AU2001266010A1 - Stabilizer mixtures - Google Patents

Stabilizer mixtures

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Publication number
AU2001266010A1
AU2001266010A1 AU2001266010A AU2001266010A AU2001266010A1 AU 2001266010 A1 AU2001266010 A1 AU 2001266010A1 AU 2001266010 A AU2001266010 A AU 2001266010A AU 2001266010 A AU2001266010 A AU 2001266010A AU 2001266010 A1 AU2001266010 A1 AU 2001266010A1
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Australia
Prior art keywords
rtm
formula
compound
hydrogen
tinuvin
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AU2001266010B2 (en
AU2001266010C1 (en
Inventor
Francois Gugumus
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BASF Schweiz AG
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Ciba Spezialitaetenchemie Holding AG
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Priority claimed from PCT/EP2001/005865 external-priority patent/WO2001092398A2/en
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Description

Stabilizer mixtures
The present invention relates to a stabilizer mixture containing a specific sterically hindered amine ester or amide, and two different low molecular weight sterically hindered amines.
Stabilizer mixtures containing blends of sterically hindered amines are for example described in US-A-4,692,468, US-A-4,863,981 , US-A-5,719,217, US-A-5,919,399, US-A-5,965,643, US-A-5,980,783, US-A-6,015,849 and US-A-6,020,406.
The present invention relates to a stabilizer mixture containing the components (A) and (B) wherein component (A) is a compound of the formula (A-1)
wherein
Ai is hydrogen or Cι-C4alkyl,
A2 is a direct bond or CrC^alkylene, and ni is a number from 2 to 50;
at least one compound of the formulae (A-2-a) and (A-2-b)
wherein n2 and n2 * are a number from 2 to 50;
a compound of the formula (A-3)
(A-3) wherein
A3 and A independently of one another are hydrogen or CrCaalkyl, or A3 and A4 together form a C2-C14alkylene group, and the variables n3 independently of one another are a number from 1 to 50; or
a compound of the formula (A-4)
wherein n is a number from 2 to 50,
A5 is hydrogen or Cι-C4alkyl, the radicals A6 and A7 independently of one another are CrC4alkyl or a group of the formula
(a-l)
wherein A8 is hydrogen, CrC8alkyl, O", -OH, -CH2CN, CrC^alkoxy, C5-C12cycloalkoxy, C3-C6alkenyl, C7-C8phenylalkyl unsubstituted or substituted on the phenyl by 1 , 2 or 3 C C4alkyl; or C Cβacyl, with the proviso that at least 50 % of the radicals A7 are a group of the formula (a-l); and component (B) is formed by two different low molecular weight sterically hindered amine compounds containing a group of the formula (I) or (II);
with the proviso that components (A) and (B) are different.
Preferably the compounds of component (B) have a molecular weight up to 1 ,000 g/mol, for example 155 to 800 g/mol or 155 to 1,000 g/mol or 300 to 800 g/mol or 300 to 1 ,000 g/mol. The two different compounds of component (B) are preferably selected from the group consisting of the following classes β-1 ) a compound of the formula (B-1 )
in which
ET is hydrogen, C C8alkyl, O", -OH, -CH2CN, C C18alkoxy, C5-C12cycloalkoxy, C3-C6alkenyl,
C7-C9phenylalkyl unsubstituted or substituted on the phenyl by 1 , 2 or 3 C C4alkyl; or
CrC8acyl, if mi is 1 , E2 is CrC25al yl, if rri! is 2, E2 is C C14alkylene or a group of the formula (b-l)
wherein E3 is CrC 0alkyl or C2-C10alkenyl, E is CrC10alkylene, and E5 and E6 independently of one another are C C alkyl, cycldhexyl or methylcyclohexyl, and if mi is 4, E2 is C4-C10alkanetetrayl;
β-2) a compound of the formula (B-2)
H2C - - CH CH CH, (B-2)
E7 E7 E7 E7
in which two of the radicals E7 are -COO-(CrC2oalkyl), and two of the radicals E7 are a group of the formula (b-ll) with E8 having one of the meanings of Ei;
β-3) a compound of the formula (B-3)
in which
E9 and E10 together form C2-Cι4alkylene,
En is hydrogen or a group -ZrCOO-Z2,
Zi is C2-C14alkylene, and
Z2 is CrC2 alkyl, and
E12 has one of the meanings of Ei;
β-4) a compound of the formula (B-4)
wherein the radicals E13 independently of one another have one of the meanings of Ei, the radicals E1 independently of one another are hydrogen or CrCaalkyl, and E15 is Cι-Cι0alkylene or C3-C10alkylidene;
β-5) a compound of the formula (B-5) wherein the radicals E16 independently of one another have one of the meanings of Ei;
β-6) a compound of the formula (B-6)
in which
E17 is CrC2 alkyl, and
Eia has one of the meanings of E^
β-7) a compound of the formula (B-7)
in which
E19, E20 and E21 independently of one another are a group of the formula (b-lll)
wherein E 2 has one of the meanings of Ei) β-8) a compound of the formula (B-8)
wherein the radicals E23 independently of one another have one of the meanings of Ei, and E2 is hydrogen, CrC12alkyl or CrC1 alkoxy;
β-9) a compound of the formula (B-9)
wherein m2 is 1 , 2 or 3,
E25 has one of the meanings of Ei, and
when m2 is 1 , E26 is a group — CHjCH^NH ) ■ when m is 2, E26 is C2-C22al ylene, and when m2 is 3, E26 is a group of the formula (b-IV) wherein the radicals E2 independently of one another are C2-Cι2alkylene, and the radicals E2s independently of one another are CrC12alkyl or C5-C12cycloalkyl;
β-10) a compound of the formula (B-10)
wherein the radicals E29 independently of one another have one of the meanings of E and
E30 is C2-C22alkylene, C5-C7cycloalkylene, CrC4alkylenedi(C5-C7cycloalkylene), phenyiene or phenylenedi(C C4alkylene); or
β-11) a compound of the formula (B-11)
in which
E31 is CrCι0alkyl, C5-C12cycloalkyl, CrC alkyl-substituted C5-Cι2cycloalkyl, phenyl or
CrC 0alkyl-substituted phenyl, E32 is C3-Cι0alkylene,
E33 has one of the meanings of Ei, and m3 is a number from 2 to 6.
One of the preferred embodiments of this invention relates to stabilizer mixtures wherein the two compounds of component (B) are selected from different classes.
Examples of component (B) are:
• A compound selected from the class β-1 and a compound selected from the class β-3, β-4, β-5, β-6,~β-7, β-8, β-9, β-10 or β-11 , preferably the class β-3, β-5, β-6, β-10 or β-1 1.
• A compound selected from the class β-3 and a compound selected from the class β-4, β-5, β-6, β-7, β-9, β-10 or β-11 , preferably β-5, β-6, β-10 or β-11.
• A compound selected from the class β-5 and a compound selected from the class β-6, β-7, β-8, β-9, β-10 or β-11 , preferably β-6, β-10 or β-11.
• A compound selected from the class β-6 and a compound selected from the class β-10 or β-11.
• A compound selected from the class β-7 and a compound selected from the class β-8, β-10 or β-11.
• A compound selected from the class β-9 and a compound selected from the class β-10 or β-11.
• A compound selected from the class β-10 and a compound selected from the class β-11.
Examples of alkyl having up to 25 carbon atoms are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1 ,3-dimethyl- butyl, 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, octadecyl, eicosyl and docosyl. One of the preferred definitions of A8, E1 f E8, Eι2, Eι3, Ele, Eι8, E22, E23, E25, E29 and E3 is CrC4alkyl, especially methyl. Examples of alkoxy having up to 18 carbon atoms are methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy and octadecyloxy. One of the preferred meanings of Ei is octoxy. E24 is preferably C C4alkoxy.
Examples of C5-C12cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclododecyl. C5-C8Cycloalkyl, especially cyclohexyl, is preferred.
C C4AIkyl-substituted C5-C12cycloalkyl is for example methylcyclohexyl or dimethylcyclohexyl.
Examples of C5-C12cycloalkoxy are cyclopentoxy, cyclohexoxy, cycloheptoxy, cyclooctoxy, cyclodecyloxy and cyclododecyloxy. C5-C8Cycloalkoxy, in particular cyclopentoxy and cyclohexoxy, is preferred.
Ci-CioAlkyl-substituted phenyl is for example methylphenyl, dimethylphenyl, trimethylphenyl or tert-butylphenyl.
Examples of C7-C9phenylalkyl are benzyl and phenylethyl.
C7-C9Phenylalkyl which is substituted on the phenyl radical by 1 , 2 or 3 CrC4alkyl is for example methylbenzyl, dimethylbenzyl, trimethylbenzyl or tert-butylbenzyl.
Examples of alkenyl having up to 10 carbon atoms are allyl, 2-methallyl, butenyl, pentenyl and hexenyl. Allyl is preferred. The carbon atom in position 1 is preferably saturated.
Examples of acyl containing not more than 8 carbon atoms are formyl, acetyl, propionyl, butyryl, pentanoyl, hexanoyl, heptanoyl, octanoyl, acryloyl, methacryioyl and benzoyl. CrC8Alkanoyl, C3-C8alkenyl and benzoyl are preferred. Acetyl and acryloyl are especially preferred.
Examples of alkylene having up to 22 carbon atoms are methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene, trimethylhexamethylene, octamethylene and decamethylene.
CH,
An example of C3-Cι0alkylidene is the group — c-
CCHr ,
An example of C4-C1Qalkanetetrayl is 1 ,2,3,4-butanetetrayl.
An example of C5-C7cycloalkylene is cyclohexylene.
An example of CrC4alkylenedi(C5-C7cycloalkylene) is methylenedicyclohexylene.
An example of phenylenedi(CrC alkylene) is methylene-phenylene-methylene or ethylene-phenylene-ethylene.
n1 ( n2, n2* and n are preferably a number from 2 to 25, in particular 2 to 20. n3 is preferably a number from 1 to 25, in particular 1 to 20.
m3 is preferably a number from 2 to 6 or 2 to 5, in particular 2 to 4.
The compounds described above as components (A) and (B) are essentially known and commercially available. All of them can be prepared by known processes.
The preparation of the compounds of component (A) is disclosed for example in US-A-4,233,412, US-A-4,340,534, WO-A-98/51 ,690 and EP-A-1 ,803.
The preparation of the compounds of component (B) is disclosed for example in US-A-5,679,733, US-A-3,640,928, US-A-4, 198,334, US-A-5,204,473, US-A-4,619,958, US-A-4,110,306, US-A-4, 110,334, US-A-4,689,416, US-A-4,408,051 , SU-A-768,175 (Derwent 88-138,751/20), US-A-5,049,604, US-A-4,769,457, US-A-4,356,307, US-A-4,619,956, US-A-5,182,390, GB-A-2,269,819, US-A-4,292,240, US-A-5,026,849, US-A-5,071 ,981 , US-A-4,547,538, US-A-4,976,889 and US-A-5,051 ,458. Component (A) is preferably TINUVIN 622 (RTM), HOSTAVIN N 30 (RTM) or FERRO AM 806 (RTM).
The compounds of component (B) are preferably selected from the group consisting of DASTIB 845 (RTM), TINUVIN 770 (RTM), TINUVIN 765 (RTM), TINUVIN 144 (RTM), TINUVIN 123 (RTM), ADK STAB LA 52 (RTM), ADK STAB LA 57 (RTM), ADK STAB LA 62 (RTM), ADK STAB LA 67 (RTM), HOSTAVIN N 20 (RTM), HOSTAVIN N 24 (RTM), SANDUVOR 3050 (RTM), DIACETAM 5 (RTM), SUMISORB TM 61 (RTM), UVINUL 4049 (RTM), SANDUVOR PR 31 (RTM), GOODRITE UV 3034 (RTM), GOODRITE UV 3150 (RTM), GOODRITE UV 3159 (RTM), GOODRITE 31 10 x 128 (RTM), UVINUL 4050 H (RTM), UVASIL 299 LM (RTM) and UVASIL 2000 LM (RTM).
The meanings of the terminal groups which saturate the free valences in the compounds of the formulae (A-1), (A-2-a), (A-2-b), (A-4) and (B-11) depend on the processes used for their preparation. The terminal groups can also be modified after the preparation of the compounds.
If the compounds of the formula (A-1) are prepared, for example, by reacting a compound of the formula
in which Ai is hydrogen or methyl, with a dicarboxylic acid diester of the formula Y-OOC-A2-COO-Y, in which Y is, for example, methyl, ethyl or propyl, and A2 is as defined above, the terminal group bonded to the 2,2,6,6-tetramethyl-4-oxypiperidin-1 -yl radical is hydrogen or -CO-A2-COO-Y, and the terminal group bonded to the diacyl radical is -O-Y or
ln the compounds of the formula (A-2-a), the terminal group bonded to the nitrogen can be, for example, hydrogen and the terminal group bonded to the 2-hydroxypropylene radical can be, for example, a
group.
