Phenyltriazine co-stabilizers for stabilized polyurethanes

Abstract

The present invention relates to a composition comprising a polyurethane; at least one UV absorber; at least one hindered amine light stabilizer; and at least one phenyltriazine having formula (A) as defined below. The invention also relates to a method for stabilizing a polyurethane, comprising the step of incorporating the at least one UV absorber, the at least one hindered amine light stabilizer, and the at least one phenyltriazine of formula (A) into the polyurethane; and to a mixture comprising the at least one UV absorber, the at least one hindered amine light stabilizer, and the at least one phenyltriazine of formula (A), which mixture prevents the degradation of polyurethanes by light, oxygen and / or heat as a stabilizer.

Description

[0001] The present invention relates to a composition comprising a polyurethane; at least one UV absorber; at least one hindered amine light stabilizer; and at least one phenyl triazine of formula (A) as defined below. The present invention also relates to a method for stabilizing a polyurethane, comprising incorporating the at least one UV absorber, the at least one hindered amine light stabilizer, and the at least one phenyl triazine of formula (A) into the polyurethane; and to a mixture comprising the at least one UV absorber, the at least one hindered amine light stabilizer, and the at least one phenyl triazine of formula (A), which acts as a stabilizer to prevent polyurethane degradation by light, oxygen, and / or heat. Combinations of preferred embodiments with other preferred embodiments are within the scope of the present invention.

[0002] Polyurethanes can be used in a wide range of applications requiring light stabilizers, including industrial applications such as conveyor belts, sports and leisure applications (e.g., sports shoes, ski boots, ski membranes), and automotive applications (artificial leather for dashboards, door panels, seat coverings). There is a continuous need to further improve light stabilizers, for example, to find light stabilizers that are not classified as PBT (persistent, bioaccumulative, and toxic) or vPvB (very persistent and very bioaccumulative) or SVHC (substances of very high concern), to find stabilizers that provide good long-term light stability, and to find low-cost stabilizers. Another object is to further improve the long-term light stability of polyurethanes that have been stabilized with UV absorbers, preferably at a low cost.

[0003] These objects are achieved by a composition comprising:

[0004] - polyurethane;

[0005] - at least one UV absorber;

[0006] - at least one hindered amine light stabilizer; and

[0007] - at least one phenyl triazine of formula (A)

[0008]

[0009] in

[0010] G1 is -O-E1, phenyl, or phenyl substituted by 1, 2 or 3 C1-C4 alkyl groups,

[0011] G2 is -O-E2 when G1 is -O-E1, or is H when G1 is not -O-E1,

[0012] E1 is hydrogen, C1-C 18 Alkyl, C3-C inserted by oxygen 50 Alkyl, C3-C inserted by oxygen50 Hydroxyalkyl, or a group having the formula P

[0013] wherein R, R' and R" are independently C1-C 18 Alkylene,

[0014] b is an integer in the range of 1 to 3, or a group having the formula Q

[0015]

[0016] Wherein T and U are independently a linear or branched C1-C 18 alkyl,

[0017] Wherein when G1 is phenyl, or phenyl substituted by 1, 2 or 3 C1-C4 alkyl groups, b is 1,

[0018] E2, E3, E4, E5 and E6 are independently hydrogen, hydroxy, C1-C 18 Alkyl, phenyl or phenyl substituted by 1, 2 or 3 C1-C4 alkyl groups, or a group of formula Q

[0019]

[0020] Wherein T and U are independently a linear or branched C1-C 18 alkyl, and

[0021] E7 are independently hydrogen or C1-C 18 alkyl.

[0022] These objects are also achieved by a process for preparing the composition comprising the steps of contacting the polyurethane with:

[0023] - at least one UV absorber,

[0024] - at least one hindered amine light stabilizer, and

[0025] - at least one phenyltriazine of formula (A).

[0026] These objects are also achieved by a method for stabilizing polyurethanes, comprising the steps of incorporating into the polyurethane:

[0027] - at least one UV absorber,

[0028] - at least one hindered amine light stabilizer, and

[0029] - at least one phenyltriazine of formula (A).

[0030] These objects are also achieved by the use of a mixture comprising:

[0031] - at least one UV absorber,

[0032] - at least one hindered amine light stabilizer, and

[0033] - at least one phenyltriazine of formula (A).

[0034] In an embodiment, G1 is -O-E1 and G2 is -OE2.

[0035] In an embodiment, G1 is phenyl, or phenyl substituted with 1, 2, or 3 C1-C4 alkyl groups, and G2 is H.

[0036] In an embodiment, E1 is hydrogen, C1-C 18 Alkyl, a group of formula P, or a group of formula (Q), preferably hydrogen, C1-C8 alkyl, a group of formula (P) wherein R, R' and R" are independently C1-C8 18 Alkylene, preferably R, R' and R" are independently C2-C 10 Alkylene, b is an integer ranging from 1 to 3, preferably b is an integer ranging from 1 to 2 - or a group having formula (Q).

[0037] In an embodiment, when b is 1, then E1 is hydrogen, alkyl, or a group having formula (Q), and when b is 2, then E1 is a group having formula (P). Preferably, b is 1.

[0038] In an embodiment, E2, E3, E4, E5 and E6 are each independently hydrogen, C1-C 18 Alkyl, phenyl, or phenyl substituted by 1, 2 or 3 C1-C4 alkyl groups, or a group of formula (Q), preferably E2, E3, E4, E5 and E6 are independently hydrogen, C1-C4 alkyl, phenyl or a group of formula (Q).

[0039] Suitable C1-C 18 Alkyl is a straight or branched C1-C 18Alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl.

[0040] Suitable C1-C 18 Alkylene is a straight or branched C1-C 18 Alkylene groups such as methylene, ethylene, propylene, isopropylene, n-butylene, sec-butylene, isobutylene, tert-butylene, 2-ethylbutylene, n-pentylene, isopentylene, 1-methylpentylene, 1,3-dimethylbutylene, n-hexylene, 1-methylhexylene, n-heptylene, isoheptylene, 1,1,3,3-tetramethylbutylene, 1-methylheptylene, 3-methylheptylene, n-octylene, 2-ethylhexylene, 1,1,3-trimethylhexylene, 1,1,3,3-tetramethylpentylene, nonylene, decylene, undecylene, 1-methylundecylene, dodecylene, 1,1,3,3,5,5-hexamethylhexylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene and octadecylene.

[0041] In an embodiment, E7 is hydrogen. In another embodiment, E7 is C1-C 18 Alkyl, preferably methyl.

[0042] Preferably, the phenyltriazine having formula (A) is selected from formulae (A1), (A2), (A3), (A4), (A5), (A6) and (A7):

[0043]

[0044]

[0045]

[0046] In another preferred form, the phenyltriazine of formula (A) is selected from formula (A1).

[0047] In another preferred form, the phenyltriazine of formula (A) is selected from formula (A2).

[0048] In another preferred form, the phenyltriazine of formula (A) is selected from formula (A3).

[0049] In another preferred form, the phenyltriazine of formula (A) is selected from formula (A4).

[0050] In another preferred form, the phenyltriazine of formula (A) is selected from formula (A5).

[0051] In another preferred form, the phenyltriazine of formula (A) is selected from formula (A6).

[0052] In another preferred form, the phenyltriazine of formula (A) is selected from formula (A7).

[0053] The composition comprises a total amount of 0.001 to 5.0 wt%, preferably 0.01 to 1.0 wt%, and especially 0.05 to 0.5 wt% of phenyltriazine having formula (A).

[0054] The composition comprises a total amount of up to 5.0 wt%, preferably up to 1.0 wt%, and in particular up to 0.5 wt% of phenyltriazine of formula (A).

[0055] The composition comprises a total amount of at least 0.001 wt%, preferably at least 0.01 wt%, and especially at least 0.05 wt% of phenyltriazine having formula (A).

[0056] The UV absorber may be selected from the group consisting of 2-(2'-hydroxyphenyl)benzotriazole, 2-hydroxybenzophenone, esters of substituted and unsubstituted benzoic acid, cyanoacrylates, formamidines, oxanilides, malonates, and mixtures thereof.

[0057] The UV absorber is preferably selected from the group consisting of 2-(2'-hydroxyphenyl)benzotriazole, cyanoacrylate, formamidine, oxanilide and mixtures thereof.

[0058] Preferred UV absorbers are selected from UV absorbers having formula (U1) to (U7)

[0059]

[0060]

[0061] In another preferred form, the UV absorber is selected from formula (U1).

[0062] In another preferred form, the UV absorber is selected from formula (U2).

[0063] In another preferred form, the UV absorber is selected from formula (U3).

[0064] In another preferred form, the UV absorber is selected from formula (U4).

[0065] In another preferred form, the UV absorber is selected from formula (U5).

[0066] In another preferred form, the UV absorber is selected from a mixture of formulae (U4) and (U5).

[0067] In another preferred form, the UV absorber is selected from formula (U6).

[0068] In another preferred form, the UV absorber is selected from formula (U7).

[0069] The composition comprises a total amount of 0.001 to 10.0 wt%, preferably 0.1 to 3.0 wt%, and especially 0.4 to 1.5 wt% of UV absorber.

[0070] The composition comprises a total amount of up to 10.0 wt%, preferably up to 3.0 wt%, and in particular up to 1.5 wt% of UV absorber.

[0071] The composition comprises a total amount of at least 0.001 wt%, preferably at least 0.1 wt%, and especially at least 0.4 wt% of UV absorbers.

[0072] The composition comprises at least one hindered amine light stabilizer, preferably one or two hindered amine light stabilizers, and particularly one hindered amine light stabilizer.

[0073] Suitable hindered amine light stabilizers are known in the art and are generally commercially available.

[0074] Preferred hindered amine light stabilizers are selected from hindered amine light stabilizers having formula (H1), (H2), (H3) and compound (H4):

[0075]

[0076]

[0077] and wherein compound (H4) is the reaction product of 1,2,2,6,6-pentamethylpiperidin-4-ol, diethyl carbonate, and ethoxylated trimethylolpropane.

