Stabilizer mixtures Number:6,828,364 from the United States Patent and Trademark Office (PTO) owispatent A stabilizer mixture containing (I) two different sterically hindered amine compounds, and (II) at least one compound selected from the group consisting of an organic salt of Zn, an inorganic salt of Zn, Zn oxide, Zn hydroxide, an organic salt of Mg, an inorganic salt of Mg, Mg oxide and Mg hydroxide.<H Stabilizer, mixtures, Stabilizer, mixt, 6828364.html, Patent, pto, 6828364

Title: Stabilizer mixtures

Abstract: A stabilizer mixture containing (I) two different sterically hindered amine compounds, and (II) at least one compound selected from the group consisting of an organic salt of Zn, an inorganic salt of Zn, Zn oxide, Zn hydroxide, an organic salt of Mg, an inorganic salt of Mg, Mg oxide and Mg hydroxide.

Patent Number: 6,828,364 Issued on 12/07/2004 to Gugumus

Inventors: Gugumus; Fran.cedilla.ois (Allschwil, CH)
Assignee: Ciba Specialty Chemicals Corporation (Tarrytown, NY)

Appl. No.: 899438

Filed: July 5, 2001

Foreign Application Priority Data


Jul 14, 2000 [EP]			00810621

Current U.S. Class: 524/95 ; 252/182.13; 252/183.12; 524/100; 524/102; 524/103

Field of Search: 524/100,95,102,103 252/183.12,182.13

References Cited [Referenced By]

U.S. Patent Documents


4929652	May 1990	Gugumus
4965301	October 1990	Leininger
5025051	June 1991	Sato et al.
5037870	August 1991	Gugumus
5679733	October 1997	Malik et al.
5919399	July 1999	Gugumus
5977221	November 1999	Gugumus
5980783	November 1999	Gugumus
6013703	January 2000	Kuhn et al.
6020406	February 2000	Gugumus
6328912	December 2001	Gugumus
6365651	April 2002	Gugumus
6368520	April 2002	Gugumus
6512029	January 2003	Gugumus
6545071	April 2003	Gugumus
6566427	May 2003	Gugumus

Foreign Patent Documents


2169124	Aug., 1996	CA
19545896	Jun., 1996	DE
0276923	Aug., 1988	EP
0429731	Jun., 1991	EP
0468923	Jan., 1992	EP
0476612	Mar., 1992	EP
0661341	Jul., 1995	EP
0690094	Jan., 1996	EP
0290388	Dec., 1997	EP
1078929	Feb., 2001	EP
2293827	Apr., 1996	GB
2316409	Feb., 1998	GB
2316410	Feb., 1998	GB
2332677	Jun., 1999	GB
2332678	Jun., 1999	GB
2354245	Mar., 2001	GB
95/25767	Sep., 1995	WO
00/11065	Mar., 2000	WO
01/92393	Dec., 2001	WO

Other References

English Abstract for EP1078929 (2001). .
Data Sheet of .RTM.Tinuvin 783, Synergistic Mixture of Oligomeric Hindered Amine Stabilizers, Ciba Specialty Chemicals Corp., (1994). .
Chem. Abstr. 132:33557 5t for JP 136272 (2000). .
2244 Research Disclosure, No. 345, (1993), 34549, pp. 32-34. .
Chem. Abstr. 106:197407z for JP 61255953 (1986). .
Derwent Abstr. 96-278994/29 for DE 19545896 (1996). .
Chem. Abstr. 125:116779q for DE 19545896 (1996)..

Primary Examiner: Toomer; Cephia D.
Attorney, Agent or Firm: Stevenson; Tyler A.

Claims

What is claimed is:

1. A stabilizer mixture containing (I) two different sterically hindered amine compounds selected from the group consisting of the classes,

(.beta.-1) a compound of the formula (B-1): ##STR87##

in which R.sub.1, R.sub.3, R.sub.4 and R.sub.5 independently of one another are hydrogen, C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.12 cycloalkyl, C.sub.1 -C.sub.4 -alkyl-substituted C.sub.5 -C.sub.12 cycloalkyl, phenyl, phenyl which is substituted by --OH and/or C.sub.1 -C.sub.10 alkyl; C.sub.7 -C.sub.9 phenylalkyl, C.sub.7 -C.sub.9 phenylalkyl which is substituted on the phenyl radical by --OH and/or C.sub.1 -C.sub.10 alkyl; or a group of the formula (b-I): ##STR88## R.sub.2 is C.sub.2 -C.sub.18 alkylene, C.sub.5 -C.sub.7 cycloalkylene or C.sub.1 -C.sub.4 alkylenedi(B5-C.sub.7 cycloalkylene), or the radicals R.sub.1, R.sub.2 and R.sub.3, together with the nitrogen atoms to which they are bonded, perform a 5- to 10-membered heterocyclic ring, or R.sub.4 and R.sub.5, together with the nitrogen atom to which they are bonded, form a 5- to 10-membered heterocyclic ring, R.sub.6 is hydrogen, C.sub.1 -C.sub.8 alkyl, O, --OH, --CH.sub.2 CN, C.sub.1 -C.sub.18 alkoxy, C.sub.5 -C.sub.12 cycloalkoxy, C.sub.3 -C.sub.6 alkenyl, C.sub.7 -C.sub.9 phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C.sub.1 -C.sub.4 alkyl; or C.sub.1 -C.sub.8 acyl, and b.sub.1 is a number from 2 to 50, with the proviso that at least one of the radicals R.sub.1, R.sub.3, R.sub.4 and R.sub.5 is a group of the formula (b-I):