In the compounds of the formula (A-2-b), the terminal group bonded to the dimethylene radical can be, for example, -OH, and the terminal group bonded to the oxygen can be, for example, hydrogen. The terminal groups can also be polyether radicals.
In the compounds of the formula (A-4), the end group bonded to the -CH2- residue can be, for example, hydrogen and the end group bonded to the -CH(CO2A7) residue can be, for example, -CH=CH-COOA7.
In the compounds of the formula (B-11 ), the terminal group bonded to the silicon atom can be, for example, (E3ι)3Si-O-, and the terminal group bonded to the oxygen can be, for example, -Si(E31)3.
The compounds of the formula (B-11) can also be in the form of cyclic compounds if m3 is a number from 3 to 6, i.e. the free valences shown in the structural formula then form a direct bond.
A8 is preferably hydrogen, C C4alkyl, CrCι0alkoxy, cyclohexyloxy, allyl, benzyl or acetyl.
Ei, E8, Ei2, E13, Ei6, E18, E22, E23, E25, E29 and E33 are preferably hydrogen, C C4alkyl, Cι-Cι0alkoxy, cyclohexyloxy, allyl, benzyl or acetyl. Aβ, EL Ea, E12, E13, Ei6, Eι8, E22, E23, E25, E29 and E33 are in particular hydrogen or methyl and Ei additionally is CrC8alkoxy.
According to a preferred embodiment
Ai is hydrogen or methyl,
A2 is a direct bond or C2-C6alkylene, and ni is a number from 2 to 25; n2 and n2* are a number from 2 to 25;
A3 and A4 independently of one another are hydrogen or C1-C4alkyl, or A3 and A4 together form a C9-C13alkylene group, and the variables n3 independently of one another are a number from 1 to 25; n is a number from 2 to 25,
A5 and A6 independently of one another are CrC4alkyl, and
A is CrC aIkyl or a group of the formula (a-l) with the proviso that at least 50 % of the radicals A7 are a group of the formula (a-l).
According to a further preferred embodiment if ITH is 1 , E2 is C12-C2oalkyl, if mi is 2, E2 is C2-C 0alkylene or a group of the formula (b-l)
E3 is CrC4alkyl,
E4 is C C6aIkylene, and
E5 and E6 independently of one another are CrC4alkyl, and if mi is 4, E2 is C4-C8alkanetetrayl; two of the radicals E7 are -COO-(C10-C 5alkyl), and two of the radicals E7 are a group of the formula (b-ll);
E9 and E10 together form C9-Cι3alkylene,
En is hydrogen or a group -ZrCOO-Z2,
Z is C2-C6alkylene, and
Z2 is Cιo-Cι6aIkyl;
E14 is hydrogen, and
Ei5 is C2-C6alkylene or C -C5alkylidene; E17 is Cιo-Cι4aIkyl; E24 is CrC alkoxy; m2 is 1 , 2 or 3,
when m is 1 , E26 is a group — CH2CH H5^-NH-
when m2 is 2, E26 is C2-C6alkylene, and when m2 is 3, E26 is a group of the formula (b-IV) the radicals E27 independently of one another are C2-C6alkyiene, and the radicals E28 independently of one another are C C alkyl or C5-C8cycloalkyi;
E30 is C2-C8alkylene; and
E3ι is CrC4alkyl,
E32 is C3-C6alkylene, and m3 is a number from 2 to 6.
A particularly preferred embodiment of this invention relates to a stabilizer mixture wherein component (A) is a compound of the formula (A-1 -a), (A-2-a), (A-2-b), (A-3-a) or (A-4-a);
wherein ^ is a number from 2 to 20;
wherein n2 and n2* are a number from 2 to 20;
(A-3-a) wherein the variables n3 independently of one another are a number from 1 to 20;
wherein n4 is a number from 2 to 20, and at least 50 % of the radicals A7 are a group of the formula (a-l)
wherein A8 is hydrogen, C C8alkyl, O", -OH, -CH2CN, C Cι8alkoxy, C5-Cι2cycloalkoxy, C3-C6alkenyl, C7-C9phenylalkyl unsubstituted or substituted on the phenyl by 1 , 2 or 3 CrC4alkyl; or CrC8acyI, and the remaining radicals A7 are ethyl; and
component (B) is formed by two different compounds selected from the group consisting of compounds of the formulae (B-1-a), (B-1-b), (B-1-c), (B-1-d), (B-2-a), (B-3-a), (B-3-b), (B-4-a), (B-4-b), (B-5), (B-6-a), (B-7), (B-8-a), (B-9-a), (B-9-b), (B-9-c), (B-10-a) and (B-11 -a);
wherein E^ is hydrogen, CrC8alkyl, O', -OH, -CH2CN, CrCι8alkoxy, Cβ-C12c cloalkoxy, C3-C6alkenyl, C7-C9phenylalkyl unsubstituted or substituted on the phenyl by 1 , 2 or 3 CrC4alkyl; or C C8acyl;
H2C- CH - CH- CH, (B-2-a)
E7 ≡τ in which two of the radicals E7 are -COO-C13H27 and
two of the radicals E7 are and E8 has one of the meanings
wherein E 2 has one of the meanings of E ;
wherein Ei3 has one of the meanings of Ei;
wherein Ei6 has one of the meanings of E1;
wherein E18 has one of the meanings of Eι;
in which Eι9, E20 and E2i independently of one another are a group of the formula (b-lll)
wherein E22 has one of the meanings of Eι; wherein E23 has one of the meanings of E1;
wherein E25 has one of the meanings of En wherein E29 has one of the meanings of Ei;
wherein m3 is a number from 2 to 6 and E33 has one of the meanings of Ei
A particularly preferred embodiment of this invention also relates to a stabilizer mixture wherein one of the two different compounds forming component (B) is a compound of the formula (B-1-b) with Ei being hydrogen.
Another preferred embodiment of this invention relates to a stabilizer mixture wherein component (A) is a compound of the formula (A-1 -a) with ni being a number from 2 to 20 or a compound of the formula (A-2-a) or (A-2-b) wherein n2 and n2 * are a number from 2 to 20; and one of the two different compounds forming component (B) is a compound of the formula
(B-1 -b) with Ei being hydrogen.
A further particularly preferred embodiment of this invention is a stabilizer mixture wherein component (A) is a compound of the formula (A-1 -a) with ni being a number from 2 to 20 or a compound of the formula (A-2-a) or (A-2-b) wherein n2 and n2 * are a number from 2 to 20; one of the two different compounds forming component (B) is a compound of the formula (B-1-b) with Ei being hydrogen; and the other of the two different compounds forming component (B) is a compound of the formula (B-1 -a) with Ei being hydrogen, (B-1-b) with Ei being methyl, (B-1-d) with Ei being hydrogen or methyl, (B-3-a) with E12 being hydrogen, (B-3-b) with Ei2 being hydrogen, (B-4-b) with E13 being hydrogen, (B-5) with Eι6 being hydrogen, (B-6-a) with Ei8 being hydrogen or methyl, (B-8-a) with E23 being methyl, (B-9-c) with E25 being hydrogen or methyl, (B-10-a) with E29 being hydrogen, or (B-11 -a) with E33 being hydrogen.
Examples of stabilizer mixtures according to the present invention are the following combinations of commercial products:
1. TINUVIN 622 (RTM + TINUVIN 770 (RTM + TINUVIN 765 (RTM)
2. TINUVIN 622 (RTM + TINUVIN 770 (RTM + TINUVIN 144 (RTM)
3. TINUVIN 622 (RTM + TINμVIN 770 (RTM + TINUVIN 123 (RTM)
4. TINUVIN 622 (RTM + TINUVIN 770 (RTM + compound of the fo mula (B-3-a) wherein E ι2 is hydrogen
5. TINUVIN 622 (RTM + TINUVIN 770 (RTM + HOSTAVIN N 24 (RTM)
6. TINUVIN 622 (RTM + TINUVIN 770 (RTM + DIACETAM 5 (RTM)
7. TINUVIN 622 (RTM + TINUVIN 770 (RTM + ADK STAB LA 52 (RTM)
8. TINUVIN 622 (RTM + TINUVIN 770 (RTM + ADK STAB LA 57 (RTM)
9. TINUVIN 622 (RTM + TINUVIN 770 (RTM + ADK STAB LA 62 (RTM)
10. TINUVIN 622 (RTM + TINUVIN 770 (RTM + ADK STAB LA 67 (RTM)
11. TINUVIN 622 (RTM + TINUVIN 770 (RTM + GOODRITE UV 3034 (RTM)
12. TINUVIN 622 (RTM + TINUVIN 770 (RTM + GOODRITE UV 3150 (RTM)
13. TINUVIN 622 (RTM + TINUVIN 770 (RTM + GOODRITE UV 3159 (RTM)
14. TINUVIN 622 (RTM + TINUVIN 770 (RTM + compound of the fo mula (B-9-a) wherein E25 is hydrogen
15. TINUVIN 622 (RTM + TINUVIN 770 (RTM + UVINUL 4049 (RTM)
16. TINUVIN 622 (RTM + TINUVIN 770 (RTM + compound of the fo mula (B-10-a) wherein E29 is hydrogen
17. TINUVIN 622 (RTM + TINUVIN 770 (RTM) + compound of the fo mula (B-1 -a) wherein Ei is hydrogen 18. TINUVIN 622 (RTM) + TINUVIN 770 (RTM + SUMISORB TM 61 (RTM)
19. TINUVIN 622 (RTM) + TINUVIN 770 (RTM + SANDUVOR 3050 (RTM)
20. TINUVIN 622 (RTM) + TINUVIN 770 (RTM + SANDUVOR PR-31 (RTM)
21. TINUVIN 622 (RTM) + TINUVIN 770 (RTM + UVASIL 299 LM (RTM)
22. TINUVIN 622 (RTM) + TINUVIN 770 (RTM + UVASIL 2000 LM (RTM)
23. TINUVIN 622 (RTM) + TINUVIN 770 (RTM + compound of the formula (B-6-a) wherein E 18 is hydrogen
24. TINUVIN 622 (RTM) + TINUVIN 770 (RTM + compound of the formula (B-6-a) wherein E is is methyl
25. TINUVIN 622 (RTM) + TINUVIN 770 (RTM + compound of the formula (B-7) with E19, E 2; 0 and E2ι being a group of the formula (b-lll) wherein E22 is hydrogen.
26. TINUVIN 622 (RTM) + TINUVIN 765 (RT + TINUVIN 144 (RTM)
27. TINUVIN 622 (RTM) + TINUVIN 765 (RTM + TINUVIN 123 (RTM)
28. TINUVIN 622 (RTM) + TINUVIN 765 (RTM + compound of the formula (B-3-a) wherein E ι2 is hydrogen
29. TINUVIN 622 (RTM) + TINUVIN 765 (RTM + HOSTAVIN N 24 (RTM)
30. TINUVIN 622 (RTM) + TINUVIN 765 (RTM + DIACETAM 5 (RTM)
31. TINUVIN 622 (RTM) + TINUVIN 765 (RTM + ADK STAB LA 52 (RTM)
32. TINUVIN 622 (RTM) + TINUVIN 765 (RTM + ADK STAB LA 57 (RTM)
33. TINUVIN 622 (RTM) + TINUVIN 765 (RTM + ADK STAB LA 62 (RTM)
34. TINUVIN 622 (RTM) + TINUVIN 765 (RTM + ADK STAB LA 67 (RTM)
35. TINUVIN 622 (RTM) + TINUVIN 765 (RTM + GOODRITE UV 3034 (RTM)
36. TINUVIN 622 (RTM) + TINUVIN 765 (RTM + GOODRITE UV 3150 (RTM)
37. TINUVIN 622 (RTM) + TINUVIN 765 (RTM + GOODRITE UV 3159 (RTM)
38. TINUVIN 622 (RTM) + TINUVIN 765 (RTM + compound of the formula (B-9-a) wherein E 25 is hydrogen
39. TINUVIN 622 (RTM) + TINUVIN 765 (RTM + UVINUL 4049 (RTM)
40. TINUVIN 622 (RTM) + TINUVIN 765 (RTM + compound of the formula (B-10-a) wherein E29 is hydrogen
41. TINUVIN 622 (RTM) + TINUVIN 765 (RTM + compound of the formula (B-1 -a) wherein E ι is hydrogen
42. TINUVIN 622 (RTM) + TINUVIN 765 (RTM + SUMISORB TM 61 (RTM)
43. TINUVIN 622 (RTM) + TINUVIN 765 (RTM + SANDUVOR 3050 (RTM) 44. TINUVIN 622 (RTM) + TINUVIN 765 (RTM) + SANDUVOR PR-31 (RTM)
45. TINUVIN 622 (RTM) + TINUVIN 765 (RTM) + UVASIL 299 LM (RTM)
46. TINUVIN 622 (RTM) + TINUVIN 765 (RTM) + UVASIL 2000 LM (RTM)
47. TINUVIN 622 (RTM) + TINUVIN 765 (RTM) + compound of the formula (B-6-a) wherein Eι8 is hydrogen
48. TINUVIN 622 (RTM) + TINUVIN 765 (RTM) + compound of the formula (B-6-a) wherein Eι8 is methyl
49. TINUVIN 622 (RTM) + TINUVIN 765 (RTM) + compound of the formula (B-7) with E19, E20 and E2ι being a group of the formula (b-lll) wherein E22 is hydrogen.
