Stabilizer compositions and methods for high clarity random polypropylene copolymers

Abstract

1. A stabilized composition for making a polymeric front sheet of a photovoltaic cell, comprising: i) a random polypropylene copolymer resin; ii) a stabilizing amount of an orthohydroxyphenyltriazine ultraviolet absorber; iii) a stabilizing amount of at least one hindered amine light stabilizer; and iv) a stabilizing amount of at least one antioxidant selected from a hindered phenol, a phosphite, a phosphonite, or a mixture thereof.

Description

[Background technology]

[0001] Photovoltaics have long been utilized in the power generation field, using semiconductor materials that convert light into electricity through the photovoltaic effect. As the efficiency of solar panels in photovoltaic systems improves, the demand for materials to extend the lifespan of outdoor components is increasing. Therefore, photovoltaic cells are typically located between protective layers, which together form a photovoltaic composite. These protective layers are generally made of glass. Given their location, it is usually desirable for the top sheet / front sheet to have high transparency to the required incident light to allow efficient transmission of sunlight to the photovoltaic cells.

[0002] Polypropylene resins are known to degrade over time after exposure to heat, light, and / or oxygen. This degradation is accompanied by UV degradation and a decrease in the performance of the material, typically manifesting as changes in overall color and gloss, as well as a decrease in transmittance. While various light-stabilizing additive component mixtures have been used to mitigate these deficiencies, the use of additives to achieve desired performance in all areas remains an ongoing challenge.

[0003] Therefore, polypropylene resins used in solar cells, especially in the front transparent sheet, are required to have stabilizing properties that not only reduce the performance degradation of the material but also maintain the transparency and efficient transmission of the layers used in photovoltaic applications. Summary of the Invention

[0004] This Summary is provided to introduce selected concepts that are described in more detail below in the Detailed Description. This Summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used as an aid in limiting the scope of the claimed subject matter.

[0005] In one aspect, embodiments disclosed herein comprise a composition comprising: i) a random polypropylene copolymer resin; ii) a stabilizing amount of an orthohydroxyphenyltriazine ultraviolet absorber (TZN-UVA); and iii) a composition comprising a hydroxyphenyltriazine-based ultraviolet absorber having formula (II): [ka] (In the formula, R 31 are H, OH, C1-C 20 Hydrocarbyl, -CHCN, C1-C 12 Acyl or C1-C 18 alkoxy; R 38 is selected from H or C1-C8 hydrocarbyl; R 29 , R 30 , R 32 , and R 33 Each of these is C1~C 20 independently selected from hydrocarbyl, or R 29 and R 30 , and / or R 32 and R 33 together with the carbons to which they are attached, C5 to C 10 forming a cycloalkyl) or a functional group according to formula (IIa): [ka] (wherein m is an integer of 1 to 2, and R 39 are H, OH, C1-C 20 Hydrocarbyl; -CHCN; C1-C 12 Acyl; or C1-C 18 alkoxy; each of G1-G4 is independently selected from C1-C 20 hydrocarbyl) or a mixture of HALS compounds having functional groups according to formula (II) and formula (IIa), and iv) a stabilizing amount of at least one antioxidant selected from hindered phenols, phosphites, phosphonites, or mixtures thereof.

[0006] In another aspect, embodiments disclosed herein relate to a stabilized polymer front sheet of a photovoltaic cell comprising a stabilizing composition comprising: i) a random polypropylene copolymer resin; ii) a stabilizing amount of an orthohydroxyphenyltriazine ultraviolet absorber; iii) a stabilizing amount of at least one hindered amine light stabilizer comprising a functional group according to Formula (II) or Formula (IIa), or a mixture of HALS compounds having functional groups according to Formula (II) and Formula (IIa); and iv) a stabilizing amount of at least one antioxidant selected from a hindered phenol, a phosphite, a phosphonite, or a mixture thereof.

[0007] In another aspect, embodiments disclosed herein relate to a photovoltaic cell comprising a polymeric front sheet and a photovoltaic component, wherein the polymeric front sheet comprises a stabilizing composition comprising: i) a random polypropylene copolymer resin; ii) a stabilizing amount of an orthohydroxyphenyltriazine ultraviolet absorber; iii) a stabilizing amount of at least one hindered amine light stabilizer comprising a functional group according to Formula (II) or Formula (IIa), or a mixture of HALS compounds having functional groups according to Formula (II) and Formula (IIa); and iv) a stabilizing amount of at least one antioxidant selected from a hindered phenol, a phosphite, a phosphonite, or a mixture thereof.

[0008] In yet another aspect, embodiments disclosed herein relate to a method for making a stabilized polymeric front sheet of a photovoltaic cell, comprising extruding or molding a stabilizing composition comprising: i) a random polypropylene copolymer resin; ii) a stabilizing amount of an orthohydroxyphenyltriazine ultraviolet absorber; iii) a stabilizing amount of at least one hindered amine light stabilizer comprising a functional group according to Formula (II) or Formula (IIa), or a mixture of HALS compounds having functional groups according to Formula (II) and Formula (IIa); and iv) a stabilizing amount of at least one antioxidant selected from a hindered phenol, a phosphite, a phosphonite, or a mixture thereof.

[0009] Other aspects and advantages of the claimed subject matter will become apparent from the following description and appended claims. [Brief explanation of the drawings]

[0010] [Figure 1A] 1 shows microscope images of a gas fade test of a random polypropylene copolymer stabilized with a stabilizing composition comprising LMW-HALS and a triazine UVA, taken before (left) and after (right) gas fade. [Figure 1B] 1 shows microscope images of a gas fade test of a random polypropylene copolymer stabilized with a stabilizing composition containing HMW-HALS, LMW-HALS, and a triazine UVA, taken before (left) and after (right) gas fade. [Figure 1C] 1 shows microscope images of a gas fade test of a random polypropylene copolymer stabilized with a stabilizing composition comprising a secondary HMW-HALS and a triazine UVA, taken before (left) and after (right) gas fade. [Figure 1D] 1 shows microscope images of a gas fade test of a random polypropylene copolymer stabilized with a stabilizing composition comprising a tertiary HMW-HALS and a triazine UVA, taken before (left) and after (right) gas fade. DETAILED DESCRIPTION OF THE INVENTION

[0011]

[0003] Embodiments disclosed herein relate to the use of stabilizing compositions in forming highly transparent polymer front sheets for photovoltaic cells. To overcome the technical obstacles described above, the present disclosure provides stabilizing compositions for use in solar cells to stabilize transparent front sheets for photovoltaics, particularly with improved weather resistance, UV stability, and mechanical performance.

[0012] The embodiments disclosed herein include: i.) a random polypropylene copolymer resin; ii.) a stabilizing amount of an orthohydroxyphenyltriazine ultraviolet absorber (TZN-UVA); iii.) a stabilizing amount of at least one hindered amine light stabilizer (HALS); iv.) a stabilizing amount of at least one antioxidant selected from a hindered phenol, a phosphite, a phosphonite, or mixtures thereof; The present invention relates to a stabilized composition comprising:

[0013] In this disclosure, the total amount of all components of a composition is 100 wt.%, based on the total weight of the composition. It is further contemplated that the stabilized composition may be first formulated as a masterbatch composition, in which case the stabilizers and other additives may be present in higher concentrations than in the final formulation, and the masterbatch composition is diluted prior to forming the molded article.

[0014] In some embodiments, the stabilized composition may comprise a random polypropylene copolymer resin in an amount ranging from 10% to 99.99% by weight, based on the total weight of the composition. For example, the random polypropylene copolymer resin may be present in an amount ranging from a lower limit of 10, 20, 50, 75, 90, or 95% by weight to an upper limit of 50, 75, 90, 95, 98, 99, 99.5, or 99.99% by weight, with any lower limit being used in combination with any mathematically reasonable upper limit. However, in one or more embodiments of the stabilized composition in a final formulation for forming a molded article, the random polypropylene copolymer resin may be present in an amount ranging from a lower limit of 90, 92, or 95% by weight to an upper limit of 98, 99, 99.5, or 99.99% by weight, with any lower limit being used in combination with any mathematically reasonable upper limit. In embodiments involving masterbatch formulations, the random polypropylene copolymer resin may be present in lower concentrations, such as, for example, amounts less than 80 wt%, less than 60 wt%, less than 50 wt%.

