylthiopropionate), [310] Pentaerythryl tetrakis (3-tert-octylthiopropionate), [311] Pentaerythryl tetrakis (3- (2-ethylhexyl) thiopropionate), [312] Pentaerythryl tetrakis (3-nonylthiopropionate), [313] Pentaerythryl tetrakis (3-decylthiopropionate), [314] Pentaerythryl tetrakis (3-undecylthiopropionate), [315] Pentaerythryl tetrakis (3-dodecylthiopropionate), [316] Pentaerythryl tetrakis (3-tridecylthiopropionate), [317] Pentaerythryl tetrakis (3-tetradecylthiopropionate), [318] Pentaerythryl tetrakis (3-pentadedecylthiopropionate), [319] Pentaerythryl tetrakis (3-hexadecylthiopropionate), [320] Pentaerythryl tetrakis (3-heptadecylthiopropionate), [321] Pentaerythryl tetrakis (3-octadecylthiopropionate), [322] Pentaerythryl tetrakis (3-nonadecylthiopropionate), [323] Pentaerythryl tetrakis (3-icosylthiopropionate) is preferred. [324] In formula (8), R 19 , R 20 and R 21 each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms. [325] As the alkyl group, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, tert-pentyl, iso-octyl, tert-octyl, 2-ethylhexyl, nonyl , Decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl and the like. Of these, preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, tert-pentyl, iso-octyl, tert-octyl, 2-ethylhexyl and the like Used. [326] As the aralkyl group, for example, benzyl, α-methylbenzyl, α, α-dimethylbenzyl and the like are mentioned. As the aryl group, for example, phenyl, methylphenyl, dimethylphenyl and the like are mentioned. [327] Examples of the sulfide represented by the formula (8), [328] 4,4'-thiobis (2,5-dimethylphenol) [329] 4,4'-thiobis (2-ethyl-5-methylphenol); [330] 4,4'-thiobis (2-n-propyl-5-methylphenol); [331] 4,4'-thiobis (2-isopropyl-5-methylphenol) [332] 4,4'-thiobis (2-n-butyl-5-methylphenol); [333] 4,4'-thiobis (2-isobutyl-5-methylphenol); [334] 4,4'-thiobis (2-sec-butyl-5-methylphenol); [335] 4,4'-thiobis (2-tert-butyl-5-methylphenol); [336] 4,4'-thiobis (2-tert-pentyl-5-methylphenol); [337] 4,4'-thiobis (2-iso-octyl-5-methylphenol); [338] 4,4'-thiobis (2-tert-octyl-5-methylphenol); [339] 4,4'-thiobis (2- (2-ethylhexyl) -5-methylphenol); [340] 4,4'-thiobis (2-nonyl-5-methylphenol); [341] 4,4'-thiobis (2-decyl-5-methylphenol); [342] 4,4'-thiobis (2-tert-butyl-5-ethylphenol); [343] 4,4'-thiobis (2-tert-butyl-5-n-propylphenol); [344] 4,4'-thiobis (2-tert-butyl-5-isopropylphenol); [345] 4,4'-thiobis (2-tert-butyl-5-n-butylphenol); [346] 4,4'-thiobis (2-tert-butyl-5-iso-butylphenol); [347] 4,4'-thiobis (2-tert-butyl-5-sec-butylphenol); [348] 4,4'-thiobis (2-tert-butyl-5-tert-butylphenol); [349] 4,4'-thiobis (2-tert-butyl-5-tert-pentylphenol) and the like. [350] Especially, [351] 4,4'-thiobis (2-n-propyl-5-methylphenol); [352] 4,4'-thiobis (2-isopropyl-5-methylphenol); [353] 4,4'-thiobis (2-n-butyl-5-methylphenol); [354] 4,4'-thiobis (2-isobutyl-5-methylphenol); [355] 4,4'-thiobis (2-sec-butyl-5-methylphenol); [356] 4,4'-thiobis (2-tert-butyl-5-methylphenol) [357] 4,4'-thiobis (2-tert-pentyl-5-methylphenol); [358] 4,4'-thiobis (2-iso-octyl-5-methylphenol); [359] 4,4'-thiobis (2-tert-octyl-5-methylphenol); [360] 4,4'-thiobis (2- (2-ethylhexyl) -5-methylphenol); [361] 4,4'-thiobis (2-nonyl-5-methylphenol); [362] 4,4'-thiobis (2-decyl-5-methylphenol); [363] 4,4'-thiobis (2-tert-butyl-5-ethylphenol); [364] 4,4'-thiobis (2-tert-butyl-5-n-propylphenol); [365] 4,4'-thiobis (2-tert-butyl-5-isopropylphenol) etc. are preferable. [366] Furthermore, in formula (9), R 22 represents an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms. [367] As the alkyl group, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, tert-pentyl, iso-octyl, tert-octyl, 2-ethylhexyl, nonyl , Decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl and the like are mentioned, but are not limited thereto. [368] As the aralkyl group, for example, benzyl, α-methylbenzyl, α, α-dimethylbenzyl and the like are mentioned. As the aryl group, for example, phenyl, methylphenyl, dimethylphenyl and the like are mentioned, but not limited thereto. [369] Examples of the sulfide represented by the formula (9) include methyl 3,3'-thiodipropionate; Ethyl 3,3'-thiodipropionate; n-propyl 3,3'-thiodipropionate; Isopropyl 3,3'-thiodipropionate; n-butyl 3,3'-thiodipropionate; Isobutyl 3,3'-thiodipropionate; sec-butyl 3,3'-thiodipropionate; tert-butyl 3,3'-thiodipropionate; tert-pentyl 3,3'-thiodipropionate; Isooctyl 3,3'-thiodipropionate; tert-octyl 3,3'-thiodipropionate; 2-ethylhexyl 3,3'-thiodipropionate; Nonyl 3,3'-thiodipropionate; Decyl 3,3'-thiodipropionate; Undecyl 3,3'-thiodipropionate; Dodecyl 3,3'-thiodipropionate; Tridecyl 3,3'-thiodipropionate; Tetradecyl 3,3'-thiodipropionate; Pentadecyl 3,3'-thiodipropionate; Hexadecyl 3,3'-thiodipropionate; Heptadecyl 3,3'-thiodipropionate; Octadecyl 3,3'-thiodipropionate; Nonadecyl 3,3'-thiodipropionate; Iconic 3,3'-thiodipropionate; Cyclopentyl 3,3'-thiodipropionate; Cyclohexyl 3,3'-thiodipropionate; Cycloheptyl 3,3'-thiodipropionate; Cyclooctyl 3,3'-thiodipropionate; 1-methylcyclopentyl 3,3'-thiodipropionate; 1-methylcyclohexyl 3,3'-thiodipropionate; 1-methyl-4-isopropylcyclohexyl 3,3'-thiodipropionate; Benzyl 3,3'-thiodipropionate; α-methylbenzyl 3,3'-thiodipropionate; α, α-dimethylbenzyl 