50. TINUVIN 622 (RTM) + TINUVIN 144 (RTM) + TINUVIN 123 (RTM)
51. TINUVIN 622 (RTM) + TINUVIN 144 (RTM) + compound of the formula (B-3-a) wherein E 2 is hydrogen
52. TINUVIN 622 (RTM) + TINUVIN 144 (RTM) + HOSTAVIN N 24 (RTM)
53. TINUVIN 622 (RTM) + TINUVIN 144 (RTM) + DIACETAM 5 (RTM)
54. TINUVIN 622 (RTM) + TINUVIN 144 (RTM) + ADK STAB LA 52 (RTM)
55. TINUVIN 622 (RTM) + TINUVIN 144 (RTM) + ADK STAB LA 57 (RTM)
56. TINUVIN 622 (RTM) + TINUVIN 144 (RTM) + ADK STAB LA 62 (RTM)
57. TINUVIN 622 (RTM) + TINUVIN 144 (RTM) + ADK STAB LA 67 (RTM)
58. TINUVIN 622 (RTM) + TINUVIN 144 (RTM) + GOODRITE UV 3034 (RTM)
59. TINUVIN 622 (RTM) + TINUVIN 144 (RTM) + GOODRITE UV 3150 (RTM)
60. TINUVIN 622 (RTM) + TINUVIN 144 (RTM) + GOODRITE UV 3159 (RTM)
61. TINUVIN 622 (RTM) + TINUVIN 144 (RTM) + compound of the formula (B-9-a) wherein E25 is hydrogen
62. TINUVIN 622 (RTM) + TINUVIN 144 (RTM) + UVINUL 4049 (RTM)
63. TINUVIN 622 (RTM) + TINUVIN 144 (RTM) + compound of the formula (B-10-a) wherein E2g is hydrogen
64. TINUVIN 622 (RTM) + TINUVIN 144 (RTM) + compound of the formula (B-1 -a) wherein Ei is hydrogen
65. TINUVIN 622 (RTM) + TINUVIN 144 (RTM) + SUMISORB TM 61 (RTM)
66. TINUVIN 622 (RTM) + TINUVIN 144 (RTM) + SANDUVOR 3050 (RTM)
67. TINUVIN 622 (RTM) + TINUVIN 144 (RTM) + SANDUVOR PR-31 (RTM)
68. TINUVIN 622 (RTM) + TINUVIN 144 (RTM) + UVASIL 299 LM (RTM)
69. TINUVIN 622 (RTM) + TINUVIN 144 (RTM) + UVASIL 2000 LM (RTM) 70. TINUVIN 622 (RTM) + TINUVIN 144 (RTM) + compound of the formula (B-6-a) wherein Eι8 is hydrogen
71. TINUVIN 622 (RTM) + TINUVIN 144 (RTM) + compound of the formula (B-6-a) wherein Eι8 is methyl
72. TINUVIN 622 (RTM) + TINUVIN 144 (RTM) + compound of the formula (B-7) with Eι9, E20 and E2ι being a group of the formula (b-III) wherein E22 is hydrogen. 7.3. TINUVIN 622 (RTM) + TINUVIN 123 (RTM) + compound of the formula (B-3-a) wherein E12 is hydrogen
74. TINUVIN 622 (RTM) + TINUVIN 123 (RTM) + HOSTAVIN N 24 (RTM)
75. TINUVIN 622 (RTM) + TINUVIN 123 (RTM) + DIACETAM 5 (RTM)
76. TINUVIN 622 (RTM) + TINUVIN 123 (RTM) + ADK STAB LA 52 (RTM)
77. TINUVIN 622 (RTM) + TINUVIN 123 (RTM) + ADK STAB LA 57 (RTM)
78. TINUVIN 622 (RTM) + TINUVIN 123 (RTM) + ADK STAB LA 62 (RTM)
79. TINUVIN 622 (RTM) + TINUVIN 123 (RTM) + ADK STAB LA 67 (RTM)
80. TINUVIN 622 (RTM) + TINUVIN 123 (RTM) + GOODRITE UV 3034 (RTM)
81. TINUVIN 622 (RTM) + TINUVIN 123 (RTM) + GOODRITE UV 3150 (RTM)
82. TINUVIN 622 (RTM) + TINUVIN 123 (RTM) + GOODRITE UV 3159 (RTM)
83. TINUVIN 622 (RTM) + TINUVIN 123 (RTM) + compound of the formula (B-9-a) wherein E25 is hydrogen
84. TINUVIN 622 (RTM) + TINUVIN 123 (RTM) + UVINUL 4049 (RTM)
85. TINUVIN 622 (RTM) + TINUVIN 123 (RTM) + compound of the formula (B-10-a) wherein E29 is hydrogen
86. TINUVIN 622 (RTM) + TINUVIN 123 (RTM) + compound of the formula (B-1 -a) wherein Ei is hydrogen
87. TINUVIN 622 (RTM) + TINUVIN 123 (RTM) + SUMISORB TM 61 (RTM)
88. TINUVIN 622 (RTM) + TINUVIN 123 (RTM) + SANDUVOR 3050 (RTM)
89. TINUVIN 622 (RTM) + TINUVIN 123 (RTM) + SANDUVOR PR-31 (RTM)
90. TINUVIN 622 (RTM) + TINUVIN 123 (RTM) + UVASIL 299 LM (RTM)
91. TINUVIN 622 (RTM) + TINUVIN 123 (RTM) + UVASIL 2000 LM (RTM)
92. TINUVIN 622 (RTM) + TINUVIN 123 (RTM) + compound of the formula (B-6-a) wherein E18 is hydrogen
93. TINUVIN 622 (RTM) + TINUVIN 123 (RTM) + compound of the formula (B-6-a) wherein E18 is methyl 94. TINUVIN 622 (RTM) + TINUVIN 123 (RTM) + compound of the formula (B-7) with Eι9, E20 and E21 being a group of the formula (b-lll) wherein E22 is hydrogen.
95. TINUVIN 622 (RTM) + compound of the formula (B-3-a) wherein E12 is hydrogen + HOSTAVIN N 24 (RTM)
96. TINUVIN 622 (RTM) + compound of the formula (B-3-a) wherein E12 is hydrogen + DIACETAM 5 (RTM)
97. TINUVIN 622 (RTM) + compound of the formula (B-3-a) wherein Ei2 is hydrogen + ADK STAB LA 52 (RTM)
98. TINUVIN 622 (RTM) + compound of the formula (B-3-a) wherein Ei2 is hydrogen + ADK STAB LA 57 (RTM)
99. TINUVIN 622 (RTM) + compound of the formula (B-3-a) wherein Eι2 is hydrogen + ADK STAB LA 62 (RTM)
100. TINUVIN 622 (RTM) + compound of the formula (B-3-a) wherein E12 is hydrogen + ADK STAB LA 67 (RTM)
101. TINUVIN 622 (RTM) + compound of the formula (B-3-a) wherein E12 is hydrogen + GOODRITE UV 3034 (RTM)
102. TINUVIN 622 (RTM) + compound of the formula (B-3-a) wherein E12 is hydrogen + GOODRITE UV 3150 (RTM)
103. TINUVIN 622 (RTM) + compound of the formula (B-3-a) wherein E12 is hydrogen + GOODRITE UV 3159 (RTM)
104. TINUVIN 622 (RTM) + compound of the formula (B-3-a) wherein E12 is hydrogen + compound of the formula (B-9-a) wherein E25 is hydrogen
105. TINUVIN 622 (RTM) + compound of the formula (B-3-a) wherein E12 is hydrogen + UVINUL 4049 (RTM)
106. TINUVIN 622 (RTM) + compound of the formula (B-3-a) wherein E12 is hydrogen + compound of the formula (B-10-a) wherein E29 is hydrogen
107. TINUVIN 622 (RTM) + compound of the formula (B-3-a) wherein E12 is hydrogen + compound of the formula (B- -a) wherein Ei is hydrogen
108. TINUVIN 622 (RTM) + compound of the formula (B-3-a) wherein E12 is hydrogen + SUMISORB TM 61 (RTM)
109. TINUVIN 622 (RTM) + compound of the formula (B-3-a) wherein E12 is hydrogen + SANDUVOR 3050 (RTM)
110. TINUVIN 622 (RTM) + compound of the formula (B-3-a) wherein E12 is hydrogen + SANDUVOR PR-31 (RTM)
111. TINUVIN 622 (RTM) + compound of the formula (B-3-a) wherein E12 is hydrogen + UVASIL 299 LM (RTM)
112. TINUVIN 622 (RTM) + compound of the formula (B-3-a) wherein Ei2 is hydrogen + UVASIL 2000 LM (RTM)
113. TINUVIN 622 (RTM) + compound of the formula (B-3-a) wherein Ei2 is hydrogen + compound of the formula (B-6-a) wherein Eι8 is hydrogen
114. TINUVIN 622 (RTM) + compound of the formula (B-3-a) wherein Ei2 is hydrogen + compound of the formula (B-6-a) wherein E18 is methyl
115. TINUVIN 622 (RTM) + compound of the formula (B-3-a) wherein E12 is hydrogen + compound of the formula (B-7) with Ei9, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
116. TINUVIN 622 (RTM) + HOSTAVIN N 24 (RTM + DIACETAM 5 (RTM)
117. TINUVIN 622 (RTM) + HOSTAVIN N 24 (RTM + ADK STAB LA 52 (RTM)
118. TINUVIN 622 (RTM) + HOSTAVIN N 24 (RTM + ADK STAB LA 57 (RTM)
119. TINUVIN 622 (RTM) + HOSTAVIN N 24 (RTM + ADK STAB LA 62 (RTM)
120. TINUVIN 622 (RTM) + HOSTAVIN N 24 (RTM + ADK STAB LA 67 (RTM)
121. TINUVIN 622 (RTM) + HOSTAVIN N 24 (RTM + GOODRITE UV 3034 (RTM)
122. TINUVIN 622 (RTM) + HOSTAVIN N 24 (RTM + GOODRITE UV 3150 (RTM)
123. TINUVIN 622 (RTM) + HOSTAVIN N 24 (RTM + GOODRITE UV 3159 (RTM)
124. TINUVIN 622 (RTM) + HOSTAVIN N 24 (RTM + compound of the formula (B-9-a) wherein E 5 is hydrogen
125. TINUVIN 622 (RTM) + HOSTAVIN N 24 (RTM + UVINUL 4049 (RTM)
126. TINUVIN 622 (RTM) + HOSTAVIN N 24 (RTM + compound of the formula (B-10-a) wherein E29 is hydrogen
127. TINUVIN 622 (RTM) + HOSTAVIN N 24 (RTM + compound of the formula (B-1 -a) wherein E^ is hydrogen
128. TINUVIN 622 (RTM) + HOSTAVIN N 24 (RTM + SUMISORB TM 61 (RTM)
129. TINUVIN 622 (RTM) + HOSTAVIN N 24 (RTM + SANDUVOR 3050 (RTM)
130. TINUVIN 622 (RTM) + HOSTAVIN N 24 (RTM + SANDUVOR PR-31 (RTM)
131. TINUVIN 622 (RTM) + HOSTAVIN N 24 (RT + UVASIL 299 LM (RTM)
132. TINUVIN 622 (RTM) + HOSTAVIN N 24 (RTM + UVASIL 2000 LM (RTM)
133. TINUVIN 622 (RTM) + HOSTAVIN N 24 (RTM + compound of the formula (B-6-a) wherein Eι8 is hydrogen 134. TINUVIN 622 (RTM) + HOSTAVIN N 24 (RTM) + compound of the formula (B-6-a) wherein E18 is methyl
135. TINUVIN 622 (RTM) + HOSTAVIN N 24 (RTM) + compound of the formula (B-7) with E19, E20 and E21 being a group of the formula (b- wherein E22 is hydrogen.
