Phenyltriazine co-stabilizers for stabilizing 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 of formula (A) as defined below. The present invention also relates to a process for stabilizing a polyurethane, comprising incorporating into the polyurethane at least one UV absorber, at least one hindered amine light stabilizer, and at least one phenyltriazine of formula (A), and to a mixture comprising at least one UV absorber, at least one hindered amine light stabilizer, and at least one phenyltriazine of formula (A) as a stabilizer of the polyurethane against degradation by light, oxygen, and / or heat.

Description

[Technical Field]

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

[0002] Polyurethanes can be used in a wide range of applications requiring light stabilizers, ranging from conveyor belts, sports and leisure applications (e.g., sports shoes, ski boots, ski films), and industrial applications such as automotive applications (artificial leather for instrument panels, door panels, seat covers). There is a continuing 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 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 objective was to further improve the long-term light stabilization of polyurethanes that have already been stabilized with UV absorbers, preferably at low cost. Summary of the Invention [Means for solving the problem]

[0003] The purpose of this is to polyurethane, at least one UV absorber; at least one hindered amine light stabilizer, at least one formula (A) [ka] [In the formula, G1 is -O-E1, phenyl, or phenyl substituted with 1, 2, or 3 C1-C4 alkyl; G2 is -O-E2 when G1 is -O-E1, or H when G1 is not -O-E1; E1 is hydrogen, C1 to C 18 Alkyl, C3-C interrupted by oxygen 50 Alkyl, C3-C interrupted by oxygen 50 Hydroxyalkyl, or a group of formula P [ka] (In the formula, R, R′, and R″ are each independently C1 to C 18 alkylene), Or formula Q [ka] (wherein T and U are each independently a straight or branched C1-C 18 alkyl), b is an integer ranging from 1 to 3; when G1 is phenyl or phenyl substituted with 1, 2 or 3 C1-C4 alkyl, b is 1; E2, E3, E4, E5 and E6 are independently hydrogen, hydroxy, C1-C 18 alkyl, phenyl or phenyl substituted with 1, 2 or 3 C1-C4 alkyl or a group of formula Q [ka] (Wherein, T and U are each independently a straight-chain or branched C1-C 18 alkyl), E7 are each independently hydrogen or C1-C18 This was achieved by a composition comprising a phenyl triazine of which the alkyl group is ...

[0004] The present invention also relates to a polyurethane and at least one UV absorber; at least one hindered amine light stabilizer, at least one phenyltriazine of formula (A), This was achieved by a process for preparing the composition, which comprises contacting

[0005] The present invention also relates to polyurethanes. at least one UV absorber; at least one hindered amine light stabilizer, at least one phenyltriazine of formula (A), This was achieved by a process for stabilizing polyurethanes which includes incorporating

[0006] The object is also to provide a method for the preparation of polyurethanes as stabilizers against degradation by light, oxygen and / or heat. at least one UV absorber; at least one hindered amine light stabilizer, at least one phenyltriazine of formula (A), This was achieved by the use of a mixture comprising: DETAILED DESCRIPTION OF THE INVENTION

[0007] In one embodiment, G1 is -O-E1 and G2 is -OE2.

[0008] In one embodiment, G1 is phenyl or phenyl substituted with 1, 2, or 3 C1-C4 alkyl; and G2 is H.

[0009] In one embodiment, E1 is hydrogen, C1-C 18alkyl, 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 each independently C1-C 18 alkylene, and preferably R, R' and R'' are each independently C2 to C 10 alkylene) or a group of formula (Q), where b is an integer in the range of 1 to 3, preferably b is an integer in the range of 1 to 2.

[0010] In one embodiment, when b is 1, E1 is hydrogen, alkyl or a group of formula (Q), and when b is 2, E1 is a group of formula (P). Preferably, b is 1.

[0011] In one 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 or a group of formula (Q), preferably E2, E3, E4, E5 and E6 are each independently hydrogen, C1-C4 alkyl, phenyl or a group of formula (Q).

[0012] Suitable C1~C 18 The alkyl is a straight or branched C1-C 18 Alkyl, examples of which are 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.

[0013] Suitable C1~C 18The alkylene is a straight or branched C1-C 18 Alkylene, examples of which include 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-methylhexylene, n-heptylene, isoheptylene, 1,1,3,3-tetramethylbutylene, 1-methylhexylene, n-hexylene ... 1-methylhexylene, n-hexylene, isoheptylene, 1,1,3,3-tetramethylbutylene, butylene, 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.

[0014] In one embodiment, E7 is hydrogen. In another embodiment, E7 is C1-C 18 It is alkyl, preferably methyl.

[0015] Preferably, the formula (A) phenyltriazine has the formula (A1), (A2), (A3), (A4), (A5), (A6) and (A7): [ka] [ka] is selected from.

[0016] In another preferred embodiment, the phenyltriazine of formula (A) is selected from formula (A1). In another preferred embodiment, the phenyltriazine of formula (A) is selected from formula (A2). In another preferred embodiment, the phenyltriazine of formula (A) is selected from formula (A3). In another preferred embodiment, the phenyltriazine of formula (A) is selected from formula (A4). In another preferred embodiment, the phenyltriazine of formula (A) is selected from formula (A5). In another preferred embodiment, the phenyltriazine of formula (A) is selected from formula (A6). In another preferred embodiment, the phenyltriazine of formula (A) is selected from formula (A7).

[0017] The composition contains the phenyltriazine of formula (A) in a total amount of 0.001 to 5.0% by weight, preferably 0.01 to 1.0% by weight, in particular 0.05 to 0.5% by weight.

[0018] The composition comprises phenyltriazines of formula (A) in a total amount of at most 5.0% by weight, preferably at most 1.0% by weight, in particular at most 0.5% by weight.

[0019] The composition comprises phenyltriazines of formula (A) in a total amount of at least 0.001% by weight, preferably at least 0.01% by weight, in particular at least 0.05% by weight.

[0020] The UV absorber may be selected from the group consisting of 2-(2'-hydroxyphenyl)benzotriazoles, 2-hydroxybenzophenones, esters of substituted and unsubstituted benzoic acid, cyanoacrylates, formamidines, oxanilides, malonates, and mixtures thereof.

[0021] The UV absorber is preferably selected from the group consisting of 2-(2'-hydroxyphenyl)benzotriazoles, cyanoacrylates, formamidines, oxanilides, and mixtures thereof.

[0022] Preferred UV absorbers are those of formula (U1) to (U7) [ka] [ka] The UV absorbers are selected from the group consisting of:

[0023] In another preferred embodiment, the UV absorber is selected from formula (U1). In another preferred embodiment, the UV absorber is selected from formula (U2). In another preferred embodiment, the UV absorber is selected from formula (U3). In another preferred embodiment, the UV absorber is selected from formula (U4). In another preferred embodiment, the UV absorber is selected from formula (U5). In another preferred embodiment, the UV absorber is selected from a mixture of formulas (U4) and (U5). In another preferred embodiment, the UV absorber is selected from formula (U6). In another preferred embodiment, the UV absorber is selected from formula (U7).

[0024] The composition contains UV absorbers in a total amount of 0.001 to 10.0% by weight, preferably 0.1 to 3.0% by weight, in particular 0.4 to 1.5% by weight.

[0025] The composition comprises UV absorbers in a total amount of up to 10.0% by weight, preferably up to 3.0% by weight, in particular up to 1.5% by weight.

[0026] The composition comprises UV absorbers in a total amount of at least 0.001% by weight, preferably at least 0.1% by weight, in particular at least 0.4% by weight.

[0027] The composition comprises at least one hindered amine light stabilizer, preferably one or two hindered amine light stabilizers, especially one hindered amine light stabilizer.

[0028] Suitable hindered amine light stabilizers are known in the art and are often commercially available.

[0029] Preferred hindered amine light stabilizers are selected from the hindered amine light stabilizers of formula (H1), (H2), (H3) and compound (H4): [ka] Here, compound (H4) is the reaction product of 1,2,2,6,6-pentamethylpiperidin-4-ol, diethyl carbonate, and ethoxylated trimethylolpropane.

[0030] Compound (H4) can be prepared according to Example 1 of WO 2009 / 068492. Ethoxylated trimethylolpropane can be preferably obtained by statistically reacting one mole of ethylene oxide per mole of hydroxy group of trimethylolpropane.

[0031] The hindered amine light stabilizers of formula (H2) and (H3) can be present as a mixture.