(.beta.-2) a compound of the formula (B-2): ##STR89##

wherein R.sub.7 and R.sub.11 independently of one another are hydrogen or C.sub.1 -C.sub.12 alkyl, R.sub.8, R.sub.9 and R.sub.10 independently of one another are C.sub.2 -C.sub.10 alkylene, and X.sub.1, X.sub.2, X.sub.3, X.sub.4, X.sub.5, X.sub.6, X.sub.7 and X.sub.8 independently of one another are a group of the formula (b-II): ##STR90## in which R.sub.12 is hydrogen, C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.12 cycloalkyl, C.sub.1 -C.sub.4 alkyl-substituted C.sub.5 -C.sub.12 cycloalkyl, phenyl, --OH-- and/or C.sub.1 -C.sub.10 alkyl-substituted phenyl, C.sub.7 -C.sub.9 phenylalkyl, C.sub.7 -C.sub.9 phenylalkyl which is substituted on the phenyl radical by --OH and/or C.sub.1 -C.sub.10 alkyl; or a group of the formula (b-I) as defined above, and R.sub.13 has one of the meanings of R.sub.6 ; (.beta.-6) a product (B-6) obtainable by reacting a product, obtained by reaction of a polyamine of the formula (B-6-1) with cyanuric chloride, with a compound of the formula (B-6-2):

##STR91##

in which b.sub.5 ', b.sub.5 " and b.sub.5 '" independently of one another are a number from 2 to 12, R.sub.31 is hydrogen, C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.12 cycloalkyl, phenyl or C.sub.7 -C.sub.9 phenylalkyl, and R.sub.32 has one of the meanings of R.sub.6 ; (.beta.-7) a compound of the formula (B-7): ##STR92## wherein A.sub.1 is hydrogen or C.sub.1 -C.sub.4 alkyl, A.sub.2 is a direct bond or C.sub.1 -C.sub.10 alkylene, and n.sub.1 is a number from 2 to 50; and (.beta.-8) at least one compound of the formulae (B-8-a) or (B-8-b): ##STR93## wherein n.sub.2 and n.sub.2 * are a number from 2 to 50; and (II) at least one compound selected from the group consisting of an organic salt of Zn, an inorganic salt of Zn, Zn oxide, Zn hydroxide, an organic salt of Mg, an inorganic salt of Mg, Mg oxide and Mg hydroxide; with the proviso that component (I) is different from the combination of the compounds (B-8-a) and (B-8-b): ##STR94## wherein n.sub.2 and n.sub.2 * are a number from 2 to 50; and with the proviso that, when component (I) is the combination of the compounds (B-1-a-1) and (B-7-a): ##STR95## wherein b.sub.1 is a number from 2 to 50, ##STR96## wherein n.sub.1 is a number from 2 to 50; and, at the same time, component (II) is a Zn carboxylate; the stabilizer mixture additionally contains as a further component (X-1) a pigment or (X-2) an UV absorber or (X-3) a pigment and an UV absorber.

2. A stabilizer mixture according to claim 1, wherein the product (B-6) is represented by a compound of the formula (B-6-.alpha.), (B-6-.beta.) or (B-6-.gamma.), or a mixture thereof: ##STR97##

wherein R.sub.31 and R.sub.32 are as defined in claim 1 and b.sub.5 is a number from 2 to 20.

3. A stabilizer mixture according to claim 1 wherein the class (.beta.-6) relates to a compound of the formula: ##STR98## with b.sub.5 being a number from 2 to 20.

4. A stabilizer mixture according to claim 1, wherein one of the two different sterically hindered amine compounds of component (I) is selected from the class (.beta.-1).

5. A stabilizer mixture according to claim 1, wherein one of the two different sterically hindered amine compounds of component (I) is selected from the class (.beta.-1), and the other of the two different sterically hindered amine compounds of component (I) is selected from the class (.beta.-7).

6. A stabilizer mixture according to claim 1, wherein one of the two different sterically hindered amine compounds of component (I) is selected from the class (.beta.-7), and the other of the two different sterically hindered amine compounds of component (I) is selected from the class (.beta.-2).

7. A stabilizer mixture according to claim 1, wherein the two different sterically hindered amine compounds of component (I) are selected from different classes.

8. A stabilizer mixture according to claim 1, wherein: R.sub.1 and R.sub.3 independently of one another are a group of the formula (b-I), R.sub.2 is C.sub.2 -C.sub.8 alkylene, R.sub.4 and R.sub.5 independently of one another are hydrogen, C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.8 cycloalkyl or a group of the formula (b-I), or the radicals R.sub.4 and R.sub.5, together with the nitrogen atom to which they are bonded, form a 5- to 10-membered heterocyclic ring, and b.sub.1 is a number from 2 to 25; R.sub.7 and R.sub.11 independently of one another are hydrogen or C.sub.1 -C.sub.4alkyl, R.sub.8, R.sub.9 and R.sub.10 independently of one another are C.sub.2 -C.sub.4 alkylene, and X.sub.1, X.sub.2, X.sub.3, X.sub.4, X.sub.5, X.sub.6, X.sub.7 and X.sub.8 independently of one another are a group of the formula (b-II), R.sub.12 is hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.5 -C.sub.8 cycloalkyl or a group of the formula (b-I); b.sub.5 ', b.sub.5 " and b.sub.5 '" independently of one another are a number from 2 to 4, and R.sub.31 is hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.5 -C.sub.8 cycloalkyl, phenyl or benzyl; A.sub.1 is hydrogen or methyl, A.sub.2 is a direct bond or C.sub.2 -C.sub.6 alkylene, and n.sub.1 is a number from 2 to 25; n.sub.2 and n.sub.2 * are a number from 2 to 25.