3,3'-thiodipropionate; And the like. [370] In particular, n-butyl 3,3'- thiodipropionate, isobutyl 3,3'- thiodipropionate, sec-butyl 3,3'- thiodipropionate, tert-butyl 3,3 ' -Thiodipropionate, tert-pentyl 3,3'- thiodipropionate, iso-octyl 3,3'- thiodipropionate, tert-octyl 3,3'- thiodipropionate, 2 -Ethylhexyl 3,3'- thiodipropionate, nonyl 3,3'- thiodipropionate, decyl 3,3'- thiodipropionate, undecyl 3,3'- thiodipropionate , Dodecyl 3,3'-thiodipropionate, tridecyl 3,3'-thiodipropionate, tetradecyl 3,3'-thiodipropionate, pentadecyl 3,3'-thiodiprop Cypionate, hexadecyl 3,3'-thiodipropionate, heptadecyl 3,3'-thiodipropionate, octadecyl 3,3'-thiodipropionate, nonadecyl 3,3'-tee Odypropionate, Icosyl 3,3'-thiodipropionate It is. [371] The polymer electrolyte composition of the present invention contains a polymer electrolyte and an antioxidant selected from the group consisting of the above-mentioned antioxidants containing trivalent phosphorus, and antioxidants containing sulfur, wherein the trivalent phosphorus-containing antioxidant and sulfur Containing antioxidants are used in combination. [372] Examples of the polymer electrolyte of the present invention include (A) a polymer electrolyte in which ion-exchange groups are introduced into a polymer whose main chain is composed of aliphatic hydrocarbons; (B) a polymer electrolyte in which ion-exchange groups are introduced into a polymer composed of aliphatic hydrocarbons in which some hydrogen atoms of the main chain are substituted with fluorine; (C) a polymer electrolyte in which ion-exchange groups are introduced into a polymer having a main chain having an aromatic ring; (D) a polymer electrolyte in which ion-exchange groups are introduced into a polymer such as polysiloxane and polyphosphazene wherein the main chain is substantially free of carbon atoms; (E) The polymer electrolyte etc. which were introduce | transduced into the ion exchangeable group are contained in the copolymer which consists of two or more repeating units selected from the repeating unit which consists of polymers (A) to (D) in which an ion exchangeable group is not introduce | transduced. . (C) is preferable from a heat resistant viewpoint. [373] As ion exchange groups, for example, cation exchange groups such as -SO 3 H (sulfonic acid group), -COOH (carboxylic acid group), -P0 (CH) 2 (phosphate group), -POH (OH) (force Pinic acid group), -SO 2 NHSO 2- (sulfonylimido group),-(S0 2 ) 3 CH (sulfonylmethylthio group), -Ph (OH) (phenolic hydroxy group, wherein Ph represents a phenyl group); Anion exchange groups such as -NH 2 (primary amino group), -NHR (secondary amino group), -NRR '(tertiary amino group), -NRR'R "(quaternary ammonium group), -NH 3 + -(ammonium group (R, R 'and R "each independently represents an alkyl group, a cycloalkyl group, an aryl group, etc.) can be exemplified. The ion exchange groups can form salts with counterions in part or in whole. [374] Moreover, two or more ion exchange groups can be introduced into one polymer electrolyte. As more preferred ion exchange groups, sulfonic acid groups (-SO 3 H) and / or phosphoric acid groups (-PO (OH) 2 ) can be mentioned, with sulfonic acid groups being more preferred. [375] As the above-mentioned polymer electrolyte of (A), for example, poly (vinyl sulfonic acid), poly (styrene sulfonic acid), poly (α-methylstyrene) sulfonic acid) and the like are mentioned. [376] Furthermore, as the polymer electrolyte of the above-mentioned (B), a sulfonic acid-type polystyrene- composed of a main chain prepared by copolymerization of a fluorohydrocarbon-based vinyl monomer and a hydrocarbon-based vinyl monomer, and a hydrocarbon-based side chain having sulfonic acid groups. Graft-ethylene-tetrafluoroethylene copolymer (ETFE: for example, Japanese Patent Application Laid-open No. Hei 9-102322), and a fluorohydrocarbon-based vinyl monomer and a hydrocarbon-based vinyl monomer are copolymerized therein, and a sulfonic acid group is introduced therein. Sulfonic acid-type poly (trifluorostyrene) -graft-ETFE membranes prepared as solid polymer electrolyte membranes obtained by graft copolymerization of α, β, β-trifluorostyrene on membranes prepared by For example, US Pat. Nos. 4,012,303 and 4,605,685); Etc. are included. [377] As the polymer electrolyte of the above-mentioned (C), polymers in which sulfonic acid groups are each introduced into a homopolymer, for example, poly (ether ether ketone), polysulfone, poly (ether sulfone), poly (arylene ether), polyphosphazene , Polyimide, poly (4-phenoxybenzoyl-1,4-phenylene), poly (phenylene sulfide), poly (phenyl quinoxalene) may be mentioned, and these may contain heteroatoms such as oxygen atoms in the main chain. Has; Aryl-sulfonated polybenzimidazoles, alkyl-sulfonated polybenzimidazoles, alkyl-phosphonated polybenzimidazoles (e.g., Japanese Patent Laid-Open No. 9-110982), phosphonated poly (phenylene ethers) Et al. (Eg, J. Appl. Polym. Sci., 18, 1969 (1974)). [378] As the polymer electrolyte of the above-mentioned (D), polysiloxanes having a phosphoric acid group, for example described in Polymer Prep., 41, No. 1, 70 (2000), and the like, are mentioned. [379] The polymer electrolyte of the above-mentioned (E) may be one in which an ion exchange