136. TINUVIN 622 (RTM) + DIACETAM 5 (RTM + ADK STAB LA 52 (RTM)
137. TINUVIN 622 (RTM) + DIACETAM 5 (RTM + ADK STAB LA 57 (RTM)
138. TINUVIN 622 (RTM) + DIACETAM 5 (RTM + ADK STAB LA 62 (RTM)
139. TINUVIN 622 (RTM) + DIACETAM 5 (RTM + ADK STAB LA 67 (RTM)
140. TINUVIN 622 (RTM) + DIACETAM 5 (RTM + GOODRITE UV 3034 (RTM)
141. TINUVIN 622 (RTM) + DIACETAM 5 (RTM + GOODRITE UV 3150 (RTM)
142. TINUVIN 622 (RTM) + DIACETAM 5 (RTM + GOODRITE UV 3159 (RTM)
143. TINUVIN 622 (RTM) + DIACETAM 5 (RTM + compound of the formula (B-9-a) wherein E 25 is hydrogen
144. TINUVIN 622 (RTM) + DIACETAM 5 (RTM + UVINUL 4049 (RTM)
145. TINUVIN 622 (RTM) + DIACETAM 5 (RTM + compound of the formula (B-10-a) wherein E29 is hydrogen
146. TINUVIN 622 (RTM) + DIACETAM 5 (RTM + compound of the formula (B-1 -a) wherein E ! is hydrogen
147. TINUVIN 622 (RTM) + DIACETAM 5 (RTM + SUMISORB TM 61 (RTM)
148. TINUVIN 622 (RTM) + DIACETAM 5 (RTM + SANDUVOR 3050 (RTM)
149. TINUVIN 622 (RTM) + DIACETAM 5 (RTM + SANDUVOR PR-31 (RTM)
150. TINUVIN 622 (RTM) + DIACETAM 5 (RTM + UVASIL 299 LM (RTM)
151. TINUVIN 622 (RTM) + DIACETAM 5 (RTM + UVASIL 2000 LM (RTM)
152. TINUVIN 622 (RTM) + DIACETAM 5 (RTM + compound of the formula (B-6-a) wherein E 18 is hydrogen
153. TINUVIN 622 (RTM) + DIACETAM 5 (RTM + compound of the formula (B-6-a) wherein E18 is methyl
154. TINUVIN 622 (RTM) + DIACETAM 5 (RTM) + compound of the formula (B-7) with Eι9, E20 and E2ι being a group of the formula (b- wherein E22 is hydrogen.
155. TINUVIN 622 (RTM) + ADK STAB LA 52 (RTM) + ADK STAB LA 57 (RTM)
156. TINUVIN 622 (RTM) + ADK STAB LA 52 (RTM) + ADK STAB LA 62 (RTM)
157. TINUVIN 622 (RTM) + ADK STAB LA 52 (RTM) + ADK STAB LA 67 (RTM) 158. TINUVIN 622 (RTM ) + ADK STAB LA 52 (RTM + GOODRITE UV 3034 (RTM)
159. TINUVIN 622 (RTM ) + ADK STAB LA 52 (RTM + GOODRITE UV 3150 (RTM)
160. TINUVIN 622 (RTM ) + ADK STAB LA 52 (RTM + GOODRITE UV 3159 (RTM)
161. TINUVIN 622 (RTM ) + ADK STAB LA 52 (RTM + compound of the fo rmula (B-9-a) wherein E25 is hydrogen
162. TINUVIN 622 (RTM ) + ADK STAB LA 52 (RTM + UVINUL 4049 (RTM)
163. TINUVIN 622 (RTM ) + ADK STAB LA 52 (RTM 'tcompound of the fo rmula (B-10-a) wherein E29 is hydrogen
164. TINUVIN 622 (RTM ) + ADK STAB LA 52 (RTM + compound of the fo rmula (B-1 -a) wherein Ei is hydrogen
165. TINUVIN 622 (RTM ) + ADK STAB LA 52 (RTM + SUMISORB TM 61 (RTM)
166. TINUVIN 622 (RTM ) + ADK STAB LA 52 (RTM + SANDUVOR 3050 (RTM)
167. TINUVIN 622 (RTM ) + ADK STAB LA 52 (RTM + SANDUVOR PR-31 (RTM)
168. TINUVIN 622 (RTM ) + ADK STAB LA 52 (RTM + UVASIL 299 LM (RTM)
169. TINUVIN 622 (RTM ) + ADK STAB LA 52 (RTM + UVASIL 2000 LM (RTM)
170. TINUVIN 622 (RTM I) + ADK STAB LA 52 (RTM + compound of the fo rmula (B-6-a) wherein Eι8 is hydrogen
171. TINUVIN 622 (RTM I) + ADK STAB LA 52 (RTM + compound of the fo rmula (B-6-a) wherein E18 is methyl
172. TINUVIN 622 (RTM) + ADK STAB LA 52 (RTM) compound of the formula (B-7) with E19, E20 and E21 being a group of the formula (b-lll) wherein E22 is hydrogen.
173. TINUVIN 622 (RTM) + ADK STAB LA 57 (RTM) + ADK STAB LA 62 (RTM)
174. TINUVIN 622 (RTM) + ADK STAB LA 57 (RTM) + ADK STAB LA 67 (RTM)
175. TINUVIN 622 (RTM) + ADK STAB LA 57 (RTM) + GOODRITE UV 3034 (RTM)
176. TINUVIN 622 (RTM) + ADK STAB LA 57 (RTM) + GOODRITE UV 3150 (RTM)
177. TINUVIN 622 (RTM) + ADK STAB LA 57 (RTM) + GOODRITE UV 3159 (RTM)
178. TINUVIN 622 (RTM) + ADK STAB LA 57 (RTM) + compound of the formula (B-9-a) wherein E25 is hydrogen
179. TINUVIN 622 (RTM) + ADK STAB LA 57 (RTM) + UVINUL 4049 (RTM)
180. TINUVIN 622 (RTM) + ADK STAB LA 57 (RTM) + compound of the formula (B-10-a) wherein E29 is hydrogen
181. TINUVIN 622 (RTM) + ADK STAB LA 57 (RTM) + compound of the formula (B-1 -a) wherein Ei is hydrogen 182. TINUVIN 622 (RTM) + ADK STAB LA 57 (RTM) + SUMISORB TM 61 (RTM)
183. TINUVIN 622 (RTM) + ADK STAB LA 57 (RTM) + SANDUVOR 3050 (RTM)
184. TINUVIN 622 (RTM) + ADK STAB LA 57 (RTM) + SANDUVOR PR-31 (RTM)
185. TINUVIN 622 (RTM) + ADK STAB LA 57 (RTM) + UVASIL 299 LM (RTM)
186. TINUVIN 622 (RTM) + ADK STAB LA 57 (RTM) + UVASIL 2000 LM (RTM)
187. TINUVIN 622 (RTM) + ADK STAB LA 57 (RTM) + compound of the formula (B-6-a) wherein E18 is hydrogen
188. TINUVIN 622 (RTM) + ADK STAB LA 57 (RTM) + compound of the formula (B-6-a) wherein E18 is methyl
189. TINUVIN 622 (RTM) + ADK STAB LA 57 (RTM) + compound of the formula (B-7) with Eι9, E20 and E2ι being a group of the formula (b-lll) wherein E22 is hydrogen.
190. TINUVIN 622 (RTM) + ADK STAB LA 62 (RTM) + ADK STAB LA 67 (RTM)
191. TINUVIN 622 (RTM) + ADK STAB LA 62 (RTM) + GOODRITE UV 3034 (RTM)
192. TINUVIN 622 (RTM) + ADK STAB LA 62 (RTM) + GOODRITE UV 3150 (RTM)
193. TINUVIN 622 (RTM) + ADK STAB LA 62 (RTM) + GOODRITE UV 3159 (RTM)
194. TINUVIN 622 (RTM) + ADK STAB LA 62 (RTM) + compound of the formula (B-9-a) wherein E25 is hydrogen
195. TINUVIN 622 (RTM) + ADK STAB LA 62 (RTM) + UVINUL 4049 (RTM)
196. TINUVIN 622 (RTM) + ADK STAB LA 62 (RTM) + compound of the formula (B-10-a) wherein E2g is hydrogen
197. TINUVIN 622 (RTM) + ADK STAB LA 62 (RTM) + compound of the formula (B-1 -a) wherein Ei is hydrogen
198. TINUVIN 622 (RTM) + ADK STAB LA 62 (RTM) + SUMISORB TM 61 (RTM)
199. TINUVIN 622 (RTM) + ADK STAB LA 62 (RTM) + SANDUVOR 3050 (RTM)
200. TINUVIN 622 (RTM) + ADK STAB LA 62 (RTM) + SANDUVOR PR-31 (RTM)
201. TINUVIN 622 (RTM) + ADK STAB LA 62 (RTM) + UVASIL 299 LM (RTM)
202. TINUVIN 622 (RTM) + ADK STAB LA 62 (RTM) + UVASIL 2000 LM (RTM)
203. TINUVIN 622 (RTM) + ADK STAB LA 62 (RTM) + compound of the formula (B-6-a) wherein Eι8 is hydrogen
204. TINUVIN 622 (RTM) + ADK STAB LA 62 (RTM) + compound of the formula (B-6-a) wherein E18 is methyl
205. TINUVIN 622 (RTM) + ADK STAB LA 62 (RTM) + compound of the formula (B-7) with Eι9, E20 and E21 being a group of the formula (b-lll) wherein E22 is hydrogen.
206. TINUVIN 622 (RTM) + ADK STAB LA 67 (RTM) + GOODRITE UV 3034 (RTM)
207. TINUVIN 622 (RTM) + ADK STAB LA 67 (RTM) + GOODRITE UV 3150 (RTM)
208. TINUVIN 622 (RTM) + ADK STAB LA 67 (RTM) + GOODRITE UV 3159 (RTM)
209. TINUVIN 622 (RTM) + ADK STAB LA 67 (RTM) + compound of the formula (B-9-a) wherein E25 is hydrogen
210. TINUVIN 622 (RTM) + ADK STAB LA 67 (RTM) + UVINUL 4049 (RTM)
211. TINUVIN 622 (RTM) + ADK STAB LA 67 (RTM) + compound of the formula (B-10-a) wherein E2g is hydrogen
212. TINUVIN 622 (RTM) + ADK STAB LA 67 (RTM) + compound of the formula (B-1 -a) wherein Ei is hydrogen
213. TINUVIN 622 (RTM) + ADK STAB LA 67 (RTM) + SUMISORB TM 61 (RTM)
214. TINUVIN 622 (RTM) + ADK STAB LA 67 (RTM) + SANDUVOR 3050 (RTM)
215. TINUVIN 622 (RTM) + ADK STAB LA 67 (RTM) + SANDUVOR PR-31 (RTM)
216. TINUVIN 622 (RTM) + ADK STAB LA 67 (RTM) + UVASIL 299 LM (RTM)
217. TINUVIN 622 (RTM) + ADK STAB LA 67 (RTM) + UVASIL 2000 LM (RTM)
218. TINUVIN 622 (RTM) + ADK STAB LA 67 (RTM) + compound of the formula (B-6-a) wherein Eι8 is hydrogen
219. TINUVIN 622 (RTM) + ADK STAB LA 67 (RTM) + compound of the formula (B-6-a) wherein E18 is methyl
220. TINUVIN 622 (RTM) + ADK STAB LA 67 (RTM) + compound of the formula (B-7) with E19, E20 and E21 being a group of the formula (b- wherein E22 is hydrogen.
221. TINUVIN 622 (RTM) + GOODRITE UV 3034 (RTM) + GOODRITE UV 3150 (RTM)
222. TINUVIN 622 (RTM) + GOODRITE UV 3034 (RTM) + GOODRITE UV 3159 (RTM)
223. TINUVIN 622 (RTM) + GOODRITE UV 3034 (RTM) + compound of the formula (B-9-a) wherein E25 is hydrogen
224. TINUVIN 622 (RTM) + GOODRITE UV 3034 (RTM) + UVINUL 4049 (RTM)
225. TINUVIN 622 (RTM) + GOODRITE UV 3034 (RTM) + compound of the formula (B-10-a) wherein E29 is hydrogen
226. TINUVIN 622 (RTM) + GOODRITE UV 3034 (RTM) + compound of the formula (B-1 -a) wherein Ei is hydrogen
227. TINUVIN 622 (RTM) + GOODRITE UV 3034 (RTM) + SUMISORB TM 61 (RTM)
228. TINUVIN 622 (RTM) + GOODRITE UV 3034 (RTM) + SANDUVOR 3050 (RTM) 229. TINUVIN 622 (RTM) + GOODRITE UV 3034 (RTM) + SANDUVOR PR-31 (RTM)
230. TINUVIN 622 (RTM) + GOODRITE UV 3034 (RTM) + UVASIL 299 LM (RTM)
231. TINUVIN 622 (RTM) + GOODRITE UV 3034 (RTM) + UVASIL 2000 LM (RTM)
232. TINUVIN 622 (RTM) + GOODRITE UV 3034 (RTM) + compound of the formula (B-6-a) wherein Eι8 is hydrogen
233. TINUVIN 622 (RTM) + GOODRITE UV 3034 (RTM) + compound of the formula (B-6-a) wherein E18 is methyl
234. TINUVIN 622 (RTM) + GOODRITE UV 3034 (RTM) + compound of the formula (B-7) with Eι9, E20 and E2ι being a group of the formula (b-lll) wherein E22 is hydrogen.