[0032] In another preferred embodiment, the hindered amine light stabilizer is selected from the formula (H1). In another preferred embodiment, the hindered amine light stabilizer is selected from the formula (H2). In another preferred embodiment, the hindered amine light stabilizer is selected from the formula (H3). In another preferred embodiment, the hindered amine light stabilizer is selected from a mixture of the formulae (H2) and (H3). In another preferred embodiment, the hindered amine light stabilizer is selected from the compound (H4).

[0033] In the hindered amine light stabilizer (H1), n ​​may have a value of 2 to 30, preferably 2 to 10. The molecular weight Mn of the hindered amine light stabilizer (H1) is usually 2000 to 5000 g / mol, preferably 2500 to 4500 g / mol.

[0034] The composition contains the hindered amine light stabilizer in a total amount of 0.001 to 10.0% by weight, preferably 0.1 to 3.0% by weight, and especially 0.4 to 1.5% by weight.

[0035] The composition comprises hindered amine light stabilizers in a total amount of up to 10.0% by weight, preferably up to 3.0% by weight, in particular up to 1.5% by weight.

[0036] The composition comprises hindered amine light stabilizers in a total amount of at least 0.001% by weight, preferably at least 0.1% by weight, in particular at least 0.4% by weight.

[0037] The composition comprises the UV absorber, the hindered amine light stabilizer and the phenyltriazine of formula (A) in a total amount of 0.01 to 15.0% by weight, preferably 0.3 to 6.0% by weight, especially 1.0 to 3.0% by weight.

[0038] The composition comprises a UV absorber, a hindered amine light stabilizer and a phenyltriazine of formula (A) in a total amount of up to 15.0% by weight, preferably up to 6.0% by weight, in particular up to 3.0% by weight.

[0039] The composition comprises a UV absorber, a hindered amine light stabilizer and a phenyltriazine of formula (A) in a total amount of at least 0.01% by weight, preferably at least 0.3% by weight, in particular at least 1.0% by weight.

[0040] The weight ratio of UV absorber to hindered amine light stabilizer may be from 3:1 to 1:3, preferably from 1.8:1 to 1:1.8, in particular from 1.3:1 to 1:1.3.

[0041] The weight ratio of the sum of the UV absorber and the hindered amine light stabilizer to the phenyltriazine of formula (A) may be from 30:1 to 4:1, preferably from 15:1 to 7:1, in particular from 12:1 to 8:1.

[0042] The UV absorber and hindered amine light stabilizer may be present in a combined weight amount of at least a 2-fold, 3-fold, 4-fold, 5-fold, 6-fold, 7-fold, 8-fold, or 9-fold excess relative to the phenyltriazine of formula (A).

[0043] In a preferred form, the composition comprises a polyurethane and a UV absorber of formula (U1), a hindered amine light stabilizer of formula (H1) phenyltriazines of formula (A4)

[0044] In another preferred form, the composition comprises a polyurethane and a UV absorber of formula (U2), hindered amine light stabilizers of the formulae (H2) and (H3), phenyltriazines of formula (A4)

[0045] In another preferred form, the composition comprises a polyurethane and a UV absorber of formula (U1), a hindered amine light stabilizer of formula (H1) phenyltriazines of formula (A3)

[0046] In another preferred form, the composition comprises a polyurethane and a UV absorber of formula (U3), a hindered amine light stabilizer of formula (H1) phenyltriazines of formula (A1)

[0047] In another preferred form, the composition comprises a polyurethane and a UV absorber of formula (U7), - a hindered amine light stabilizer of the compound (H4), phenyltriazines of formula (A7)

[0048] In another preferred form, the composition comprises a polyurethane and a UV absorber of formula (U7), - a hindered amine light stabilizer of the compound (H4), phenyltriazines of formula (A5)

[0049] In another preferred form, the composition comprises a polyurethane and UV absorbers of the formulae (U4) and (U5), - a hindered amine light stabilizer of the compound (H4), phenyltriazines of formula (A1)

[0050] In particular, the composition comprises a polyurethane and a UV absorber selected from the UV absorbers of formulae (U1), (U2), (U3), (U4), (U5) and (U7), a hindered amine light stabilizer selected from the hindered amine light stabilizers of formula (H1), (H2), (H3) and compounds (H4), a phenyltriazine selected from the formulae (A1), (A2), (A3) and (A4):

[0051] In particular, the composition comprises a polyurethane and a UV absorber selected from the UV absorbers of formulae (U1), (U2), (U3), (U4), (U5) and (U7), a hindered amine light stabilizer selected from the hindered amine light stabilizers of formula (H1), (H2), (H3) and compounds (H4), a phenyltriazine selected from the formulae (A1), (A2), (A3) and (A7):

[0052] In a preferred form, the composition comprises a polyurethane and a UV absorber of formula (U1), a hindered amine light stabilizer of formula (H1) phenyltriazines, where the formula is (A4), The weight ratio of the total 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, particularly 12:1 to 8:1.

[0053] In another preferred form, the composition comprises a polyurethane and a UV absorber of formula (U2), hindered amine light stabilizers of the formulae (H2) and (H3), phenyltriazines, where the formula is (A4), The weight ratio of the total 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, particularly 12:1 to 8:1.

[0054] In another preferred form, the composition comprises a polyurethane and a UV absorber of formula (U1), a hindered amine light stabilizer of formula (H1) phenyltriazines, where the formula is (A3), The weight ratio of the total 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, particularly 12:1 to 8:1.

[0055] In another preferred form, the composition comprises a polyurethane and a UV absorber of formula (U3), a hindered amine light stabilizer of formula (H1) phenyltriazines, where the formula is (A1), The weight ratio of the total 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, particularly 12:1 to 8:1.

[0056] In another preferred form, the composition comprises a polyurethane and a UV absorber of formula (U7), - a hindered amine light stabilizer of the compound (H4), phenyltriazines, when of formula (A7), The weight ratio of the total 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, particularly 12:1 to 8:1.

[0057] In another preferred form, the composition comprises a polyurethane and a UV absorber of formula (U7), - a hindered amine light stabilizer of the compound (H4), phenyltriazines, when of formula (A5), The weight ratio of the total 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, particularly 12:1 to 8:1.

[0058] In another preferred form, the composition comprises a polyurethane and UV absorbers of the formulae (U4) and (U5), - a hindered amine light stabilizer of the compound (H4), phenyltriazines, where the formula is (A1), The weight ratio of the total 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, particularly 12:1 to 8:1.

[0059] In a preferred form, the composition comprises a polyurethane and a UV absorber of formula (U1), a hindered amine light stabilizer of formula (H1) phenyltriazines, where the formula is (A4), The weight ratio of UV absorber to hindered amine light stabilizer is from 3:1 to 1:3, preferably from 1.8:1 to 1:1.8, in particular from 1.3:1 to 1:1.3.

[0060] In another preferred form, the composition comprises a polyurethane and a UV absorber of formula (U2), hindered amine light stabilizers of the formulae (H2) and (H3), phenyltriazines, where the formula is (A4), The weight ratio of UV absorber to hindered amine light stabilizer is from 3:1 to 1:3, preferably from 1.8:1 to 1:1.8, in particular from 1.3:1 to 1:1.3.

[0061] In another preferred form, the composition comprises a polyurethane and a UV absorber of formula (U1), a hindered amine light stabilizer of formula (H1) phenyltriazines, where the formula is (A3), The weight ratio of UV absorber to hindered amine light stabilizer is from 3:1 to 1:3, preferably from 1.8:1 to 1:1.8, in particular from 1.3:1 to 1:1.3.

[0062] In another preferred form, the composition comprises a polyurethane and a UV absorber of formula (U3), a hindered amine light stabilizer of formula (H1) phenyltriazines, where the formula is (A1), The weight ratio of UV absorber to hindered amine light stabilizer is from 3:1 to 1:3, preferably from 1.8:1 to 1:1.8, in particular from 1.3:1 to 1:1.3.

[0063] In another preferred form, the composition comprises a polyurethane and a UV absorber of formula (U7), - a hindered amine light stabilizer of the compound (H4), phenyltriazines, when of formula (A7), The weight ratio of UV absorber to hindered amine light stabilizer is from 3:1 to 1:3, preferably from 1.8:1 to 1:1.8, in particular from 1.3:1 to 1:1.3.