group is introduced into a random copolymer, an ion exchange group is introduced into another copolymer, or an ion exchange group is introduced into a block copolymer. As the sulfone group which is an ion exchangeable group is introduced into the random copolymer, for example, sulfonated poly (ether sulfone) -dihydroxybiphenyl copolymer is mentioned (for example, Japanese Patent Laid-Open No. 11-116679). ) [380] As a specific example of a block having a sulfonic acid group and / or a phosphate group as an ion exchangeable group, for example, the sulfonic acid group and / or the phosphate group may be polystyrene, poly (α-methylstyrene), poly (allyl phenyl ether), poly ( Phenyl glycidyl ether), poly (phenylene ether), poly (phenylene sulfide), poly (phenylene), poly (aniline), poly (ether ether ketone), poly (ether ether sulfone), polysulfone, Mention is made of blocks introduced into blocks such as poly (phenylmethylsiloxane), poly (diphenylsiloxane), poly (phenylmethylphosphazene), poly (diphenylphosphazene), epoxy resins. [381] The polymer electrolyte composition of the present invention contains the above-mentioned antioxidant and the above-mentioned polymer electrolyte. The amount of antioxidant is generally 0.1 to 30% by weight of the polymer electrolyte, preferably 1 to 20% by weight. If the amount of the antioxidant is too small, the effect of improving the oxidation resistance of the polymer electrolyte composition membrane obtained from the polymer electrolyte composition may be less. If the amount is too large, the polymer electrolyte composition membrane obtained from the polymer electrolyte composition may not be homogeneous. . When two or more antioxidants are used, the total amount is preferably in the above-mentioned range. [382] The method for preparing the composition is not particularly limited, and for example, a method of dissolving an antioxidant in a polymer electrolyte solution and then removing the solvent, and a solvent after removing the solvent after mixing the antioxidant under a condition previously dispersed in the solvent with the polymer electrolyte solution. It may include how to. [383] Moreover, when preparing the polymer electrolyte composition of the present invention, additives such as plasticizers, stabilizers, and release agents may be added. [384] Moreover, when preparing the polymer electrolyte composition of the present invention, or when the polymer electrolyte composition of the present invention is processed or molded by film forming or the like, an intermolecular crosslinked structure can be introduced into the polymer electrolyte. The intermolecular crosslinked structure is a state in which the polymer chains are chemically interconnected and can be introduced by irradiating the electrolyte composition with an electron beam, radiation, ultraviolet light, or the like. At this time, a well-known crosslinking agent can be used suitably. [385] Moreover, antioxidants other than the above-mentioned trivalent phosphorus-containing antioxidants and sulfur-containing antioxidants can be used in the formulation. [386] When the polymer electrolyte composition of the present invention is applied to a fuel cell, it is suitably used as the polymer electrolyte composition membrane. Although the manufacturing method of a polymer electrolyte composition membrane is not specifically limited, The membrane manufacturing method (solution casting method) of a solution state is preferable. [387] Specifically, the polymer electrolyte composition of the present invention is prepared by dissolving the polymer electrolyte composition in a suitable solvent, casting the solution on a glass plate, and removing the solvent. The solvent used for producing the film is not particularly limited as long as it can dissolve the polymer electrolyte and is removed after coating. Preferably, aprotic polar compounds such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidine, dimethyl sulfoxide; Or chlorine containing compounds such as dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, dichlorobenzene; Alcohols such as methanol, ethanol, propanol; And alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether. These may be used alone, or two or more solvent mixtures may be used if necessary. Among these, the solubility of the polymer is excellent, and dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and dimethyl sulfoxide are preferable. [388] When the polymer electrolyte composition of the present invention is used in a fuel cell, it can be used as a polymer electrolyte composition composite membrane obtained by complexing a polymer electrolyte with a support. [389] The support is impregnated with the polymer electrolyte composition and is mainly a parent material used to further improve the rigidity, flexibility, and durability of the polymer electrolyte composition composite membrane. Therefore, it can be used regardless of the form, and the shape and quality of the material such as fiber form and porous membrane form satisfy the above-mentioned use, but to use as a polymer electrolyte composition composite membrane of a polymer electrolyte fuel cell using a porous membrane It is preferable. [390] As the form of the porous membrane used for