[0015] Light absorber In disclosed embodiments, a light absorber is provided for absorbing electromagnetic radiation from a light source. In one or more embodiments, the light absorber can be an ultraviolet absorber (UVA). In particular, the UV absorber can include an orthohydroxyphenyltriazine. For example, in one or more embodiments, the UV absorber is an orthohydroxyphenyltriazine (TZN-UVA), such as a 2-(2'-hydroxyphenyl)-1,3,5-triazine compound according to formula (I): [ka] (In the formula, R 34 and R 35 are the same or different, and are independently C6 to C 10 aryl groups, C6-C 10 Aryl groups include OH, halogen, C1-C 12 Alkyl, C1-C 12 Alkoxy, C1-C 12 Alkoxyesters, C2-C12 alkanoyl, or phenyl, optionally substituted in 1 to 3 substitutable positions with one or more groups selected from hydroxyl, halogen, C1 to C6 12 Alkyl, C1-C 12 Alkoxy, C1-C 12 Alkoxy ester or C2-C 12 Alkanoyl; mono- or di-C1-C 12 Hydrocarbyl-substituted amino; C2-C 12 Alkanoyl; C1-C 12 Alkyl; C1-C 10 Acyl; or C1-C 10 R may be optionally substituted at 1 to 3 substitutable positions with one or more groups selected from alkoxyl; 36 are the same or different substituents at positions 0 to 4 of the phenoxy moiety of formula (I), and are independently selected from hydroxyl, halogen, C1 to C6 12 Alkyl, C1-C 12 Alkoxy, C1-C 12 Alkoxyesters, C2-C 12 Alkanoyl; phenyl; or C1-C 12 acyl).

[0016] For example, in some embodiments, the orthohydroxyphenyltriazine ultraviolet absorber (TZN-UVA) is a 2-(2'-hydroxyphenyl)-1,3,5-triazine compound, such as 4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-octyloxyphenyl)-s-triazine; 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-((hexyl)oxyl-phenol); 4,6-bis-(2,4-dimethylphenyl)-2-(2,4-dihydroxyphenyl)-s-triazine; Azine;2,4-Bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine;2,4-Bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine;2,4-Bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(2,4-dimethylphenyl)-s-triazine;2,4-Bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-bromophenyl)-s-triazine;2, 4-Bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine;2,4-Bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine;2,4-Bis(4-biphenylyl)-6-[2-hydroxy-4-[(octyloxycarbonyl)ethylideneoxy]phenyl]-s-triazine;2,4-Bis(4-biphenylyl)-6-[2-hydroxy-4-(2-ethylhexyloxy)phenyl]-s-triazine;2-Phenyl-4 -[2-Hydroxy-4-(3-sec-butyloxy-2-hydroxypropyloxy)phenyl]-6-[2-hydroxy-4-(3-sec-amyloxy-2-hydroxypropyloxy)phenyl]-s-triazine;2,4-Bis(2,4-dimethylphenyl)-6-[2-hydroxy-4(-3-benzyloxy-2-hydroxypropyloxy)phenyl]-s-triazine;2,4-Bis(2-hydroxy-4-n-butyloxyphenyl)-6-(2,4-di-n-butyloxyphenyl)-s-triazine;2,4-Bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-nonyloxy-2-hydroxypropyloxy)-5-α-cumylphenyl]-s-triazine; methylenebis-{2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-butyloxy-2-hydroxypropoxy)phenyl]-s-triazine}; methylene-bridged dimer mixtures bridged at the 3:5', 5:5', and 3:3' positions in a 5:4:1 ratio 2,4,6-Tris(2-hydroxy-4-isooctyloxycarbonylisopropylideneoxyphenyl)-s-triazine;2,4,6-Tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine;2,4-Bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-hexyloxy-5-α-cumylphenyl)-s-triazine;2-(2,4,6-trimethylphenyl)-4,6-bis[2-hydroxy bis-4-(3-butyloxy-2-hydroxypropyloxy)phenyl]-s-triazine; 2,4,6-tris[2-hydroxy-4-(3-sec-butyloxy-2-hydroxypropyloxy)phenyl]-s-triazine; 4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-dodecyloxy-2-hydroxypropoxy)phenyl)-s-triazine and 4,6-bis-(2,4-dimethylphenyl)-2-( 2-hydroxy-4-(3-tridecyloxy-2-hydroxypropoxy)phenyl)-s-triazine; 4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4(3-(2-ethylhexyloxy)-2-hydroxypropoxy)-phenyl)-s-triazine; 4,6-diphenyl-2-(4-hexyloxy-2-hydroxyphenyl)-s-triazine; and mixtures thereof.

[0017] In one or more embodiments, the stabilized composition includes the aforementioned light absorbers in a stabilizing amount, for example, ranging from any lower limit of 0.01, 0.02, and 0.03 wt. % to any upper limit of 0.05, 0.1, and 0.3 wt. %, any lower limit can be used in combination with any upper limit. In embodiments involving masterbatch formulations, the UV absorbers can be present in higher concentrations, for example, up to 0.5, 2.5, 5 wt. %.

[0018] In embodiments, the stabilized composition may include an additional ultraviolet absorber selected from the group consisting of orthohydroxybenzophenones, orthohydroxyphenylbenzotriazoles, benzoxazinones, oxanilides, cyanoacrylates, and mixtures thereof.

[0019] However, according to one or more embodiments, the additional UV absorber is an orthohydroxybenzophenone, and the orthohydroxybenzophenone compound is selected from the group consisting of 2-hydroxy-4-methoxybenzophenone; 2,2'-dihydroxy-4-methoxybenzophenone; 2-hydroxy-4-octyloxybenzophenone; 2,2'-dihydroxy-4,4'-dimethoxybenzophenone; 2,2'-dihydroxybenzophenone; 2,2',4,4'-tetrahydroxybenzophenone; and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone. 2,2'-Dihydroxy-4,4'-diethoxybenzophenone;2,2'-Dihydroxy-4,4'-dipropoxybenzophenone;2,2'-Dihydroxy-4,4'-dibutoxybenzophenone;2,2'-Dihydroxy-4-methoxy-4'-ethoxybenzophenone;2,2'-Dihydroxy-4-methoxy-4'-propoxybenzophenone;2,2'-Dihydroxy-4-methoxy-4'-butoxybenzophenone;2,2'-Dihydroxy-4-ethoxy-4'-propoxybenzophenone;2,2'-Dihydroxy-4-ethoxy-4'-propoxybenzophenone 2-Hydroxy-4-ethoxy-4'-butoxybenzophenone;2,3'-Dihydroxy-4,4'-dimethoxybenzophenone;2,3'-Dihydroxy-4-methoxy-4'-butoxybenzophenone;2-Hydroxy-4,4',5'-trimethoxybenzophenone;2-Hydroxy-4,4',6'-tributoxybenzophenone;2-Hydroxy-4-butoxy-4',5'-dimethoxybenzophenone;2-Hydroxy-4-ethoxy-2',4'-dibutylbenzophenone;2-Hydroxy-4-propoxy-4',6'-dichlorobenzophenone benzophenone;2-Hydroxy-4-propoxy-4',6'-dibromobenzophenone;2,4-Dihydroxybenzophenone;2-Hydroxy-4-ethoxybenzophenone;2-Hydroxy-4-propoxybenzophenone;2-Hydroxy-4-butoxybenzophenone;2-Hydroxy-4-methoxy-4'-methylbenzophenone;2-Hydroxy-4-methoxy-4'-ethylbenzophenone;2-Hydroxy-4-methoxy-4'-propylbenzophenone;2-Hydroxy-4-methoxy-4'-butylbenzophenone;2-Hydroxy-4-methoxy-4'-tert-butylbenzophenone;2-Hydroxy-4-methoxy-4'-chlorobenzophenone;2-Hydroxy-4-methoxy-2'-chlorobenzophenone;2-Hydroxy-4-methoxy-4'-bromobenzophenone;2-Hydroxy-4,4'-dimethoxybenzophenone;2-Hydroxy-4,4'-dimethoxy-3-methylbenzophenone;2-Hydroxy-4,4'-dimethoxy-2'-ethylbenzophenone;2-Hydroxy-4,4',5'-trimethoxybenzophenone;2-Hydroxy-4-ethoxy-4'-methylbenzophenone;2-Hydroxy-4 2-hydroxy-4-ethoxy-4'-ethylbenzophenone; 2-hydroxy-4-ethoxy-4'-propylbenzophenone; 2-hydroxy-4-ethoxy-4'-butylbenzophenone; 2-hydroxy-4-ethoxy-4'-methoxybenzophenone; 2-hydroxy-4,4'-diethoxybenzophenone; 2-hydroxy-4-ethoxy-4'-propoxybenzophenone; 2-hydroxy-4-ethoxy-4'-butoxybenzophenone; 2-hydroxy-4-ethoxy-4'-chlorobenzophenone; 2-hydroxy-4-ethoxy-4'-bromobenzophenone; and mixtures thereof.