[0064] In another preferred form, the composition comprises a polyurethane and a UV absorber of formula (U7), - a hindered amine light stabilizer of the compound (H4), phenyltriazines, when of formula (A5), The weight ratio of UV absorber to hindered amine light stabilizer is from 3:1 to 1:3, preferably from 1.8:1 to 1:1.8, in particular from 1.3:1 to 1:1.3.

[0065] In another preferred form, the composition comprises a polyurethane and UV absorbers of the formulae (U4) and (U5), - a hindered amine light stabilizer of the compound (H4), phenyltriazines, where the formula is (A1), The weight ratio of UV absorber to hindered amine light stabilizer is from 3:1 to 1:3, preferably from 1.8:1 to 1:1.8, in particular from 1.3:1 to 1:1.3.

[0066] The present invention also provides a method for the preparation of polyurethanes as stabilizers against degradation by light, oxygen and / or heat. at least one UV absorber; at least one hindered amine light stabilizer, at least one phenyltriazine of formula (A), The present invention relates to the use of a mixture comprising:

[0067] The weight ratio of the sum of the UV absorber and hindered amine light stabilizer to the phenyltriazine of formula (A) in the mixture may be from 30:1 to 4:1, preferably from 15:1 to 7:1, in particular from 12:1 to 8:1.

[0068] The weight ratio of UV absorber to hindered amine light stabilizer in the mixture may be from 3:1 to 1:3, preferably from 1.8:1 to 1:1.8, in particular from 1.3:1 to 1:1.3.

[0069] In a preferred form, the mixture comprises: a UV absorber of formula (U1), a hindered amine light stabilizer of formula (H1) phenyltriazines, where the formula is (A4), The weight ratio of UV absorber to hindered amine light stabilizer is from 3:1 to 1:3, preferably from 1.8:1 to 1:1.8, in particular from 1.3:1 to 1:1.3.

[0070] In another preferred form, the mixture comprises: a UV absorber of formula (U2), hindered amine light stabilizers of the formulae (H2) and (H3), phenyltriazines, where the formula is (A4), The weight ratio of UV absorber to hindered amine light stabilizer is from 3:1 to 1:3, preferably from 1.8:1 to 1:1.8, in particular from 1.3:1 to 1:1.3.

[0071] In another preferred form, the mixture comprises: a UV absorber of formula (U1), a hindered amine light stabilizer of formula (H1) phenyltriazines, where the formula is (A3), The weight ratio of UV absorber to hindered amine light stabilizer is from 3:1 to 1:3, preferably from 1.8:1 to 1:1.8, in particular from 1.3:1 to 1:1.3.

[0072] In another preferred form, the mixture comprises: a UV absorber of formula (U3), a hindered amine light stabilizer of formula (H1) phenyltriazines, where the formula is (A1), The weight ratio of UV absorber to hindered amine light stabilizer is from 3:1 to 1:3, preferably from 1.8:1 to 1:1.8, in particular from 1.3:1 to 1:1.3.

[0073] In another preferred form, the mixture comprises: a UV absorber of formula (U7), - a hindered amine light stabilizer of the compound (H4), phenyltriazines, when of formula (A7), The weight ratio of UV absorber to hindered amine light stabilizer is from 3:1 to 1:3, preferably from 1.8:1 to 1:1.8, in particular from 1.3:1 to 1:1.3.

[0074] In another preferred form, the mixture comprises: a UV absorber of formula (U7), - a hindered amine light stabilizer of the compound (H4), phenyltriazines, when of formula (A5), The weight ratio of UV absorber to hindered amine light stabilizer is from 3:1 to 1:3, preferably from 1.8:1 to 1:1.8, in particular from 1.3:1 to 1:1.3.

[0075] In another preferred form, the mixture comprises: UV absorbers of the formulae (U4) and (U5), - a hindered amine light stabilizer of the compound (H4), phenyltriazines, where the formula is (A1), The weight ratio of UV absorber to hindered amine light stabilizer is from 3:1 to 1:3, preferably from 1.8:1 to 1:1.8, in particular from 1.3:1 to 1:1.3.

[0076] Polyurethanes may result from the reaction of a polyisocyanate reactant with a polyol reactant in a reaction mixture.

[0077] The polyurethane may be an aromatic or an aliphatic polyurethane, preferably an aromatic polyurethane.

[0078] The polyurethane can be a polyurethane foam, a thermoplastic polyurethane (eg, an aromatic or aliphatic thermoplastic polyurethane), or a polyurethane coating.

[0079] Preferably, the polyurethane is a thermoplastic polyurethane, especially an aromatic thermoplastic polyurethane.

[0080] The polyisocyanate reactant may be an aromatic or aliphatic polyisocyanate. Examples of aromatic polyisocyanates include 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 (often contained in 4,4'-diphenylmethane diisocyanate as a minor isomer), 1,5-naphthylene diisocyanate, triphenylmethane-4,4',4" triisocyanate, or polyphenylpolymethylene polyisocyanates, such as polyisocyanates prepared by aniline-formaldehyde condensation followed by phosgenation ("crude MDI"). Mixtures of aromatic polyisocyanates are also included. Aliphatic polyisocyanates include, 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-diisocyanato-3,3,5-trimethylcyclohexane, 2,4- and / or 2,6-hexahydrotoluene diisocyanate, perhydro-2,4′- and / or 4,4′-diphenylmethane diisocyanate (H 12The preferred polyisocyanate reactants are aromatic polyisocyanates (TDI, MDI) or isophorone diisocyanate. Mixtures of aliphatic polyisocyanates are also included. Furthermore, derivatives and polymers of the aforementioned aromatic or aliphatic polyisocyanates are included, for example, those containing urethane, carbodiimide, allophanate, isocyanurate, acylated urea, biuret, or ester groups ("modified polyisocyanates"). Examples of aromatic polyisocyanurates are so-called "liquid MDI" products containing carbodiimide groups. It is also possible to use isocyanate group-containing distillation residues of aromatic or aliphatic polyisocyanates obtained during the industrial preparation of isocyanates, either as such or dissolved in one or more of the above-mentioned polyisocyanates. 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 are preferred. Aromatic polyisocyanates are highly preferred. Most preferred are polyisocyanates that are TDI, MDI, or MDI derivatives. Particularly preferred are TDI polyisocyanates, especially mixtures of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate.

[0081] 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 particularly preferably 105 to 112. As used herein, isocyanate index refers to 100 times the ratio of the isocyanate groups used to the theoretical equivalents required to react with the active hydrogen equivalents in the reaction mixture, for example, in the polyol reactant, water (if present), carboxylic acid, crosslinker, chain extender, and other components having functional groups reactive with isocyanate groups as active hydrogen-containing groups. An index of 100 indicates a 1:1 stoichiometric ratio, and an index of 107 indicates, for example, a 7% excess of isocyanate equivalents. The isocyanate equivalent weight is the total number of isocyanate groups. The active hydrogen equivalent weight refers to the total number of active hydrogens. An active hydrogen-containing group, such as a hydroxyl group or a secondary amine group, contributes one active hydrogen equivalent. Active hydrogen-containing groups that are primary amine groups also contribute one active hydrogen equivalent because, after reaction with an isocyanate group, the original second hydrogen is no longer an active hydrogen. Active hydrogen-containing groups that are carboxylic acids contribute one active hydrogen equivalent per carboxylic acid functional group.

[0082] The polyol reactant is a polyether polyol or a polyester polyol.

[0083] Polyether polyols are polymers obtained by polymerization of, for example, alkylene oxides or cyclic ethers having at least four ring atoms. They contain at least two active hydrogen-containing groups per molecule, and the at least two active hydrogen-containing groups per molecule are hydroxyl groups. The 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. Preferably, polyether polyols contain 2 to 8, very preferably 2 to 6, most preferably 2 to 4, and particularly preferably 2 to 3 active hydrogen-containing groups per molecule. Polyether polyols having three active hydrogen-containing groups per molecule are also called trifunctional polyether polyols. Examples of alkylene oxides include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, and styrene oxide. Examples of cyclic ethers include oxetane and tetrahydrofuran.