this purpose, the thickness is generally 1 to 100 μm, preferably 3 to 30 μm, more preferably 5 to 20 μm, and the pore diameter is generally 0.01 to 10 μm, Preferably it is 0.02-7 micrometers, and a porosity is generally 20-98%, Preferably it is 30-95%. If the thickness of the porous support is too thin, the rigid strengthening effect or the strengthening effect of improving flexibility and durability may be insufficient after preparing the composite, and thus gas leaks (cross leaks) may occur. Moreover, when the thickness of the membrane is too thick, the electrical resistance can be large and the obtained composite membrane may be undesirable as the polymer electrolyte composition composite membrane of the polymer electrolyte fuel cell. If the pore size is too small, impregnation of the solid polymer electrolyte composition may be difficult, and if the pore size is too large, the strengthening effect of the solid polymer electrolyte composition may be weakened. If the porosity is too small, the resistance as a solid electrolyte composite membrane can be large, if too large, the rigidity of the porous membrane itself can be weakened, and the strengthening effect can be reduced. [391] Moreover, as the material quality of the porous support membrane, an aliphatic polymer or a fluorine-containing polymer is preferable in view of heat resistance and physical rigidity. [392] Preferred aliphatic polymers include, but are not limited to, polyethylene, polypropylene, ethylene-propylene copolymers, and the like. Moreover, the polyethylenes mentioned herein include ethylene polymers having the crystal structure of polyethylene. Examples include high density polyethylene, copolymers of ethylene with other monomers, and specifically copolymers of ethylene with α-olefins, designated linear low density polyethylene (LLDPE), and the like. Among the above, polyethylene having a high molecular weight is preferable, and high density polyethylene having an ultra high molecular weight is more preferable. Polypropylene referred to herein includes propylene polymers and propylene block copolymers, random copolymers (which are copolymers of ethylene and 1-butene, etc.) having a crystal structure of polypropylene. Polypropylene having high molecular weight is preferred, and polypropylene having ultra high molecular weight is more preferred. When heat resistance is required for the polymer electrolyte composite membrane, polypropylene generally has higher heat resistance than polyethylene, so polypropylene is more preferable than ethylene. [393] Moreover, as the fluorine-containing polymer, a thermoplastic resin having at least one carbon-fluorine bond in the molecule is used. In general, those in which most of the hydrogen of the aliphatic polymer are all substituted with fluorine are used. [394] As examples of fluorine-containing polymers which are preferably used, polytrifluoroethylene, polytetrafluoroethylene, polychlorotrifluoroethylene, poly (tetrafluoroethylene-hexafluoropropylene), poly (tetrafluoroethylene- Perfluoroalkyl ethers), poly (vinylidene fluoride) and the like are mentioned, but are not limited to these. Of these, polytetrafluoroethylene and poly (tetrafluoroethylene-hexafluoropropylene) are preferred in the present invention, and polytetrafluoroethylene is particularly preferable. Moreover, from the viewpoint of excellent mechanical rigidity, it is preferable that the fluorine-containing polymer has an average molecular weight of 100,000 or more. [395] When the membrane or the synthetic membrane containing the polymer electrolyte composition of the present invention is used in a fuel cell, the thickness of the membrane is not particularly limited, but is generally 3 to 200 µm, preferably 4 to 100 µm, more preferably 5 To 50 μm. If the thickness of the film is too thin, the rigidity of the film may be lowered, and if the thickness of the film is too thick, the electrical resistance may be large. The thickness of the membrane can be controlled by appropriately selecting the concentration of the polymer electrolyte composition solution or the coating amount of the polymer electrolyte composition solution, the thickness of the porous support membrane and the coating thickness of the porous support membrane. [396] Next, the fuel cell of the present invention is described in detail. [397] The fuel cell of the present invention comprises a membrane containing the polymer electrolyte composition of the present invention, and can be produced by bonding an electrically conductive material and a catalyst as current collectors to both surfaces of the aforementioned membrane, respectively. [398] The catalyst is not particularly limited as long as the redox reaction is activated with hydrogen or oxygen, and a known catalyst can be used, but it is preferable to use fine particles of platinum. The fine particles of platinum are preferably used supported by carbon in the form of particles or in the form of fibers such as activated carbon or graphite. [399] In addition, a material known as an electrically conductive material may be used as the current collector, but a porous carbon fabric or carbon paper is preferable because it efficiently transfers the raw material gas to the