[0078] Compound (H4) can be prepared according to Example 1 of WO 2009 / 068492. The ethoxylated trimethylolpropane is preferably obtainable by reacting statistically 1 mol of ethylene oxide per mol of hydroxyl group of trimethylolpropane.

[0079] The hindered amine light stabilizers of formula (H2) and (H3) may be present as a mixture.

[0080] In another preferred form, the hindered amine light stabilizer is selected from formula (H1).

[0081] In another preferred form, the hindered amine light stabilizer is selected from formula (H2).

[0082] In another preferred form, the hindered amine light stabilizer is selected from formula (H3).

[0083] In another preferred form, the hindered amine light stabilizer is selected from a mixture of formulae (H2) and (H3).

[0084] In another preferred form, the hindered amine light stabilizer is selected from compound (H4).

[0085] In the hindered amine light stabilizer (H1), the value of n can be 2 to 30, preferably 2 to 10. The molecular weight Mn of the hindered amine light stabilizer (H1) is generally 2000 to 5000 g / mol, preferably 2500 to 4500 g / mol.

[0086] The composition comprises a total amount of 0.001 to 10.0 wt%, preferably 0.1 to 3.0 wt%, and especially 0.4 to 1.5 wt% of the hindered amine light stabilizer.

[0087] The composition comprises a total amount of up to 10.0 wt%, preferably up to 3.0 wt%, and especially up to 1.5 wt% of hindered amine light stabilizer.

[0088] The composition comprises a total amount of at least 0.001 wt%, preferably at least 0.1 wt%, and especially at least 0.4 wt% of hindered amine light stabilizers.

[0089] The composition comprises a total amount of 0.01 to 15.0 wt%, preferably 0.3 to 6.0 wt%, and particularly 1.0 to 3.0 wt% of a UV absorber, a hindered amine light stabilizer and a phenyl triazine having formula (A).

[0090] The composition comprises a total amount of up to 15.0 wt%, preferably up to 6.0 wt%, and especially up to 3.0 wt% of a UV absorber, a hindered amine light stabilizer and a phenyl triazine having formula (A).

[0091] The composition comprises a total amount of at least 0.01 wt%, preferably at least 0.3 wt%, and especially at least 1.0 wt% of a UV absorber, a hindered amine light stabilizer, and a phenyl triazine having formula (A).

[0092] The weight ratio of the UV absorber to the hindered amine light stabilizer may be 3:1 to 1:3, preferably 1.8:1 to 1:1.8, and particularly 1.3:1 to 1:1.3.

[0093] The weight ratio of the sum of the UV absorber and the hindered amine light stabilizer to the phenyltriazine having formula (A) may be 30:1 to 4:1, preferably 15:1 to 7:1, and particularly 12:1 to 8:1.

[0094] The UV absorber and hindered amine light stabilizer may be present in a combined weight excess of at least 2-fold, 3-fold, 4-fold, 5-fold, 6-fold, 7-fold, 8-fold or 9-fold relative to the phenyltriazine of formula (A).

[0095] In a preferred form, the composition comprises polyurethane,

[0096] - a UV absorber having formula (U1),

[0097] - a hindered amine light stabilizer having formula (H1), and

[0098] - a phenyltriazine having the formula (A4).

[0099] In another preferred form, the composition comprises polyurethane,

[0100] - a UV absorber having formula (U2),

[0101] - hindered amine light stabilizers of formula (H2) and (H3), and

[0102] - a phenyltriazine having the formula (A4).

[0103] In another preferred form, the composition comprises polyurethane,

[0104] - a UV absorber having formula (U1),

[0105] - a hindered amine light stabilizer having formula (H1), and

[0106] - a phenyl triazine having the formula (A3).

[0107] In another preferred form, the composition comprises polyurethane,

[0108] - a UV absorber having formula (U3),

[0109] - a hindered amine light stabilizer having formula (H1), and

[0110] - a phenyltriazine having the formula (A1).

[0111] In another preferred form, the composition comprises polyurethane,

[0112] - a UV absorber having formula (U7),

[0113] - a hindered amine light stabilizer as compound (H4), and

[0114] - a phenyl triazine having the formula (A7).

[0115] In another preferred form, the composition comprises polyurethane,

[0116] - a UV absorber having formula (U7),

[0117] - a hindered amine light stabilizer as compound (H4), and

[0118] - a phenyltriazine having the formula (A5).

[0119] In another preferred form, the composition comprises polyurethane,

[0120] - UV absorbers of formula (U4) and (U5),

[0121] - a hindered amine light stabilizer as compound (H4), and

[0122] - a phenyl triazine having the formula (A1).

[0123] In particular, the composition comprises polyurethane,

[0124] - a UV absorber selected from the group consisting of UV absorbers having formula (U1), (U2), (U3), (U4), (U5) and (U7);

[0125] - a hindered amine light stabilizer selected from the group consisting of hindered amine light stabilizers of formula (H1), (H2), (H3) and compound (H4); and

[0126] - a phenyltriazine selected from the group consisting of formulae (A1), (A2), (A3) and (A4).

[0127] In particular, the composition comprises polyurethane,

[0128] - a UV absorber selected from the group consisting of UV absorbers having formula (U1), (U2), (U3), (U4), (U5) and (U7);

[0129] - a hindered amine light stabilizer selected from the group consisting of hindered amine light stabilizers of formula (H1), (H2), (H3) and compound (H4); and

[0130] - a phenyltriazine selected from the group consisting of formulae (A1), (A2), (A3) and (A7).

[0131] In a preferred form, the composition comprises polyurethane,

[0132] - a UV absorber having formula (U1),

[0133] - a hindered amine light stabilizer having formula (H1), and

[0134] - a phenyltriazine of formula (A4), and

[0135] The weight ratio of the sum of the UV absorber and the hindered amine light stabilizer to the phenyltriazine is 30:1 to 4:1, preferably 15:1 to 7:1, and particularly 12:1 to 8:1.

[0136] In another preferred form, the composition comprises polyurethane,

[0137] - a UV absorber having formula (U2),

[0138] - hindered amine light stabilizers of formula (H2) and (H3), and

[0139] - a phenyltriazine of formula (A4), and

[0140] The weight ratio of the sum of the UV absorber and the hindered amine light stabilizer to the phenyltriazine is 30:1 to 4:1, preferably 15:1 to 7:1, and particularly 12:1 to 8:1.

[0141] In another preferred form, the composition comprises polyurethane,

[0142] - a UV absorber having formula (U1),

[0143] - a hindered amine light stabilizer having formula (H1), and

[0144] - a phenyltriazine of formula (A3), and

[0145] The weight ratio of the sum of the UV absorber and the hindered amine light stabilizer to the phenyltriazine is 30:1 to 4:1, preferably 15:1 to 7:1, and particularly 12:1 to 8:1.

[0146] In another preferred form, the composition comprises polyurethane,

[0147] - a UV absorber having formula (U3),

[0148] - a hindered amine light stabilizer having formula (H1), and

[0149] - a phenyltriazine of formula (A1), and

[0150] The weight ratio of the sum of the UV absorber and the hindered amine light stabilizer to the phenyltriazine is 30:1 to 4:1, preferably 15:1 to 7:1, and particularly 12:1 to 8:1.

[0151] In another preferred form, the composition comprises polyurethane,

[0152] - a UV absorber having formula (U7),

[0153] - a hindered amine light stabilizer as compound (H4), and

[0154] - a phenyltriazine of formula (A7), and

[0155] The weight ratio of the sum of the UV absorber and the hindered amine light stabilizer to the phenyltriazine is 30:1 to 4:1, preferably 15:1 to 7:1, and particularly 12:1 to 8:1.

[0156] In another preferred form, the composition comprises polyurethane,

[0157] - a UV absorber having formula (U7),

[0158] - a hindered amine light stabilizer as compound (H4), and

[0159] - a phenyltriazine of formula (A5), and

[0160] The weight ratio of the sum of the UV absorber and the hindered amine light stabilizer to the phenyltriazine is 30:1 to 4:1, preferably 15:1 to 7:1, and particularly 12:1 to 8:1.

[0161] In another preferred form, the composition comprises polyurethane,

[0162] - UV absorbers of formula (U4) and (U5),

[0163] - a hindered amine light stabilizer as compound (H4), and

[0164] - a phenyltriazine of formula (A1), and

[0165] The weight ratio of the sum of the UV absorber and the hindered amine light stabilizer to the phenyltriazine is 30:1 to 4:1, preferably 15:1 to 7:1, and particularly 12:1 to 8:1.

[0166] In a preferred form, the composition comprises polyurethane,

[0167] - a UV absorber having formula (U1),

[0168] - a hindered amine light stabilizer having formula (H1), and

[0169] - a phenyltriazine of formula (A4), and

[0170] The weight ratio of UV absorber to hindered amine light stabilizer is 3:1 to 1:3, preferably 1.8:1 to 1:1.8, and particularly 1.3:1 to 1:1.3.

[0171] In another preferred form, the composition comprises polyurethane,

[0172] - a UV absorber having formula (U2),

[0173] - hindered amine light stabilizers of formula (H2) and (H3), and

[0174] - a phenyltriazine of formula (A4), and

[0175] The weight ratio of UV absorber to hindered amine light stabilizer is 3:1 to 1:3, preferably 1.8:1 to 1:1.8, and particularly 1.3:1 to 1:1.3.

[0176] In another preferred form, the composition comprises polyurethane,

[0177] - a UV absorber having formula (U1),

[0178] - a hindered amine light stabilizer having formula (H1), and

[0179] - a phenyltriazine of formula (A3), and

[0180] The weight ratio of UV absorber to hindered amine light stabilizer is 3:1 to 1:3, preferably 1.8:1 to 1:1.8, and particularly 1.3:1 to 1:1.3.

[0181] In another preferred form, the composition comprises polyurethane,

[0182] - a UV absorber having formula (U3),

[0183] - a hindered amine light stabilizer having formula (H1), and

[0184] - a phenyltriazine of formula (A1), and

[0185] The weight ratio of UV absorber to hindered amine light stabilizer is 3:1 to 1:3, preferably 1.8:1 to 1:1.8, and particularly 1.3:1 to 1:1.3.