[0084] Polyether polyols are prepared, for example, by polymerizing alkylene oxides alone, in mixtures, 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 polyhydric alcohol, ammonia, or a primary or secondary amine containing a second reactive hydrogen atom. Examples of polyhydric alcohols include ethylene glycol, propane-1,2-diol, propane-1,3-diol, glycerin, trimethylolpropane, 4,4'-dihydroxydiphenylpropane, or alpha-methyl glucoside. Examples of primary amines include ethanolamine, ethylenediamine, diethylenetriamine, or aniline. Examples of secondary amines containing a second reactive hydrogen atom include diethanolamine, triethanolamine, or N-(2-hydroxyethyl)piperazine. The initiator component containing at least two reactive hydrogen atoms is preferably water or a polyhydric alcohol. Initiator components containing at least two reactive hydrogen atoms preferably contain 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 in the polyether polyol. The nominal functionality of the polyether polyol is preferably 2 to 6, more preferably 2 to 4, most preferably 2 to 3.5, and particularly preferably 2 to 3.3.

[0085] The polyether polyol has a molecular weight of, for example, 400 to 10,000 daltons, preferably 800 to 10,000 daltons. The molecular weight is more preferably the number average molecular weight (M n The equivalent weight of a polyether polyol is defined herein as its molecular weight divided by the average number of active hydrogen-containing groups per molecule, and preferably the number average molecular weight (M n ) is used. nThe equivalent weight of the polyether polyol as determined by the above formula is preferably 400 to 5,000, more preferably 800 to 2,500, very preferably 900 to 1,300, and particularly preferably 1,000 to 1,200.

[0086] Preferred are polyether polyols containing predominantly (up to 90% by weight, based on total hydroxyl groups present in the polyether polyol) active hydrogen-containing groups that are secondary hydroxyl groups.

[0087] Polyester polyols are produced, for example, by polycondensation of diacids and diols, where the diol is used in excess. Partial replacement of the diol with a polyol having two or more 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, glycerin, trimethylolpropane, or pentaerythritol.

[0088] Crosslinkers are, for example, further components of the reaction mixture. Crosslinkers can improve the elasticity of polyurethanes. As defined herein, crosslinkers have three to eight, preferably three to four, active hydrogen-containing groups per molecule. Thus, crosslinkers react with the polyisocyanate reactant and, if present, are considered as a reactant for calculating the Polyisocyanate Index. Crosslinkers do not contain ester bonds and, in particular, have a number average molecular weight (M n When a crosslinker is present, the polyether polyol has an equivalent weight, as determined by the number average molecular weight (M nThe equivalent weight of the polyether polyol determined by the above method is preferably 400 to 5000. The crosslinking agent is, for example, an alkylene triol or an alkanolamine. The alkylene triol is, for example, glycerin 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.

[0089] Chain extenders, for example, are further components of the reaction mixture. Chain extenders, as defined herein, have two active hydrogen-containing groups, i.e., hydroxyl groups, per molecule. Thus, chain extenders react with the polyisocyanate reactant and, if present, are considered as reactants for the calculation of the Polyisocyanate Index. Chain extenders do not contain ester bonds and, in particular, have a number average molecular weight (M n ) is 31 to 300, preferably 31 to 150. When a chain extender is present, the polyether polyol preferably has a number average molecular weight (M n The equivalent weight as determined by the JIS K 1995-1999 is 400 to 5000. The chain extender is, for example, an alkylene glycol or a glycol ether. Examples of the alkylene glycol include ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, and 1,6-hexamethylene glycol. Examples of the glycol ether include diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, and 1,4-cyclohexanedimethanol.

[0090] If used, the total amount of crosslinker and chain extender in the reaction mixture is less than 50 parts by weight, based on 100 parts by weight of polyol reactant. The total amount is preferably less than 20 parts by weight, and more preferably less than 5 parts by weight.

[0091] The reaction mixture prior to reaction comprises a polyisocyanate reactant and a polyol reactant, and 60 to 100 parts by weight of the polyol reactant, based on 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, and most preferably 98 to 100 parts by weight of the polyol reactant is a polyether polyol, and especially preferably, the polyol reactant is a polyether polyol.

[0092] The polyurethane is obtained from the reaction of the reaction mixture. The aforementioned selectivity can also be expressed in another way, i.e., the polyurethane is preferably obtained from the reaction of the polyisocyanate reactant with the polyol in the reaction mixture, the polyol reactant being 60 to 100 parts by weight, based on 100 parts by weight of the polyol reactant being a polyether polyol.

[0093] A catalyst for the reaction between the polyisocyanate reactant and the polyol reactant is preferably added to the reaction mixture. The catalyst may be, for example, an amine catalyst or an organometallic catalyst. The amine catalyst may be, for example, triethylenediamine or a derivative based thereon, such as N-methylmorpholine, N-ethylmorpholine, diethylethanolamine, N-coconut morpholine, 1-methyl-4-dimethylaminoethylpiperazine, 3-methoxy-N-dimethylpropylamine, N,N-diethyl-3-diethylaminopropylamine, dimethylbenzylamine, bis-(2-dimethylaminoethyl)ether, or dimethylbenzylamine. Preferred is triethylenediamine or a derivative based thereon. The organometallic catalyst may be, for example, an organic salt of tin, bismuth, iron, mercury, zinc, or lead. Preferred is an organotin compound. Examples of organotin compounds include dimethyltin dilaurate, dibutyltin dilaurate, or stannous octoate. Preferred is stannous octoate. Preferably, the amount of 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 polyol reactant. Preferably, the amount of organometallic catalyst is 0.001 to 3 parts by weight, based on 100 parts by weight of polyol reactant. Preferably, the amine catalyst and organometallic catalyst are added to the reaction mixture.

[0094] In the production of polyurethane foam, gas evolution occurs during the reaction, which can be caused by adding water or carboxylic acids to the reaction mixture prior to the reaction to generate chemical gases, or by adding a blowing agent to the reaction mixture prior to the reaction.

[0095] As used herein, a blowing agent refers to an organic compound having a boiling point at 101.32 kPa between −15° C. and the maximum temperature generated during the reaction of the reaction mixture, preferably between −15° C. and 110° C., more preferably between −10° C. and 80° C., and most preferably between −5° C. and 70° C. Furthermore, the blowing agent does not react with the polyisocyanate or polyol reactants in the reaction mixture under the conditions of the reaction to form chemical bonds. 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.

[0096] Examples of alkanes having 4 to 10 carbon atoms include butane, pentane, hexane, and heptane. Examples of cycloalkanes having 5 to 10 carbon atoms include cyclopentane and cyclohexane. Examples of partially or completely halogenated alkanes include 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, and CFC-151. Among the partially or completely halogenated alkanes having 1 to 5 carbon atoms, those having at least one hydrogen atom, such as methylene chloride, CFC-123, CFC-141b, CFC-124, and 1,1,1-trichloroethane, are preferred.

[0097] When water is used for gas generation, it is preferred to add water 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 polyol reactant. More preferably, 1 to 8 parts of water is added. Most preferably, 2 to 7 parts of water is added, such as 3 to 7 parts or 4 to 7 parts of water. In particular, 16 to 32 kg / m 3 For polyurethane foams with densities between 3 and 8 parts of water are added.3 Exceeding 48kg / m 3 For polyurethane foams with densities less than 2 to 5 parts water is added.

[0098] 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 polyol reactant. More preferably, 3 to 45 parts of blowing agent are added. Highly preferably, 4 to 30 parts of blowing agent are added, e.g., 5 to 25 parts of blowing agent.

[0099] The use of water or carboxylic acid, or the use of a blowing agent, provides the desired reduction in polyurethane density. When water or carboxylic acid, especially water, is used, the reaction exotherm increases. The use of water increases the amount of urea bonds in the polyurethane foam, hardening the foam. In contrast, the use of a blowing agent moderates the temperature inside the reaction mixture, softening the foam. Nevertheless, the use of water is attractive, but increases the requirement for stabilization of the polyurethane foam generated during the reaction.

[0100] The polyurethane foam has a lower density than polyurethanes obtained from the same reaction mixture but without the inclusion of water or carboxylic acid or blowing agent. The polyurethane foam preferably has a density of 5 to 500 kg / m at 20°C and 101.3 kPa. 3 , more preferably 10 to 300 kg / m 3 , very preferably 15 to 100 kg / m 3 , most preferably 16 to 48 kg / m 3 If the polyurethane foam is a self-skinning foam (structural foam), the density is determined as the average density of the entire foam structure. In many cases, the density of self-skinning polyurethane foam is 10 times higher than that of regular polyurethane foam.

[0101] The polyurethane may be a thermoplastic polyurethane. Thermoplastic polyurethanes are known in principle. Preparation is typically carried out by reacting components (a) isocyanate, (b) isocyanate-reactive compound, and optionally (c) chain extender, optionally in the presence of at least one (d) catalyst and / or (e) conventional auxiliary and / or additive. Components (a) isocyanate, (b) isocyanate-reactive compound, and (c) chain extender are also individually or collectively referred to as building block components.