[0020] Furthermore, according to one or more embodiments, the additional UV absorber may be an orthohydroxyphenylbenzotriazole compound, and the orthohydroxyphenylbenzotriazole may be 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole; 2-(2'-hydroxy-5'-tert-butylphenyl)-benzotriazole; 2-(2'-hydroxy-3'-methyl-5'-tert-butylphenyl)-benzotriazole; 2-(2'-hydroxy-5'-cyclohexylphenyl)-benzotriazole; 2-(2'-hydroxy-5'-cyclohexylphenyl)-benzotriazole; '-Hydroxy-3',5'-dimethylphenyl)-benzotriazole;2-(2'-hydroxy-5'-tert-butylphenyl)-5-chlorobenzotriazole;2-(2'-hydroxy-5-tert-octylphenyl)-2H-benzotriazole;2-(2'-hydroxy-5-octylphenyl)-2H-benzotriazole;2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole;2-(3'-tert-butyl-5'-methylbutyl-2'hydroxyphenyl) -5-Chlorobenzotriazole;2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole;2-(3',5'-bis(α,α-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole;2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotriazole;2,2'-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol];2-[3'-tert-butyl-5 Transesterification products of '-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol 300;2-[2'-hydroxy-3'-(α,α-dimethylbenzyl)-5'-(1,1,3,3-tetramethylbutyl)phenyl]benzotriazole;5-Trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole;2-(2'-Hydroxy-5'-(2-hydroxyethyl)phenyl)benzotriazole;2-(2'-Hydroxy-5'-(2-methacryloyloxyethyl)phenyl)benzotriazole;2-(3'-tert-butyl-5'-methyl-2'-hydroxyphenyl)-5-chlorobenzotriazole;2-(3'-sec-butyl-5'-tert.butyl-2'-hydroxyphenyl)benzotriazole;2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole;2-(5'-tert-octyl-2'-hydroxyphenyl)benzotriazole;2-(3'-dodecahydro-2-hydroxyphenyl)benzotriazole 2-(3'-tert-butyl-5'-(2-octyloxycarbonylethyl)-2'-hydroxyphenyl)-5-chlorobenzotriazole; 2-(5'-methyl-2'-hydroxyphenyl)-benzotriazole; 2-(5'-tert-butyl-2'-hydroxyphenyl)-benzotriazole; 2-(2'-hydroxy-3'-di-tert-butylphenyl)-benzotriazole, and mixtures thereof.

[0021] According to one or more embodiments, the additional UV absorber may be a benzoxazinone compound, and the benzoxazinone may be 2-methyl-3,1-benzoxazin-4-one; 2-butyl-3,1-benzoxazin-4-one; 2-phenyl-3,1-benzoxazin-4-one; 2-(1- or 2-naphthyl)-3,1-benzoxazin-4-one; 2-(4-biphenyl)-3,1-benzoxazin-4-one; 2-p-nitrophenyl-3,1-benzoxazin-4-one; 2-m-nitrophenyl-3,1-benzoxazine -4-one;2-p-Benzoylphenyl-3,1-benzoxazin-4-one;2-p-Methoxyphenyl-3,1-benzoxazin-4-one;2-O-Methoxyphenyl-3,1-benzoxazin-4-one;2-Cyclohexyl-3,1-benzoxazin-4-one;2-p-(or m-)phthalimidophenyl-3,1-benzoxazin-4-one;N-Phenyl-4-(3,1-benzoxazin-4-one-2-yl)phthalimide;N-Benzoyl-4-(3,1-benzoxazin-4-one-2-yl)aniline ;N-Benzoyl-N-methyl-4-(3,1-benzoxazin-4-one-2-yl)aniline;2-[p-(N-phenylcarbamonyl)phenyl]-3,1-benzoxazin-4-one;2-[p-(N-phenylN-methylcarbamoyl)phenyl]-3,1-benzoxazin-4-one;2,2'-Bis(3,1-benzoxazin-4-one);2,2'-Ethylenebis(3,1-benzoxazin-4-one);2,2'-Tetramethylenebis(3,1-benzoxazin-4-one);2,2'-Hexamethylenebis(3 ,1-benzoxazin-4-one; 2,2'-decamethylenebis(3,1-benzoxazin-4-one); 2,2'-p-phenylenebis(3,1-benzoxazin-4-one); 2,2'-m-phenylenebis(3,1-benzoxazin-4-one); 2,2'-(4,4'-diphenylene)bis(3,1-benzoxazin-4-one); 2,2'-(2,6- or 1,5-naphthalene)bis(3,1-benzoxazin-4-one); 2,2'-(2-methyl-p-phenylene)bis(3,1-benzoxazin-4-one);2,2'-(2-nitro-p-phenylene)bis(3,1-benzoxazin-4-one);2,2'-(2-chloro-p-phenylene)bis(3,1-benzoxazin-4-one);2,2'-(1,4-cyclohexylene)bis(3,1-benzoxazin-4-one);Np-(3,1-benzoxazin-4-one-2-yl)phenyl;4-(3,1-benzoxazin-4-one-2-yl)phthalimide;Np- It may be selected from the group consisting of (3,1-benzoxazin-4-one-2-yl)benzoyl; 4-(3,1-benzoxazin-4-one-2-yl)aniline; 1,3,5-tri(3,1-benzoxazin-4-one-2-yl)benzene; 1,3,5-tri(3,1-benzoxazin-4-one-2-yl)naphthalene; and 2,4,6-tri(3,1-benzoxazin-4-one-2-yl)naphthalene;

[0022] In one or more embodiments, the stabilized composition includes the aforementioned additional UV absorbers in an amount ranging from any lower limit of 0.01, 0.1, and 0.2 wt. % to any upper limit of 0.5, 0.75, and 1.0%, any lower limit being usable in combination with any upper limit. In embodiments involving masterbatch compositions, the additional UV absorbers may be present in higher concentrations, such as in amounts up to 0.5, 2.5, or 5 wt. %.

[0023] Hindered amine light stabilizers (HALS) In embodiments described herein, the hindered amine light stabilizers can include low molecular weight hindered amine light stabilizers (LMW-HALS) having a molecular weight of less than 1000 g / mol and high molecular weight hindered amine light stabilizers (HMW-HALS) having a molecular weight of 1000 g / mol or greater. Additionally, amines in this molecular weight range can include secondary amines, tertiary amines, or combinations thereof.

[0024] In one or more embodiments, the stabilized composition has formula (II): [ka] (In the formula, R 31 are H, OH, C1-C 20 Hydrocarbyl, -CHCN, C1-C 12 Acyl or C1-C 18 alkoxy; R 38 is selected from H or C1-C8 hydrocarbyl; R 29 , R 30 , R 32 , and R 33 Each of these is C1~C 20 independently selected from hydrocarbyl, or R 29 and R 30 , and / or R 32 and R 33 together with the carbons to which they are attached, C5 to C 10 forming a cycloalkyl) or a functional group according to formula (IIa): [ka] (wherein m is an integer of 1 to 2, and R 39 are H, OH, C1-C 20 Hydrocarbyl; -CHCN; C1-C 12 Acyl; or C1-C 18 each of G1 to G4 is independently selected from C1 to C 20 hydrocarbyl) or a mixture of HALS compounds having functional groups according to formula (II) and formula (IIa).