[0186] In another preferred form, the composition comprises polyurethane,

[0187] - a UV absorber having formula (U7),

[0188] - a hindered amine light stabilizer as compound (H4), and

[0189] - a phenyltriazine of formula (A7), and

[0190] The weight ratio of UV absorber to hindered amine light stabilizer is 3:1 to 1:3, preferably 1.8:1 to 1:1.8, and particularly 1.3:1 to 1:1.3.

[0191] In another preferred form, the composition comprises polyurethane,

[0192] - a UV absorber having formula (U7),

[0193] - a hindered amine light stabilizer as compound (H4), and

[0194] - a phenyltriazine of formula (A5), and

[0195] The weight ratio of UV absorber to hindered amine light stabilizer is 3:1 to 1:3, preferably 1.8:1 to 1:1.8, and particularly 1.3:1 to 1:1.3.

[0196] In another preferred form, the composition comprises polyurethane,

[0197] - UV absorbers of formula (U4) and (U5),

[0198] - a hindered amine light stabilizer as compound (H4), and

[0199] - a phenyltriazine of formula (A1), and

[0200] The weight ratio of UV absorber to hindered amine light stabilizer is 3:1 to 1:3, preferably 1.8:1 to 1:1.8, and particularly 1.3:1 to 1:1.3.

[0201] The invention also relates to the use of a mixture comprising:

[0202] - at least one UV absorber,

[0203] - at least one hindered amine light stabilizer, and

[0204] - at least one phenyltriazine of formula (A).

[0205] The weight ratio of the sum of the UV absorber and hindered amine light stabilizer to the phenyltriazine having formula (A) in the mixture may be 30:1 to 4:1, preferably 15:1 to 7:1, and particularly 12:1 to 8:1.

[0206] The weight ratio of the UV absorber to the hindered amine light stabilizer in the mixture can be 3:1 to 1:3, preferably 1.8:1 to 1:1.8, and especially 1.3:1 to 1:1.3.

[0207] In a preferred form, the mixture comprises

[0208] - a UV absorber having formula (U1),

[0209] - a hindered amine light stabilizer having formula (H1), and

[0210] - a phenyltriazine of formula (A4), and

[0211] The weight ratio of UV absorber to hindered amine light stabilizer is 3:1 to 1:3, preferably 1.8:1 to 1:1.8, and particularly 1.3:1 to 1:1.3.

[0212] In another preferred form, the mixture comprises

[0213] - a UV absorber having formula (U2),

[0214] - hindered amine light stabilizers of formula (H2) and (H3), and

[0215] - a phenyltriazine of formula (A4), and

[0216] The weight ratio of UV absorber to hindered amine light stabilizer is 3:1 to 1:3, preferably 1.8:1 to 1:1.8, and particularly 1.3:1 to 1:1.3.

[0217] In another preferred form, the mixture comprises

[0218] - a UV absorber having formula (U1),

[0219] - a hindered amine light stabilizer having formula (H1), and

[0220] - a phenyltriazine of formula (A3), and

[0221] The weight ratio of UV absorber to hindered amine light stabilizer is 3:1 to 1:3, preferably 1.8:1 to 1:1.8, and particularly 1.3:1 to 1:1.3.

[0222] In another preferred form, the mixture comprises

[0223] - a UV absorber having formula (U3),

[0224] - a hindered amine light stabilizer having formula (H1), and

[0225] - a phenyltriazine of formula (A1), and

[0226] The weight ratio of UV absorber to hindered amine light stabilizer is 3:1 to 1:3, preferably 1.8:1 to 1:1.8, and particularly 1.3:1 to 1:1.3.

[0227] In another preferred form, the mixture comprises

[0228] - a UV absorber having formula (U7),

[0229] - a hindered amine light stabilizer as compound (H4), and

[0230] - a phenyltriazine of formula (A7), and

[0231] The weight ratio of UV absorber to hindered amine light stabilizer is 3:1 to 1:3, preferably 1.8:1 to 1:1.8, and particularly 1.3:1 to 1:1.3.

[0232] In another preferred form, the mixture comprises

[0233] - a UV absorber having formula (U7),

[0234] - a hindered amine light stabilizer as compound (H4), and

[0235] - a phenyltriazine of formula (A5), and

[0236] The weight ratio of UV absorber to hindered amine light stabilizer is 3:1 to 1:3, preferably 1.8:1 to 1:1.8, and particularly 1.3:1 to 1:1.3.

[0237] In another preferred form, the mixture comprises

[0238] - UV absorbers of formula (U4) and (U5),

[0239] - a hindered amine light stabilizer as compound (H4), and

[0240] - a phenyltriazine of formula (A1), and

[0241] The weight ratio of UV absorber to hindered amine light stabilizer is 3:1 to 1:3, preferably 1.8:1 to 1:1.8, and particularly 1.3:1 to 1:1.3.

[0242] Polyurethanes can be obtained by reacting a polyisocyanate reactant and a polyol reactant in a reaction mixture.

[0243] The polyurethane may be an aromatic or aliphatic polyurethane, preferably an aromatic polyurethane.

[0244] The polyurethane can be a polyurethane foam, a thermoplastic polyurethane (eg, an aromatic or aliphatic thermoplastic polyurethane), or a polyurethane coating.

[0245] Preferably, the polyurethane is a thermoplastic polyurethane, in particular an aromatic thermoplastic polyurethane.

[0246] The polyisocyanate reactant is an aromatic polyisocyanate or an aliphatic polyisocyanate. Aromatic polyisocyanates are, for example, 2,4- and / or 2,6-toluene diisocyanate (TDI), 2,4′-diphenylmethane diisocyanate, 1,3- and 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 2,4′-diphenylmethane diisocyanate (usually contained as a minor isomer in 4,4′-diphenylmethane diisocyanate), 1,5-naphthalene diisocyanate, triphenylmethane-4,4′,4″-triisocyanate or polyphenylpolymethylene polyisocyanates, as prepared, for example, by aniline-formaldehyde condensation and subsequent phosgenation. Polyisocyanates ("crude MDI") of the present invention are also included. Mixtures of aromatic polyisocyanates are also included. Aliphatic polyisocyanates are, for example, ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutene-1,3-diisocyanate, cyclohexane-1,3- and 1,4-diisocyanate, 1,5-diisocyanate-3,3,5-trimethylcyclohexane, 2,4- and / or 2,6-hexahydrotoluene diisocyanate, perhydro-2,4'- and / or 4,4'-diphenylmethane diisocyanate (H 12 MDI) or isophorone diisocyanate. Also included are mixtures of aliphatic polyisocyanates. In addition, derivatives and prepolymers of the aforementioned aromatic polyisocyanates or aliphatic polyisocyanates are included, such as those containing carbamate, carbodiimide, allophanate, isocyanurate, acylated urea, biuret or ester groups ("modified polyisocyanates"). For aromatic polyisocyanates, the so-called "liquid MDI" product containing carbodiimide groups is an example. It is also possible to use distillation residues containing isocyanate groups of aromatic polyisocyanates or aliphatic polyisocyanates, which are one or more of the above-mentioned polyisocyanates obtained in the industrial preparation process of isocyanates or are dissolved therein. Preferred polyisocyanate reactants are aromatic polyisocyanates TDI, MDI or derivatives of MDI, and aliphatic polyisocyanates isophorone diisocyanate, H 12 MDI, hexamethylene diisocyanate, or cyclohexane diisocyanate. Aromatic polyisocyanates are highly preferred. Most preferred are polyisocyanates of TDI, MDI, or MDI derivatives. Particularly preferred are polyisocyanates of TDI, in particular a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate.

[0247] The polyisocyanate reactant is preferably used in an amount that provides an isocyanate index of 90 to 130, more preferably 95 to 115, most preferably 100 to 113, and especially preferably 105 to 112. The isocyanate index, as used herein, refers to 100 times the theoretical number of isocyanate groups used relative to the theoretical number of equivalents required to react with the active hydrogen equivalents in the reaction mixture, such as in the polyol reactant and, if present, water, carboxylic acid, crosslinker, chain extender, and other components having functional groups that are active hydrogen-containing and therefore reactive toward isocyanates. An index of 100 indicates a 1:1 stoichiometric ratio, and an index of 107 indicates, for example, a 7% excess of isocyanate equivalents. Isocyanate equivalents are the total number of isocyanate groups. Active hydrogen equivalents refer to the total number of active hydrogens. An active hydrogen-containing group, such as a hydroxyl group or a secondary amine group, contributes 1 active hydrogen equivalent. An active hydrogen-containing group, such as a primary amine group, also contributes 1 active hydrogen equivalent. This is because after reaction with an isocyanate group, the second original hydrogen is no longer an active hydrogen. Active hydrogen containing groups - being carboxylic acids - contribute one active hydrogen equivalent for each carboxylic acid function.

[0248] The polyol reactant is a polyether polyol or a polyester polyol.

[0249] Polyether polyols are polymers, such as those obtainable by polymerizing alkylene oxides or cyclic ethers having at least four ring atoms, containing at least two active hydrogen-containing groups per molecule, at least two of which are hydroxyl groups. Active hydrogen-containing groups are, for example, primary hydroxyl groups, secondary hydroxyl groups, primary amines, or secondary amines. The intended function of the active hydrogen-containing groups is to react with isocyanates to form covalent bonds therewith. Preferably, the polyether polyol contains 2 to 8, very preferably 2 to 6, most preferably 2 to 4, and especially preferably 2 to 3 active hydrogen-containing groups per molecule. A polyether polyol containing three active hydrogen-containing groups per molecule is also referred to as a trifunctional polyether polyol. Examples of alkylene oxides include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, or styrene oxide. Examples of cyclic ethers include oxetane or tetrahydrofuran.