[0102] The organic isocyanates (a) preferably used are aliphatic, cycloaliphatic, araliphatic and / or aromatic isocyanates, more preferably tri-, tetra-, penta-, hexa-, hepta- and / or octamethylene diisocyanate, 2-methylpentamethylene 1,5-diisocyanate, 2-ethylbutylene 1,4-diisocyanate, pentamethylene 1,5-diisocyanate, butylene 1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1,4- and / or 1,3-bis(isocyanatomethyl)cyclohexane. Examples of suitable isocyanates include hexane (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-toluylene diisocyanate (TDI), 3,3'-dimethyldiphenyl diisocyanate, 1,2-diphenylmethane diisocyanate and / or phenylene diisocyanate. It is particularly preferred to use 4,4'-MDI.

[0103] In a further embodiment, the present invention therefore relates to a composition as described herein above, wherein the thermoplastic polyurethane is based on diphenylmethane diisocyanate (MDI).

[0104] Usable isocyanate-reactive components (b) include, in principle, all suitable compounds known to those skilled in the art. According to the present invention, at least one diol is used as isocyanate-reactive compound (b).

[0105] In the context of the present invention, any suitable diol can be used, for example a polyether diol or a polyester diol or a mixture of two or more thereof.

[0106] In principle, any suitable polyester diol can be used in accordance with the present invention, where in the context of the present invention the term polyester diol also includes polycarbonate diols.

[0107] One embodiment of the present invention uses polycarbonate diol or polytetrahydrofuran polyol. Suitable polytetrahydrofuran polyols have 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.

[0108] Suitable polycarbonate diols include, for example, polycarbonate diols based on alkanediols.Suitable polycarbonate diols are strictly difunctional OH-functional polycarbonate diols, preferably strictly difunctional OH-functional aliphatic polycarbonate diols.Suitable polycarbonate diols are, for example, 1,4-butanediol, 1,5-pentanediol or 1,6-hexanediol, particularly 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. Preferably, in the context of the present invention, 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 are used.

[0109] The composition according to the invention preferably comprises The composition according to the present invention comprises at least one thermoplastic polyurethane 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 polytetrahydrofuran polyol. Thus, the preparation of the polyurethane present in the composition according to the present invention uses as component (b) at least one polycarbonate diol or polytetrahydrofuran polyol.

[0110] 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 polytetrahydrofuran polyol. Thus, 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 polytetrahydrofuran polyol.

[0111] The composition can be part of a molded article or can be an entire molded article. Preferably, the composition is an entire molded article. Examples of molded articles are: 1) Floating devices for marine applications. 2) Automotive applications, in particular bumpers, dashboards, rear and front linings, under hood moulding parts, hat shelves, trunk linings, interior linings, airbag covers, instrument panels, exterior linings, upholstery, interior and exterior trim, door panels (πανελσ), seat backings, exterior panels, cladding, pillar covers, chassis parts, convertible tops, front end modules, pressed / stamped parts, side impact protection, sound deadening / heat insulation and sunroofs. 3) Aircraft equipment and railway equipment. 4) Architectural and design devices, acoustic silencing systems, shelters. 5) Coatings for steel or other materials such as textiles, e.g. cable coatings. 6) Electrical appliances, especially washing machines, tumblers, ovens (microwave ovens), dishwashers, and mixers. 7) Rotor blades, ventilators and windmill blades, swimming pool covers, swimming pool liners, pond liners, closets, wardrobes, bulkheads, slat walls, folding walls, roofs, shutters (e.g. roller shutters), sealing. 8) Packaging and packaging, isolated bottles. 9) General furniture, foam products (cushions, mattresses, shock absorbers), foam, sponges, dishwashing cloths, mats. 10) Shoes, soles, insoles, spats, adhesives, structural adhesives, sofas.

[0112] The composition may preferably comprise further additives such as antioxidants, metal deactivators, phosphites and phosphonates, hydroxylamines and amine N-oxides, nitrones, thiosynergists, peroxide scavengers, basic co-stabilizers, nucleating agents, fillers and reinforcing agents, benzofuranones and indolinones, flame retardants, or other additives such as plasticizers, lubricants, emulsifiers, pigments, rheological additives, catalysts, flow control agents, optical brighteners, flame retardants, antistatic and foaming agents, heat stabilizers, anti-fogging agents, anti-misting agents, anti-blocking additives, slip agents, anti-scratch agents, etc. The further additives may, for example, be selected from the following list:

[0113] 1. Antioxidants 1.1. Alkylated monophenols, such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di-methylphenol, 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-tricyclohexyl-4-methylphenol, xylphenol, 2,6-di-tert-butyl-4-methoxymethyl-phenol, nonylphenols whose side chains are linear or branched, such as 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1'-methylundecundec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methylheptadec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methyl-1'-tetradecyl-methyl)-phenol, and mixtures thereof.

[0114] 1.2. Alkylthiomethylphenols, such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecyl-thiomethyl-4-nonylphenol.

[0115] 1.3. Hydroquinone and alkylated hydroquinones, such as 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, bis(3,5-di-tert-butyl-4-hydroxyphenyl)adipate.

[0116] 1.4. Tocopherols, such as α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E), vitamin E acetate. In particular, it is preferable to add commercially available vitamin E, 2,5,7,8-tetramethyl-2-[4,8,12-trimethyltridecyl]-chroman-6-ol (e.g., Irganox E 201 (trademark)).

[0117] 1.5. Hydroxylated thiodiphenyl ethers, for example, 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-amylphenol), 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl) disulfide.

[0118] 1.6. Alkylidene 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-butylphenol), 2,2'-ethylidenebis( 4,6-di-tert-butylphenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-(α,α-dimethylbenzyl)-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 Benzene, 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-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

[0119] 1.7. O-, N-, and S-benzyl compounds, such as 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl mercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzyl mercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxy-benzyl)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-hydroxybenzyl mercaptoacetate.

[0120] 1.8. Hydroxybenzylated malonates, for example, dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, di-dodecylmercaptoethyl-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.

[0121] 1.9. Aromatic hydroxybenzyl compounds, such as 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, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

[0122] 1.10. Triazine compounds, such as 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.

[0123] 1.11. Benzyl phosphonates, 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, calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, (3,5-di-tert-butyl-4-hydroxy-phenyl)methylphosphonic acid.

[0124] 1.12. Acylaminophenols, such as 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

[0125] 1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with monohydric or polyhydric alcohols, such as methanol, ethanol, n-octanol, i-octanol, mixtures of linear or branched C7-C9 alkanols, octadecanol, linear or branched C 13 ~C 15 -Mixtures of alkanols, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, oligoethylene glycols with 3 to 15 ethylene glycol units, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis-(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, and esters with 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane. Preferred are esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, in particular esters with octadecanol, such as the adduct of octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, which is commercially available (e.g., Irganox 1076™).

[0126] 1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with monohydric or polyhydric alcohols, such as methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isothiazolinone, Cyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane; ester with 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane.

[0127] 1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, such as methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, 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.

[0128] 1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with monohydric or polyhydric alcohols, such as methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0129] 1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, such as 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)hydrazide, N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide (Naugard XL-1®, supplied by SI Group).

[0130] 1.18. Ascorbic acid (vitamin C).

[0131] 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 amine, 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, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4-(p-toluenesulfamoyl)diphenylamine, N,N'-dimethyl-N,N'-sec-butyl-p-phenylenediamine diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-(4-(tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, nonylated diphenylamine, octylated diphenylamine such as 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 dialkylated tert-butyl / tert-octyldiphenylamines, mixtures of mono- and dialkylated nonyldiphenylamines, mixtures of mono- and dialkylated dodecyldiphenylamines, mixtures of mono- and dialkylated isopropyl / isohexyldiphenylamines, mixtures of mono- and dialkylated tert-butyldiphenylamines phenothiazine, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixture of mono- and dialkylated tert-butyl / tert-octylphenothiazines or a mixture 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-naphthalenamine] (commercially available as Irganox L06™), nonylated diphenylamine.