9. A stabilizer mixture according to claim 1, wherein the two different sterically hindered amine compounds of component (I) are selected from the group consisting of the compounds of the formulae (B-1-a), (B-1-b), (B-1-c), (B-1-d) and (B-2-a), a product (B-6-a) and the compounds of the formulae (B-7-a), (B-8-a) and (B-8-b): ##STR99## wherein b.sub.1 is a number from 2 to 20 and R.sub.6 is hydrogen, C.sub.1 -C.sub.8 alkyl, O, --OH, --CH.sub.2 CN, C.sub.1 -C.sub.18 alkoxy, C.sub.5 -C.sub.12 cycloalkoxy, C.sub.3 -C.sub.6 alkenyl, C.sub.7 -C.sub.9 phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C.sub.1 -C.sub.4 alkyl; or C.sub.1 -C.sub.8 acyl; ##STR100## wherein R.sub.13 has one of the meanings of R.sub.6, a product (B-6-a) obtainable by reacting a product, obtained by reaction of a polyamine of the formula (B-6-1-a) with cyanuric chloride, with a compound of the formula (B-6-2-a): ##STR101## in which R.sub.32 has one of the meanings of R.sub.6 ; ##STR102## wherein n.sub.1 is a number from 2 to 20 ##STR103## wherein n.sub.2 and n.sub.2 * are a number from 2 to 20.

10. A stabilizer mixture according to claim 9 wherein the two different sterically hindered amine compounds of component (I) are 1) a compound of the formula (B-1-a) wherein R.sub.6 is hydrogen, and a compound of the formula (B-7-a); or 2) a compound of the formula (B-2-a) wherein R.sub.13 is methyl, and a compound of the formula (B-7-a).

11. A stabilizer mixture according to claim 1 wherein R.sub.6, R.sub.13 and R.sub.32 are hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.10 alkoxy, cyclohexyloxy, allyl, benzyl or acetyl.

12. A stabilizer mixture according to claim 9 wherein R.sub.6, R.sub.13 and R.sub.32 are hydrogen or methyl and R.sub.6 additionally is C.sub.1 -C.sub.8 alkoxy.

13. A stabilizer mixture according to claim 1, wherein the compound of component (II) is selected from the group consisting of Mg carboxylates, Zn carboxylates, Mg oxides, Zn oxides, Mg hydroxides, Zn hydroxides, Mg carbonates and Zn carbonates.

14. A stabilizer mixture according to claim 1, which additionally contains as a further component (X-1) a pigment or (X-2) an UV absorber or (X-3) a pigment and an UV absorber.

15. A stabilizer mixture according to claim 1, which additionally contains as a further component (XX) an organic salt of Ca, an inorganic salt of Ca, Ca oxide or Ca hydroxide.

16. A composition comprising an organic material subject to degradation induced by light, heat or oxidation and a stabilizer mixture according to claim 1.

17. A composition according to claim 16 wherein the organic material is a synthetic polymer.

18. A composition according to claim 16 wherein the organic material is a polyolefin.

19. A composition according to claim 16 wherein the organic material is polyethylene, polypropylene, a polyethylene copolymer or a polypropylene copolymer.

20. Polypropylene containing a compound of the formula (B-1), a compound of the formula (B-7) and a Zn-carboxylate: ##STR104##

in which R.sub.1, R.sub.3, R.sub.4 and R.sub.5 independently of one another are hydrogen, C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.12 cycloalkyl, C.sub.1 -C.sub.4 -alkyl-substituted C.sub.5 -C.sub.12 cycloalkyl, phenyl, phenyl which is substituted by --OH and/or C.sub.1 -C.sub.10 alkyl; C.sub.7 -C.sub.9 phenylalkyl, C.sub.7 -C.sub.9 phenylalkyl which is substituted on the phenyl radical by --OH and/or C.sub.1 -C.sub.10 alkyl; or a group of the formula (b-I): ##STR105## R.sub.2 is C.sub.2 -C.sub.18 alkylene, C.sub.5 -C.sub.7 cycloalkylene or C.sub.1 -C.sub.4 alkylenedi(B.sub.5 --C.sub.7 cycloalkylene), or the radicals R.sub.1, R.sub.2 and R.sub.3, together with the nitrogen atoms to which they are bonded, perform a 5- to 10-membered heterocyclic ring, or R.sub.4 and R.sub.5, together with the nitrogen atom to which they are bonded, form a 5- to 10-membered heterocyclic ring, R.sub.6 is hydrogen, C.sub.1 -C.sub.8 alkyl, O, --OH, --CH.sub.2 CN, C.sub.1 -C.sub.18 alkoxy, C.sub.5 -C.sub.12 cycloalkoxy, C.sub.3 -C.sub.6 alkenyl, C.sub.7 -C.sub.9 phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C.sub.1 -C.sub.4 alkyl; or C.sub.1 -C.sub.8 acyl, and b.sub.1 is a number from 2 to 50, with the proviso that at least one of the radicals R.sub.1, R.sub.3, R.sub.4 and R.sub.5 is a group of the formula (b-I): ##STR106## wherein A.sub.1 is hydrogen or C.sub.1 -C.sub.4 alkyl, A.sub.2 is a direct bond or C.sub.1 -C.sub.10 alkylene, and n.sub.1 is a number from 2 to 50.

21. 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.

Description

The present invention relates to a stabilizer mixture containing two different sterically hindered amine compounds and at least one Mg- and/or Zn-compound, the use of this mixture for stabilizing an organic material, in particular a polyolefin, against degradation induced by light, heat or oxidation and the organic material thus stabilized. The stabilization of polyolefins is described in numerous publications, for example in U.S. Pat. Nos. 4,929,652, 5,025,051, 5,037,870, EP-A-276,923, EP-A-290,388, EP-A-429,731, EP-A-468,923, EP-A-661,341, EP-A-690,094, DE-A-19,545,896 (Derwent 96-278,994/29; Chemical Abstracts 125:116779q), WO-A-95/25,767, GB-A-2,293,827, Chemical Abstracts 106:197407z, GB-A-2,332,678, WO-A-00/11,065, GB-A-2,316,409, GB-A-2, 332,677, Chemical Abstracts 132: 335,575t and Research Disclosure 34,549.