235. TINUVIN 622 (RTM) + GOODRITE UV 3150 (RTM) + GOODRITE UV 3159 (RTM)
236. TINUVIN 622 (RTM) + GOODRITE UV 3150 (RTM) + compound of the formula (B-9-a) wherein E25 is hydrogen
237. TINUVIN 622 (RTM) + GOODRITE UV 3150 (RTM) + UVINUL 4049 (RTM)
238. TINUVIN 622 (RTM) + GOODRITE UV 3150 (RTM) + compound of the formula (B-10-a) wherein E29 is hydrogen
239. TINUVIN 622 (RTM) + GOODRITE UV 3150 (RTM) + compound of the formula (B-1 -a) wherein is hydrogen
240. TINUVIN 622 (RTM) + GOODRITE UV 3150 (RTM) + SUMISORB TM 61 (RTM)
241. TINUVIN 622 (RTM) + GOODRITE UV 3150 (RTM) + SANDUVOR 3050 (RTM)
242. TINUVIN 622 (RTM) + GOODRITE UV 3150 (RTM) + SANDUVOR PR-31 (RTM)
243. TINUVIN 622 (RTM) + GOODRITE UV 3150 (RTM) + UVASIL 299 LM (RTM)
244. TINUVIN 622 (RTM) + GOODRITE UV 3150 (RTM) + UVASIL 2000 LM (RTM)
245. TINUVIN 622 (RTM) + GOODRITE UV 3150 (RTM) + compound of the formula (B-6-a) wherein E18 is hydrogen
246. TINUVIN 622 (RTM) + GOODRITE UV 3150 (RTM) + compound of the formula (B-6-a) wherein Eι8 is methyl
247. TINUVIN 622 (RTM) + GOODRITE UV 3150 (RTM) + compound of the formula (B-7) with E19, E20 and E2ι being a group of the formula (b-lll) wherein E 2 is hydrogen.
248. TINUVIN 622 (RTM) + GOODRITE UV 3159 (RTM) + compound of the formula (B-9-a) wherein E25 is hydrogen
249. TINUVIN 622 (RTM) + GOODRITE UV 3159 (RTM) + UVINUL 4049 (RTM)
250. TINUVIN 622 (RTM) + GOODRITE UV 3159 (RTM) + compound of the formula (B-10-a) wherein E29 is hydrogen
251. TINUVIN 622 (RTM) + GOODRITE UV 3159 (RTM) + compound of the formula (B-1 -a) wherein Ei is hydrogen
252. TINUVIN 622 (RTM) + GOODRITE UV 3159 (RTM) + SUMISORB TM 61 (RTM)
253. TINUVIN 622 (RTM) + GOODRITE UV 3159 (RTM) + SANDUVOR 3050 (RTM)
254. TINUVIN 622 (RTM) + GOODRITE UV 3159 (RTM) + SANDUVOR PR-31 (RTM)
255. TINUVIN 622 (RTM) + GOODRITE UV 3159 (RTM) + UVASIL 299 LM (RTM)
256. TINUVIN 622 (RTM) + GOODRITE UV 3159 (RTM) + UVASIL 2000 LM (RTM)
257. TINUVIN 622 (RTM) + GOODRITE UV 3159 (RTM) + compound of the formula (B-6-a) wherein E18 is hydrogen
258. TINUVIN 622 (RTM) + GOODRITE UV 3159 (RTM) + compound of the formula (B-6-a) wherein Eι8 is methyl
259. TINUVIN 622 (RTM) + GOODRITE UV 3159 (RTM) + compound of the formula (B-7) with E19, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
260. TINUVIN 622 (RTM) + compound of the formula (B-9-a) wherein E25 is hydrogen + UVINUL 4049 (RTM)
261. TINUVIN 622 (RTM) + compound of the formula (B-9-a) wherein E25 is hydrogen + compound of the formula (B-10-a) wherein E29 is hydrogen
262. TINUVIN 622 (RTM) + compound of the formula (B-9-a) wherein E25 is hydrogen + compound of the formula (B-1 -a) wherein Ei is hydrogen
263. TINUVIN 622 (RTM) + compound of the formula (B-9-a) wherein E25 is hydrogen + SUMISORB TM 61 (RTM)
264. TINUVIN 622 (RTM) + compound of the formula (B-9-a) wherein E25 is hydrogen + SANDUVOR 3050 (RTM)
265. TINUVIN 622 (RTM) + compound of the formula (B-9-a) wherein E25 is hydrogen + SANDUVOR PR-31 (RTM)
266. TINUVIN 622 (RTM) + compound of the formula (B-9-a) wherein E25 is hydrogen + UVASIL 299 LM (RTM)
267. TINUVIN 622 (RTM) + compound of the formula (B-9-a) wherein E25 is hydrogen + UVASIL 2000 LM (RTM)
268. TINUVIN 622 (RTM) + compound of the formula (B-9-a) wherein E25 is hydrogen + compound of the formula (B-6-a) wherein Eι8 is hydrogen
269. TINUVIN 622 (RTM) + compound of the formula (B-9-a) wherein E25 is hydrogen + compound of the formula (B-6-a) wherein E18 is methyl
270. TINUVIN 622 (RTM) + compound of the formula (B-9-a) wherein E25 is hydrogen + compound of the formula (B-7) with Eig, E20 and E2ι being a group of the formula (b-lll) wherein E22 is hydrogen.
271. TINUVIN 622 (RTM) + UVINUL 4049 (RTM) + compound of the formula (B-10-a) wherein E29 is hydrogen
272. TINUVIN 622 (RTM) + UVINUL 4049 (RTM) + compound of the formula (B-1 -a) wherein Ei is hydrogen
273. TINUVIN 622 (RTM) + UVINUL 4049 (RTM) + SUMISORB TM 61 (RTM)
274. TINUVIN 622 (RTM) + UVINUL 4049 (RTM) + SANDUVOR 3050 (RTM)
275. TINUVIN 622 (RTM) + UVINUL 4049 (RTM) + SANDUVOR PR-31 (RTM)
276. TINUVIN 622 (RTM) + UVINUL 4049 (RTM) + UVASIL 299 LM (RTM)
277. TINUVIN 622 (RTM) + UVINUL 4049 (RTM) + UVASIL 2000 LM (RTM)
278. TINUVIN 622 (RTM) + UVINUL 4049 (RTM) + compound of the formula (B-6-a) wherein Eι8 is hydrogen
279. TINUVIN 622 (RTM) + UVINUL 4049 (RTM) + compound of the formula (B-6-a) wherein E18 is methyl
280. TINUVIN 622 (RTM) + UVINUL 4049 (RTM) + compound of the formula (B-7) with Eι9, E20 and E2ι being a group of the formula (b-lll) wherein E22 is hydrogen.
281. TINUVIN 622 (RTM) + compound of the formula (B-10-a) wherein E29 is hydrogen + compound of the formula (B-1 -a) wherein Ei is hydrogen
282. TINUVIN 622 (RTM) + compound of the formula (B-10-a) wherein E29 is hydrogen + SUMISORB TM 61 (RTM)
283. TINUVIN 622 (RTM) + compound of the formula (B-10-a) wherein E29 is hydrogen + SANDUVOR 3050 (RTM)
284. TINUVIN 622 (RTM) + compound of the formula (B-10-a) wherein E29 is hydrogen + SANDUVOR PR-31 (RTM)
285. TINUVIN 622 (RTM) + compound of the formula (B-10-a) wherein E29 is hydrogen + UVASIL 299 LM (RTM)
286. TINUVIN 622 (RTM) + compound of the formula (B-10-a) wherein E29 is hydrogen + UVASIL 2000 LM (RTM)
287. TINUVIN 622 (RTM) + compound of the formula (B-10-a) wherein E29 is hydrogen + compound of the formula (B-6-a) wherein Eι8 is hydrogen 288. TINUVIN 622 (RTM) + compound of the formula (B-10-a) wherein E29 is hydrogen + compound of the formula (B-6-a) wherein E18 is methyl
289. TINUVIN 622 (RTM) + compound of the formula (B-10-a) wherein E29 is hydrogen + compound of the formula (B-7) with Eι9, E20 and E21 being a group of the formula (b-III) wherein E22 is hydrogen.
290. TINUVIN 622 (RTM) + compound of the formula (B-1 -a) wherein Ei is hydrogen + SUMISORB TM 61 (RTM)
291. TINUVIN 622 (RTM) + compound of the formula (B-1 -a) wherein Ei is hydrogen + SANDUVOR 3050 (RTM)
292. TINUVIN 622 (RTM) + compound of the formula (B-1 -a) wherein Ei is hydrogen + SANDUVOR PR-31 (RTM)
293. TINUVIN 622 (RTM) + compound of the formula (B-1 -a) wherein Ei is hydrogen + UVASIL 299 LM (RTM)
294. TINUVIN 622 (RTM) + compound of the formula (B-1 -a) wherein Ei is hydrogen + UVASIL 2000 LM (RTM)
295. TINUVIN 622 (RTM) + compound of the formula (B-1 -a) wherein Ei is hydrogen + compound of the formula (B-6-a) wherein Eι8 is hydrogen
296. TINUVIN 622 (RTM) + compound of the formula (B-1 -a) wherein Ei is hydrogen + compound of the formula (B-6-a) wherein E18 is methyl
297. TINUVIN 622 (RTM) + compound of the formula (B-1 -a) wherein En is hydrogen + compound of the formula (B-7) with E1β, E20 and E2i being a group of the formula (b-lll) wherein E22 is hydrogen.
298. TINUVIN 622 (RTM) + SUMISORB TM 61 (RTM) + SANDUVOR 3050 (RTM)
299. TINUVIN 622 (RTM) + SUMISORB TM 61 (RTM) + SANDUVOR PR-31 (RTM)
300. TINUVIN 622 (RTM) + SUMISORB TM 61 (RTM) + UVASIL 299 LM (RTM)
301. TINUVIN 622 (RTM) + SUMISORB TM 61 (RTM) + UVASIL 2000 LM (RTM)
302. TINUVIN 622 (RTM) + SUMISORB TM 61 (RTM) + compound of the formula (B-6-a) wherein Eι8 is hydrogen
303. TINUVIN 622 (RTM) + SUMISORB TM 61 (RTM) + compound of the formula (B-6-a) wherein Eι8 is methyl
304. TINUVIN 622 (RTM) + SUMISORB TM 61 (RTM) + compound .of the formula (B-7) with E1β, E20 and E2i being a group of the formula (b-lll) wherein E22 is hydrogen.
305. TINUVIN 622 (RTM) + SANDUVOR 3050 (RTM) + SANDUVOR PR-31 (RTM) 306. TINUVIN 622 (RTM) + SANDUVOR 3050 (RTM) + UVASIL 299 LM (RTM)
307. TINUVIN 622 (RTM) + SANDUVOR 3050 (RTM) + UVASIL 2000 LM (RTM)
308. TINUVIN 622 (RTM) + SANDUVOR 3050 (RTM) + compound of the formula (B-6-a) wherein E18 is hydrogen
309. TINUVIN 622 (RTM) + SANDUVOR 3050 (RTM) + compound of the formula (B-6-a) wherein E18 is methyl
310. TINUVIN 622 (RTM) + SANDUVOR 3050 (RTM) + compound of the formula (B-7) with E19, E20 and E2ι being a group of the formula (b-lll) wherein E22 is hydrogen.
311. TINUVIN 622 (RTM) + SANDUVOR PR-31 (RTM) + UVASIL 299 LM (RTM)
312. TINUVIN 622 (RTM) + SANDUVOR PR-31 (RTM) + UVASIL 2000 LM (RTM)
313. TINUVIN 622 (RTM) + SANDUVOR PR-31 (RTM) + compound of the formula (B-6-a) wherein E1β is hydrogen
314. TINUVIN 622 (RTM) + SANDUVOR PR-31 (RTM) + compound of the formula (B-6-a) wherein E18 is methyl
315. TINUVIN 622 (RTM) + SANDUVOR PR-31 (RTM) + compound of the formula (B-7) with E19, E20 and E2ι being a group of the formula (b-III) wherein E22 is hydrogen.
316. TINUVIN 622 (RTM) + UVASIL 299 LM (RTM) + compound of the formula (B-6-a) wherein E18 is hydrogen
317. TINUVIN 622 (RTM) + UVASIL 299 LM (RTM) + compound of the formula (B-6-a) wherein E18 is methyl
318. TINUVIN 622 (RTM) + UVASIL 299 LM (RTM) + compound of the formula (B-7) with Eι9, E20 and E2ι being a group of the formula (b-lll) wherein E22 is hydrogen.
319. TINUVIN 622 (RTM) + UVASIL 2000 LM (RTM) + compound of the formula (B-6-a) wherein E18 is hydrogen
320. TINUVIN 622 (RTM) + UVASIL 2000 LM (RTM) + compound of the formula (B-6-a) wherein E18 is methyl
321. TINUVIN 622 (RTM) + UVASIL 2000 LM (RTM) + compound of the formula (B-7) with Eι9, E20 and E2i being a group of the formula (b-lll) wherein E22 is hydrogen.
322. TINUVIN 622 (RTM) + compound of the formula (B-6-a) wherein E18 is hydrogen + compound of the formula (B-6-a) wherein E18 is methyl 323. TINUVIN 622 (RTM) + compound of the formula (B-6-a) wherein E18 is hydrogen + compound of the formula (B-7) with E19, E20 and E2ι being a group of the formula (b-III) wherein E22 is hydrogen.