[0132] Alternatively or additionally, mixtures of commercially available additives can be used, of which particularly preferred is Irganox 5057™, obtained by reaction of diphenylamine with diisobutylene and comprising: (A) 5057 Diphenylamine; (B) 5057 4-tert-butyldiphenylamine; (C) 5057 Compounds of the group i) 4-tert-octyldiphenylamine, ii) 4,4'-di-tert-butyldiphenylamine, iii) 2,4,4'-tris-tert-butyldiphenylamine, (D) 5057 Compounds of the group i) 4-tert-butyl-4'-tert-octyldiphenylamine, ii) o,o', m,m' or p,p'-di-tert-octyldiphenylamine, iii) 2,4-di-tert-butyl-4'-tert-octyldiphenylamine, (E) 5057 Compounds of the group i) 4,4'-di-tert-octyldiphenylamine, ii) 2,4-di-tert-octyl-4'-tert-butyldiphenylamine, wherein 5% by weight or less of component (A) 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 exists.

[0133] 3. Metal deactivators, such as N,N'-diphenyloxamide, N-salicylal-N'-salicyloylhydrazine, N,N'-bis(salicyloyl)hydrazine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenyl-propionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide, N,N'-bis-(salicyloyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide.

[0134] 4. Phosphites and phosphonates such as trisalkyl (C12-C15) phosphite, triisodecyl phosphite, triisotridecyl phosphite, dioleylhydrogen phosphite, triisooctyl phosphite, heptakis(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 or phosphonates are, for example, liquids such as di-n-octyl hydrogen phosphite or di-iso-octyl hydrogen phosphite or, for example, triphenyl phosphite, tris(nonylphenyl) phosphite, phenyl diisodecyl phosphite, diphenyl isodecyl phosphite, [triphenyl phosphite, polymer of 1,4-cyclohexanedimethanol and polypropylene glycol, C10-16 alkyl ester (CAS Registry Number 1821217-71-3)]. Further 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, dodecylnonylphenol phosphite blend, phenyl neopentylene glycol phosphite, poly 4,4' isopropylidenediphenol-C10 alcohol phosphite, poly 4,4' isopropylidenediphenol-C12-15 alcohol phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, C 12 -C 18 Alkylbis[4-(1-methyl-1-phenyl-ethyl)phenyl]phosphite, C 12 -C 18Alkenyl bis[4-(1-methyl-1-phenyl-ethyl)phenyl]phosphite, bis[4-(1-methyl-1-phenyl-ethyl)phenyl][(E)-octadec-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)-octadec-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-di-cumylphenyl)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, bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, [2-tert-butyl-4-[1-[5-tert-butyl-4-di(tridecoxy)phosphanyloxy-2-methyl-phenyl]butyl]-5-methyl-phenyl]ditridecyl phosphite, tristearyl sorbitol triphosphite, mixtures of at least two different tris(mono-C1-C8-alkyl)phenyl phosphites, for example, the products of Examples 1 and 2 of U.S. Pat. No. 74 68410B2, mixtures of phosphites containing at least two different tris(amylphenyl)phosphites, such as those described in U.S. Pat. No. 8,008,383B2 as mixtures 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25 and 26, 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,a mixture of at least four different phosphites including tris[2,4-bis(1,1-dimethylpropyl)phenyl]phosphite and tris[2,4-bis(1,1-dimethylpropyl)phenyl]phosphite, for example a mixture of phosphites including at least two different tris(butylphenyl)phosphites as described in U.S. Pat. No. 8,008,383 B2 as mixtures 34, 35, 36, 37, 38, 39, and 40; an oxyalkylene-bridged bis-(di-C6-aryl)diphosphite; or (i) a tris[2,4-bis(1,1-dimethylpropyl)phenyl]phosphite. Oligomeric phosphites obtained by condensation of triphenylphosphite with (ii) dihydroxyalkanes interrupted by one or more oxygen atoms, and (iii) monohydroxy-C6-arenes, such as the products of Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 and 17, as described in U.S. Pat. No. 8,304,477 B2, under elimination of hydrogen chloride, (i) triphenylphosphite, (ii) dihydroxyalkanes optionally interrupted by one or more oxygen atoms and / or bis(hydroxyalkyl)(alkyl)amines, and (iii) monohydroxyalkanes optionally interrupted by one or more oxygen atoms, such as the products of Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 and 11, as described in U.S. Pat. No. 8,563,637 B2, with the elimination of phenol. 1,3,2-Dioxaphosphocin, bis(2,4-di-tert-butyl-6-methylphenyl)methyl 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-dibenz[d,g]-1,3,2-dioxaphosphocin, 1,3,7,9-tetra-tert-butyl-11-octoxy-5H-benzo[d][1,3,2]benzodioxaphosphocin, 2,2',2''-nitrilo[triethyltris(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphite], j, triphenyl ester, polymer with α-hydro-ω-hydroxypoly[oxy(methyl-1,2-ethanediyl)], C10-16-alkyl ester (CAS Registry Number [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-dioxaphosphiran, phosphorous acid, mixed 2,4-bis(1,1-dimethylpropyl)phenyl and 4-(1,1-dimethylpropyl)phenyl triester (CAS Registry Number [939402-02-5]). The following phosphites are particularly preferred: tris(2,4-di-tert-butylphenyl)phosphite (Irgafos® 168, Ciba Specialty Chemicals Inc.), tris(nonylphenyl)phosphite, [ka]

[0135] 5. Hydroxylamines and amine N-oxides, such as N,N-dibenzylhydroxylamine, N,N-di-ethylhydroxylamine, 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-dialkylhydroxylamines derived from hydrogenated tallow amine, bis(hydrogenated palm oil alkyl)hydroxyamines, N,N-bis-(hydrogenated rapeseed oil alkyl)-N-methylamine N-oxide or trialkylamine N-oxides.

[0136] 6. Nitrones, such as N-benzyl-α-phenyl nitrone, N-ethyl-α-methyl nitrone, N-octyl-α-heptyl nitrone, N-lauryl-α-undecyl nitrone, N-tetradecyl-α-tridecyl nitrone, N-hexadecyl-α-pentadecyl nitrone, N-octadecyl-α-heptadecyl nitrone, N-hexadecyl-α-heptadecyl nitrone, N-octadecyl-α-pentadecyl nitrone, N-heptadecyl-α-heptadecyl nitrone, N-octadecyl-α-hexadecyl nitrone, nitrones derived from N,N-dialkylhydroxylamines derived from hydrogenated tallow amines (optionally of vegetable origin).

[0137] 7. Thiosynergists, such as dilauryl thiodipropionate, dimistryl thiodipropionate, distearyl thiodipropionate and pentaerythritol tetrakis-[3-(n-lauryl)propionate].

[0138] 8. Peroxide scavengers, for example, esters of α-thiodipropionic acid, such as the lauryl, stearyl, myristyl or tridecyl ester, zinc salts of mercaptobenzimidazole or 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(β-dodecylmercapto)propionate.

[0139] 10. Polyamide stabilizers, such as copper salts in combination with iodides and / or phosphorus compounds and salts of divalent manganese.

[0140] 11. Basic co-stabilizers, for example, melamine, polyvinylpyrrolidone, 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 pyrocatecholate or zinc pyrocatecholate, zeolites, hydrotalcites, calcium hydroxides, zinc oxide.

[0141] 12. Nucleating agents, for example, inorganic substances such as talcum, metal oxides such as titanium dioxide or magnesium oxide, phosphoric acid, including phosphates 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, preferably alkaline earth metal carbonates or sulfates, organic compounds, for example Mono- or polycarboxylic acids and their salts, for example, 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate, calcium 1,2-cyclohexanedicarboxylic acid, disodium bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, polymeric compounds such as ionic copolymers (ionomers), triaminobenzene derivatives such as 1,3,5-tris[2,2-dimethylpropionylamine]benzene, zinc glycerate, and nonitol derivatives. 1,3:2,4-bis(3',4'-dimethylbenzylidene)sorbitol, 1,3:2,4-di(paramethyldibenzylidene)sorbitol, and 1,3:2,4-di(benzylidene)sorbitol are particularly preferred.

[0142] 13. Fillers and reinforcing agents, for example, calcium carbonate, silicates, glass fibers, glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and other natural product flours or fibers, synthetic fibers.

[0143] 14. Other additives, such as plasticizers, lubricants, emulsifiers, pigments, rheological additives, catalysts, flow control agents, optical brighteners, flame retardants, antistatic and foaming agents, heat stabilizers, anti-fog agents, anti-misting agents, anti-blocking additives, slip agents, anti-scratch agents.