In more detail, the present invention relates to a stabilizer mixture containing (I) two different sterically hindered amine compounds, and (II) at least one compound selected from the group consisting of an organic salt of Zn, an inorganic salt of Zn, Zn oxide, Zn hydroxide, an organic salt of Mg, an inorganic salt of Mg, Mg oxide and Mg hydroxide; with the proviso that component (I) is different from the combination of the compounds (B-8-a) and (B-8-b): ##STR1## wherein n.sub.2 and n.sub.2 * are a number from 2 to 50; and with the proviso that, when component (I) is the combination of the compounds (B-1-a-1) and (B-7-a): ##STR2## wherein b.sub.1 is a number from 2 to 50, ##STR3## wherein n.sub.1 is a number from 2 to 50; and, at the same time, component (II) is a Zn carboxylate; the stabilizer mixture additionally contains as a further component (X-1) a pigment or (X-2) an UV absorber or (X-3) a pigment and an UV absorber.

A preferred embodiment of the present invention relates to a stabilizer mixture containing as component (I) two different sterically hindered amine compounds wherein one sterically hindered amine compound is a compound of the formula (B-1-b) or (B-1-d): ##STR4## wherein b.sub.1 is a number from 2 to 20 and R.sub.6 is hydrogen, C.sub.1 -C.sub.8 alkyl, O.sup.-, --OH, --CH.sub.2 CN, C.sub.1 -C.sub.18 alkoxy, C.sub.5 -C.sub.12 cycloalkoxy, C.sub.3 -C.sub.6 alkenyl, C.sub.7 -C.sub.9 phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C.sub.1 -C.sub.4 alkyl; or C.sub.1 -C.sub.8 acyl; and the other sterically hindered amine compound is a compound of the formula (B-7-a) ##STR5## wherein n.sub.1 is a number from 2 to 20; and component (II) is an organic salt of Zn, an inorganic salt of Zn, Zn oxide or Zn hydroxide; preferably Zn carboxylate.

Preferably, a stabilizer mixture containing a compound of the class (.beta.-1) as defined below, a compound of the class (.beta.-7) as defined below and Zn-carboxylate, in particular an organic salt of Zn, is disclaimed.

According to a preferred embodiment of the present invention, component (II) is an organic salt of Mg, an inorganic salt of Mg, Mg oxide or Mg hydroxide, when component (I) is the combination of a compound of the class (.beta.-1) as defined below, and a compound of the class (.beta.-7) as defined below.

The stabilizer mixtures according to the present invention preferably do not contain a mineral oil.

The two different sterically hindered amine compounds of component (I) are preferably selected from the group consisting of the following classes (.alpha.-1) a compound of the formula (A-1): ##STR6##

in which E.sub.1 is hydrogen, C.sub.1 -C.sub.8 alkyl, O.sup.-, --OH, --CH.sub.2 CN, C.sub.1 -C.sub.18 alkoxy, C.sub.5 -C.sub.12 cycloalkoxy, C.sub.3 -C.sub.6 alkenyl, C.sub.7 -C.sub.9 phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C.sub.1 -C.sub.4 alkyl; or C.sub.1 -C.sub.8 acyl, m.sub.1 is 1, 2 or 4, if m.sub.1 is 1, E.sub.2 is C.sub.1 -C.sub.25 alkyl, if m.sub.1 is 2, E.sub.2 is C.sub.1 C.sub.14 alkylene or a group of the formula (a-I): ##STR7## wherein E.sub.3 is C.sub.1 -C.sub.10 alkyl or C.sub.2 -C.sub.10 alkenyl, E.sub.4 is C.sub.1 -C.sub.10 alkylene, and E.sub.5 and E.sub.6 independently of one another are C.sub.1 -C.sub.4 alkyl, cyclohexyl or methylcyclohexyl, and if m.sub.1 is 4, E.sub.2 is C.sub.4 -C.sub.10 alkanetetrayl; (.alpha.-2) a compound of the formula (A-2): ##STR8##

in which two of the radicals E.sub.7 are --COO--(C.sub.1 -C.sub.20 alkyl), and two of the radicals E.sub.7 are a group of the formula (a-II): ##STR9## with E.sub.8 having one of the meanings of E.sub.1 ; (.alpha.-3) a compound of the formula (A-3): ##STR10##

in which E.sub.9 and E.sub.10 together form C.sub.2 -C.sub.14 alkylene, E.sub.11 is hydrogen or a group --Z.sub.1 --COO--Z.sub.2, Z.sub.1 is C.sub.2 -C.sub.14 alkylene, and Z.sub.2 is C.sub.1 -C.sub.24 alkyl, and E.sub.12 has one of the meanings of E.sub.1 ; (.alpha.-4) a compound of the formula (A-4): ##STR11##

wherein the radicals E.sub.13 independently of one another have one of the meanings of E.sub.1, the radicals E.sub.14 independently of one another are hydrogen or C.sub.1 -C.sub.12 alkyl, and E.sub.15 is C.sub.1 -C.sub.10 alkylene or C.sub.3 -C.sub.10 alkylidene; (.alpha.-5) a compound of the formula (A-5): ##STR12##

wherein the radicals E.sub.16 independently of one another have one of the meanings of E.sub.1 ; (.alpha.-6) a compound of the formula (A-6): ##STR13##