[0250] Polyether polyols are prepared, for example, by polymerizing alkylene oxides alone or in mixture or sequentially with an initiator component containing at least two reactive hydrogen atoms. The initiator component containing at least two reactive hydrogen atoms is, for example, water, a polyol, ammonia, a primary amine, or a secondary amine containing a second reactive hydrogen atom. The polyol is, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, glycerol, trimethylolpropane, 4,4'-dihydroxydiphenylpropane, or α-methyl glucoside. The primary amine is, for example, ethanolamine, ethylenediamine, diethylenetriamine, or aniline. The secondary amine containing a second reactive hydrogen atom is, for example, diethanolamine, triethanolamine, or N-(2-hydroxyethyl)piperazine. The initiator component containing at least two reactive hydrogen atoms is preferably water or a polyol. The initiator component containing at least two reactive hydrogen atoms preferably contains 2 to 6, more preferably 2 to 4, and most preferably 2 to 3 reactive hydrogen atoms. The average number of reactive hydrogen atoms in the initiator component used to prepare the polyether polyol defines the "nominal functionality" of the polyether polyol, i.e., the average number of active hydrogen-containing groups of the polyether polyol. The nominal functionality of the polyether polyol is preferably from 2 to 6, more preferably from 2 to 4, most preferably from 2 to 3.5, and especially preferably from 2 to 3.3.

[0251] The polyether polyols have a molecular weight of, for example, 400 to 10,000 Daltons, preferably 800 to 10,000 Daltons. The molecular weight is more preferably determined as the number average molecular weight (M n The equivalent weight of a polyether polyol is defined herein as the molecular weight of the polyether polyol divided by the average number of active hydrogen-containing groups per molecule, preferably the number average molecular weight (M n ) to determine the equivalent weight. In particular, the number average molecular weight (M n ) The equivalent weight of the polyether polyol determined is preferably from 400 to 5000, more preferably from 800 to 2500, very preferably from 900 to 1300 and especially preferably from 1000 to 1200.

[0252] Preference is given to polyether polyols which contain predominantly (up to 90% by weight, based on all hydroxyl groups present in the polyether polyol) active hydrogen-containing groups which are secondary hydroxyl groups.

[0253] Polyester polyols are produced, for example, by polycondensation of diacids and diols, wherein the diols are used in excess. Partial replacement of the diols with polyols having more than two hydroxyl groups results in branched polyester polyols. Diacids are, for example, adipic acid, glutaric acid, succinic acid, maleic acid, or phthalic acid. Diols are, for example, ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, or 1,6-hexanediol. Polyols having more than two hydroxyl groups are, for example, glycerol, trimethylolpropane, or pentaerythritol.

[0254] Crosslinking agents are, for example, additional components of the reaction mixture. Crosslinking agents can improve the elasticity of the polyurethane. As defined herein, a crosslinking agent has three (3) to eight, preferably three to four, active hydrogen-containing groups per molecule. Thus, the crosslinking agent reacts with the polyisocyanate reactant and, if present, is considered a reactant for purposes of calculating the polyisocyanate index. The crosslinking agent does not contain ester bonds and has an equivalent weight below 200, particularly when measured by a number average molecular weight (M). n ) is determined. In the presence of a crosslinking agent, the polyether polyol preferably has a polyether polyol equivalent weight of 400 to 5000, in particular using a number average molecular weight (M n ). The crosslinking agent is, for example, an alkylene triol or an alkanolamine. The alkylene triol is, for example, glycerol or trimethylolpropane. The alkanolamine is, for example, diethanolamine, triisopropanolamine, triethanolamine, diisopropanolamine, an adduct of 4 to 8 moles of ethylene oxide and ethylenediamine, or an adduct of 4 to 8 moles of propylene oxide and ethylenediamine. The crosslinking agent is preferably an alkanolamine, more preferably diethanolamine.

[0255] Chain extenders are, for example, additional components of the reaction mixture. As defined herein, chain extenders have two active hydrogen-containing groups per molecule that are hydroxyl groups. Thus, chain extenders react with the polyisocyanate reactant and, if present, are considered a reactant for purposes of calculating the polyisocyanate index. Chain extenders do not contain ester bonds and have an equivalent weight between 31 and 300, preferably 31 to 150, particularly as measured by number average molecular weight (M). n In the presence of a chain extender, the polyether polyol preferably has a polyether polyol equivalent weight of 400 to 5000, in particular using a number average molecular weight (M n ) is determined. The chain extender is, for example, an alkylene glycol or a glycol ether. The alkylene glycol is, for example, ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, or 1,6-hexamethylene glycol. The glycol ether is, for example, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, or 1,4-cyclohexanedimethanol.

[0256] If used, the combined amount of crosslinker and chain extender in the reaction mixture is less than 50 parts by weight based on 100 parts by weight of the polyol reactant. The combined amount is preferably less than 20 parts by weight, more preferably less than 5 parts by weight.

[0257] The reaction mixture before the reaction comprises a polyisocyanate reactant and a polyol reactant, and based on 100 parts by weight of the polyol reactant, 60 to 100 parts by weight of the polyol reactant is preferably a polyether polyol. More preferably, 80 to 100 parts by weight, very preferably 95 to 100 parts by weight, most preferably 98 to 100 parts by weight of the polyol reactant is a polyether polyol, and it is particularly preferred that the polyol reactant is a polyether polyol.

[0258] The polyurethane is obtained by reacting the reaction mixture. The above preferred situation can be expressed in an alternative form, that is, the polyurethane is preferably obtained by reacting the polyisocyanate reactant and the polyol in the reaction mixture, and based on 100 parts by weight of the polyol reactant, 60 to 100 parts by weight of the polyol reactant is a polyether polyol.

[0259] Preferably, a catalyst for the reaction of the polyisocyanate reactant and the polyol reactant is added to the reaction mixture. The catalyst is, for example, an amine catalyst or an organometallic catalyst. The amine catalyst is, for example, triethylenediamine or a derivative thereof, N-methylmorpholine, N-ethylmorpholine, diethylethanolamine, N-cocoylmorpholine, 1-methyl-4-dimethylaminoethylpiperazine, 3-methoxy-N-dimethylpropylamine, N,N-diethyl-3-diethylaminopropylamine, dimethylbenzylamine, di(2-dimethylaminoethyl)ether or dimethylbenzylamine. Preferred are triethylenediamine or a derivative thereof. The organometallic catalyst is, for example, an organic salt of tin, bismuth, iron, mercury, zinc or lead. Preferred are organotin compounds. Examples of organotin compounds are dimethyltin dilaurate, dibutyltin dilaurate or stannous octoate. Preferred are stannous octoate. Preferably, the amount of the amine catalyst is 0.01 to 5 parts by weight, more preferably 0.03 to 2 parts by weight, based on 100 parts by weight of the polyol reactant. Preferably, the amount of the organometallic catalyst is 0.001 to 3 parts by weight, based on 100 parts by weight of the polyol reactant. Preferably, the amine catalyst and the organometallic catalyst are added to the reaction mixture.

[0260] To generate polyurethane foam, gas generation occurs during the reaction. Gas generation during the reaction can be induced by adding water or carboxylic acid to the reaction mixture before the reaction to generate chemical gas or by adding a blowing agent to the reaction mixture before the reaction.

[0261] As used herein, a blowing agent is an organic compound having a boiling point at 101.32 kPa at or below the maximum temperature generated during the reaction with the reaction mixture at -15°C, preferably between -15°C and 110°C, more preferably between -10°C and 80°C, and very preferably between -5°C and 70°C. Furthermore, the blowing agent does not react under the reaction conditions to form a chemical bond with the polyisocyanate reactant or the polyol reactant in the reaction mixture. Examples of blowing agents are alkanes having 4 to 10 carbon atoms, preferably 5 to 8 carbon atoms, cycloalkanes having 5 to 10 carbon atoms, acetone, methyl formate, carbon dioxide (added in liquid form), or partially or fully halogenated alkanes having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms.

[0262] Alkanes with 4 to 10 carbon atoms are, for example, butane, pentane, hexane or heptane. Cycloalkanes with 5 to 10 carbon atoms are, for example, cyclopentane or cyclohexane. Partially or fully halogenated alkanes are, for example, methylene chloride, 1,1,1-trichloroethane, CFC-11, CFC-113, CFC-114, CFC-123, CFC-123a, CFC-124, CFC-133, CFC-134, CFC-134a, CFC-141b, CFC-142, CFC-151. Among the partially or fully halogenated alkanes with 1 to 5 carbon atoms, those that are partially halogenated, i.e., those having at least one hydrogen atom, such as methylene chloride, CFC-123, CFC-141b, CFC-124 or 1,1,1-trichloroethane are preferred.

[0263] When water is used for gas generation, it is preferably added to the reaction mixture prior to the reaction in an amount of 0.5 to 12 parts by weight based on 100 parts by weight of the polyol reactant. More preferably, 1 to 8 parts of water are added. Most preferably, 2 to 7 parts of water, such as 3 to 7 or 4 to 7 parts of water are added. This is particularly true for a reaction mixture having a gas concentration between 16 and 32 kg / m 3 For polyurethane foams with a density between 32 kg / m 3 and less than 48kg / m 3 To make polyurethane foam of a certain density, add 2 to 5 parts water.

[0264] When a blowing agent is used for gas generation, the blowing agent is preferably added to the reaction mixture in an amount of 2 to 50 parts by weight based on 100 parts by weight of the polyol reactant. More preferably, 3 to 45 parts of blowing agent are added. Very preferably, 4 to 30 parts of blowing agent are added, for example 5 to 25 parts of blowing agent.

[0265] The use of water or carboxylic acid or the use of a blowing agent provides a desired reduction in polyurethane density. When using water or carboxylic acid, particularly water, the exothermic heat of reaction increases. With the use of water, the amount of urea bonds in the polyurethane foam increases, which causes the foam to harden. In contrast, the use of a blowing agent moderates the temperature in the reaction mixture and softens the foam. However, the use of water is attractive, but it increases the requirements for the stability of the polyurethane foam generated during the reaction.

[0266] The polyurethane foam has a reduced density relative to a polyurethane obtained from an identical reaction mixture except for the water or carboxylic acid content or blowing agent content. The polyurethane foam has a density of preferably 5 to 500 kg / m at 20°C and 101.3 kPa. 3 between 10 and 300 kg / m 3 between 15 and 100 kg / m 3 , and most preferably 16 to 48 kg / m 3In the case of integral skin polyurethane foam (structural foam), the density is determined as the average density of the entire foam structure. The density of integral skin polyurethane foam is typically 10 times that of ordinary polyurethane foam.