[0025] In at least one embodiment, the stabilized composition may include a stabilizing amount of at least one hindered amine light stabilizer (HALS) selected from high molecular weight hindered amine light stabilizers (HMW-HALS).

[0026] In another preferred embodiment, the stabilized composition comprises a HALS selected exclusively from high molecular weight hindered amine light stabilizers (HMW-HALS) having a weight average molecular weight greater than 1000 g / mol, i.e., in one or more embodiments, the HALS consists of HMW-HALS.

[0027] In at least one embodiment, the at least one hindered amine light stabilizer is selected from the group consisting of a condensate of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid; 2,2,6,6-tetramethylpiperidin-4-yl stearate; a condensate of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine; tetrakis(2,2,6,6-tetramethylpiperidin-4-yl) )-1,2,3,4-butanetetracarboxylate;Condensation product of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine with 4-morpholino-2,6-dichloro-1,3,5-triazine;Methylated condensation product of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine with 4-morpholino-2,6-dichloro-1,3,5-triazine;2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3, Condensation products of 5-triazine and 1,2-bis(3-aminopropylamino)ethane;Condensation products of 2-chloro-4,6-bis(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane;Condensation products of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine;Condensation products of 1,2-bis(3-aminopropylamino)ethane and 2,4,6- Condensation product of trichloro-1,3,5-triazine with 4-butylamino-2,2,6,6-tetramethylpiperidine; oxo-piperandinyl-triazine; 1,2,2,6,6-pentamethyl-4-piperdinyl ester of polymer of 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]-undecane-3,9-diethanol; 2,2,6,6-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]-undecane-3,9-diethanol of 1,2,3,4-butanetetracarboxylic acid.2,2,6,6-Tetramethyl-4-piperidinyl ester of polymer with 5]-undecane-3,9-diethanol; Bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate; Reaction product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol with dimethyl succinate; 2,2,4,4-Tetramethyl-7-oxa-3 ,20-diazadispiro[5.1.11.2]heneicosan-21-one; polymers with 1H-pyrrole-2,5-dione, 1-octadecyl-, (1-methylethenyl)benzene and 1-(2,2,6,6-tetramethyl-4-piperidinyl)-1H-pyrrole-2,5-dione; 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4.5] Reaction products of decane with epichlorohydrin; Condensation products of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine with 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine; 1,2-bis(3-aminopropylamino)ethane, 2,4,6-trichloro-1,3,5-triazine and 4-butylamino-2,2,6,6-tetramethylpiperidin Condensation products of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine with 4-morpholino-2,6-dichloro-1,3,5-triazine;Condensation products of 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine with 1,2-bis(3-aminopropylamino)ethane;Condensation products of 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine with 1,2-bis(3-aminopropylamino)ethane Condensation products of bis(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazine with 1,2-bis-(3-aminopropylamino)ethane;2-[(2-hydroxyethyl)amino]-4,6-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino-1,3,5-triazine;1-(2-hydroxyethyl)-2, Condensation product of 2,6,6-tetramethyl-4-hydroxypiperidine with succinic acid; Condensation product of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine with 4-tert-octylamino-2,6-dichloro-1,3,5-triazine; Copolymer of methyl methacrylate with ethyl acrylate and 2,2,6,6-tetramethylpiperidin-4-yl acrylate; C. 20 ~C 24The HMW-HALS may be selected from the group consisting of copolymers of α-olefin mixtures and (2,2,6,6-tetramethylpiperidin-4-yl)succinimide; 1,2,2,6,6-pentamethyl-4-piperidinyl ester of polymers of 1,2,3,4-butanetetracarboxylic acid with β,β,β',β'-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanol; 2,2,6,6-tetramethyl-4-piperidinyl ester copolymers of polymers of 1,2,3,4-butanetetracarboxylic acid with β,β,β',β'-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanol; and mixtures thereof.

[0028] In one or more embodiments, the stabilized composition includes the aforementioned hindered amine light stabilizer in an amount ranging from, for example, any lower limit of 0.05, 0.075, or 0.1 wt. % to an upper limit of 0.25, 0.5, or 1 wt. %, any lower limit can be used in combination with any upper limit. In embodiments involving masterbatch compositions, the hindered amine light stabilizer can be present in higher concentrations, for example, up to 2.5, 10, 20 wt. %.

[0029] In one or more embodiments, the hindered amine light stabilizers can include both low and high molecular weight hindered amine light stabilizers, while one or more other embodiments are 100% high molecular weight hindered amine light stabilizers.

[0030] antioxidants In embodiments, the stabilized composition may include a stabilizing amount of at least one antioxidant. The antioxidant may be selected from the group consisting of a hindered phenol, a phosphite, a phosphonite, or a mixture thereof.

[0031] In at least one embodiment, hindered phenolic antioxidants suitable for the stabilized composition include (1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione; 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione; 1,1,3-tris(2'-methyl-4'-hydroxy-5'-t-butylphenyl)butane; triethylene glycol bis[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate]; 4,4'-thiobis(2-t-butyl-5-methylphenyl)propionate]; octadecyl 3-(3'-t-butyl-4'-hydroxy-5'-methylphenyl)propionate; tetrakismethylene(3-t-butyl-4-hydroxy-5-methylhydrocinnamate)methane; N,N'-hexamethylenebis[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionamide]; di(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)thiodipropionate; and octadecyl 3,5-di-(tert)-butyl-4-hydroxyhydrocinnamate.

[0032] In some embodiments, the antioxidant is an organic phosphite or phosphonite, such as triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, trilauryl phosphite, trioctadecyl phosphite; distearyl pentaerythritol phosphite; tris(2,4-di-t-butylphenyl) phosphite; tris(nonylphenyl) phosphite; a compound of any of formulas (A), (B), (C), (D), (E), (F), (G), (H), (J), (K), and (L): [ka] [ka] [ka] , and 2-butyl-2-ethyl-1,3-propanediol 2,4,6-tri-t-butylphenol phosphite, bis-(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, 2-butyl-2-ethyl-1,3-propanediol 2,4-di-cumylphenol phosphite, 2-butyl-2-ethyl-1,3-propanediol 4-methyl-2,6-di-t-butylphenol phosphite, and bis(2,4,6- tris(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite (IRGAFOS® 168); bis(2,4-dicumylphenyl)pentaerythritol diphosphite (DOVERPHOS® S9228); and tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylene-diphosphonite (IRGAFOS® P-EPQ).

[0033] In addition to the aforementioned components, the stabilized composition may further comprise a stabilizing aid. In at least one embodiment, the stabilized composition comprises a compound represented by formula (VII): [ka] (In the formula, R 21 and R 22 Each of the following is independently 1~ C 12 alkyl; T is selected from O or NR 24 Selected from R 24 is H or C1 ~C30 R is hydrocarbyl; 23 is H or C 1~ C 30 hydrocarbyl) The composition may include a stabilizing aid which may be a hindered benzoate or benzamide compound according to

[0034] In at least one embodiment, the stabilized composition may include a hindered benzoate as a stabilizing aid, examples of which include 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate; hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; octadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; octyl-3,5-di-tert-butyl-4-hydroxybenzoate; decyl-3,5-di-tert-butyl-4-hydroxybenzoate. dodecyl-3,5-di-tert-butyl-4-hydroxybenzoate; tetradecyl-3,5-di-tert-butyl-4-hydroxybenzoate; behenyl-3,5-di-tert-butyl-4-hydroxybenzoate; 2-methyl-4,6-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate; butyl-3-[3-t-butyl-4-(3,5-di-t-butyl-4-hydroxybenzoyloxy)phenyl]propionate, and mixtures thereof.