in which E.sub.17 is C.sub.1 -C.sub.24 alkyl, and E.sub.18 has one of the meanings of E.sub.1 ; (.alpha.-7) a compound of the formula (A-7): ##STR14##

in which E.sub.19, E.sub.20 and E.sub.21 independently of one another are a group of the formula (a-IlI): ##STR15## wherein E.sub.22 has one of the meanings of E.sub.1 ; (.alpha.-8) a compound of the formula (A-8): ##STR16##

wherein the radicals E.sub.23 independently of one another have one of the meanings of E.sub.1, and E.sub.24 is hydrogen, C.sub.1 -C.sub.12 alkyl or C.sub.1 -C.sub.12 alkoxy; (.alpha.-9) a compound of the formula (A-9): ##STR17##

wherein m.sub.2 is 1, 2 or 3, E.sub.25 has one of the meanings of E.sub.1, and when m.sub.2 is 1, E.sub.26 is a group ##STR18## when m.sub.2 is 2, E.sub.26 is C.sub.2 -C.sub.22 alkylene, and when m.sub.2 is 3, E.sub.26 is a group of the formula (a-IV): ##STR19## wherein the radicals E.sub.27 independently of one another are C.sub.2 -C.sub.12 alkylene, and the radicals E.sub.28 independently of one another are C.sub.1 -C.sub.12 alkyl or C.sub.5 -C.sub.12 cycloalkyl; (.alpha.-10) a compound of the formula (A-10): ##STR20##

wherein the radicals E.sub.29 independently of one another have one of the meanings of E.sub.1, and E.sub.30 is C.sub.2 -C.sub.22 alkylene, C.sub.5 -C.sub.7 cycloalkylene, C.sub.1 -C.sub.4 alkylenedi(C.sub.5 -C.sub.7 cycloalkylene), phenylene or phenylenedi(C.sub.1 -C.sub.4 alkylene); (.beta.-1) a compound of the formula (B-1): ##STR21##

in which R.sub.1, R.sub.3, R.sub.4 and R.sub.5 independently of one another are hydrogen, C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.12 cycloalkyl, C.sub.1 -C.sub.4 -alkyl-substituted C.sub.5 -C.sub.12 cycloalkyl, phenyl, phenyl which is substituted by --OH and/or C.sub.1 -C.sub.10 alkyl; C.sub.7 -C.sub.9 phenylalkyl, C.sub.7 -C.sub.9 phenylalkyl which is substituted on the phenyl radical by --OH and/or C.sub.1 -C.sub.10 alkyl; or a group of the formula (b-I): ##STR22## R.sub.2 is C.sub.2 -C.sub.18 alkylene, C.sub.5 -C.sub.7 cycloalkylene or C.sub.1 -C.sub.4 alkylenedi(B.sub.5 --C.sub.7 cycloalkylene), or the radicals R.sub.1, R.sub.2 and R.sub.3, together with the nitrogen atoms to which they are bonded, perform a 5- to 10-membered heterocyclic ring, or R.sub.4 and R.sub.5, together with the nitrogen atom to which they are bonded, form a 5- to 10-membered heterocyclic ring, R.sub.6 is hydrogen, C.sub.1 -C.sub.8 alkyl, O.sup.-, --OH, --CH.sub.2 CN, C.sub.1 -C.sub.18 alkoxy, C.sub.5 -C.sub.12 cycloalkoxy, C.sub.3 -C.sub.6 alkenyl, C.sub.7 -C.sub.9 phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C.sub.1 -C.sub.4 alkyl; or C.sub.1 -C.sub.8 acyl, and b.sub.1 is a number from 2 to 50, with the proviso that at least one of the radicals R.sub.1, R.sub.3, R.sub.4 and R.sub.5 is a group of the formula (b-I); (.beta.-2) a compound of the formula (B-2): ##STR23##

wherein R.sub.7 and R.sub.11 independently of one another are hydrogen or C.sub.1 -C.sub.12 alkyl, R.sub.8, R.sub.9 and R.sub.10 independently of one another are C.sub.2 -C.sub.10 alkylene, and X.sub.1, X.sub.2, X.sub.3, X.sub.4, X.sub.5, X.sub.6, X.sub.7 and X.sub.8 independently of one another are a group of the formula (b-II): ##STR24## in which R.sub.12 is hydrogen, C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.12 cycloalkyl, C.sub.1 -C.sub.4 alkyl-substituted C.sub.5 -C.sub.12 cycloalkyl, phenyl, --OH-- and/or C.sub.1 -C.sub.10 alkyl-substituted phenyl, C.sub.7 -C.sub.9 phenylalkyl, C.sub.7 -C.sub.9 phenylalkyl which is substituted on the phenyl radical by --OH and/or C.sub.1 -C.sub.10 alkyl; or a group of the formula (b-I) as defined above, and R.sub.13 has one of the meanings of R.sub.6 ; (.beta.-3) a compound of the formula (B-3): ##STR25##

in which R.sub.14 is C.sub.1 -C.sub.10 alkyl, C.sub.5 -C.sub.12 cycloalkyl, C.sub.1 -C.sub.4 alkyl-substituted C.sub.5 -C.sub.12 cycloalkyl, phenyl or C.sub.1 -C.sub.10 alkyl-substituted phenyl, R.sub.15 is C.sub.3 -C.sub.10 alkylene, R.sub.16 has one of the meanings of R.sub.6, and b.sub.2 is a number from 2 to 50; (.beta.-4) a compound of the formula (B-4): ##STR26##