catalyst. [400] For a method of contacting carbon or platinum fine particles supported with fine particles of platinum to a porous carbon cloth or carbon paper and a method of contacting the polymer electrolyte composition film, for example, see J. Electrochem. Soc .: Electrochemical Science and Technology, 1988, 135 (9), 2209. [401] Example [402] The present invention is described in detail according to the following examples, but the present invention is not limited to the following examples. [403] Preparation Example 1 [Polymer Electrolyte (P1)] [404] Anhydrous copper chloride (I) and 2-methylbenzimidazole were stirred at room temperature under air for 15 minutes. To this was added 2-phenylphenol, 4,4'-dihydroxybiphenyl and toluene, the mixture was stirred at 50 ° C. under an oxygen atmosphere for 10 hours, after which methanol containing hydrochloric acid was poured to precipitate the polymer, Was filtered and dried to afford poly (phenylphenylene ether). Subsequently, in a flask equipped with an azeotropic distillation apparatus, SUMIKAEXEL PES5003P (manufactured by Sumitomo Chemical Co., Ltd .; polyether sulfone having hydroxyl group (s) at the end (s)), potassium carbonate, N, N-dimethylacetamide ( Then toluene) and toluene were added, the mixture was heated and stirred, dehydration was carried out under azeotropic distillation conditions of toluene and and toluene was distilled off, and then 4,4'-difluorobenzophenone Was added and the mixture was heated to 160 ° C. and stirred for 10 h. The reaction solution was added dropwise to a large amount of hydrogen chloride-acidic methanol, and the resulting precipitate was collected by filtration and dried to obtain a block copolymer. The obtained block copolymer was dissolved in 98% sulfuric acid with stirring at room temperature, sulfonated, and the product was added dropwise to ice water to precipitate, and the precipitate was collected by filtration, rinsed and dried to obtain a sulfonated block copolymer. The polymer electrolyte is hereinafter abbreviated (P1). [405] Preparation Example 2 [Polymer Electrolyte (P2)] [406] 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybiphenyl and 4,4'-dichlorodiphenyl sulfone, using diphenyl sulfone at a temperature of 200 to 290 DEG C as a solvent, Co-condensed with a molar ratio of 7: 3: 10. The obtained polymer was sulfonated with concentrated sulfuric acid to obtain a random copolymer having sulfonic acid group introduced into the biphenyl unit. The polymer electrolyte is hereinafter abbreviated as P2. [407] Antioxidant [408] S-1: 2,4,8,10-tetra-tert-butyl-6- [3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propoxy] dibenzo [d, f] [1,3,2] dioxaphosphine; Sumitomo Chemical Co., Ltd. Manufactured by trade name: SUMILIZER GP. [409] S-2: tris (2,4-di-tert-butylphenyl) phosphite; Sumitomo Chemical Co., Ltd. Manufacture, trade name: SUMILIZER P-16. [410] S-3: tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene-di-phosphonite; Clearant Co., Ltd. Manufacture, Trade Name: SANDOSTAB P-EPQ. [411] S-4: di-octadecylpentaerythritol diphosphonite; ASAHIDENKA Co., Ltd. Manufacture, trade name: ADEKASTAB PEP-8. [412] S-5: bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-diphosphite; ASAHIDENKA Co., Ltd. Manufactured by trade name: ADEKASTAB PEP-36. [413] S-6: bis (2,4-di-tert-butylphenyl) pentaerythritol-di-phosphite; GE Specialty Chemicals Co., Ltd. Manufacture, trade name: ULTRANOX 626. [414] S-7: 2,2'-methylenebis (4,6-di-tert-butylphenyl)-(2-ethylhexyl); ASAHIDENKA Co., Ltd. Manufactured by trade name: ADEKASTAB HP-1O. [415] S-8: tetrakis (2,4-di-tert-butyl-5-methylphenyl) -4,4'-biphenylene-di-phosphonite; YOSHITOMI Fine Chemicals Co., Ltd. Manufacture, Trade Name: GSYP-101. [416] S-9: pentaerythryl-tetrakis- (3-dodecylthiopropionate); Sumitomo Chemical Co., Ltd. Manufacture, Trade Name: SUMILIZER TP-D. [417] S-10: 4,4'-thiobis (2-tert-butyl-5-methylphenol); Sumitomo Chemical Co., Ltd. Manufacture, Trade Name: SUMILIZER WX-R. [418] S-11: tetradecyl-3,3'-thiodipropionate; Sumitomo Chemical Co., Ltd. Manufacture, Trade Name: SUMILIZER TPM. [419] S-12: octadecyl-3,3'-thiodipropionate; Sumitomo Chemical Co., Ltd. Manufacture, Trade Name: SUMILIZER TPS. [420] S-13: dodecyl-3,3'-thiodipropionate; Sumitomo Chemical Co., Ltd. Manufacture, Trade Name: SUMILIZER TPL-R. [421] O-1: 4,4'-butylene-bis (2-tert-butyl-5-methylphenol); Sumitomo Chemical Co., Ltd. Manufacture, Trade Name: SUMILIZER BBM-S. [422] Evaluation of radical resistance [423] Each polymer electrolyte membrane was immersed in an aqueous solution in which ferric chloride was added to a 3% aqueous hydrogen peroxide solution at 90 ° C. at 0.25 ppm, and evaluation of oxidation resistance was performed by weight change of the membrane after 20 minutes. The weight retention rate (%) is expressed by a value obtained by dividing the weight after 20 minutes of deposition by the weight before deposition by 100%. [424] Measurement of Proton Conductivity [425] The measurement of proton conductivity is carried out by SI12 60-TYPE IMPEDANCE GAIN / PHASE ANALYZER (IMPEDANCE / GAIN-PHASE ANALYZER, Solartoron Co., Ltd.) under the AC impedance measurement method at 80W and 90% RH in a container of constant humidity and