[0035] In one or more embodiments, the stabilized composition includes a stabilizing amount of the aforementioned antioxidants (total antioxidants), for example, in an amount ranging from any lower limit of 0.01, 0.05, 0.07, 0.1, or 0.2 wt. % to any upper limit of 0.8, 1.25, or 2.25 wt. %, any lower limit can be used in combination with any upper limit. In embodiments involving masterbatch compositions, the antioxidants can be present in higher concentrations, such as, for example, in amounts up to greater than 4 wt. %, greater than 15 wt. %, or greater than 30 wt. %.

[0036] In one or more embodiments, the stabilized composition comprises a hindered phenolic antioxidant in an amount ranging from a lower limit of any of 0.01, 0.02, or 0.05 wt. % to an upper limit of any of 0.15, 0.2, or 0.25 wt. %, any lower limit can be used in combination with any upper limit. In embodiments involving masterbatch compositions, the hindered phenolic light stabilizer can be present in higher concentrations, such as, for example, in amounts up to 2, 7.5, or 15 wt. %.

[0037] In one or more embodiments, the stabilized composition comprises an amount of phosphite and / or phosphonite antioxidant ranging from a lower limit of any of 0.01, 0.02, or 0.05 wt. % to an upper limit of any of 0.25, 0.5, or 1 wt. %, any lower limit can be used in combination with any upper limit. In embodiments involving masterbatch compositions, the phosphite and / or phosphonite can be present in higher concentrations, such as, for example, in amounts up to 2, 7.5, or 15 wt. %.

[0038] In one or more embodiments, the stabilized composition includes an amount of hindered benzoate antioxidant ranging from a lower limit of any of 0.05, 0.07, or 0.1 wt. % to an upper limit of any of 0.4, 0.5, or 1 wt. %, any lower limit can be used in combination with any upper limit. In embodiments involving masterbatch compositions, the hindered benzoate can be present in higher concentrations, such as, for example, in amounts up to 3, 15, or 25 wt. %.

[0039] Concomitant additives In embodiments, the stabilized composition may further comprise one or more co-additives and mixtures thereof. Co-additives such as those selected from the group consisting of nucleating agents, fillers, thioesters, hydroxylamines, metal stearates, metal oxides, reinforcing agents, plasticizers, lubricants, rheology modifiers, catalysts, leveling agents, optical brighteners, antistatic agents, blowing agents, flame retardants, and mixtures thereof may be suitable for use in embodiments.

[0040] In one or more embodiments, the stabilized composition optionally includes such additives in amounts up to 5, 4, 3, 2, or 1 wt. %. In embodiments involving masterbatch compositions, the co-additives may be present in higher concentrations, such as, for example, in amounts up to 1, 5, or 10 wt. %.

[0041] As previously mentioned, according to some embodiments, the stabilized composition may be a concentrated mixture used as a masterbatch, which can be diluted with additional amounts of the random polypropylene copolymer and any of the optional additives described above, including stabilizers, prior to subsequent processing. In one or more embodiments, the stabilized masterbatch composition comprises a random polypropylene copolymer in an amount of 10-95% and the additives described above, including a light stabilizer, in a total amount ranging from 5% to 90%.

[0042] Solar Cell Components As described above, the compositions of the present disclosure can be used to form components of photovoltaic cells, such as the front sheet of the photovoltaic cell. The stabilized, high-transparency polymer front sheet of the photovoltaic cell can have a total stabilizer content ranging from 0.01 wt % to 10 wt %, preferably 0.02 wt % to 5 wt %, and more preferably 0.02 wt % to 2 wt %, based on the total weight of the polymer front sheet, where the total stabilizer content is the sum of the weight % contents of the light-stabilizing ultraviolet absorber, the hindered amine light stabilizer, and any stabilizing additives and other co-additives described above, with the remainder being the random polypropylene copolymer resin.

[0043] The present disclosure also relates to a method for producing a stabilized, highly transparent polymer front sheet of a photovoltaic cell, comprising the stabilizing composition. The front sheet polymer layer element can be produced by extrusion, such as cast film extrusion using conventional extruders and film forming equipment, or molding, such as injection molding. It is also envisioned that the front sheet may be a multilayer element. It is understood that when such multiple layers are used, they may be coextruded or laminated.

[0044] In one or more embodiments, the front sheet can have improved gas fade resistance, resulting in better color, better transparency, and higher energy. Better weathering performance results in longer solar cell life.

[0045] Photovoltaic cells of the present disclosure can include a front sheet (formed from the present compositions), a solar cell surrounded or encapsulated by a light-transmitting protective encapsulant, a back sheet element, and an optional protective cover such as a metal frame. Although the compositions are described as being used to form the front sheet, it is also contemplated that these compositions, alone or in combination with other polymers, can be used to manufacture other photovoltaic cell components, including, but not limited to, back sheets and encapsulating polymers.

[0046] The various components of a photovoltaic cell or module are typically assembled together by conventional means to produce the final photovoltaic cell or module. The components may be supplied to such an assembly process separately or in a partially integrated form. The different components are then typically joined together by lamination using lamination techniques conventional in the art. [Example]

[0047] These examples demonstrate the UV weatherability and gas fade performance of stabilized random polypropylene copolymer compositions.

[0048] The commercially available materials used are listed in Table 1. These materials were mixed with high-clarity random polypropylene copolymers (Pro-fax Sr549M from Lyondell Basell Industries, hereafter "Resin A," and RP350 from Braskem, hereafter "Resin B") and processed using conventional single-screw extrusion with a temperature profile of 210°C to 220°C. After processing, standard 2 x 2.5 x 0.125 inch plaques were injection molded using an Engel injection molding machine. Conditions during injection molding were standard injection molding procedures. All additives were used as received.

[0049] [Table 1]

[0050] Test Method Samples were exposed to combustion gases at 60°C to 65°C and rotated on a rotating platform for the gas fading test. For oven aging tests, samples were exposed to 80°C in a standard forced-convection Blue M oven. For UV weathering, samples were exposed to ASTM G154 conditions in a QUV-313 accelerated weathering tester. Discoloration was measured using the sample's color change (Delta E or ΔE) and yellowness index (Delta YI or ΔYI). Gloss values ​​(at 60°C), YI, and ΔE values ​​were measured at increasing exposure intervals for all tests. High gloss values ​​indicate a smooth surface, while low gloss values ​​may indicate phenomena such as surface cracking or additive migration. The higher the ΔE, the greater the color change or discoloration of the sample from its initial state. The higher the YI, the more yellow the sample appears.

[0051] The samples prepared and their stabilizer compositions are shown in Table 2. The stabilizer compositions are combined with Resin A and / or B as indicated below.

[0052] [Table 2]

[0053] Weathering performance of stabilized random polypropylene copolymers. All formulations were compounded in a single-screw extruder and injection molded into plaques. These plaques were exposed to ASTM G-154 conditions in an accelerated weathering tester 313. Color data were collected at intervals. As shown in Table 3, the benzotriazole-containing samples (CS1A and CS1B) exhibit very strong color development during the QUV-313 weathering test. The triazine UVA-containing samples (S2A and S2B) exhibit better weathering performance (less overall color change) for both random polypropylene copolymers.

[0054] [Table 3]

[0055] Gas Fade Testing of Stabilized Random Polypropylene Copolymers All formulations were compounded in a single-screw extruder and injection molded into plaques. These plaques were exposed to combustion gases at 60-65°C. Gloss data were collected at intervals. As shown in Table 4 and Figures 1A-1D, samples containing low molecular weight hindered amine light stabilizers, either alone or in combination with high molecular weight hindered amine light stabilizers, exhibited adverse additive migration effects, resulting in reduced gloss in gas fade tests for both random polypropylene copolymer resins.

[0056] [Table 4]

[0057] As shown in Table 5, all Resin A formulations, including the samples containing low molecular weight hindered amine light stabilizers, either alone or in combination with high molecular weight hindered amine light stabilizers, develop more color than either the samples containing tertiary or secondary HMW-HALS after 168 hours of gas exposure.