324. TINUVIN 622 (RTM) + compound of the formula (B-6-a) wherein E18 is methyl + compound of the formula (B-7) with E19, E20 and E2ι being a group of the formula (b-lll) wherein E22 is hydrogen.
Further examples of stabilizer mixtures are those wherein in the above combinations 1 to 324 the commercial product TINUVIN 622 (RTM) is replaced by a compound of the formula (A-2-a) and / or (A-2-b)
wherein n2 and n2* are a number from 2 to 20.
Additional examples of stabilizer mixtures are those wherein in the above combinations 1 to 324 the commercial product TINUVIN 622 (RTM) is replaced by a compound of the formula (A-4-a)
wherein n4 is a number from 2 to 20, and
at least 50 % of the radicals A7 are a group of the formula and the remaining radicals A7 are ethyl.
Combinations of particular interest are numbers 1 , 4, 7, 8, 12, 13 and 15 to 24, and the corresponding combinations wherein TINUVIN 622 (RTM) is replaced by a compound of the formula (A-2-a) and / or (A-2-b).
Further combinations of particular interest are numbers 3, 4, 8, 17 and 31.
The commercial product TINUVIN 622 (RTM) corresponds to the compound of the formula
(A-1 -a).
The commercial product TINUVIN 770 (RTM) corresponds to the compound of the formula
(B-1-b) wherein E^ is hydrogen.
The commercial product TINUVIN 765 (RTM) corresponds to the compound of the formula
(B-1 -b) wherein Ei is methyl.
The commercial product TINUVIN 123 (RTM) corresponds to the compound of the formula
(B-1 -b) wherein Ei is octyloxy.
The commercial product TINUVIN 144 (RTM) corresponds to the compound of the formula
(B-1 -c) wherein Ei is methyl.
The commercial product ADK STAB LA 57 (RTM) corresponds to the compound of the formula (B-1-d) wherein Ei is hydrogen.
The commercial product ADK STAB LA 52 (RTM) corresponds to the compound of the formula (B-1-d) wherein Ei is methyl. The commercial product ADK STAB LA 67 (RTM) corresponds to the compound of the formula (B-2-a) wherein E8 is hydrogen.
The commercial product ADK STAB LA 62 (RTM) corresponds to the compound of the formula (B-2-a) wherein E- is methyl.
The commercial product HOSTAVIN N 24 (RTM) corresponds to the compound of the formula (B-3-b) wherein E12 is hydrogen.
The commercial product SANDUVOR 3050 (RTM) corresponds to the compound of the formula (B-3-b-1) shown below, wherein E12 is hydrogen.
The commercial product DIACETAM 5 (RTM) corresponds to the compound of the formula
(B-4-a) wherein E13 is hydrogen.
The commercial product SUMISORB TM 61 corresponds to the compound of the formula
(B-4-b) wherein Eι3 is hydrogen.
The commercial product UVINUL 4049 (RTM) corresponds to the compound of the formula
(B-5) wherein Eι6 is hydrogen.
The commercial product SANDUVOR PR 31 (RTM) corresponds to the compound of the formula (B-8-a) wherein E23 is methyl.
The commercial product GOODRITE 3034 (RTM) corresponds to the compound of the formula (B-9-b) wherein E25 is hydrogen.
The commercial product GOODRITE 3150 (RTM) corresponds to the compound of the formula (B-9-c) wherein E25 is hydrogen.
The commercial product GOODRITE 3159 (RTM) corresponds to the compound of the formula (B-9-c) wherein E25 is methyl.
The commercial product UVASIL 299 LM (RTM) or UVASIL 2000 LM (RTM) contains as active ingredient the compound of the formula (B-11-a) wherein Ri6 is hydrogen.
The compound of the formula (B-3-b-1) has the following structure:
The stabilizer mixture according to this invention is suitable for stabilizing organic materials against degradation induced by light, heat or oxidation. Examples of such organic materials are the following:
1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, po- lybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).
Polyolefins, i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods:
a) radical polymerisation (normally under high pressure and at elevated temperature).
b) catalytic polymerisation using a catalyst that normally contains one or more than one metal of groups IVb, Vb, Vlb or VIII of the Periodic Table. These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either π- or σ-coordinated. These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(lll) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerisation medium. The catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups la, lla and/or Ilia of the Periodic Table. The activators may be modified conveniently with further ester, ether, amine or silyl ether groups. These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC). 2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE).
3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1 -ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethy- lene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers and their copolymers with carbon monoxide or ethyl ene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with one another and with polymers mentioned in 1) above, for example polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random polyalkylene/carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides.
4. Hydrocarbon resins (for example C5-C9) including hydrogenated modifications thereof (e.g. tackifiers) and mixtures of polyalkylenes and starch.
5. Polystyrene, poly(p-methylstyrene), poly(oc-methylstyrene).
6. Copolymers of styrene or α-methylstyrene with dienes or acrylic derivatives, for example styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acryloni- trile/ ethyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/propylene/diene terpo- lymer; and block copolymers of styrene such as styrene/butadiene/styrene, styrene/iso- prene/styrene, styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/ styrene. 7. Graft copolymers of styrene or α-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene terpolymers; styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadiene copolymers, as well as mixtures thereof with the copolymers listed under 6), for example the copolymer mixtures known as ABS, MBS, ASA or AES polymers.
8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfo- chlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
9. Polymers derived from ,β-unsaturated acids and derivatives thereof such as polyacry- lates and poiymethacrylates; polymethyl methacrylates, polyacrylamides and polyacryloni- triles, impact-modified with butyl acrylate.
10. Copolymers of the monomers mentioned under 9) with each other or with other unsatu- rated monomers, for example acrylonitrile/ butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acrylonitrile/ alkyl methacrylate/butadiene terpolymers.
11. Polymers derived from unsaturated alcohols and amines or the acyl derivatives or ace- tals thereof, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1) above. 12. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.
13. Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with styrene polymers or polyamides.
15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybutadi- enes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as precursors thereof.
16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly- m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (RIM polyamide systems).
17. Polyureas, polyimides, polyamide-imides, polyetherimids, polyesterimids, polyhydantoins and polybenzimidazoles.
18. Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones, for example polyethylene terephthalate, polybutylene tereph- thalate, poly-1 ,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate (PAN) and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS. 19. Polycarbonates and polyester carbonates.
20. Polysulfones, polyether sulfones and polyether ketones.
21. Crosslinked polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenol/formaldehyde resins, urea formaldehyde resins and melamine/formaldehyde resins.
22. Drying and non-drying alkyd resins.
23. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications thereof of low flammability.
24. Crosslinkable acrylic resins derived from substituted acrylates, for example epoxy acry- lates, urethane acrylates or polyester acrylates.
25. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.
26. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidyl ethers of bisphenol A and bisphenol F, which are crosslinked with customary hardeners such as anhydrides or amines, with or without accelerators.
27. Natural polymers such as cellulose, rubber, gelatin and chemically modified homologous derivatives thereof, for example cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins and their derivatives.
28. Blends of the aforementioned polymers (polyblends), for example PP/EPDM, Poly- amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.
29. Naturally occurring and synthetic organic materials which are pure monomeric compounds or mixtures of such compounds, for example mineral oils, animal and vegetable fats, oil and waxes, or oils, fats and waxes based on synthetic esters (e.g. phthalates, adipates, phosphates or trimellitates) and also mixtures of synthetic esters with mineral oils in any weight ratios, typically those used as spinning compositions, as well as aqueous emulsions of such materials.
30. Aqueous emulsions of natural or synthetic rubber, e.g. natural latex or latices of carbo- xylated styrene/butadiene copolymers.
This invention therefore additionally relates to a composition comprising an organic material subject to degradation induced by light, heat or oxidation and the stabilizer mixture described herein above.
A further embodiment of the present invention is a method for stabilizing an organic material against degradation induced by light, heat or oxidation, which comprises incorporating into the organic material the stabilizer mixture described herein above.
The organic material is preferably a synthetic polymer, in particular from one of the above groups. Polyolefins are preferred and polyethylene, polypropylene, a polyethylene copolymer and a polypropylene copolymer are particularly preferred.
The compounds of components (A) and (B) may be added to the organic material to be stabilized either individually or mixed with one another.
Each of the compounds of components (A) and (B) may be present in the organic material in an amount of preferably 0.005 to 5 %, in particular 0.01 to 1 % or 0.05 to 1 %, relative to the weight of the organic material. The weight ratio of the components (A):(B) is preferably 10 : 1 to 1 : 100, in particular 10 : 1 to 1 : 10 or 5 : 1 to 1 : 5 . Further examples for the weight ratio are also 1 : 1 to 1 : 10, for example 1 : 2 to 1 : 5.
The weight ratio of the two components forming component (B) is for example 1 : 10 to 10 : 1 or 1 : 5 to 5 : 1 , preferably 1 : 2 to 2 : 1 , in particular 1 : 1.
The above components can be incorporated into the organic material to be stabilized by known methods, for example before or during shaping or by applying the dissolved or dispersed compounds to the organic material, if necessary with subsequent evaporation of the solvent. The components can be added to the organic material in the form of a powder, granules or a masterbatch, which contains these components in, for example, a concentration of from 2.5 to 25% by weight.
If desired, the compounds of components (A) and (B) can be blended with each other before incorporation in the organic material. They can be added to a polymer before or during the polymerization or before the crosslinking.
The materials stabilized according to this invention can be used in a wide variety of forms, for example as films, fibres, tapes, moulding compositions, profiles or as binders for paints, adhesives or putties.
The stabilized material may additionally also contain various conventional additives, for example:
1. Antioxidants
1.1. Alkylated monophenols. for example 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-bu- tyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenoI, 2-(α-methylcyclohexyl)-4,6-dimethyl- phenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexyIphenol, 2,6-di-tert-butyl-4-meth- oxymethylphenol, nonylphenols which are linear or branched in the side chains, for example 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1 '-methylundec-1 '-yl)phenol, 2,4-dimethyl-6-(1 '- methylheptadec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol and mixtures thereof.
1.2. Alkylthiomethylphenols. for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctyl- thiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4- nonylphenol.
1.3. Hvdroquinones and alkylated hvdroαuinones. for example 2,6-di-tert-butyl-4-methoxy- phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octade- cyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-bu- tyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hy- droxyphenyl) adipate.
1.4. Tocopherols. for example α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E).
1.5. Hvdroxylated 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-amylphenoI), 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl)- disulfide.
1.6. Alkylidenebisphenols. for example 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'- methylenebis(6-tert-butyl-4-ethylphenoI), 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-butyl- phenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-(α-methylben- zyl)-4-nonylphenol], 2,2'-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol], 4,4'-methy- lenebis(2,6-di-tert-butylphenol), 4,4'-methylenebis(6-tert-butyl-2-methylphenol), 1 ,1-bis(5- tert-butyl-4-hydrόxy-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)dicyclopenta- diene, bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephtha- late, 1 ,1 -bis-(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di-tert-butyl-4-hydroxyphe- nyl)propane, 2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane, 1 ,1 ,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyI)pentane.
1.7. O-. N- and S-benzyl compounds, for example 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydi- benzyl 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-hydroxy- benzyl)sulfide, isooctyI-3,5-di-tert-butyI-4-hydroxybenzylmercaptoacetate.
1.8. Hvdroxybenzylated malonates. for example dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hy- droxybenzyl)malonate, di-octadecyI-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, di- dodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyI-4-hydroxybenzyl)malonate, bis[4-(1 ,1 ,3,3-te- tramethyIbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
1.9. Aromatic hvdroxybenzyl compounds, for example 1,3,5-tris(3,5-di-tert-butyl-4-hydroxy- benzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetrame- thylbenzene, 2,4,6-tris(3,5-di-tert-butyI-4-hydroxybenzyl)phenol.
1.10. Triazine compounds, for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxy- anilino)-1 ,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1 ,3,5-tri- azine, 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-hydroxyben- zyl)isocyanurate, 1 ,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,4,6-tris- (3,5-di-tert-butyI-4-hydroxyphenylethyl)-1 ,3,5-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxy- phenylpropionyI)-hexahydro-1 ,3,5-triazine, 1 ,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)iso- cyanurate.
1.11. Benzylphosphonates. for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphospho- nate, diethyl-3,5-di-tert-butyI-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4-hy- droxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid. 1.12. Acylaminophenols. for example 4-hydroxyIauranilide, 4-hydroxystearanilide, octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
1.13. Esters of β-(3,5-di-tert-butyl-4-hvdroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1 ,9- nonanediol, ethylene glycol,..1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethy- lene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyI)isocyanurate, N,N'-bis(hy- droxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylol- propane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.14. Esters of β-(5-tert-butyl-4^hvdroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1 ,6-hexanedi- ol, 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, trimethyl- olpropane, 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.