temperature. Production) and SI1287-TYPE POTENTIOSTAT (manufactured by ELECTRCCHEMICAL INTERFACE, Solartoron Co., Ltd.). The unit is S / cm. [426] Evaluation of Fuel Cell Characteristics [427] Fibrous carbon as an electrically conductive material and a platinum catalyst on a porous carbon woven fabric were bonded to both sides of the polymer electrolyte composition membrane. Humidified oxygen gas was flowed to one side of the unit, humidified hydrogen gas was flowed to the other side, and power generation characteristics of the contact were measured. [428] Examples 1-8 [429] [Preparation of Polymer Electrolyte Membrane Containing Polymer Electrolyte (P1) and Trivalent Phosphorus-containing Antioxidant] [430] A solution was prepared by mixing 1.425 g of P1, 0.075 g of trivalent phosphorus-containing antioxidant and 9.075 g of DMAc, and applying the mixture onto a glass plate to develop. The solvent was dried under atmospheric pressure to obtain a polymer electrolyte composition membrane. Any polymer electrolyte membrane had a homogeneous appearance. The evaluation results of the radical resistance are shown in Table 1 below. [431] Comparative Example 1 [432] [Production of Polymer Electrolyte Membrane Containing Only Polymer Electrolyte (P1)] [433] The polymer electrolyte membrane was obtained in the same manner as in Examples 1 to 8 except that no oxidizing agent was added. The obtained polymer electrolyte membrane had a homogeneous appearance. The results of evaluating the radical resistance are shown in Tables 1 and 5 below. [434] Comparative Example 2 [435] [Preparation of Polymer Electrolyte Membrane Containing Polymer Electrolyte (P1) and Phenolic-Based Antioxidant] [436] A polymer electrolyte membrane was obtained in the same manner as in Examples 1 to 8, except that a phenol-based antioxidant was used instead of the trivalent phosphorus-containing antioxidant. The obtained polymer electrolyte membrane had a homogeneous appearance. The results of evaluating the radical resistance are shown in Tables 1 and 5 below. [437] ExampleAntioxidantWeight retention (%) Example 1S-190 Example 2S-290 Example 3S-389 Example 4S-489 Example 5S-584 Example 6S-681 Example 7S-785 Example 8S-889 Comparative Example 1-70 Comparative Example 2O-176 [438] Example 9 [439] [Production of Polymer Electrolyte Composite Membrane] [440] As the porous membrane, a porous support membrane made of polytetrafluoroethylene (membrane thickness: 15 mu m, porosity: 90%, pore diameter: 3 mu m) was used. The porous membrane was fixed on a glass plate. A solution was prepared by mixing 1.425 g of P1, 0.075 g of trivalent phosphorus containing antioxidant used in Example 3 and 9.075 g of DMAc, and spreading the mixture evenly on the porous membrane. At this time, it was observed that the opaque porous support membrane became transparent by the phenomenon that the above-mentioned solution penetrated into the porous support and reached the back side of the porous support membrane. It was dried at 80 ° C. under atmospheric pressure. Subsequently, rinsing with ion-exchanged water gave a polymer electrolyte composite membrane. Table 2 shows the results of the evaluation of the radical resistance. [441] Example 10 [442] [Production of Polymer Electrolyte Composite Membrane] [443] As the porous membrane, a porous membrane made of polyethylene (membrane thickness: 9 mu m, porosity: 36%, pore diameter: 0.04 mu m) was used. The porous membrane was fixed on a glass plate. A solution was prepared by mixing 1.425 g of P1, 0.075 g of trivalent phosphorus containing antioxidant used in Example 3 and 9.075 g of DMAc, and spreading the mixture evenly on the porous membrane. At this time, it was observed that the opaque porous support membrane became transparent by the phenomenon that the above-mentioned solution penetrated into the porous support and reached the back side of the porous support membrane. It was dried at 80 ° C. under atmospheric pressure. Subsequently, rinsing with ion-exchanged water gave a polymer electrolyte composite membrane. Table 2 shows the results of the evaluation of the radical resistance. [444] Comparative Example 3 [445] [Production of Polymer Electrolyte Composite Membrane] [446] A polymer electrolyte composite membrane was obtained in the same manner as in Example 9 except that no antioxidant was used. Table 2 shows the results of the evaluation of the radical resistance. [447] Comparative Example 4 [448] [Production of Polymer Electrolyte Composite Membrane] [449] A polymer electrolyte composite membrane was obtained in the same manner as in Example 10 except that no antioxidant was used. The obtained polymer electrolyte composite membrane had a homogeneous appearance. The results of evaluating the radical resistance are shown in Tables 2 and 6. [450] ExampleAntioxidantWeight retention (%) Example 9S-398 Comparative Example 3-81 Example 10S-395 Comparative Example 4-75 [451] Example 11 [452] [Production of Polymer Electrolyte Membrane] [453] A solution was prepared by suitably mixing 1.425 g of P2, 0.075 g of the trivalent phosphorus-containing antioxidant used in Example 3 and 9.075 g of DMAc, and spreading the mixture evenly on a glass plate. The solvent was dried under atmospheric