in which R.sub.17 and R.sub.21 independently of one another are a direct bond or a --N(X.sub.9)--CO--X.sub.10 --CO--N(X.sub.11)-group, where X.sub.9 and X.sub.11 independently of one another are hydrogen, C.sub.1 -C.sub.8 alkyl, C.sub.5 -C.sub.12 cycloalkyl, phenyl, C.sub.7 -C.sub.9 phenylalkyl or a group of the formula (b-I), X.sub.10 is a direct bond or C.sub.1 -C.sub.4 alkylene, R.sub.18 has one of the meanings of R.sub.6, R.sub.19, R.sub.20, R.sub.23 and R.sub.24 independently of one another are hydrogen, C.sub.1 -C.sub.30 alkyl, C.sub.5 -C.sub.12 cycloalkyl or phenyl, R.sub.22 is hydrogen, C.sub.1 -C.sub.30 alkyl, C.sub.5 -C.sub.12 cycloalkyl, phenyl, C.sub.7 -C.sub.9 phenylalkyl or a group of the formula (b-I), and b.sub.3 is a number from 1 to 50; (.beta.-5) a compound of the formula (B-5): ##STR27##

in which R.sub.25, R.sub.26, R.sub.27, R.sub.28 and R.sub.29 independently of one another are a direct bond or C.sub.1 -C.sub.10 alkylene, R.sub.30 has one of the meanings of R.sub.6, and b.sub.4 is a number from 1 to 50; (.beta.-6) a product (B-6) obtainable by reacting a product, obtained by reaction of a polyamine of the formula (B-6-1) with cyanuric chloride, with a compound of the formula (B-6-2):

##STR28##

in which b.sub.5 ', b.sub.5 " and b.sub.5 '" independently of one another are a number from 2 to 12, R.sub.31 is hydrogen, C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.12 cycloalkyl, phenyl or C.sub.7 -C.sub.9 phenylalkyl, and R.sub.32 has one of the meanings of R.sub.6 ; (.beta.-7) a compound of the formula (B-7): ##STR29## wherein A.sub.1 is hydrogen or C.sub.1 -C.sub.4 alkyl, A.sub.2 is a direct bond or C.sub.1 -C.sub.10 alkylene, and n.sub.1 is a number from 2 to 50; (.beta.-8) at least one compound of the formulae (B-8-a) and (B-8-b): ##STR30## ##STR31##

wherein n.sub.2 and n.sub.2 * are a number from 2 to 50; (.beta.-9) a compound of the formula (B-9): ##STR32## wherein A.sub.3 and A.sub.4 independently of one another are hydrogen or C.sub.1 -C.sub.8 alkyl, or A.sub.3 and A.sub.4 together form a C.sub.2 -C.sub.14 alkylene group, and the variables n.sub.3 independently of one another are a number from 1 to 50; and (.beta.-10) a compound of the formula (B-10): ##STR33## wherein n.sub.4 is a number from 2 to 50, A.sub.5 is hydrogen or C.sub.1 -C.sub.4 alkyl, the radicals A.sub.6 and A.sub.7 independently of one another are C.sub.1 -C.sub.4 alkyl or a group of the formula (b-I), with the proviso that at least 50% of the radicals A.sub.7 are a group of the formula (b-I).

Examples of component (I) are: A compound selected from the class .alpha.-1 and a compound selected from the class .alpha.-3, .alpha.-5, .alpha.-6, .alpha.-7, .alpha.-9, .alpha.-10, .beta.-1, .beta.-2, .beta.-3, .beta.-4, .beta.-5, .beta.-6, .beta.-7, .beta.-8 or .beta.-9. A compound selected from the class .alpha.-3 and a compound selected from the class .alpha.-5, .alpha.-6, .alpha.-7, .alpha.-9, .alpha.-10, .beta.-1, .beta.-2, .beta.-3, .beta.-4, .beta.-5, .beta.-6, .beta.-7, .beta.-8 or .beta.-9. A compound selected from the class .alpha.-5 and a compound selected from the class .alpha.-6, .alpha.-7, .alpha.-9, .alpha.-10, .beta.-1, .beta.-2, .beta.-3, .beta.-4, .beta.-5, .beta.-6, .beta.-7, .beta.-8 or .beta.-9. A compound selected from the class .alpha.-6 and a compound selected from the class .alpha.-9, .alpha.-10, .beta.-1, .beta.-2, .beta.-3, .beta.-4, .beta.-5, .beta.-6, .beta.-7, .beta.-8 or .beta.-9. A compound selected from the class .alpha.-7 and a compound selected from the class .alpha.-9, .alpha.-10, .beta.-1, .beta.-2, .beta.-3, .beta.-4, .beta.-5, .beta.-6, .beta.-7, .beta.-8 or .beta.-9. A compound selected from the class .alpha.-10 and a compound selected from the class .beta.-1, .beta.-2, .beta.-3, .beta.-4.beta.-5, .beta.-6, .beta.-7, .beta.-8 or .beta.-9. A compound selected from the class .beta.-1 and a compound selected from the class .beta.-2, .beta.-3, .beta.-4, .beta.-5, .beta.-6, .beta.-7, .beta.-8, .beta.-9 or .beta.-10. A compound selected from the class .beta.-2 and a compound selected from the class .beta.-3, .beta.-4, .beta.-5, .beta.-6, .beta.-7, .beta.-8, .beta.-9 or .beta.-10. A compound selected from the class .beta.-3 and a compound selected from the class .beta.-4, .beta.-5, .beta.-6, .beta.-7, .beta.-8, .beta.-9 or .beta.-10. A compound selected from the class .beta.-4 and a compound selected from the class .beta.-5, .beta.-6, .beta.-7, .beta.-8, .beta.-9 or .beta.-10. A compound selected from the class .beta.-5 and a compound selected from the class .beta.-6, .beta.-7, .beta.-8, .beta.-9 or .beta.-10. A compound selected from the class .beta.-6 and a compound selected from the class .beta.-7, .beta.-8, .beta.-9 or .beta.-10. A compound selected from the class .beta.-7 and a compound selected from the class .beta.-8, .beta.-9 or .beta.-10. A compound selected from the class .beta.-8 and a compound selected from the class .beta.-9 or .beta.-10. A compound selected from the class .beta.-9 and a compound selected from the class .beta.-10.