[0058] [Table 5]

[0059] As shown in Table 6, all samples, including those containing low molecular weight hindered amine light stabilizers, either alone or in combination with high molecular weight hindered amine light stabilizers, develop an overall stronger color than the samples containing only high molecular weight hindered amine light stabilizers after 1000 hours of exposure to QUV-313.

[0060] [Table 6]

[0061] Advantageously, the stabilized compositions of the present disclosure can reduce the impact on the transmission and transparency of polypropylene resins, allowing polypropylene-based compositions to be exposed to weather and other outdoor elements. That is, while the front sheet of a photovoltaic cell is traditionally made of glass, the stabilized compositions of the present disclosure can allow a polypropylene-based composition to be used in place of glass and still have the properties required for the life of the photovoltaic cell.

[0062] While the scope of the compositions and methods has been described using several embodiments, those skilled in the art will appreciate that many examples, variations, and modifications to the compositions and methods described herein are within the scope and spirit of the present disclosure. Accordingly, the described embodiments are set forth without loss of generality and without imposing limitations on the present disclosure. Those skilled in the art will appreciate that all possible combinations and uses of the specific features described herein are included within the scope.

Claims

1. 1. A stabilized composition for producing a polymeric front sheet of a photovoltaic cell, comprising: i) a random polypropylene copolymer resin; ii) a stabilizing amount of an orthohydroxyphenyltriazine ultraviolet absorber (TZN UVA); and iii) Formula (II): 【Chemistry 1】 (In the formula, R ３１ is H, OH, C １ ~C ２０ Hydrocarbyl, —CH ２ C.N., C. １ ~C １２ Acyl, or C １ ~C １８ alkoxy; R ３８ is H or C １ ~C ８ R is selected from hydrocarbyl; ２９ , R ３０ , R ３２ , and R ３３ Each of the １ ~C ２０ independently selected from hydrocarbyl, or R ２９ and R ３０ , and / or R ３２ and R ３３ together with the carbon to which they are attached, C ５ ~C １０ forming a cycloalkyl) a functional group conforming to or formula (IIa): 【Chemistry 2】 (In the formula, m is an integer from 1 to 2, R ３９ is H;OH;C １ ~C ２０ Hydrocarbyl; —CH ２ CN;C １ ~C １２ acyl; or C １ ~C １８ alkoxy; G １ ~G ４ Each of the groups independently represents C １ ~C ２０ hydrocarbyl) a stabilizing amount of at least one hindered amine light stabilizer (HALS) comprising a functional group according to a mixture of HALS compounds having functional groups according to formula (II) and formula (IIa); iv) a stabilizing amount of at least one antioxidant selected from a hindered phenol, a phosphite, a phosphonite, or mixtures thereof; A composition comprising:

2. The stabilized composition of claim 1, wherein the orthohydroxyphenyltriazine ultraviolet absorber (TZN UVA) is a 2-(2'-hydroxyphenyl)-1,3,5-triazine compound according to formula (I): 【Transformation 3】 (In the formula, R ３４ and R ３５ are the same or different and independently C ６ ~C １０ aryl groups, C ６ ~C １０ The aryl group is OH, halogen, C １ ~C １２ Alkyl, C １ ~C １２ Alkoxy, C １ ~C １２ Alkoxyesters, C ２ ~C １２ alkanoyl, or phenyl, wherein the phenyl is optionally substituted in 1 to 3 substitutable positions with one or more groups selected from hydroxyl, halogen, C １ ~ １２ Alkyl, C １ ~ １２ Alkoxy, C １ ~ １２ Alkoxyester, or C ２ ~ １２ Alkanoyl; Mono- or di-C １ ~C １２ hydrocarbyl-substituted amino; C ２ ~C １２ Alkanoyl; C １ ~C １２ Alkyl; C １ ~C １０ acyl; or C １ ~C １０ optionally substituted in 1 to 3 substitutable positions with one or more groups selected from alkoxyl; R ３６ are the same or different substituents at positions 0 to 4 of the phenoxy moiety of formula (I), and are independently selected from hydroxyl, halogen, C １ ~C １２ Alkyl, C １ ~C １２ Alkoxy, C １ ~C １２ Alkoxyesters, C ２ ~C １２ alkanoyl; phenyl; or C １ ~C １２ acyl).

3. The 2-(2'-hydroxyphenyl)-1,3,5-triazine compound is 4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-octyloxyphenyl)-s-triazine; 2-(4,6-diphenyl-1,3,5-triazin-2-yl-)-5-((hexyl)oxyl-phenol; 4,6-bis-(2,4-dimethylphenyl)-2-(2,4-dihydroxyphenyl)-s-triazine; 2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine; 2,4-bis[2-hydroxy-4-(2-hydroxy-ethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine; 2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxy-ethoxy)phenyl]-6-(2,4-dimethylphenyl)-s-triazine; 2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-bromophenyl)-s-triazine; 2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine; 2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine; 2,4-bis(4-biphenylyl)-6-[2-hydroxy-4-[(octyloxycarbonyl)ethylideneoxy]phenyl]-s-triazine; 2,4-bis(4-biphenylyl)-6-[2-hydroxy-4-(2-ethylhexyloxy)phenyl]-s-triazine; 2-phenyl-4-[2-hydroxy-4-(3-sec-butyloxy-2-hydroxypropyloxy)phenyl]-6-[2-hydroxy-4-(3-sec-amyloxy-2-hydroxypropyloxy)phenyl]-s-triazine; 2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4(-3-benzyloxy-2-hydroxypropyloxy)phenyl]-s-triazine; 2,4-bis(2-hydroxy-4-n-butyloxyphenyl)-6-(2,4-di-n-butyloxyphenyl)-s-triazine; 2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-nonyloxy-2-hydroxypropyloxy)-5-α-cumylphenyl]-s-triazine; methylenebis-{2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-butyloxy-2-hydroxypropoxy)phenyl]-s-triazine}; a mixture of methylene-bridged dimers bridged at the 3:5', 5:5' and 3:3' positions in a ratio of 5:4:1; 2,4,6-tris(2-hydroxy-4-isooctyloxycarbonyliso-propylpropylideneoxy-phenyl)-s-triazine; 2,4,6-tris(2-hydroxy-4-octyloxy-phenyl)-1,3,5-triazine; 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-hexyloxy-5-α-cumylphenyl)-s-triazine; 2-(2,4,6-trimethylphenyl)-4,6-bis[2-hydroxy-4-(3-butyloxy-2-hydroxypropyloxy)phenyl]-s-triazine; 2,4,6-tris[2-hydroxy-4-(3-sec-butyloxy-2-hydroxypropyloxy)-phenyl]-s-triazine; a mixture of 4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-dodecyloxy-2-hydroxypropoxy)phenyl)-s-triazine and 4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-tridecyloxy-2-hydroxypropoxy)phenyl)-s-triazine; 4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4(3-(2-ethylhexyloxy)-2-hydroxypropoxy)-phenyl)-s-triazine; 4,6-diphenyl-2-(4-hexyloxy-2-hydroxyphenyl)-s-triazine; and mixtures thereof The stabilized composition according to claim 1 or 2, wherein the stabilized composition is selected from the group consisting of:

4. 4. The stabilized composition according to claim 1, wherein the hindered amine light stabilizer is selected from high molecular weight hindered amine light stabilizers having a weight average molecular weight of more than 1000 g / mol.

5. 5. The stabilized composition of claim 4, wherein the hindered amine light stabilizer comprises a high molecular weight hindered amine light stabilizer.