[0267] The polyurethane may be a thermoplastic polyurethane. Thermoplastic polyurethanes are known in principle. They are typically produced by reacting the components (a) an isocyanate and (b) an isocyanate-reactive compound and optionally (c) a chain extender, optionally in the presence of at least one (d) catalyst and / or (e) conventional auxiliaries and / or additives. The components (a) isocyanate, (b) isocyanate-reactive compound, and (c) chain extender are also referred to individually or collectively as building block components.

[0268] Preferred organic isocyanates (a) include aliphatic, alicyclic, araliphatic and / or aromatic isocyanates, more preferably tri-, tetra-, penta-, hexa-, hepta- and / or octamethylene diisocyanate, 2-methylpentamethylene 1,5-diisocyanate, 2-ethylbutene 1,4-diisocyanate, pentamethylene 1,5-diisocyanate, butene 1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1,4- and / or 1,3-bis(isocyanatomethyl)cyclohexane (HXDI), 1,4-cyclohexane diisocyanate, 1-methyl-2,4- and / or -2,6-cyclohexane diisocyanate and / or 4,4'-, 2,4'- and 2,2'-dicyclohexylmethane diisocyanate, 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate (NDI), 2,4- and / or 2,6-toluene diisocyanate (TDI), 3,3'-dimethyldiphenyl diisocyanate, 1,2-diphenylethane diisocyanate and / or phenylene diisocyanate. Particular preference is given to using 4,4'-MDI.

[0269] Therefore, in a further embodiment, the present invention relates to a composition as described above, wherein the thermoplastic polyurethane is based on diphenylmethane diisocyanate (MDI).

[0270] Isocyanate-reactive components (b) which can be employed include in principle all suitable compounds known to the person skilled in the art. According to the invention, at least one diol is used as isocyanate-reactive compound (b).

[0271] Any suitable diol may be employed in the context of the present invention, such as a polyether diol or a polyester diol or a mixture of two or more thereof.

[0272] According to the invention, in principle any suitable polyester diol can be used, wherein in the context of the present invention the term polyester diol also includes polycarbonate diols.

[0273] One embodiment of the present invention uses polycarbonate diol or polytetramethylene glycol. Suitable polytetramethylene glycol has a molecular weight in the range of, for example, 500 to 5000 g / mol, preferably 500 to 2000 g / mol, particularly preferably 800 to 1200 g / mol.

[0274] Suitable polycarbonate diols include, for example, polycarbonate diols based on alkane diols. Suitable polycarbonate diols are strictly difunctional OH-functional polycarbonate diols, preferably strictly difunctional OH-functional aliphatic polycarbonate diols. Suitable polycarbonate diols are, for example, based on 1,4-butanediol, 1,5-pentanediol or 1,6-hexanediol, in particular 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methylpentane-(1,5)-diol or mixtures thereof, particularly preferably 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol or mixtures thereof. Preference is given in the context of the present invention to polycarbonate diols based on 1,4-butanediol and 1,6-hexanediol, polycarbonate diols based on 1,5-pentanediol and 1,6-hexanediol, polycarbonate diols based on 1,6-hexanediol, and mixtures of two or more of these polycarbonate diols.

[0275] The composition according to the invention preferably comprises at least one thermoplastic

[0276] Polyurethane, it is selected from the group consisting of: thermoplastic polyurethane based on at least one diisocyanate and at least one polycarbonate diol, and thermoplastic polyurethane based on at least one diisocyanate and polytetramethylene glycol. Therefore, the production of the polyurethane present in the composition according to the invention adopts at least one polycarbonate diol or polytetramethylene glycol as component (b).

[0277] Therefore, in a further embodiment, the present invention relates to a composition as described above, wherein the thermoplastic polyurethane is selected from the group consisting of: thermoplastic polyurethanes based on at least one diisocyanate and at least one polycarbonate diol, and thermoplastic polyurethanes based on at least one diisocyanate and polytetramethylene glycol. Therefore, in a further embodiment, the present invention relates to a composition as described above, wherein the thermoplastic polyurethane is selected from the group consisting of: thermoplastic polyurethanes based on at least one aromatic diisocyanate and at least one polycarbonate diol, and thermoplastic polyurethanes based on at least one aromatic diisocyanate and polytetramethylene glycol.

[0278] It is possible that the composition is a part of a shaped article or a complete shaped article. Preferably, the composition is a complete shaped article. Examples of shaped articles are:

[0279] 1) Floating devices for offshore applications.

[0280] 2) Automotive applications, specifically bumpers, instrument panels, front and rear linings, molded parts under the hood, hat racks, trunk linings, inner liners, airbag covers, instrument panels, outer liners, trim, interior and exterior trim, door panels, seat backs, exterior wall panels, plating, pillar covers, chassis parts, folding roofs, front-end modules, stamped parts, side impact protection, sound absorbers / insulators, and sunroofs.

[0281] 3) Aircraft equipment and railway equipment.

[0282] 4)Architectural and design installations, sound attenuation systems, and shelters.

[0283] 5) For sheathing of other materials such as steel or textiles, e.g. cable sheathing.

[0284] 6) Electrical appliances, especially washing machines, drums, ovens (microwave ovens), dishwashers, and mixers.

[0285] 7) Rotating blades, ventilator and windmill blades, swimming pool covers, pool liners, pond liners, closets, wardrobes, partition walls, slatted walls, folding walls, roofs, shutters (e.g. roller shutters), seals.

[0286] 8) Packaging and wrapping, isolating bottles.

[0287] 9) General furniture, foam products (cushions, mattresses, buffers), foam, sponges, dishcloths, mats.

[0288] 10) Shoes, soles, insoles, shoe covers, adhesives, structural adhesives, sofas.

[0289] The composition may preferably contain additional additives such as antioxidants, metal deactivators, phosphites and phosphonates, hydroxylamine and amine N-oxides, nitrones, thiosynergists, peroxide scavengers, alkaline co-stabilizers, nucleating agents, fillers and reinforcing agents, benzofuranones and indolones, flame retardants, or other additives such as plasticizers, lubricants, emulsifiers, pigments, rheological additives, catalysts, flow control agents, optical brighteners, flame retardants, antistatic agents and blowing agents, heat stabilizers, antifog agents, anti-fog agents, anti-caking agents, slip agents, anti-scratch agents. These additional additives may, for example, be selected from the following list:

[0290] 1. Antioxidants

[0291] 1.1. Alkylated monophenols, such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(α-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6 - di-tert-butyl-4-methoxymethylphenol, nonylphenols having linear or branched side chains, for example 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6-(1'-methylundec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methylheptadecan-1'-yl)phenol, 2,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methyl-1'-tetradecylmethyl)phenol, and mixtures thereof.

[0292] 1.2. Alkylthiomethylphenols, for example, 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, and 2,6-di-dodecylthiomethyl-4-nonylphenol.

[0293] 1.3. Hydroquinones and alkylated hydroquinones, for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, and bis(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

[0294] 1.4. Tocopherols, such as α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E), vitamin E acetate. Particularly preferred is the addition of 2,5,7,8-tetramethyl-2-[4,8,12-trimethyltridecyl]-chroman-6-ol], a commercially available vitamin E (e.g., Irganox E 201 TM ).

[0295] 1.5. Hydroxylated thiodiphenyl ethers, such as 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2-methylphenol), 4,4'-thiobis(3,6-di-sec-pentylphenol), and 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl) disulfide.

[0296] 1.6. Alkylene bisphenols, such as 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4-methylphenol), 2,2'-methylenebis(4,6-di-tert-butyl ... Ethylbis(4,6-di-tert-butylphenol), 2,2'-ethylenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-(α-methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol], 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-methylenebis(6-tert-butyl-2-methylphenol), 1,1-bis(5-tert-butyl-4-hydroxy-2 -methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene, Bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane, 1,1,5,5-tetrakis(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

[0297] 1.7. O-, N- and S-benzyl compounds, for example 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl 4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl 4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

[0298] 1.8. Hydroxybenzylated malonates, for example dioctadecyl 2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, dioctadecyl 2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, didodecylmercaptoethyl 2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

[0299] 1.9. Aromatic hydroxybenzyl compounds, for example, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, and 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

[0300] 1.10. Triazine compounds, for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-Tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

[0301] 1.11. Benzylphosphonates, for example dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl 5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, (3,5-di-tert-butyl-4-hydroxyphenyl)methylphosphonic acid.

[0302] 1.12. Acylaminophenols, for example 4-hydroxylauroylanilide, 4-hydroxystearylanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

[0303] 1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, for example, esters with methanol, ethanol, n-octanol, isooctyl alcohol, mixtures of linear and branched C7-C9-alkanols, octadecyl alcohol, linear and branched C 13 -C 15 - mixtures of alkanols, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propylene glycol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, oligoethylene glycols having 3 to 15 ethylene glycol units, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis-(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane. Preference is given to esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, especially with octadecyl alcohol, such as the addition of octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, which is available, for example, as Irganox 1076 TM Commercially available.

[0304] 1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols, for example, esters with methanol, ethanol, n-octanol, isooctyl alcohol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propylene glycol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis( hydroxyethyl)oxalamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane; 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane.

[0305] 1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, for example, esters with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propylene glycol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0306] 1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with mono- or polyhydric alcohols, for example, esters with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propylene glycol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0307] 1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, for example N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamide, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide (Naugard XL-1 (RTM), supplied by SI Group).

[0308] 1.18. Ascorbic acid (vitamin C)

[0309] 1.19. Amine antioxidants, such as N,N'-diisopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,N'-bis(1-methylheptyl)-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine, diamines, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4-(p-toluenesulfamoyl)diphenylamine, N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, nonylated diphenylamines, octylated diphenylamines, for example p,p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol , bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane, (o-tolyl)biguanide, bis[4-(1',3'-dimethylbutyl)phenyl]amine, tert-octylated N-phenyl-1-naphthylamine, mixtures of mono- and di-alkylated tert-butyl / tert-octyldiphenylamines, mixtures of mono- and di-alkylated nonyldiphenylamines mixtures of mono- and dialkylated dodecyldiphenylamine, mixtures of mono- and dialkylated isopropyl / isohexyldiphenylamine, mixtures of mono- and dialkylated tert-butyldiphenylamine, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, mixtures of mono- and dialkylated tert-butyl / tert-octylphenothiazines or mixtures of mono- and dialkylated tert-octylphenothiazines, N-allylphenothiazine, N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene, N-[(1,1,3,3-tetramethylbutyl)phenyl]-1-naphthylamine] (as Irganox L06 TM Commercially available), nonylated diphenylamine.