According to a preferred embodiment, the two different sterically hindered amine compounds of component (I) are selected from the group consisting of the classes (.alpha.-1), (.alpha.-2), (.alpha.-3), (.alpha.-4), (.alpha.-5), (.alpha.-6), (.alpha.-7), (.alpha.-8), (.alpha.-9) and (.alpha.-10).

According to a further preferred embodiment, the two different sterically hindered amine compounds of component (I) are selected from the group consisting of the classes (.beta.-1), (.beta.-2), (.beta.-3), (.beta.-4), (.beta.-5), (.beta.-6), (.beta.-7), (.beta.-8), (.beta.-9) and (.beta.-10).

According to another preferred embodiment, one of the two different sterically hindered amine compounds of component (I) is selected from the group consisting of the classes (.alpha.-1), (.alpha.-2), (.alpha.-3), (.alpha.-4), (.alpha.-5), (.alpha.-6), (.beta.-7), (.beta.-8), (.alpha.-9) and (.alpha.-10), and the other of the two different sterically hindered amine compounds of component (I) is selected from the group consisting of the classes (.beta.-1), (.beta.-2), (.beta.-3), (.beta.-4), (.beta.-5), (.beta.-6), (.beta.-7), (.beta.-8), (.beta.-9) and (.beta.-10).

One of the two different sterically hindered amine compounds of component (I) is preferably selected from the class (.beta.-1).

According to a particularly preferred embodiment, one of the two different sterically hindered amine compounds of component (I) is selected from the class (.beta.-1), and the other of the two different sterically hindered amine compounds of component (I) is selected from the class (.alpha.-1) or (.beta.-7).

According to another particularly preferred embodiment, one of the two different sterically hindered amine compounds of component (I) is selected from the class (.beta.-7), and the other of the two different sterically hindered amine compounds of component (I) is selected from the class (.beta.-2).

The two different sterically hindered amine compounds of component (I) are preferably selected from different classes.

Examples of alkyl having up to 30 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, docosyl and triacontyl. One of the preferred definitions of E.sub.1, E.sub.8, E.sub.12, E.sub.13, E.sub.16, E.sub.18, E.sub.22, E.sub.23, E.sub.25, E.sub.29, R.sub.6, R.sub.13, R.sub.16, R.sub.18, R.sub.30 and R.sub.32 is C.sub.1 -C.sub.4 alkyl, especially methyl. R.sub.31 is preferably butyl.

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 E.sub.1 is octoxy. E.sub.24 is preferably C.sub.1 -C.sub.4 alkoxy and one of the preferred meanings of R.sub.6 is propoxy.

Examples of C.sub.5 -C.sub.12 cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclododecyl. C.sub.5 -C.sub.8 Cycloalkyl, especially cyclohexyl, is preferred.

C.sub.1 -C.sub.4 Alkyl-substituted C.sub.5 -C.sub.12 cycloalkyl is for example methylcyclohexyl or dimethylcyclohexyl.

Examples of C.sub.5 -C.sub.12 cycloalkoxy are cyclopentoxy, cyclohexoxy, cycloheptoxy, cyclooctoxy, cyclodecyloxy and cyclododecyloxy. C.sub.5 -C.sub.8 Cycloalkoxy, in particular cyclopentoxy and cyclohexoxy, is preferred.

--OH-- and/or C.sub.1 -C.sub.10 alkyl-substituted phenyl is for example methylphenyl, dimethylphenyl, trimethylphenyl, tert-butylphenyl or 3,5-di-tert-butyl-4-hydroxyphenyl.

Examples of C.sub.7 -C.sub.9 phenylalkyl are benzyl and phenylethyl.

C.sub.7 -C.sub.9 Phenylalkyl which is substituted on the phenyl radical by --OH and/or by alkyl having up to 10 carbon atoms is for example methylbenzyl, dimethylbenzyl, trimethylbenzyl, tert-butylbenzyl or 3,5-di-tert-butyl-4-hydroxybenzyl.

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, methacryloyl and benzoyl. C.sub.1 -C.sub.8 Alkanoyl, C.sub.3 -C.sub.8 alkenyl 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.

An example of C.sub.3 -C.sub.10 alkylidene is the group ##STR34##

An example of C.sub.4 -C.sub.10 alkanetetrayl is 1,2,3,4-butanetetrayl.

An example of C.sub.5 -C.sub.7 cycloalkylene is cyclohexylene.

An example of C.sub.1 -C.sub.4 alkylenedi(C.sub.5 -C.sub.7 cycloalkylene) is methylenedicyclohexylene.

An example of phenylenedi(C.sub.1 -C.sub.4 alkylene) is methylene-phenylene-methylene or ethylene-phenylene-ethylene.

Where the radicals R.sub.1, R.sub.2 and R.sub.3, together with the nitrogen atoms to which they are attached, form a 5- to 10-membered heterocyclic ring, this ring is for example: ##STR35##

A 6-membered heterocyclic ring is preferred.

Where the radicals R.sub.4 and R.sub.5, together with the nitrogen atom to which they are attached, form a 5- to 10-membered heterocyclic ring, this ring is for example 1-pyrrolidyl, piperidino, morpholino, 1-piperazinyl, 4-methyl-1-piperazinyl, 1-hexahydroazepinyl, 5,5,7-trimethyl-1-homopiperazinyl or 4,5,5,7-tetramethyl-1-homopiperazinyl. Morpholino is particularly preferred.

One of the preferred definitions of R.sub.19 and R.sub.23 is phenyl.