6. The high molecular weight hindered amine light stabilizer is a condensate of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid; 2,2,6,6-Tetramethylpiperidin-4-yl stearate; Condensation product of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine; Tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)-1,2,3,4-butanetetracarboxylate; N,N'-bis(2,2,6,6-tetramethylpiperidine-4- methylated condensation product of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine with 4-morpholino-2,6-dichloro-1,3,5-triazine; methylated condensation product of 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine with 1,2-bis(3-amino- condensation product of 2-chloro-4,6-bis(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazine with 1,2-bis(3-aminopropylamino)ethane; condensation product of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine with 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine; condensation product of 1,2-bis(3-aminopropylamino)ethane with N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine with Condensation products of (2,4,6-trichloro-1,3,5-triazine and 4-butylamino-2,2,6,6-tetramethylpiperidine with ethane; oxo-piperandinyl-triazine; 1,2,2,6,6-pentamethyl-4-piperdinyl ester of the polymer of 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]-undecane-3,9-diethanol; 2,2,6,6-tetramethyl-4-piperidinyl ester of polymer of 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]-undecane-3,9-diethanol; bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate; reaction products of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol and dimethylsuccinate; 2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro[5.1.11.2]heneicosan-21-one; polymers with 1H-pyrrole-2,5-dione, 1-octadecyl-, (1-methylethenyl)benzene and 1-(2,2,6,6-tetramethyl-4-piperidinyl)-1H-pyrrole-2,5-dione; Reaction products of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane with epichlorohydrin; Condensation products of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine with 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine; Condensation products of 1,2-bis(3-aminopropylamino)ethane with 2,4,6-trichloro-1 condensation product of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine; condensation product of 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine and 1,2-bis(3-aminopropanol) 2-chloro-4,6-bis(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazine and 1,2-bis-(3-aminopropylamino)ethane; 2-[(2-hydroxyethyl)amino]-4,6-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino-1,3,5-triazine; 1-(2 -hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid condensation product; N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine condensation product; copolymer of methyl methacrylate with ethyl acrylate and 2,2,6,6-tetramethylpiperidin-4-yl acrylate; C ２０ ~C ２４ Copolymers of α-olefin mixtures and (2,2,6,6-tetramethylpiperidin-4-yl)succinimide; 6. The stabilized composition of claim 4, wherein the stabilized composition is selected from the group consisting of 1,2,2,6,6-pentamethyl-4-piperidinyl ester of a polymer of 1,2,3,4-butanetetracarboxylic acid with β,β,β',β'-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanol; 2,2,6,6-tetramethyl-4-piperidinyl ester copolymer of 1,2,3,4-butanetetracarboxylic acid with β,β,β',β'-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanol; and mixtures thereof.

7. The hindered phenol antioxidant is (1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione; 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione; 1,1,3-tris(2'-methyl-4'-hydroxy-5'-t-butylphenyl)butane; Triethylene glycol bis[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate]; 4,4'-thiobis(2-t-butyl-5-methylphenol); 2,2'-thiodiethylene bis[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate]; Octadecyl 3-(3'-t-butyl-4'-hydroxy-5'-methylphenyl)propionate; tetrakismethylene(3-t-butyl-4-hydroxy-5-methylhydrocinnamate)methane; N,N'-hexamethylenebis[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionamide]; The stabilized composition of any one of claims 1 to 6, wherein the hydroxybenzoate is selected from di(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)thiodipropionate; and octadecyl 3,5-di-(tert)-butyl-4-hydroxyhydrocinnamate.

8. The organic phosphite or phosphonite may be selected from the group consisting of triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, trilauryl phosphite, trioctadecyl phosphite; distearyl pentaerythritol phosphite; tris(2,4-di-t-butylphenyl)phosphite; tris(nonylphenyl)phosphite; compounds of formula (A), (B), (C), (D), (E), (F), (G), (H), (J), (K), and (L): 【Chemistry 4】 【Transformation 5】 【Transformation 6】 , and 2-butyl-2-ethyl-1,3-propanediol 2,4,6-tri-t-butylphenol phosphite, bis-(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, 2-butyl-2-ethyl-1,3-propanediol 2,4-di-cumylphenol phosphite, 2-butyl-2-ethyl-1,3-propanediol 4-methyl-2,6-di-t-butylphenol phosphite, and bis(2,4,6-tri-t-butylphenyl) 8. The stabilized composition of any one of claims 1 to 7, wherein the stabilizer is selected from pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite (IRGAFOS® 168); bis(2,4-dicumylphenyl)pentaerythritol diphosphite (DOVERPHOS® S9228); and tetrakis(2,4-di-tert-butylphenyl)4,4'-biphenylene-diphosphonite (IRGAFOS® P-EPQ).

9. Formula (VII): 【Transformation 7】 (In the formula, R ２１ and R ２２ Each of the １～ C １２ independently selected from alkyl; T is O or NR ２４ and R ２４ is H or C １～ C ３０ is a hydrocarbyl; R ２３ is H or C １ ~C ３０ hydrocarbyl) 9. The stabilized composition of claim 1, further comprising a stabilizing aid which is a hindered benzoate or benzamide compound according to

10. The hindered benzoate compound may be 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate; hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; octadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; octyl-3,5-di-tert-butyl-4-hydroxybenzoate; decyl-3,5-di-tert-butyl-4-hydroxybenzoate; dodecyl-3,5-di-tert-butyl-4-hydroxybenzoate 10. The stabilized composition of claim 9, wherein the hydroxybenzoate is selected from the group consisting of tetradecyl-3,5-di-tert-butyl-4-hydroxybenzoate; behenyl-3,5-di-tert-butyl-4-hydroxybenzoate; 2-methyl-4,6-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate; butyl-3-[3-t-butyl-4-(3,5-di-t-butyl-4-hydroxybenzoyloxy)phenyl]propionate, and mixtures thereof.

11. 11. The stabilized composition of any one of claims 1 to 10, further comprising an ultraviolet absorber (UVA) selected from the group consisting of orthohydroxybenzophenones, orthohydroxyphenylbenzotriazoles, benzoxazinones, oxanilides, cyanoacrylates, and mixtures thereof.

12. The orthohydroxybenzophenone compound may be 2-hydroxy-4-methoxybenzophenone; 2,2'-dihydroxy-4-methoxybenzophenone; 2-hydroxy-4-octyloxybenzophenone; 2,2'-dihydroxy-4,4'-dimethoxybenzophenone; 2,2'-dihydroxybenzophenone; 2,2',4,4'-tetrahydroxybenzophenone; 2,2'-dihydroxy-4,4'-dimethoxybenzophenone; 2,2'-dihydroxy-4,4'-diethoxybenzophenone; 2,2'-dihydroxy-4,4'-dipropoxybenzophenone; 2,2'-dihydroxy-4,4'-dibutoxybenzophenone; 2,2'-dihydroxy-4-methoxy-4'-ethoxybenzophenone; 2,2'-dihydroxy-4-methoxy-4'-propoxybenzophenone; 2,2'-Dihydroxy-4-methoxy-4'-butoxybenzophenone; 2,2'-Dihydroxy-4-ethoxy-4'-propoxybenzophenone; 2,2'-Dihydroxy-4-ethoxy-4'-butoxybenzophenone; 2,3'-Dihydroxy-4,4'-dimethoxybenzophenone; 2,3'-Dihydroxy-4-methoxy-4'-butoxybenzophenone; 2-Hydroxy-4,4',5'-trimethoxybenzophenone; 2-Hydroxy-4,4',6'-tributoxybenzophenone; 2-Hydroxy-4-butoxy-4' ,5'-Dimethoxybenzophenone; 2-Hydroxy-4-ethoxy-2',4'-dibutylbenzophenone; 2-Hydroxy-4-propoxy-4',6'-dichlorobenzophenone; 2-Hydroxy-4-propoxy-4',6'-dibromobenzophenone; 2,4-Dihydroxybenzophenone; 2-Hydroxy-4-ethoxybenzophenone; 2-Hydroxy-4-propoxybenzophenone; 2-Hydroxy-4-butoxybenzophenone; 2-Hydroxy-4-methoxy-4'-methylbenzophenone; 2-Hydroxy-4-methoxy 4'-ethylbenzophenone; 2-hydroxy-4-methoxy-4'-propylbenzophenone; 2-hydroxy-4-methoxy-4'-butylbenzophenone; 2-hydroxy-4-methoxy-4'-tert-butylbenzophenone; 2-hydroxy-4-methoxy-4'-chlorobenzophenone; 2-hydroxy-4-methoxy-2'-chlorobenzophenone; 2-hydroxy-4-methoxy-4'-bromobenzophenone; 2-hydroxy-4,4'-dimethoxybenzophenone; 2-hydroxy-4,4'-dimethoxy-3-methylbenzophenone 2-hydroxy-4,4'-dimethoxy-2'-ethylbenzophenone; 2-hydroxy-4,4',5'-trimethoxybenzophenone; 2-hydroxy-4-ethoxy-4'-methylbenzophenone; 2-hydroxy-4-ethoxy-4'-ethylbenzophenone; 2-hydroxy-4-ethoxy-4'-propylbenzophenone; 2-hydroxy-4-ethoxy-4'-butylbenzophenone; 2-hydroxy-4-ethoxy-4'-methoxybenzophenone; 2-hydroxy-4,4'-diethoxybenzophenone;2-hydroxy-4-ethoxy-4'-propoxybenzophenone; 2-hydroxy-4-ethoxy-4'-butoxybenzophenone; 12. The stabilized composition of claim 11, wherein the hydroxybenzophenone is selected from the group consisting of 2-hydroxy-4-ethoxy-4'-chlorobenzophenone; 2-hydroxy-4-ethoxy-4'-bromobenzophenone; and mixtures thereof.