[0310] Alternatively or in addition, mixtures of commercially available additives may also be used, with Irganox 5057 being particularly preferred. TM , obtained by the reaction of diphenylamine with diisobutylene, and comprising

[0311] (A) 5057 diphenylamine;

[0312] (B) 5057 4-tert-Butyldiphenylamine;

[0313] (C) 5057 Compounds of the following groups

[0314] i) 4-tert-octyldiphenylamine,

[0315] ii) 4,4'-di-tert-butyldiphenylamine,

[0316] iii) 2,4,4'-tri-tert-butyldiphenylamine,

[0317] (D) 5057 Compounds of the following groups

[0318] i) 4-tert-butyl-4'-tert-octyldiphenylamine,

[0319] ii) o,o', m,m' or p,p'-di-tert-octyldiphenylamine,

[0320] iii) 2,4-tert-butyl-4'-tert-octyldiphenylamine,

[0321] (E) 5057 Compounds of the following groups

[0322] i) 4,4'-di-tert-octyldiphenylamine,

[0323] ii) 2,4-di-tert-octyl-4'-tert-butyldiphenylamine, and

[0324] wherein not more than 5% by weight of component (A) is present 5057 8 to 15% by weight of component (B) 5057 , 24 to 32% by weight of component (C) 5057 , 23% to 34% by weight of component (D) 5057 and 21 to 34% by weight of component (E) 5057 .

[0325] 3. Metal deactivators, for example N,N'-diphenyloxamide, N-salicylaldehyde-N'-salicyloylhydrazine, N,N'-bis(salicyloyl)hydrazine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyldihydrazide, oxanilide, isophthaloyldihydrazide, sebacoylbisphenylhydrazine, N,N'-diacetyladipoyldihydrazide, N,N'-bis(salicyloyl)oxalyldihydrazide, N,N'-bis(salicyloyl)thiopropionyldihydrazide.

[0326] 4. Phosphites and phosphonates, such as trialkyl (C12-C15) phosphite, triisodecyl phosphite, triisotridecyl phosphite, dioleyl hydrogen phosphite, triisooctyl phosphite, heptaphan (dipropylene glycol) triphosphite, trilauryl trithiophosphite, tris (dipropylene glycol) phosphite, dimethyl hydrogen phosphite, dibutyl hydrogen phosphite, dilauryl hydrogen phosphite, tri-C12-C14 phosphite or bis (2-ethylhexyl) hydrogen phosphite. Other phosphites and phosphonates, for example liquid ones, such as di-n-octyl hydrogen phosphite or di-isooctyl hydrogen phosphite, or for example triphenyl phosphite, tris(nonylphenyl) phosphite, phenyl diisodecyl phosphite, diphenyl isodecyl phosphite, [polymer of triphenyl phosphite with 1,4-cyclohexanedimethanol and polypropylene glycol C10-16 alkyl esters (CAS Reg. No.: 1821217-71-3)]. Other optional phosphite or phosphonate additives include, for example, alkyl (C12-C15) bisphenol A phosphite, alkyl (C10) bisphenol A phosphite, poly (dipropylene glycol) phenyl phosphite, tris (tridecyl) phosphite, diphenyl phosphite, dodecyl nonylphenol phosphite blend, phenyl neopentyl glycol phosphite, poly 4,4'-isopropylidene diphenol-C10 alcohol phosphite, poly 4,4'-isopropylidene diphenol-C12-15 alcohol phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, C 12 -C 18 Alkyl bis[4-(1-methyl-1-phenyl-ethyl)phenyl] ester, phosphorous acid C 12 -C 18Alkenyl bis[4-(1-methyl-1-phenyl-ethyl)phenyl] ester, bis[4-(1-methyl-1-phenyl-ethyl)phenyl][(E)-octadecan-9-enyl] phosphite, decyl bis[4-(1-methyl-1-phenyl-ethyl)phenyl] phosphite, didecyl[4-(1-methyl-1-phenyl-ethyl)phenyl] phosphite, [4-(1-methyl-1-phenyl-ethyl)phenyl]bis[(E)-octadecan-9-enyl] phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, Bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, [2-tert-butyl-4-[1-[5-tert-butyl-4-di(tridecyloxy)phosphatyloxy-2-methyl-phenyl]butyl]-5-methyl-phenyl]di-tridecyl phosphite, tristearyl sorbitol triphosphite, for example as in US Mixtures of at least two different tris(mono-C1-C8-alkyl)phenyl phosphites mentioned as products of Examples 1 and 2 in US Pat. No. 7,468,410 B2, for example, phosphite mixtures comprising at least two different tris(pentylphenyl) phosphites, such as those mentioned as mixtures 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25 and 26 in US Pat. No. 8,008,383 B2, comprising tris[4-(1,1-dimethylpropyl)phenyl]phosphite, [2,4-bis(1,1-dimethylpropyl)phenyl]bis[4-(1,1-dimethylpropyl)phenyl]phosphite, bis[2,4-bis(1,1-dimethylpropyl)phenyl][4-(1,1-dimethylpropyl)phenyl]phosphite and tris[2,4-bis(1,1-dimethylpropyl)phenyl]phosphite.mixtures of at least four different phosphites of tris(butylphenyl)phosphites, such as, for example, the phosphite mixtures comprising at least two different tris(butylphenyl)phosphites mentioned in US Pat. No. 8,008,383 B2 as mixtures 34, 35, 36, 37, 38, 39 and 40, oxyalkylene-bridged bis-(di-C6-aryl)diphosphites, or oligomeric phosphites obtainable by condensation of (i) trichlorophosphine with (ii) dihydroxyalkanes having one or more inserted oxygen atoms and with (iii) mono-hydroxy-C6-aromatics with elimination of hydrogen chloride, such as, for example, the products of Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 and 17 mentioned in US Pat. No. 8,304,477 B2, such as, for example, the products of Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 and 17 ... Polymer phosphites obtainable by transesterification of (i) triphenyl phosphite with (ii) dihydroxyalkanes and / or bis(hydroxyalkyl)(alkyl)amines optionally interrupted by one or more oxygen atoms and with (iii) mono-hydroxyalkanes optionally interrupted by one or more oxygen atoms, with removal of phenol, tetrakis(2,4-di-tert-butylphenyl)-4,4′-biphenylene diphosphonite, 6-Isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphosphocine, bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo[d,g] ]-1,3,2-dioxaphosphocane, 1,3,7,9-tetra-tert-butyl-11-octyloxy-5H-benzo[d][1,3,2]benzodioxaphosphocane, 2,2',2"-nitrilo[triethyltris(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphite], polymers of triphenyl phosphite with α-hydrogen-ω-hydroxypoly[oxy(methyl-1,2-ethanediyl)] C10-16-alkyl esters (CAS Registry No. [1227937-46-3]), 2-ethylhexyl (3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite, 5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphocene, mixed 2,4-bis(1,1-dimethylpropyl)phenyl and 4-(1,1-dimethylpropyl)phenyl triesters (CAS Registry No. [939402-02-5]).

[0327] The following phosphites are particularly preferred:

[0328] Tris(2,4-di-tert-butylphenyl)phosphite ( 168, Ciba Specialty Chemicals Inc., tris(nonylphenyl)phosphite,

[0329]

[0330]

[0331] 5. Hydroxylamines and amine N-oxides, for example N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallowamine, bis(hydrogenated palm oil alkyl)hydroxylamine, N,N-bis-(hydrogenated rape oil alkyl)-N-methyl-amine N-oxide or trialkylamine N-oxide.

[0332] 6. Nitrones, for example N-benzyl-α-phenylnitrone, N-ethyl-α-methylnitrone, N-octyl-α-heptylnitrone, N-lauryl-α-undecylnitrone, N-tetradecyl-α-tridecylnitrone, N-hexadecyl-α-pentadecylnitrone, N-octadecyl-α-heptadecylnitrone, N-hexadecyl-α-heptadecylnitrone, N-octadecyl-α-pentadecylnitrone, N-heptadecyl-α-heptadecylnitrone, N-octadecyl-α-hexadecylnitrone, nitrones derived from N,N-dialkylhydroxylamines derived from hydrogenated tallowamine, optionally of vegetable origin.

[0333] 7. Thiosynergists, for example dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate and pentaerythritol tetrakis-[3-(n-lauryl)-propionate].

[0334] 8. Peroxide scavengers, for example esters of α-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, bis-octadecyl disulfide, pentaerythritol tetrakis(β-dodecylmercapto)propionate.

[0335] 10. Polyamide stabilizers, for example copper salts and divalent manganese salts in combination with iodides and / or phosphorus compounds.

[0336] 11. Alkaline co-stabilizers, for example melamine, polyvinyl pyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids (for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate), antimony or zinc pyrocatecholate, zeolite, hydrotalcite, hydrated calcium aluminate (hydrocaluminate), zinc oxide.

[0337] 12. Nucleating agents, for example inorganic substances such as talc, metal oxides such as titanium dioxide or magnesium oxide, phosphoric acid esters including phosphoric acid ester salts such as 2,2'-methylene-bis(4,6-di-tert-butylphenol)phosphate sodium salt, 2,2'-methylene-bis(4,6-di-tert-butylphenol)phosphate aluminum salt or 2,2'-methylene-bis(4,6-di-tert-butylphenol)phosphate lithium salt, carbonates or sulfates (preferably alkaline earth metal carbonates or sulfates); Organic compounds, such as monocarboxylic acids or polycarboxylic acids and their salts, for example, 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate, 1,2-cyclohexanedicarboxylic acid calcium salt, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid disodium salt; polymeric compounds, such as ionic copolymers (ionomers), triaminobenzene derivatives such as 1,3,5-tris[2,2-dimethylpropionamido]benzene, zinc glycerate, and nonytol derivatives. Particularly preferred are 1,3:2,4-bis(3',4'-dimethylbenzylidene)sorbitol, 1,3:2,4-di(p-methyldibenzylidene)sorbitol, and 1,3:2,4-di(benzylidene)sorbitol.