[0144] 15. Benzofuranones and indolinones, for example, U.S. Pat. No. 4,325,863A; U.S. Pat. No. 4,338,244A; U.S. Pat. No. 5,175,312A; U.S. Pat. No. 5,216,052A; U.S. Pat. No. 5,252,643A; German Patent No. 4316611A; German Patent No. 4316622A; German Patent No. 4316876A; European Patent Application Publication No. 0589839A or European Patent Application Publication No. 0591102A, International Patent Application Publication No. WO 2015 / 121445A and those disclosed in the publication No. WO 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-(2-hydroxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]phenyl]-3H-benzofuran-2-one, 3-[4-(2-hydroxyethoxy)ethoxy]ethoxy]ethoxy]phenyl]-3H-benzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxy-ethoxy)phenyl]benzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxy-ethoxy)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 Zofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butylbenzofuran-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-tetramethylbutyl)benzofuran-2-one, [6-[6-[6-[2-[4-(5,7-di-tert-butyl-2-oxo-3H-benzofuran-3-yl)phenoxy]ethoxy]-6-oxohexoxy]-6-oxohexoxy]-6-oxohexyl]6-hydroxyhexanoate, [4-tert-butyl-2-(5-tert-butyl-2-oxo-3H-benzofuran-3-yl)phenyl]benzoate, [4-tert-butyl-2-(5-tert-butyl-2-oxo-3H-benzo-furan-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.

[0145] 16. Flame retardants 16.1. Phosphorus-containing flame retardants, such as the following reactive phosphorous-containing flame retardants: tetraphenylresorcinol diphosphite (Fyrolflex RDP, RTM, Akzo Nobel), tetrakis(hydroxy-methyl)phosphonium sulfide, triphenyl phosphate, diethyl-N,N-bis(2-hydroxyethyl)aminomethyl phosphonate, hydroxyalkyl esters of phosphoric acid, alkyl phosphate oligomers, ammonium polyphosphate (APP), resorcinol diphosphate oligomer (RDP), phosphazene flame retardants or ethylenediamine diphosphate (EDAP).

[0146] 16.2. Nitrogen-containing flame retardants, for example melamine-based flame retardants, isocyanurates, polyisocyanurates; tris(2-hydroxyethyl)isocyanurate, tris(hydroxymethyl)isocyanurate, tris(3-hydroxy-n-propyl)isocyanurate; esters of isocyanuric acid such as triglycidyl isocyanurate; melamine cyanurate, melamine borate, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine ammonium polyphosphate, ammonium melamine pyrophosphate, dimelamine phosphate, dimelamine pyrophosphate, benzoguanamine, allantoin, glycoluril, urea cyanurate; condensation products and / or higher condensation compounds of melamine from the melem, melam, melon series; or reaction products of melamine with phosphoric acid or mixtures thereof.

[0147] 16.3. Organic halogen flame retardants, such as polybrominated diphenyl oxides, decabromodiphenyl oxide (DBDPO), tris[3-bromo-2,2-bis(bromomethyl)propyl]phosphate (PB 370, (RTM, FMC Corp.)), tris(2,3-dibromopropyl)phosphate, chloroalkyl phosphate esters, such as tris(chloropropyl)phosphate, tris(2,3-dichloropropyl)phosphate, tris(1,3-dichloro-2-propyl)phosphate (Fyrol FR 2 (RTM) ICL), chloroalkyl phosphate oligomer, chlorendic acid, tetrachlorophthalic acid, tetrabromophthalic acid, poly-b-chloroethyl triphosphonate mixture; tetrabromobisphenol A-bis(2,3-dibromopropyl ether) (PE68), brominated epoxy resin, brominated aryl ester, ethylene-bis(tetrabromophthalimide) (Saytex BT-93 (RTM, Albemarle)), bis(hexachlorocyclopentadieno)cyclooctane (Declorane Plus (RTM, Oxychem)), chlorinated paraffins, octabromodiphenyl ether, hexachlorocyclopentadiene derivatives, 1,2-bis(tribromophenoxy)ethane (FF680), tetrabromobisphenol A (Saytex RB100 (RTM, Albemarle)), ethylene bis-(dibromonorbornanedicarboximide) (Saytex BN-451 (RTM, Albemarle), bis(hexachlorocycloentadeno)cyclooctane, PTFE, tris(2,3-dibromopropyl) isocyanurate, or ethylene-bis-tetrabromophthalimide. Some of the above halogenated flame retardants are routinely combined with inorganic oxide synergists. Some of the above halogenated flame retardants can be used in combination with triaryl phosphates (such as propylated and butylated triphenyl phosphates) and / or oligomeric aryl phosphates (such as resorcinol bis(diphenyl phosphate), bisphenol A bis(diphenyl phosphate), neopentyl glycol bis(diphenyl phosphate)).

[0148] 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. In terms of synergistic effects in combination with halogenated flame retardants, the most common inorganic oxide synergists are zinc oxide, antimony oxides such as Sb2O3 or Sb2O5, or boron compounds.

[0149] The incorporation or contact of the phenyl triazine of formula (A), the hindered amine light stabilizer, and the UV absorber, and optionally further additives, into the polyurethane can be achieved by conventional methods, such as adding a modifier blend or a single component thereof to a polymer material. The 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 further additives, can be added to the polyurethane individually or mixed together. The phenyl triazine of formula (A), the UV absorber, and the hindered amine light stabilizer are preferably added together, such as in the form of a masterbatch. [Example]

[0150] Unless otherwise indicated, all parts and percentages are by weight. Weight percent (wt %) is based on the total composition, excluding volatile materials, unless otherwise indicated.

[0151] UV absorbers UV1: Ethanediamide, N-(2-ethoxyphenyl)-N'-(2-ethylphenyl) UV2: N'-(4-ethoxycarbonylphenyl)-N-methyl-N-phenylformamidine UV3:2 Phenol, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl) UV4 / 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-oxopropoxy]poly(oxy-1,2-ethanediyl) in a weight ratio of approximately 3:1 UV6: 1,3-bis-((2'-cyano-3',3'-diphenylacryloyl)oxy)-2,2-bis-(((2'-cyano-3',3'-diphenylacryloyl)oxy)methyl)-propane UV7: 2-Ethylhexyl 2-cyano-3,3-diphenylacrylate

[0152] Hindered amine light stabilizers: HALS1: Dimethyl succinate-4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol copolymer HALS2 / 3: Reaction mass of bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate with methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate contains a mixture of bis(1,2,2,6,6-pentamethyl-4-piperidyl) decanedioate and methyl 1,2,2,6,6-pentamethyl-4-piperidinyl sebacate HALS4: Tertiary HALS, liquid, prepared according to Example 1 of WO 2009 / 068492.

[0153] Phenyltriazine: HPT1: phenol, 2-[4,6-bis([1,1'-biphenyl]-4-yl)-1,3,5-triazin-2-yl]-5-[(ethylhexyl)oxy] HPT2: phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxy HPT3: 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)phenol HPT4: 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-[(2-ethylhexyl)oxy]-2-hydroxypropoxy]phenol HPT5: 2,2'-[6-(2,4-dibutoxyphenyl)-1,3,5-triazine-2,4-diyl]bis[5-butoxyphenol HPT6: 2,2',2''-(1,3,5-triazine-2,4,6-triyl)tris[5-(hexyloxy)-6-methylphenol] HPT7: 5-[(2-ethylhexyl)oxy]-2-(4-{4-[(2-ethylhexyl)oxy]-2-hydroxyphenyl}-6-(4-methoxyphenyl)-1,3,5-triazin-2-yl)phenol

[0154] Example 1 Manufacture of thermoplastic polyurethane test panels (plaques) Thermoplastic polyurethane (aromatic TPU) was used (polyester type, extrusion and injection molding grade, Shore A85).

[0155] combination 2.5 kg of pellets were ground in a cryogenic mill and dried under vacuum at 80°C until the moisture content was less than 0.05%. The TPU powder was mixed with 2% of a stabilizer composition, as reported in Tables 1 and 2 below, in a tumbler mixer until homogeneous. These blends were then immediately extruded in a twin-screw extruder Berstorff ZE25Ax47D at temperatures up to 210°C. The resulting granulate was dried again under dry air at 80°C until the moisture content was less than 0.03%.

[0156] injection molding Test panels (plaques) measuring 64 mm x 44 mm x 2 mm were molded from the obtained granulate using an injection molding machine (Engel® E-Mac 100) at a maximum temperature of 210°C (molding temperature: 40°C).