1.15. Esters of β-(3,5-dicvclohexyl-4-hvdroxyphenvflpropionic acid with mono- or polyhydric alcohols, e.g. with 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)ox- amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy- droxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.16. Esters of 3,5-di-tert-butyl-4-hvdroxyphenyl acetic acid with mono- or polyhydric alcohols, e.g. with 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)ox- amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy- droxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane. 1.17. Amides of β-(3.5-di-tert-butyl-4-hvdroxyphenvhpropionic acid e.g. N,N'-bis(3,5-di-tert- butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxy- phenylpropionyl)trimethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hy- drazide, N,N'-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyI]propionyloxy)ethyl]oxamide (Nau- gard®XL-1 , supplied by Uniroyal).
1.18. Ascorbic acid (vitamin C)
1.19. Aminic antioxidants. for example N,N'-di-isopropyl-p-phenyIenediamine, N,N'-di-sec-bu- tyl-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'-dicy- clohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naphthyl)-p- phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1 ,3-dimethyJbutyl)-N'-phe- nyl-p-phenylenediamine, N-(1 -methylheptyl)-N'-phenyI-p-phenylenediamine, N-cyclohexyl-N'- phenyl-p-phenylenediamine, 4-(p-toluenesuIfamoyl)diphenylamine, N,N'-dimethyl-N,N'-di- sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenyl- amine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naph- thylamine, octylated diphenylamine, for example p,p'-di-tert-octyldiphenylamine, 4-n-butyl- aminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4- octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylamino- methylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N,N,N',N'-tetra- methyl-4,4'-diaminodiphenylmethane, 1 ,2-bis[(2-methyIphenyl)amino]ethane, 1 ,2-bis(phenyl- amino)propane, (o-tolyl)biguanide, bis[4-(1',3'-dimethylbutyl)phenyl]amine, tert-octylated N- phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl/tert-octyldiphenyl- amines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl/isohexyl- diphenylamines, a mixture of mono- and dialkylated tert-butyldiphenylamines, 2,3-dihydro- 3,3-dimethyl-4H-1 ,4-benzothiazine, phenothiazine, a mixture of mono- and dialkylated tert- butyl/tert-octylphenothiazines, a mixture of mono- and dialkylated tert-octylphenothiazines, N-allylphenothiazine, N,N,N',N'-tetraphenyl-1 ,4-diaminobut-2-ene, N,N-bis(2,2,6,6-tetra- methylpiperid-4-yl-hexamethylenediamine, bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.
2. UV absorbers and light stabilisers 2.1. 2-(2'-Hvdroxyphenyl)benzotriazoles. for example 2-(2'-hydroxy-5'-methylphenyl)benzo- triazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazoleI 2-(5'-tert-butyl-2'-hydroxyphe- nyl)benzotriazole, 2-(2'-hydroxy-5'-(1 ,1 ,3,3-tetramethylbuty!)phenyl)benzotriazole, 2-(3',5'-di- tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-methylphe- nyl)-5-chlorobenzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'- hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3',5'-di-tert-amyI-2'-hydroxyphenyl)benzotriazole, 2-(3',5'-bis(α,α-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, 2-(3'-tert-butyi-2'-hydroxy-5'- (2-octyloxycarbonylethyI)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyl- oxy)carbonylethyl]-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2- methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-meth- oxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonyl- ethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxy- phenyl)benzotriazo!e, 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(3'-tert-butyl- 2'-hydroxy-5'-(2-isooctyloxycarbonyIethyl)phenylbenzotriazole, 2,2'-methyIenebis[4-(1 ,1 ,3,3- tetramethylbutyl)-6-benzotriazole-2-ylphenol]; the transesterification product of 2-[3'-tert-bu- tyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol
300; [R-CH2CH2— COO-CH2CH2-^- , where R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotri-
azol-2-ylphenyl, 2-[2'-hydroxy-3'-(α,α-dimethylbenzyl)-5'-(1 ,1 ,3,3-tetramethylbutyl)phenyl]- benzotriazole; 2-[2'-hydroxy-3'-(1 ,1 ,3,3-tetramethylbutyl)-5'-(α,α-dimethylbenzyl)phenyl]ben- zotriazole.
2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyl- oxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.
2.3. Esters of substituted and unsubstituted benzoic acids, for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylben- zoyl)resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyI-4-hydroxybenzo- ate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxyben- zoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
2.4. Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate, isooctyl α-cyano-β,β-diphe- nylacrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinna- mate, butyl α-cyano-β-methyl-p-methoxycinnamate, methyl α-carbomethoxy-p-methoxycin- namate and N-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.
2.5. Nickel compounds, for example nickel complexes of 2,2'-thiobis[4-(1,1 ,3,3-tetramethyl- butyl)phenol], such as the 1 :1 or 1 :2 complex, with or without additional ligands such as n- butyiamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert- butylbenzylphosphonic acid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphe- nylundecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazoie, with or without additional ligands.
2.6. Oxamides, for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy- 5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxaniIide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxaniIide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
2.7. 2-(2-Hvdroχyphenv -1.3.5-triazines, for example 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)- 1 ,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyI)-1 ,3,5-triazine, 2- (2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine, 2,4-bis(2-hydroxy-4-propyl- oxyphenyl)-6-(2,4-dimethylphenyl)-1 ,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4- methylphenyl)-1 ,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)- 1 ,3,5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine, 2- [2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1 ,3,5-triazine, 2-[2- hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethyI)-1 ,3,5-triazine, 2-[4- (dodecyloxy/tridecyIoxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-
1 ,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl- phenyl)-1 ,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1 ,3,5-triazine, 2-(2-hy- droxy-4-methoxyphenyl)-4,6-diphenyl-1 ,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hy- droxypropoxy)phenyl]-1 ,3,5-triazine, 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyI- 1 ,3,5-triazine, 2-{2-hydroxy-4-[3-(2-ethylhexyl-1 -oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4- dimethy!phenyl)-1 ,3,5-triazine. 3. Metal deactivators. for example N,N'-diphenyloxamide, N-salicylal-N'-salicyloyl hydrazine, N,N'-bis(salicyIoyl)hydrazine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1 ,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide, N,N'-bis(salicyl- oyl)oxalyi dihydrazide, N,N'-bis(saIicyloyl)thiopropionyI dihydrazide.
4. Phosphites and phosphonites. for example triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-di- cumylphenyI)pentaerythritol diphosphite, bis(2,6-di-tert-butyI-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, tristea- ryl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphonite, 6- isooctyIoxy-2,4,8, 10-tetra-tert-butyl-12H-dibenz[d,g]-1 ,3,2-dioxaphosphocin, 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, 2,2',2"-nitrilo- [triethyltris(3,3',5,5'-tetra-tert-butyl-1 ,1'-biphenyl-2,2'-diyl)phosphite], 2-ethylhexyl(3,3',5,5'-te- tra-tert-butyl-1 , 1 '-biphenyl-2,2'-diyl)phosphite, 5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)- 1 ,3,2-dioxaphosphirane.
The following phosphites are especially preferred:
Tris(2,4-di-tert-butylphenyl) phosphite (lrgafos®168, Ciba-Geigy), tris(nonylphenyl) phosphite,
5. Hvdroxylamines. for example N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N- dioctylhydroxylamine, N,N-dilauryIhydroxylamine, N,N-ditetradecylhydroxylamine, N,N- dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydrox- ylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-diaIkylhydroxylamine derived from hydrogenated tallow amine. 6. Nitrones. for example N-benzyl-alpha-phenylnitrone, N-ethyl-alpha-methylnitrone, N-octyl- alpha-heptylnitrone, N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnitrone, N- hexadecyl-alpha-pentadecylnitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-al- pha-heptadecylnitrone, N-ocatadecyl-alpha-pentadecylnitrone, N-heptadecyl-alpha-hepta- decylnitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,N-dialkylhydroxyl- amine derived from hydrogenated tallow amine.
7. Thiosvnerqists, for example dilauryl thiodipropionate or distearyl thiodipropionate.
8. Peroxide scavengers, for example esters of β-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercapto- benzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(β- dodecylmercapto)propionate.
9. Polyamide stabilisers, for example copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
10. Basic co-stabilisers, 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.
11. Nucleating agents, for example inorganic substances, such as talcum, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals; organic compounds, such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, such as ionic copolymers (ionomers). Especially preferred are 1,3:2,4-bis(3',4'-dimethylbenzylidene)sorbitol, 1,3:2,4-di(paramethyl- dibenzylidene)sorbitol, and 1,3:2,4-di(benzylidene)sorbitol.
12. Fillers and reinforcing agents, for example calcium carbonate, silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, car¬ bon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers. 13. Other additives, for example plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents.
14. Benzofuranones and indolinones. for example those disclosed in U.S. 4,325,863; U.S. 4,338,244; U.S. 5,175,312; U.S. 5,216,052; U.S. 5,252,643; DE-A-4316611 ; DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102 or 3-[4-(2-acetoxyethoxy)- phenyl]-5,7-di-tert-butylbenzofuran-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-butylbenzo- furan-2-one, 3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(2,3-dimethylphe- nyl)-5,7-di-tert-butylbenzofuran-2-one.
The weight ratio of the total amount of components (A) and (B) to the total amount of the conventional additives can be, for example, 100:1 to 1 :100 or 10:1 to 1 :10.
The examples below illustrate the invention in greater detail. All percentages and parts are by weight, unless stated otherwise.
Light stabilizers used in the following Examples 1 and 2: TINUVIN 622 (RTM
Mixture (A-2 :
Mixture of the compounds (A-2-a) and (A-2-b) in a weight ratio of 4:1
Compound (B-1 -a-1):
TINUVIN 770 (RTM):
TINUVIN 765 (RTM):
TINUVIN 123 (RTM):
TINUVIN 144 (RTM):
ADK STAB LA 52 (RTM):
ADK STAB LA 57 (RTM):
ADK STAB LA 62 (RTM):
in which two of the radicals E7 are -COO-Cι3H2 and
two of the radicals E7 are co° CH,
ADK STAB LA 67 (RTM):
in which two of the radicals E7 are -COO-Cι3H27 and
two of the radicals E7 are H
HOSTAVIN N 20 (RTM):
SANDUVOR 3050 (RTM):
HOSTAVIN N 24 (RTM):
UVINUL 4049 H (RTM):
Compound (B-6-a-1 ):
Compound (B-6-a-2):
SANDUVOR PR 31 (RTM):
GOODRITE UV 3034 (RTM):
GOODRITE UV 3150 (RTM):
Compound (B-10-a-1):
Compound (B-7-1):
in which E19, E20 and E21 are the group
Example 1 : Light stabilization of polypropylene homopolymer films. 100 parts of unstabilized polypropylene powder (melt flow index: 2.4 g/10 minutes at 230°C and 2160 g) are homogenized at 200°C for 10 minutes in a Brabender plastograph with 0.05 parts of pentaerythrityl-tetrakis{3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate}, 0.05 parts of tris{2,4-di-tert-butylphenyl} phosphite, 0.1 parts of Ca stearate, 0.25 parts of titanium dioxide (anatase) and the stabilizer system indicated Table 1. The material thus obtained is compression molded in a laboratory press between two aluminum foils for 6 minutes at 260°C to a 0.5 mm thick film which is cooled immediately to room temperature in a water- cooled press. Samples of 60 mm x 25 mm are cut out of these 0.5 mm films and are exposed in a WEATHER-OMETER Ci 65 (black panel temperature 63±2°C, without water- spraying).
Periodically, these samples are removed from the exposure apparatus and their carbonyl content is measured with an infrared spectrophotometer.
The exposure time (To. corresponding to the formation of a carbonyl absorbance of 0.1 is a measure for the efficiency of the light stabilizer system. The values obtained are summarized in Table 1. High T0.ι values are desired.
Table 1 :
*)The overall concentration of the light stabilizers is 0.15 %. Example 2: Light stabilization of polypropylene homopolymer films. 100 parts of unstabilized polypropylene powder (melt flow index: 3.8 g/10 minutes at 230°C and 2160 g) are homogenized at 200°C for 10 minutes in a Brabender plastograph with 0.05 parts of pentaerythrityl {tetrakis-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate}, 0.05 parts of tris{2,4-di-tert-butylphenyl)phosphite}, 0.1 parts of Ca stearate, 0.25 parts of titanium dioxide (anatase) and the stabilizer system indicated in Tables 2A to 2H. The material thus obtained is compression molded in a laboratory press between two aluminum foils for 6 minutes at 260°C to a 0.5 mm thick film which is cooled immediately to room temperature in a water-cooled press. Samples of 60 mm x 25 mm are cut out of these 0.5 mm films and are exposed in a WEATHER-OMETER Ci 65 (black panel temperature 63+2°C, without water- spraying).
Periodically, these samples are removed from the exposure apparatus and their carbonyl content is measured with an infrared spectrophotometer.
The exposure time (T0.ι) corresponding to the formation of a carbonyl absorbance of 0.1 is a measure for the efficiency of the light stabilizer system. The values obtained are summarized in the following tables. High T0.ι values are desired.
Table 2A:
*)The overall concentration of the light stabilizers is 0.20 %.
Table 2B:
Table 2C:
Table 2D:
Table 2E:
*)The overall concentration of the light stabilizers is 0.20 %.