[0338] 13. Fillers and reinforcing agents, for example calcium carbonate, silicates, glass fibres, glass beads, asbestos, talc, kaolin, mica, barium sulphate, metal oxides and hydroxides, carbon black, graphite, wood and flour flour or fibres of other natural products, synthetic fibres.

[0339] 14. Other additives, such as plasticizers, lubricants, emulsifiers, pigments, rheological additives, catalysts, flow control agents, optical brighteners, fire retardants, antistatic agents and blowing agents, heat stabilizers, antifogging agents, antihaze agents, antiblocking additives, slip agents, anti-scratch agents.

[0340] 15. Benzofuranones and indolones, for example, as described in US-A-4,325,863; US-A-4,338,244; US-A-5,175,312; US-A-5,216,052; US-A-5,252,643; DE-A-4316611; DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102, WO 2015 / 121445, WO those disclosed in 2017 / 025431, or 5,7-di-tert-butyl-3-(4-hydroxyphenyl)-3H-benzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-hydroxyethoxy)phenyl]-3H-benzofuran-2-one, 5,7-di-tert-butyl-3-[4-[2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethoxy]phenyl]-3H-benzofuran-2-one, 3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butylbenzene Benzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one, 3,3'-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one], 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl Benzofuran-2-one, 3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(2,3-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(2-acetoxy-4-(1,1,3,3-tetramethylbutyl)-phenyl)-5-(1,1,3,3-tetramethyl-butyl)benzofuran-2-one, 6-hydroxyhexanoic acid [6-[6-[2-[4-(5,7-di-tert-butyl-2-oxo-3H-benzofuran-3-yl)phenoxy]ethoxy] benzoate, [4-tert-butyl-2-(5-tert-butyl-2-oxo-3H-benzofuran-3-yl)phenyl] 3,5-di-tert-butyl-4-hydroxybenzoate and [4-tert-butyl-2-(5-tert-butyl-2-oxo-3H-benzofuran-3-yl)phenyl] 3-(3,5-di-tert-butyl-4-hydroxy-phenyl)propanoate.

[0341] 16. Flame retardants

[0342] 16.1. Phosphorus-containing flame retardants, including reactive phosphorus-containing flame retardants, such as tetraphenylresorcinol diphosphite (Fyrolflex RDP, RTM, Akzo Nobel), tetrakis(hydroxymethyl)phosphonium sulfide, triphenyl phosphate, diethyl-N,N-bis(2-hydroxyethyl)aminomethyl phosphonate, hydroxyalkyl phosphates, alkyl phosphate oligomers, ammonium polyphosphate (APP), resorcinol diphosphate oligomers (RDP), phosphazene flame retardants, or ethylenediamine diphosphate (EDAP).

[0343] 16.2. Nitrogen-containing flame retardants, for example flame retardants based on melamine, isocyanurates, polyisocyanurates, esters of isocyanuric acid (such as tris(2-hydroxyethyl)isocyanurate, tris(hydroxymethyl)isocyanurate, tris(3-hydroxy-n-propyl)isocyanurate, triglycidyl isocyanurate), melamine cyanurate, melamine borate, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine ammonium polyphosphate, melamine ammonium pyrophosphate, dimelamine phosphate, dimelamine pyrophosphate, benzoguanamine, allantoin, glycoluril, urea cyanurate, condensation products of melamine from the series of melem, melam, melon and / or higher condensation compounds or reaction products of melamine with phosphoric acid or mixtures thereof.

[0344] 16.3. Organohalogen flame retardants, for example polybrominated diphenyl ether, decabromodiphenyl ether (DBDPO), tris[3-bromo-2,2-bis(bromomethyl)propyl] phosphate (PB 370, (RTM, FMC Corp.)), tris(2,3-dibromopropyl) phosphate, chloroalkyl phosphates such as tris(chloropropyl) phosphate, tris(2,3-dichloropropyl) phosphate, tris(1,3-dichloro-2-propyl) phosphate (Fyrol FR 2 (RTM ICL)), oligomeric chloroalkyl phosphates, chlorendic acid, tetrachlorophthalic acid, tetrabromophthalic acid, poly-b-chloroethyl triphosphonate mixture, tetrabromobisphenol A-bis(2,3-dibromopropyl ether) (PE68), brominated epoxy resins, brominated aryl esters, ethylene-bis(tetrabromophthalimide) (Saytex BT-93 (RTM, Albemarle), bis(hexachlorocyclopenta)cyclooctane (Declorane Plus (RTM, Oxychem), chlorinated paraffins, octabromodiphenyl ether, hexachlorocyclopentadiene derivatives, 1,2-bis(tribromophenoxy)ethane (FF680), tetrabromobisphenol A (Saytex RB100 (RTM, Albemarle), ethylenebis-(dibromonorbornanedicarboximide) (Saytex BN-451 (RTM, Albemarle), bis-(hexachlorocyclopenta)cyclooctane, PTFE, tris(2,3-dibromopropyl)isocyanurate or ethylene-bis-tetrabromophthalimide. Some of the halogenated flame retardants mentioned above are often combined with inorganic oxide synergists. Some of the halogenated flame retardants mentioned above can be used in combination with triaryl phosphates (such as propylated, butylated triphenyl phosphate) and / or oligomeric aryl phosphates (such as resorcinol bis(diphenyl phosphate), bisphenol A bis(diphenyl phosphate), neopentyl glycol bis(diphenyl phosphate)).

[0345] 16.4 Inorganic flame retardants, such as aluminum trihydroxide (ATH), boehmite (AlOOH), magnesium dihydroxide (MDH), zinc borate, CaCO₃, organically modified layered silicates, organically modified layered double hydroxides, and mixtures thereof. For synergistic combinations with halogenated flame retardants, the most common inorganic oxide synergists are zinc oxide, antimony oxides such as Sb₂O₃ or Sb₂O₅, or boron compounds.

[0346] The combination or contact of the phenyl triazine of formula (A), the hindered amine light stabilizer and the UV absorber and optionally other additives in the polyurethane can be achieved by conventional methods, such as adding the modifier blend or its single component to the polymer material. These components can be added to the polyurethane in the form of a liquid, powder, granules or masterbatch. The phenyl triazine of formula (A), the UV absorber and the hindered amine light stabilizer and optionally other additives can be added to the polyurethane individually or mixed with each other. It is preferred that the phenyl triazine of formula (A), the UV absorber and the hindered amine light stabilizer are added together, such as in the form of a masterbatch.

[0347] Examples

[0348] Unless otherwise indicated, all parts and percentages are by weight. If not otherwise indicated, weight percentages (wt %) are based on the entire composition excluding any volatiles.

[0349] UV absorbers:

[0350] UV 1: oxalamide, N-(2-ethoxyphenyl)-N'-(2-ethylphenyl)

[0351] UV 2: N'-(4-ethoxycarbonylphenyl)-N-methyl-N-phenylformamidine

[0352] UV 3: 2-phenol, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)

[0353] UV 4 / 5: A mixture of α-[3-[3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropyl]-ω-hydroxypoly(oxy-1,2-ethanediyl) and α-[3-[3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropyl]-ω-[3-[3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropyloxy]poly(oxy-1,2-ethanediyl), in a weight ratio of approximately 3:1.

[0354] UV 6: 1,3-bis-((2'-cyano-3',3'-diphenylacryloyl)oxy)-2,2-bis-(((2'-cyano-3',3'-diphenylacryloyl)oxy)methyl)-propane

[0355] UV 7: 2-Ethylhexyl 2-cyano-3,3-diphenylacrylate

[0356] Hindered amine light stabilizers:

[0357] HALS1: Dimethyl succinate-4-hydroxy-2,2,6,6-tetramethyl-1-piperidinylethanol copolymer

[0358] HALS2 / 3: Reaction mass of bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate and 1,2,2,6,6-pentamethyl-4-piperidinyl sebacate methyl ester, containing a mixture of bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate and 1,2,2,6,6-pentamethyl-4-piperidinyl sebacate methyl ester

[0359] HALS 4: tertiary HALS, liquid, prepared according to Example 1 of WO 2009 / 068492.

[0360] Phenyl triazine:

[0361] HPT 1: Phenol, 2-[4,6-bis([1,1'-biphenyl]-4-yl)-1,3,5-triazin-2-yl]-5-[(ethylhexyl)oxy]

[0362] HPT 2: Phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxy

[0363] HPT 3: 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)phenol

[0364] HPT 4: 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-[(2-ethylhexyl)oxy]-2-hydroxypropoxy]phenol

[0365] HPT 5: 2,2'-[6-(2,4-dibutoxyphenyl)-1,3,5-triazine-2,4-diyl]bis[5-butoxyphenol

[0366] HPT 6: 2,2',2"-(1,3,5-triazine-2,4,6-triyl)tris[5-(hexyloxy)-6-methylphenol

[0367] HPT 7: 5-[(2-ethylhexyl)oxy]-2-(4-{4-[(2-ethylhexyl)oxy]-2-hydroxyphenyl}-6-(4-methoxyphenyl)-1,3,5-triazin-2-yl)phenol

[0368] Example 1

[0369] Manufacturing of thermoplastic polyurethane test panels (substrates)

[0370] Thermoplastic polyurethane (aromatic TPU) (polyester type, extrusion and injection molding grade, Shore A 85) was used.

[0371] Mixing

[0372] 2.5 kg of pellets were ground in a cryogenic mill and dried under vacuum at 80°C until the water content was less than 0.05%. The TPU powder was mixed with 2% of the stabilizer composition in a tumble mixer until homogeneous, as reported in Tables 1 and 2 below. These blends were then immediately extruded in a twin-screw extruder Berstorff ZE25A x 47D at temperatures up to 210°C. The resulting pellets were again dried at 80°C under dry air until the water content was less than 0.03%.