[0157] Weather resistance test To evaluate the light stability performance achieved with various light stabilizer packages, the prepared plaques were subjected to artificial accelerated weathering according to method ASTM G155-dry (xenon lamp, using the same conditions as ASTM G 155, cycle 1, but without the rain cycle) and method SAE J 2412 (xenon lamp).

[0158] Color measurement The color change at the midpoint and end of exposure was measured with a spectrophotometer CM-3700 d (Minolta). The yellowness index according to ASTM E313, unitless. Delta E in CIELAB units, taken as the square root of the difference between the CIELAB color coordinates L*, a*, and b* at recall minus time zero, as defined in ISO 11664-4, was measured to provide information on the color change of the plaque upon exposure relative to the initial value. The results obtained are reported in Tables 1 and 2.

[0159] [Table 1]

[0160] The above results showed that the inventive examples provided TPU plaques with improved light stability and less discoloration upon exposure to light compared to the comparative examples.

[0161] [Table 2]

[0162] The above results showed that the inventive examples provided TPU plaques with improved light stability and less discoloration upon exposure to light compared to the comparative examples.

[0163] Example 2 Manufacture of thermoplastic polyurethane test panels (plaques) Thermoplastic polyurethane (aromatic TPU) was used (polyether type, extrusion and injection molding grade, Shore A87).

[0164] combination 2.5 kg of pellets were ground in a cryogenic mill and dried under vacuum at 80°C until the moisture content was less than 0.05%. The TPU powder was mixed with 2% of a stabilizer composition, as reported in Table 3 below, in a tumbler mixer until homogeneous. These blends were then immediately extruded in a twin-screw extruder Berstorff ZE25Ax47D at temperatures up to 210°C. The resulting granulate was dried again under dry air at 80°C until the moisture content was less than 0.03%.

[0165] injection molding Test panels (plaques) measuring 64 mm x 44 mm x 2 mm were molded from the obtained granulate using an injection molding machine (Engel® E-Mac 100) at a maximum temperature of 210°C (mold temperature: 30°C).

[0166] Weather resistance test To evaluate the light stability performance achieved with the various light stabilizer packages, the produced plaques were exposed to artificial accelerated weathering according to method ISO 105 B06 (xenon lamp).

[0167] Color measurement The color change at the midpoint and end of exposure was measured with a spectrophotometer CM-3700 d (Minolta). Delta E in CIELAB units, taken as the square root of the difference between the CIELAB color coordinates L*, a*, and b* at recall minus time zero, as defined in ISO 11664-4, was measured to provide information on the color change of the plaque upon exposure relative to the initial value. The results are reported in Table 3.

[0168] [Table 3]

[0169] The above results showed that the inventive examples provided TPU plaques with improved light stability and less discoloration upon exposure to light compared to the comparative examples.

[0170] Example 3 Manufacture of thermoplastic polyurethane test panels (plaques) Thermoplastic polyurethane (aromatic TPU) was used (polyether type, extrusion and injection molding grade, Shore A87).

[0171] combination 2.5 kg of pellets were ground in a cryogenic mill and dried under vacuum at 80°C until the moisture content was less than 0.05%. The TPU powder was mixed with 2% of a stabilizer composition, as reported in Table 4 below, in a tumbler mixer until homogeneous. These blends were then immediately extruded in a twin-screw extruder Berstorff ZE25Ax47D at temperatures up to 210°C. The resulting granulate was dried again under dry air at 80°C until the moisture content was less than 0.03%.

[0172] injection molding Test panels (plaques) measuring 64 mm x 44 mm x 2 mm were molded from the obtained granulate using an injection molding machine (Engel® E-Mac 100) at a maximum temperature of 210°C (mold temperature: 30°C).

[0173] Weather resistance test To evaluate the light stability performance achieved with the various light stabilizer packages, the produced plaques were subjected to artificial accelerated weathering according to method Adidas FT 11 (neon lamp).

[0174] Color measurement The color change at the midpoint and end of exposure was measured with a spectrophotometer CM-3700 d (Minolta). The yellowness index according to ASTM E313, unitless. Delta E in CIELAB units, taken as the square root of the difference between the CIELAB color coordinates L*, a*, and b* at recall minus time zero, as defined in ISO 11664-4, was measured to provide information on the color change of the plaque upon exposure relative to the initial value.

[0175] The results obtained are reported in Table 4.

[0176] [Table 4]

Claims

1. - polyurethane, at least one UV absorber, at least one hindered amine light stabilizer, at least one compound of formula (A) 【Chemistry 1】 [In the formula, G １ Is -O-E １ , phenyl, or 1, 2 or 3 C １ ~C ４ phenyl substituted with alkyl; G ２ is G １ Ga-O-E １ If -O-E ２ or G １ Ga-O-E １ otherwise, H; E １ is hydrogen, C １ ~C １８ Alkyl, oxygen-interrupted C ３ ~C ５０ Alkyl, oxygen-interrupted C ３ ~C ５０ hydroxyalkyl, or a group of formula P 【Chemistry 2】 wherein R, R′, and R″ are independently C １ ~C １８ alkylene), Or formula Q 【Transformation 3】 wherein T and U are, independently of one another, linear or branched C １ ~C １８ alkyl), b is an integer ranging from 1 to 3; G １ is phenyl or 1, 2 or 3 C １ ~C ４ When it is phenyl substituted by alkyl, b is 1; E ２ , E ３ , E ４ , E ５ and E ６ are independently hydrogen, hydroxy, C １ ~C １８ alkyl, phenyl or 1, 2 or 3 C １ ~C ４ Phenyl substituted with alkyl or a compound of formula Q: 【Chemistry 4】 wherein T and U are each independently a straight or branched chain C １ ~C １８ alkyl), E ７ are each independently hydrogen or C １ ~C １８ and a phenyltriazine of formula (I) wherein the phenyltriazine is alkyl.

2. 2. The composition of 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 from 30:1 to 4:1, preferably from 15:1 to 7:1, in particular from 12:1 to 8:

1.

3. 3. The composition according to claim 1, wherein the weight ratio of the UV absorber to the hindered amine light stabilizer is from 3:1 to 1:3, preferably from 1.8:1 to 1:1.8, in particular from 1.3:1 to 1:1.

3.

4. The phenyltriazine of formula (A) is selected from the group consisting of the following formulas (A1), (A2), (A3), (A4), (A5), (A6) and (A7): 【Transformation 5】 【Transformation 6】 【Transformation 7】 The composition according to any one of claims 1 to 3, selected from:

5. The at least one hindered amine light stabilizer is selected from the group consisting of formulas (H1), (H2), (H3) and (H4): 【Transformation 8】 The composition according to any one of claims 1 to 4, wherein the compound (H4) is a reaction product of 1,2,2,6,6-pentamethylpiperidin-4-ol, diethyl carbonate and ethoxylated trimethylolpropane.

6. The at least one UV absorber is represented by the formula (U1) to (U7): 【Chemistry 9】 【Chemistry 10】 The composition of claim 1 or 5, wherein the composition is selected from the group consisting of:

7. The composition of claim 1 or 6, wherein the polyurethane is an aromatic polyurethane.

8. The composition of claim 1 or 7, wherein the polyurethane is a polyurethane foam, a thermoplastic polyurethane, or a polyurethane coating.

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

10. 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.-%, in particular 0.4 to 1.5 wt.-%.

11. 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. %, in particular 0.4 to 1.5 wt. %.

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

13. The polyurethane; - at least one UV absorber according to any one of claims 1 to 12, - at least one hindered amine light stabilizer according to any one of claims 1 to 12, at least one phenyltriazine of formula (A) according to any one of claims 1 to 12, 13. A process for preparing the composition of any one of claims 1 to 12, comprising contacting

14. The polyurethane comprises: - at least one UV absorber according to any one of claims 1 to 13, - at least one hindered amine light stabilizer according to any one of claims 1 to 13, at least one phenyltriazine of formula (A) according to any one of claims 1 to 13, A process for stabilizing the polyurethane of any one of claims 1 to 13, comprising the step of incorporating

15. The polyurethane according to any one of claims 1 to 14, as a stabilizer against degradation by light, oxygen and / or heat. - at least one UV absorber according to any one of claims 1 to 14, - at least one hindered amine light stabilizer according to any one of claims 1 to 14, at least one phenyltriazine of formula (A) according to any one of claims 1 to 14, Use of mixtures, including

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