pressure to obtain a polymer electrolyte membrane. Table 3 shows the results of the evaluation of the radical resistance. [454] Comparative Example 5 [455] [Production of Polymer Electrolyte Membrane] [456] A polymer electrolyte membrane was obtained in the same manner as in Example 11 except that no antioxidant was added. The polymer electrolyte membrane had a homogeneous appearance. Table 3 shows the results of the evaluation of the radical resistance. [457] ExampleAntioxidantWeight retention (%) Example 11S-398 Comparative Example 5-85 [458] For Example 3, Example 9 and Comparative Example 1, evaluation of proton conductivity and fuel cell characteristics (operation of start and stop for 1 week were repeated) was performed. The results are shown in Table 4. [459] Proton Conductivity (S / cm)Fuel Cell Characterization Example 39 × 10 -2 No fuel cell deterioration and no gas leaks observed Example 99 × 10 -2 No fuel cell deterioration and no gas leaks observed Comparative Example 19 × 10 -2 Gas leaks occur and fuel cell deterioration observed [460] Examples 12-16 [461] [Production of Polymer Electrolyte Membrane] [462] A solution was prepared by suitably mixing 1.425 g of P1, 0.075 g of a sulfur-containing antioxidant and 9.075 g of DMAc, and applying the mixture on a glass plate to develop uniformly. The solvent was dried under atmospheric pressure to obtain a polymer electrolyte membrane. Any polymer electrolyte membrane had a homogeneous appearance. Table 5 shows the results of the evaluation of the radical resistance. [463] ExampleAntioxidantWeight retention (%) Example 12S-987 Example 13S-1078 Example 14S-1184 Example 15S-1285 Example 16S-1387 Comparative Example 1-70 Comparative Example 2O-176 [464] Example 17 [465] [Production of Polymer Electrolyte Composition Composite Membrane] [466] As the porous membrane, a porous membrane made of polytetrafluoroethylene (membrane thickness: 15 mu m, porosity: 90%, pore diameter: 3.0 mu m) was used. The porous membrane was fixed on a glass plate. A solution was prepared by mixing 1.425 g of P1, 0.075 g of sulfur-containing antioxidant used in Example 12 and 9.075 g of DMAc, and spreading the mixture evenly on the porous membrane. At this time, it was observed that the opaque porous support membrane became transparent by the phenomenon that the above-mentioned solution penetrated into the porous support and reached the back side of the porous support membrane. It was dried at 80 ° C. under atmospheric pressure. Subsequently, it was rinsed with ion-exchanged water to obtain a polymer electrolyte composite membrane. Table 6 shows the results of the evaluation of the radical resistance. [467] Example 18 [468] [Production of Polymer Electrolyte Composite Membrane] [469] As the porous membrane, a porous membrane made of polyethylene (membrane thickness: 9 mu m, porosity: 36%, pore diameter: 0.04 mu m) was used. The porous membrane was fixed on a glass plate. A solution was prepared by mixing 1.425 g of P1, 0.075 g of sulfur-containing antioxidant used in Example 11 and 9.075 g of DMAc, and spreading the mixture evenly on the porous membrane. At this time, it was observed that the opaque porous support membrane became transparent by the phenomenon that the above-mentioned solution penetrated into the porous support and reached the back side of the porous support membrane. It was dried at 80 ° C. under atmospheric pressure. Then, it was rinsed with ion-exchanged water to obtain a polymer electrolyte composition composite membrane. Table 6 shows the results of the evaluation of the radical resistance. [470] ExampleAntioxidantWeight retention (%) Example 17S-995 Comparative Example 3-81 Example 18S-992 Comparative Example 4-75 [471] Example 19 [472] [Production of Polymer Electrolyte Composition Membrane] [473] A solution was prepared by mixing 1.425 g of P2, 0.075 g of sulfur-containing antioxidant used in Example 12 and 9.075 g of DMAc, and spreading the mixture by applying on a glass plate. The solvent was dried under atmospheric pressure to obtain a polymer electrolyte composition membrane. Table 7 shows the results of the evaluation of the radical resistance. [474] ExampleAntioxidantWeight retention (%) Example 19S-995 Comparative Example 5-85 [475] Example 20 [476] For Example 14, Example 17, and Comparative Example 1, evaluation of proton conductivity and fuel cell characteristics (operation of start and stop for 1 week were repeated) was performed. The results are shown in Table 8. [477] Proton Conductivity (S / cm)Evaluation of Fuel Cell Characteristics Example 149 × 10 -2 No fuel cell deterioration and no gas leaks observed Example 179 × 10 -2 No fuel cell deterioration and no gas leaks observed Comparative Example 19 × 10 -2 Gas leaks occur and fuel cell deterioration observed [478] Since the polymer electrolyte composition of this invention contains a special phosphorus containing compound as a trivalent phosphorus containing antioxidant or a special sulfur containing compound as a sulfur containing antioxidant, it showed the outstanding radical resistance. Moreover, a fuel cell with excellent durability is obtained by using the polymer electrolyte composition as a polymer electrolyte membrane of a fuel cell.