13. The orthohydroxyphenylbenzotriazole compound is selected from the group consisting of 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole; 2-(2'-hydroxy-5'-tert-butylphenyl)-benzotriazole; 2-(2'-hydroxy-3'-methyl-5'-tert-butylphenyl)-benzotriazole; 2-(2'-hydroxy-5'-cyclohexylphenyl)-benzotriazole; 2-(2'-hydroxy-3',5'-dimethylphenyl)-benzotriazole; 2-(2'-hydroxy-5'-ter 2-(2'-hydroxy-5-tert-butylphenyl)-2H-benzotriazole; 2-(2'-hydroxy-5-octylphenyl)-2H-benzotriazole; 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole; 2-(3'-tert-butyl-5'-methylbutyl-2'hydroxyphenyl)-5-chlorobenzotriazole; 2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzyl 2-(3',5'-bis(α,α-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole; 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2,2'-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol]; 2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole and polyethers Transesterification products with ethylene glycol 300; 2-[2'-hydroxy-3'-(α,α-dimethylbenzyl)-5'-(1,1,3,3-tetramethylbutyl)phenyl]benzotriazole; 5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole; 2-(2'-hydroxy-5'-(2-hydroxyethyl)phenyl)benzotriazole; 2-(2'-hydroxy-5'-(2-methacryloyloxyethyl)phenyl)benzotriazole;2-(3'-tert-butyl-5'-methyl-2'-hydroxyphenyl)-5-chloro-benzotriazole; 2-(3'-sec-butyl-5'-tert.butyl-2'-hydroxyphenyl)-benzotriazole; 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-benzotriazole; 2-(5'-tert-octyl-2'-hydroxyphenyl)-benzotriazole; 2-(3'-dodecyl-5'-methyl-2'-hydroxyphenyl)-benzotriazole 12. The stabilized composition of claim 11, wherein the benzotriazole is selected from the group consisting of azoles; 2-(3'-tert-butyl-5'-(2-octyloxycarbonylethyl)-2'-hydroxyphenyl)-5-chlorobenzotriazole; 2-(5'-methyl-2'-hydroxyphenyl)-benzotriazole; 2-(5'-tert-butyl-2'-hydroxyphenyl)-benzotriazole; 2-(2'-hydroxy-3'-di-tert-butylphenyl)-benzotriazole, and mixtures thereof.

14. The benzoxazinone compound as the ultraviolet absorber is 2-methyl-3,1-benzoxazin-4-one; 2-butyl-3,1-benzoxazin-4-one; 2-phenyl-3,1-benzoxazin-4-one; 2-(1- or 2-naphthyl)-3,1-benzoxazin-4-one; 2-(4-biphenyl)-3,1-benzoxazin-4-one; 2-p-nitrophenyl-3,1-benzoxazin-4-one; 2-m-nitrophenyl-3,1-benzoxazin-4-one; 2-p-benzoylphenyl-3,1-benzoxazin-4-one; 2-p-methoxyphenyl-3,1-benzoxazin-4-one; 2-O-methoxyphenyl-3,1-benzoxazin-4-one; 2-cyclohexyl-3,1-benzoxazin-4-one; 2-p-(or m-)phthalimidophenyl-3,1-benzoxazin-4-one; N-phenyl-4-(3,1-benzoxazin-4-one-2-yl)phthalimide; N-benzoyl-4-(3,1-benzoxazin-4-one-2-yl)aniline; N-Benzoyl-N-methyl-4-(3,1-benzoxazin-4-one-2-yl)aniline; 2-[p-(N-phenylcarbamonyl)phenyl]-3,1-benzoxazin-4-one; 2-[p-(N-phenyl-N-methylcarbamoyl)phenyl]-3,1-benzoxazin-4-one; 2,2'-bis(3,1-benzoxazin-4-one); 2,2'-ethylenebis(3,1-benzoxazin-4-one); 2,2'-tetramethylenebis(3,1-benzoxazin-4-one); 2,2'-hexamethylenebis(3,1-benzoxazin-4-one); 2,2'-decamethylenebis(3,1-benzoxazin-4-one); 2,2'-p-phenylenebis(3,1-benzoxazin- 4-one); 2,2'-m-phenylenebis(3,1-benzoxazin-4-one); 2,2'-(4,4'-diphenylene)bis(3,1-benzoxazin-4-one); 2,2'-(2,6- or 1,5-naphthalene)bis(3,1-benzoxazin-4-one); 2,2'-(2-methyl-p-phenylene)bis(3,1-benzoxazin-4-one); 2,2'-(2-nitro-p-phenylene)bis(3,1-benzoxazin-4-one); 2,2'-(2-chloro-p-phenylene)bis(3,1-benzoxazin-4-one); 2,2'-(1,4-cyclohexylene)bis(3,1-benzoxazin-4-one); N-p-(3,1-benzoxazin-4-one-2-yl)phenyl; 4-(3,1-benzoxazin-4-one-2-yl)phthalimide; N-p-(3,1-benzoxazin-4-one-2-yl)benzoyl; 4-(3,1-benzoxazin-4-one-2-yl)aniline; 1,3,5-tri(3,1-benzoxazin-4-one-2-yl)benzene; 1,3,5-tri(3,1-benzoxazin-4-one-2-yl)naphthalene; 12. The stabilized composition of claim 11, wherein the hydroxybenzoate is selected from the group consisting of 2,4,6-tri(3,1-benzoxazin-4-one-2-yl)naphthalene and 2,4,6-tri(3,1-benzoxazin-4-one-2-yl)naphthalene.

15. 15. The stabilized composition of any one of claims 1 to 14, further comprising co-additives selected from the group consisting of nucleating agents, fillers, thioesters, hydroxylamines, metal stearates, metal oxides, reinforcing agents, plasticizers, lubricants, rheology modifiers, catalysts, leveling agents, optical brighteners, antistatic agents, blowing agents, flame retardants, and mixtures thereof.

16. 16. The stabilized composition according to any one of claims 1 to 15, wherein the random polypropylene copolymer comprises from 10% to 99.99% by weight, preferably from 90% to 99.99% by weight, of the total weight of the composition for the front sheet.

17. 17. The stabilized composition according to any one of the preceding claims, wherein the total content of the stabilizers is from 0.01 to 10% by weight, preferably from 0.02 to 5% by weight, more preferably from 0.02 to 2% by weight of the total weight of the composition for the front sheet.

18. A stabilized polymeric front sheet of a photovoltaic cell comprising the stabilizing composition of any one of claims 1 to 17.

19. 20. A photovoltaic cell comprising the polymeric front sheet of claim 18 and a photovoltaic component.

20. A method for producing a stabilized polymeric front sheet for a photovoltaic cell, comprising extruding or molding the stabilized composition of any one of claims 1 to 17.

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