[0373] Injection molding

[0374] With the help of injection molding machine ( From the obtained granules, test panels (substrates) having dimensions of 64 mm x 44 mm x 2 mm were molded using a PTFE e-mac 100) at a temperature of up to 210° C. (mold temperature: 40° C.).

[0375] Weather resistance test

[0376] In order to evaluate the photostability performance achieved with different photostabilizer packages, according to

[0377] The produced panels were exposed to artificial accelerated weathering using the ASTM G155-Dry method (Xenon arc, using the same conditions as ASTM G 155, Cycle 1 but without the rain cycle) and the SAE J2412 (Xenon arc) method.

[0378] Color measurement

[0379] Color change was measured at intermediate exposure times and at the end of exposure using a spectrophotometer CM-3700d (Minolta). The yellowness index, unitless, was determined according to ASTM E313. ΔE (in CIELAB units, the square root of the square of the difference between the CIELAB color coordinates L*, a*, and b* at the recall time minus the CIELAB color coordinates L*, a*, and b* at time zero, as defined in ISO 11664-4) was measured to provide information on the color change of the substrate after exposure relative to the initial value. The results are reported in Tables 1 and 2.

[0380] Table 1: Color change of TPU substrates after exposure to accelerated aging for 14 to 14 hours according to ASTM G 155 - Drying method.

[0381]

[0382] a) Comparative data

[0383] b) According to the present invention

[0384] The above results show that the examples of the present invention provide TPU substrates with improved light stability and lower discoloration upon exposure compared to the comparative examples.

[0385] Table 2: Color change of TPU substrate after exposure to accelerated aging for 750 hours according to SAE J 2412 method.

[0386]

[0387] a) Comparative data

[0388] b) According to the present invention

[0389] The above results show that the examples of the present invention provide TPU substrates with improved light stability and lower discoloration upon exposure compared to the comparative examples.

[0390] Example 2

[0391] Manufacturing of thermoplastic polyurethane test panels (substrates)

[0392] Thermoplastic polyurethane (aromatic TPU) (polyether type, extrusion and injection molding grade, Shore A 87) was used.

[0393] Mixing

[0394] 2.5 kg of pellets were ground in a cryogenic mill and dried under vacuum at 80°C until the water content was less than 0.05%. The TPU powder was mixed with 2% of the stabilizer composition in a tumble mixer until homogeneous, as reported in Table 3 below. These blends were then immediately extruded in a twin-screw extruder Berstorff ZE25A x 47D at temperatures up to 210°C. The resulting pellets were again dried at 80°C under dry air until the water content was less than 0.03%.

[0395] Injection molding

[0396] With the help of injection molding machine ( From the obtained granules, test panels (substrates) having dimensions of 64 mm x 44 mm x 2 mm were molded using a TEFLON® e-mac 100 at a temperature of up to 210° C. (mold temperature: 30° C.).

[0397] Weather resistance test

[0398] In order to evaluate the light stability performance achieved with the different light stabilizer packages, the produced substrates were exposed to artificial accelerated weathering according to the ISO 105-B06 method (Xenon arc).

[0399] Color measurement

[0400] Color change was measured at intermediate exposure times and at the end of exposure using a spectrophotometer CM-3700d (Minolta). ΔE (in CIELAB units, the square root of the square of the difference between the CIELAB color coordinates L*, a*, and b* at the recall time minus the CIELAB color coordinates L*, a*, and b* at time zero, as defined in ISO 11664-4) was measured to provide information on the color change of the substrate after exposure relative to the initial value. The results are reported in Table 3.

[0401] Table 3: Color change of TPU substrates after exposure to accelerated aging for 1000 hours according to ISO 105-B06 method.

[0402]

[0403] a) Comparative data

[0404] b) According to the present invention

[0405] The above results show that the examples of the present invention provide TPU substrates with improved light stability and lower discoloration upon exposure compared to the comparative examples.

[0406] Example 3

[0407] Manufacturing of thermoplastic polyurethane test panels (substrates)

[0408] Thermoplastic polyurethane (aromatic TPU) (polyether type, extrusion and injection molding grade, Shore A 87) was used.

[0409] Mixing

[0410] 2.5 kg of pellets were ground in a cryogenic mill and dried under vacuum at 80°C until the water content was less than 0.05%. The TPU powder was mixed with 2% of the stabilizer composition in a tumble mixer until homogeneous, as reported in Table 4 below. These blends were then immediately extruded in a twin-screw extruder Berstorff ZE25A x 47D at temperatures up to 210°C. The resulting pellets were again dried at 80°C under dry air until the water content was less than 0.03%.

[0411] Injection molding

[0412] With the help of injection molding machine ( From the obtained granules, test panels (substrates) having dimensions of 64 mm x 44 mm x 2 mm were molded using a TEFLON® e-mac 100 at a temperature of up to 210° C. (mold temperature: 30° C.).

[0413] Weather resistance test

[0414] In order to evaluate the light stability performance achieved with the different light stabilizer packages, the produced substrates were exposed to artificial accelerated weathering according to the Adidas FT 11 method (neon lamp).

[0415] Color measurement

[0416] Color change was measured at intermediate exposure times and at the end of exposure using a spectrophotometer CM-3700d (Minolta). Yellowness index, unitless, was determined according to ASTM E313. Delta E (in CIELAB units, the square root of the square of the difference between the CIELAB color coordinates L*, a*, and b* at the recall time minus the CIELAB color coordinates L*, a*, and b* at time zero, as defined in ISO 11664-4) was measured to provide information about the color change of the substrate after exposure relative to the initial value.

[0417] The obtained results are reported in Table 4.

[0418] Table 4 Color change of TPU substrate after exposure to accelerated aging for 8 hours according to the Adidas FT 11 method.

[0419]

[0420] a) Comparative data

[0421] b) According to the present invention

Claims

1. A composition comprising - polyurethane; - at least one UV absorber; - at least one hindered amine light stabilizer; and - at least one phenyl triazine of formula (A) in G1 is -O-E1, phenyl, or phenyl substituted by 1, 2 or 3 C1-C4 alkyl groups, G2 is -O-E2 when G1 is -O-E1, or is H when G1 is not -O-E1, E1 is hydrogen, C1-C 18 Alkyl, C3-C inserted by oxygen 50 Alkyl, C3-C inserted by oxygen 50 Hydroxyalkyl, or a group having the formula P wherein R, R' and R" are independently C1-C 18 Alkylene, b is an integer in the range of 1 to 3, or a group having the formula Q Wherein T and U are independently a linear or branched C1-C 18 alkyl, Wherein when G1 is phenyl, or phenyl substituted by 1, 2 or 3 C1-C4 alkyl groups, b is 1, E2, E3, E4, E5 and E6 are independently hydrogen, hydroxy, C1-C 18 Alkyl, phenyl or phenyl substituted by 1, 2 or 3 C1-C4 alkyl groups, or a group of formula Q Wherein T and U are independently a linear or branched C1-C 18 alkyl, and E7 are independently hydrogen or C1-C 18 alkyl.

2. The composition according to claim 1, wherein The weight ratio of the sum of the UV absorber and the hindered amine light stabilizer to the phenyltriazine of formula (A) is 30:1 to 4:1, preferably 15:1 to 7:1, and particularly 12:1 to 8:

1.

3. The composition according to claim 1 or 2, wherein The weight ratio of the UV absorber to the hindered amine light stabilizer is 3:1 to 1:3, preferably 1.8:1 to 1:1.8, and particularly 1.3:1 to 1:1.

3.

4. The composition according to claim 1 or 3, wherein The phenyl triazine having formula (A) is selected from formula (A1), (A2), (A3), (A4), (A5), (A6) and (A7) 5. The composition according to claim 1 or 4, wherein The at least one hindered amine light stabilizer is selected from the group consisting of formula (H1), (H2), (H3) and compound (H4) as well as The compound (H4) is the reaction product of 1,2,2,6,6-pentamethylpiperidin-4-ol, diethyl carbonate and ethoxylated trimethylolpropane.

6. The composition according to claim 1 or 5, wherein The at least one UV absorber is selected from formula (U1) to (U7) 7. The composition according to claim 1 or 6, wherein The polyurethane is an aromatic polyurethane.

8. The composition according to claim 1 or 7, wherein The polyurethane is polyurethane foam, thermoplastic polyurethane, or polyurethane coating.

9. The composition according to claim 1 or 8, wherein The composition comprises the UV absorber, the hindered amine light stabilizer and the phenyl triazine having formula (A) in a total amount of 0.01 to 15.0 wt%, preferably 0.3 to 6.0 wt%, and particularly 1.0 to 3.0 wt%.

10. The composition according to claim 1 or 9, wherein The composition comprises the UV absorber in a total amount of 0.001 to 10.0 wt%, preferably 0.1 to 3.0 wt%, and especially 0.4 to 1.5 wt%.

11. The composition according to claim 1 or 10, wherein The composition comprises the hindered amine light stabilizer in a total amount of 0.001 to 10.0 wt%, preferably 0.1 to 3.0 wt%, and especially 0.4 to 1.5 wt%.

12. The composition according to claim 1 or 11, wherein The composition comprises the phenyl triazine of formula (A) in a total amount of 0.001 to 5.0 wt%, preferably 0.01 to 1.0 wt%, and especially 0.05 to 0.5 wt%.

13. A process for preparing a composition according to the preceding claim, comprising the step of contacting the polyurethane with: - at least one UV absorber as defined in the preceding claims, - at least one hindered amine light stabilizer as defined in the preceding claims, and - at least one phenyltriazine of formula (A) as defined in the preceding claims.

14. A method for stabilizing a polyurethane as defined in the preceding claim, comprising the step of incorporating into the polyurethane: - at least one UV absorber as defined in the preceding claims, - at least one hindered amine light stabilizer as defined in the preceding claims, and - at least one phenyltriazine of formula (A) as defined in the preceding claims.

15. Use of a mixture comprising: as a stabilizer for preventing degradation of a polyurethane as defined in the preceding claims by light, oxygen and / or heat: - at least one UV absorber as defined in the preceding claims, - at least one hindered amine light stabilizer as defined in the preceding claims, and - at least one phenyltriazine of formula (A) as defined in the preceding claims.

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