权利要求:
Claims (8) [1" claim-type="Currently amended] A polymer electrolyte composition comprising one or more antioxidants and a polymer electrolyte selected from the group consisting of trivalent phosphorus-containing antioxidants and sulfur-containing antioxidants. [2" claim-type="Currently amended] The polymer electrolyte composition according to claim 1, wherein the trivalent phosphorus-containing antioxidant is one selected from the following Chemical Formulas 1 to 6. [Formula 1] (WhereinOne, R2, R4And R5 Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms, R3Represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, X represents a sulfur atom, -CHRa-Group (RaRepresents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, an alkylene group having 2 to 8 carbon atoms or a direct bond, and A represents an alkylene group having 2 to 8 carbon atoms, a -CO- group (carbonyl group), or (*)- CORb-Group (RbRepresents an alkylene group having 1 to 8 carbon atoms, (*) represents a bond to the oxygen side), any one of Y or Z represents a hydroxyl group or an alkoxy group having 1 to 20 carbon atoms, and the other is hydrogen An atom or an alkyl group having 1 to 20 carbon atoms), [Formula 2] (In formula, R <6> , R <7> and R <8> respectively independently represents a hydrogen atom, a C1-C20 alkyl group, or a C1-C20 alkoxy group., [Formula 3] (In formula, R <9> and R <10> respectively independently represents a hydrogen atom, a C1-C20 alkyl group, or a C1-C20 alkoxy group., [Formula 4] (Wherein11And R12 Each independently represent an alkyl group having 1 to 20 carbon atoms), [Formula 5] (Wherein13, R14And R15 Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms), [Formula 6] (Wherein B represents a direct bond, a sulfur atom, a -CHR c -group (R c represents an alkyl group having 1 to 8 carbon atoms), or an alkylene group having 2 to 8 carbon atoms, and R 16 and R 17 are each independently Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms, and E represents an alkoxy group or halogen atom having 1 to 20 carbon atoms). [3" claim-type="Currently amended] The polymer electrolyte composition according to claim 1, wherein the sulfur-containing antioxidant is one sulfide compound selected from the following Chemical Formulas 7-9: [Formula 7] (Wherein, R 18 represents an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms), [Formula 8] (Wherein, R 19 , R 20 and R 21 each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms), [Formula 9] (In formula, R <22> represents a C1-C30 alkyl group, a C7-C30 aralkyl group, or a C6-C30 aryl group.). [4" claim-type="Currently amended] A polymer electrolyte composition membrane comprising the polymer electrolyte composition according to any one of claims 1 to 3. [5" claim-type="Currently amended] A polymer electrolyte composition composite membrane comprising the polymer electrolyte composition according to any one of claims 1 to 3 and a support. [6" claim-type="Currently amended] 6. The polymer electrolyte composition composite membrane according to claim 5, wherein the support is a porous support membrane containing an aliphatic polymer or a fluorine-containing polymer. [7" claim-type="Currently amended] A fuel cell comprising the polymer electrolyte composition membrane according to claim 4. [8" claim-type="Currently amended] A fuel cell comprising the polymer electrolyte composition composite membrane according to claim 5.
类似技术:
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同族专利:
公开号 | 公开日 EP1289041B1|2008-03-12| US20060257706A1|2006-11-16| EP1947725B1|2011-10-19| EP1289041A2|2003-03-05| US20030113605A1|2003-06-19| CA2396836A1|2003-02-09| EP1947725A2|2008-07-23| EP1289041A3|2004-03-03| KR100923899B1|2009-10-28| CN1262586C|2006-07-05| TW589760B|2004-06-01| DE60225512T2|2009-03-26| CN1405217A|2003-03-26| DE60225512D1|2008-04-24| EP1947725A3|2008-09-17|
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公开号 | 申请日 | 公开日 | 申请人 | 专利标题
法律状态:
2001-08-09|Priority to JP2001241897 2001-08-09|Priority to JPJP-P-2001-00241897 2001-08-30|Priority to JP2001261127 2001-08-30|Priority to JPJP-P-2001-00261127 2002-08-07|Application filed by 스미또모 가가꾸 고오교오 가부시끼가이샤 2003-02-19|Publication of KR20030014621A 2009-10-28|Application granted 2009-10-28|Publication of KR100923899B1
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