Table 2F:
Table 2G:
Table 2H:

Claims (17)

Claims:
1. A stabilizer mixture containing the components (A) and (B) wherein component (A) is a compound of the formula (A-1)
wherein
Ai is hydrogen or C C4aIkyl,
A2 is a direct bond or Cι-Cι0alkylene, and n! is a number from 2 to 50;
at least one compound of the formulae (A-2-a) and (A-2-b)
wherein n2 and n2 * are a number from 2 to 50;
a compound of the formula (A-3)
(A-3) wherein
A3 and A4 independently of one another are hydrogen or CrC8alkyl, or A3 and A4 together form a C2-Cι4alkylene group, and the variables n3 independently of one another are a number from 1 to 50; or
a compound of the formula (A-4)
wherein n4 is a number from 2 to 50,
A5 is hydrogen or Cι-C4alkyl, the radicals A6 and A7 independently of one another are C C4alkyl or a group of the formula
(a-l)
wherein A8 is hydrogen, CrC8alkyl, O", -OH, -CH2CN, C C 8alkoxy, C5-Cι2cycloalkoxy, C3-C6alkenyl, C7-C9phenylalkyl unsubstituted or substituted on the phenyl by 1 , 2 or 3 CrC alkyl; or Cι-C8acyl, with the proviso that at least 50 % of the radicals A7 are a group of the formula (a-l); and component (B) is formed by two different low molecular weight sterically hindered amine compounds containing a group of the formula (I) or (II);
with the proviso that components (A) and (B) are different.
2. A stabilizer mixture according to claim 1 wherein the two different compounds of component (B) are selected from the group consisting of the classes β-1) a compound of the formula (B-1)
in which
Ei is hydrogen, C C8alkyl, O', -OH, -CH2CN, CrCι8aIkoxy, C5-Cι2cycloalkoxy, C3-C6alkenyl,
C7-C9phenylalkyl unsubstituted or substituted on the phenyl by 1 , 2 or 3 C C4alkyl; or
Cι-C8acyl, if mi is 1 , E2 is C Caalkyl, if mi is 2, E2 is C^C^alkylene or a group of the formula (b-l)
wherein E3 is CrCι0alkyl or C2-Cι0alkenyl, E4 is C C10alkylene, and E5 and E6 independently of one another are CrC4alkyl, cyclohexyl or methylcyclohexyl, and if mi is 4, E2 is C4-C-|0alkanetetrayl;
β-2) a compound of the formula (B-2)
H2C CH CH CH2 (B-2)
E7 E7 E7 E7
in which two of the radicals E7 are -COO-(CrC20alkyl), and two of the radicals E7 are a group of the formula (b-ll)
with E8 having one of the meanings of Ei
β-3) a compound of the formula (B-3)
in which
E9 and E10 together form C2-C 4alkylene,
En is hydrogen or a group -ZrCOO-Z2,
Z1 is C -C14alkylene, and
Z2 is C C24alkyl, and
Eι2 has one of the meanings of Ei;
β-4) a compound of the formula (B-4) wherein the radicals E13 independently of one another have one of the meanings of E^ the radicals Eι4 independently of one another are hydrogen or CrCaalkyl, and Ei5 is CrCioalkylene or C3-C10alkylidene;
β-5) a compound of the formula (B-5)
wherein the radicals Eι6 independently of one another have one of the meanings of Ei;
β-6) a compound of the formula (B-6)
in which
Eι7 is C C24alkyl, and
E18 has one of the meanings of Ei;
β-7) a compound of the formula (B-7) in which
Eig, E20 and E2ι independently of one another are a group of the formula (b-lll)
wherein E22 has one of the meanings of E^
β-8) a compound of the formula (B-8)
wherein the radicals E23 independently of one another have one of the meanings of E^ and E24 is hydrogen, C Cι2alkyl or C C12alkoxy;
β-9) a compound of the formula (B-9)
wherein m2 is 1 , 2 or 3,
E25 has one of the meanings of Ei, and
when m2 is 1 , E26 is a group — C^CH^ H-^ ,
when m2 is 2, E26 is C2-C22alkylene, and when m2 is 3, E26 is a group of the formula (b-IV)
wherein the radicals E27 independently of one another are C2-C alkylene, and the radicals E28 independently of one another are Cι-Cι2alkyl or C5-Cι2cycloalkyl;
β-10) a compound of the formula (B-10)
wherein the radicals E2g independently of one another have one of the meanings of Ei, and
E30 is C2-C22alkylene, C5-C7cycloalkylene, C C4alkylenedi(C5-C7cycloalkylene), phenyiene or phenylenedi(CrC4alkylene); or β-11) a compound of the formula (B-11)
in which
E3 is C Cι0alkyl, C5-C 2cycloalkyl, CrC alkyl-substituted C5-C12cycloalkyl, phenyl or
CrCι0alkyl-substituted phenyl,
E32 is C3-Cιoalkylene,
E33 has one of the meanings of Ei, and m is a number from 2 to 6.
3. A stabilizer mixture according to claim 1 wherein
A1 is hydrogen or methyl,
A2 is a direct bond or C2-C6alkylene, and n1 is a number from 2 to 25; n2 and n2 * are a number from 2 to 25;
A3 and A4 independently of one another are hydrogen or C C4alkyl, or A3 and A together form a C9-C13alkylene group, and the variables n3 independently of one another are a number from 1 to 25; n is a number from 2 to 25,
A5 and A6 independently of one another are CrC4alkyl, and
A7 is d-C4alkyl or a group of the formula (a-l) with the proviso that at least 50 % of the radicals A7 are a group of the formula (a-l).
4. A stabilizer mixture according to claim 2 wherein if mi is 1 , E2 is C12-C20alkyl, if mi is 2, E2 is C2-C10alkylene or a group of the formula (b-l)
E3 is C C4alkyl,
E4 is C C6alkylene, and
E5 and E6 independently of one another are CrC alkyl, and if mi is 4, E2 is C4-C8alkanetetrayl; two of the radicals E7 are -COO-(Cι0-Cι5alkyl), and two of the radicals E7 are a group of the formula (b-ll);
E9 and E 0 together form C9-C13alkylene,
En is hydrogen or a group -ZrCOO-Z2,
Zi is C2-C6alkylene, and
Z2 is C10-Cι6alkyl;
EM is hydrogen, and
E15 is C2-C6alkylene or C3-C5alkylidene;
Ei7 is C10-Cι4alkyl;
E24 is CrC4alkoxy; m2 is 1 , 2 or 3,
when m2 is 1 , E26 is a group — when m2 is 2, E26 is C2-C6alkylene, and when m2 is 3, E26 is a group of the formula (b-IV) the radicals E27 independently of one another are C2-C6alkylene, and the radicals E28 independently of one another are C C alkyl or C5-C8cycloalkyl;
E30 is C2-C8alkylene; and
E3ι is CrC4alkyl,
E32 is C3-C6alkylene, and m3 is a number from 2 to 6.
5. A stabilizer mixture according to claim 1 wherein component (A) is a compound of the formula (A-1 -a), (A-2-a), (A-2-b), (A-3-a) or (A-4-a);
wherein ni is a number from 2 to 20;
wherein n2 and n2* are a number from 2 to 20;
(A-3-a) wherein the variables n3 independently of one another are a number from 1 to 20; (A-4-a)
wherein n4 is a number from 2 to 20, and at least 50 % of the radicals A7 are a group of the formula (a-l)
wherein A8 is hydrogen, C C8alkyl, O', -OH, -CH2CN, CrC18alkoxy, C5-C12cycloalkoxy, C3-C6alkenyl, C7-C9phenylalkyl unsubstituted or substituted on the phenyl by 1 , 2 or 3 C C4alkyI; or CrC8acyl, and the remaining radicals A7 are ethyl; and
component (B) is formed by two different compounds selected from the group consisting of compounds of the formulae (B-1 -a), (B-1-b), (B-1-c), (B-1-d), (B-2-a), (B-3-a), (B-3-b), (B-4-a), (B-4-b), (B-5), (B-6-a), (B-7), (B-8-a), (B-9-a), (B-9-b), (B-9-c), (B-10-a) and (B-11 -a);
wherein Ei is hydrogen, CrC8alkyl, O\ -OH, -CH2CN, CrC18alkoxy, C5-Cι2cycloaIkoxy, C3-C6alkenyl, C7-C9phenylalkyl unsubstituted or substituted on the phenyl by 1 , 2 or 3 CrC alkyl; or C C8acyl;
H2C — CH CH CH, (B-2-a)
in which two of the radicals E7 are -COO-C13H2 and
two of the radicals E7 are ■COO E8 and E8 has one of the meanings of E,; wherein Eι2 has one of the meanings of Ei;
wherein E13 has one of the meanings of E^
H-C CH,
wherein Ei6 has one of the meanings of E1; wherein E18 has one of the meanings of Ei;
in which Eι9, E20 and E21 independently, of one another are a group of the formula (b-lll)
wherein E22 has one of the meanings of Eι;
wherein E23 has one of the meanings of En
wherein E25 has one of the meanings of E^
wherein E29 has one of the meanings of Ei;
wherein m3 is a number from 2 to 6 and E33 has one of the meanings of E-\.
6. A stabilizer mixture according to claim 1 wherein A8 is hydrogen, C C4alkyl, CrCι0alkoxy, cyclohexyloxy, allyl, benzyl or acetyl.
7. A stabilizer mixture according to claim 2 wherein Ei, E8l E12) E13, E 6, E18, E22, E23, E25, E2g and E33 are hydrogen, CrC4alkyl, CrCι0alkoxy, cyclohexyloxy, allyl, benzyl or acetyl.
8. A stabilizer mixture according to claim 5 wherein As, E1 ( E8, E12l E13, E16, E 8, E22, E23, E25, E2g and E33 are hydrogen or methyl and Ei additionally is C C8alkoxy.
9. A stabilizer mixture according to claim 5 wherein one of the two different compounds forming component (B) is a compound of the formula (B-1-b) with E1 being hydrogen.
10. A stabilizer mixture according to claim 5 wherein component (A) is a compound of the formula (A-1 -a) with ni being a number from 2 to 20 or a compound of the formula (A-2-a) or (A-2-b) wherein n2 and n2 * are a number from 2 to 20; and one of the two different compounds forming component (B) is a compound of the formula
(B-1-b) with E-\ being hydrogen.
11. A stabilizer mixture according to claim 5 wherein component (A) is a compound of the formula (A-1 -a) with ni being a number from 2 to 20 or a compound of the formula (A-2-a) or (A-2-b) wherein n2 and n2 * are a number from 2 to 20; one of the two different compounds forming component (B) is a compound of the formula (B-1 -b) with Ei being hydrogen; and the other of the two different compounds forming component (B) is a compound of the formula (B-1 -a) with Ei being hydrogen, (B-1-b) with Ei being methyl, (B-1-d) with Ei being hydrogen or methyl, (B-3-a) with E12 being hydrogen, (B-3-b) with Ei2 being hydrogen, (B-4-b) with E13 being hydrogen, (B-5) with E16 being hydrogen, (B-6-a) with E18 being hydrogen or methyl, (B-8-a) with E23 being methyl, (B-9-c) with E25 being hydrogen or methyl, (B-10-a) with E29 being hydrogen, or (B-11 -a) with E33 being hydrogen.
12. A stabilizer mixture according to claim 5 wherein component (A) is a compound of the formula (A-1 -a) with ni being a number from 2 to 20, component (B) is a compound of the formula (B-1-b) wherein Ei is hydrogen, and component (C) is a compound of the formula (B-1-b) wherein Ei is octyloxy; or
component (A) is a compound of the formula (A-1 -a) with ni being a number from 2 to 20, component (B) is a compound of the formula (B-1-b) wherein E^ is hydrogen, and component (C) is a compound of the formula (B-3-a) wherein Eι2 is hydrogen; or
component (A) is a compound of the formula (A-1 -a) with ni being a number from 2 to 20, component (B) is a compound of the formula (B-1-b) wherein Ei is hydrogen, and component (C) is a compound of the formula (B-1-d) wherein Ei is hydrogen; or
component (A) is a compound of the formula (A-1 -a) with ni being a number from 2 to 20, component (B) is a compound of the formula (B-1-b) wherein E1 is hydrogen, and component (C) is a compound of the formula (B-1 -a) wherein Ei is hydrogen; or
component (A) is a compound of the formula (A-1 -a) with n^ being a number from 2 to 20, component (B) is a compound of the formula (B-1-b) wherein Ei is methyl, and component (C) is a compound of the formula (B-1-d) wherein Ei is methyl.
13. A composition comprising an organic material subject to degradation induced by light, heat or oxidation and a stabilizer mixture according to claim 1.
14. A composition according to claim 13 wherein the organic material is a synthetic polymer.
15. A composition according to claim 13 wherein the organic material is a polyolefin.
16. A composition according to claim 13 wherein the organic material is polyethylene, polypropylene, a polyethylene copolymer or a polypropylene copolymer.
17. A method for stabilizing an organic material against degradation induced by light, heat or oxidation, which comprises incorporating into the organic material a stabilizer mixture according to claim 1.
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