R.sub.26 is preferably a direct bond.

n.sub.1, n.sub.2, n.sub.2 * and n.sub.4 are preferably a number from 2 to 25, in particular 2 to 20. n.sub.3 is preferably a number from 1 to 25, in particular 1 to 20.

b.sub.1 and b.sub.2 are preferably a number from 2 to 25, in particular 2 to 20.

b.sub.3 and b.sub.4 are preferably a number from 1 to 25, in particluar 1 to 20.

b.sub.5 ' and b.sub.5 '" are preferably 3 and b.sub.5 " is preferably 2.

The compounds described above as components (I) and (II) are essentially known and commercially available. All of them can be prepared by known processes.

The preparation of the compounds of component (I) is disclosed, for example, in U.S. Pat. Nos. 5,679,733, 3,640,928, 4,198,334, 5,204,473, 4,619,958, 4,110,306, 4,110,334, 4,689,416, 4,408,051, SU-A-768,175 (Derwent 88-138,751/20), U.S. Pat. Nos. 5,049,604, 4,769,457, 4,356,307, 4,619,956, 5,182,390, GB-A-2,269,819, U.S. Pat. Nos. 4,292,240, 5,026,849, 5,071,981, 4,547,538, 4,976,889, 4,086,204, 6,046,304, 4,331,586, 4,108,829, 5,051,458, WO-A-94/12,544 (Derwent 94-177,274/22), DD-A-262,439 (Derwent 89-122,983/17), U.S. Pat. Nos. 4,857,595, 4,529,760, 4,477,615, CAS 136,504-96-6, U.S. Pat. Nos. 4,233,412, 4,340,534, WO-A-98/51,690 and EP-A-1,803.

The product (B-6) can be prepared analogously to known processes, for example by reacting a polyamine of formula (B-6-1) with cyanuric chloride in a molar ratio of from 1:2 to 1:4 in the presence of anhydrous lithium carbonate, sodium carbonate or potassium carbonate in an organic solvent such as 1,2-dichloroethane, toluene, xylene, benzene, dioxane or tert-amyl alcohol temperature of from -20.degree. C. to +10.degree. C., preferably from -10.degree. C. to +10.degree. C., in particular from 0.degree. C. to +10.degree. C., for from 2 to 8 hours, followed by reaction of the resultant product with a 2,2,6,6-tetramethyl-4-piperidylamine of the formula (B-6-2). The molar ratio of the 2,2,6,6-tetramethyl-4-piperidylamine to polyamine of the formula (B-6-1) employed is for example from 4:1 to 8:1. The quantity of the 2,2,6,6-tetramethyl-4-piperidylamine can be added in one portion or in more than one portion at intervals of a few hours.

The molar ratio of polyamine of the formula (B-6-1) to cyanuric chloride to 2,2,6,6-tetramethyl-4-piperidylamine of the formula (B-6-2) is preferebly from 1:3:5 to 1:3:6.

The following example indicates one way of preparing a preferred product (B-6-a).

EXAMPLE

23.6 g (0.128 mol) of cyanuric chloride, 7.43 g (0.0426 mol) of N,N'-bis[3-aminopropyl]ethylenediamine and 18 g (0.13 mol) of anhydrous potassium carbonate are reacted at 5.degree. C. for 3 hours with stirring in 250 ml of 1,2-dichloroethane. The mixture is warmed at room temperature for a further 4 hours. 27.2 g (0.128 mol) of N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine are added and the resultant mixture is warmed at 60.degree. C. for 2 hours. A further 18 g (0.13 mol) of anhydrous potassium carbonate are added and the mixture is warmed at 60.degree. C. for a further 6 hours. The solvent is removed by distillation under a slight vacuum (200 mbar) and replaced by xylene. 18.2 g (0.085 mol) of N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine and 5.2 g (0.13 mol) of ground sodium hydroxide are added, the mixture is heated at reflux for 2 hours and, for a further 12 hours, the water formed during the reaction is removed by azeotropic distillation. The mixture is filtered. The solution is washed with water and dried over Na.sub.2 SO.sub.4. The solvent is evaporated and the residue is dried at 120-130.degree. C. in vacuo (0.1 mbar). The desired product is obtained as a colourless resin.

In general, the product (B-6) can, for example, be represented by a compound of the formula (B-6-.alpha.), (B-6-.beta.) or (B-6-.gamma.). It can also be in the form of a mixture of these three compounds: ##STR36##

A preferred meaning of the formula (B-6-.alpha.) is: ##STR37##

A preferred meaning of the formula (B-6-.beta.) is: ##STR38##

A preferred meaning of the formula (B-6-.gamma.) is: ##STR39##

In the above formulae (B-6-.alpha.) to (B-6-.gamma.), b.sub.5 is preferably 2 to 20, in particular 2 to 10.

The two different sterically hindered amine compounds of component (I) are preferably selected from the group consisting of the following commercial products:

DASTIB 845 (RTM), TINUVIN 770 (RTM), TINUVIN 765 (RTM), TlNUVIN 144 (RTM), TINUVIN 123 (RTM), MARK LA 52 (RTM), MARK LA 57 (RTM), MARK LA 62 (RTM), MARK 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 3110 x 128 (RTM), UVINUL 4050 H (RTM), CHIMASSORB 944 (RTM), CHIMASSORB 2020 (RTM), CYASORB UV 3346 (RTM), CYASORB UV 3529 (RTM), DASTIB 1082 (RTM), CHIMASSORB 119 (RTM), UVASIL 299 (RTM), UVASIL 125 (RTM), UVASIL 2000 (RTM), UVINUL 5050 H (RTM), LICHTSCHUTZSTOFF UV 31 (RTM), LUCHEM HA B 18 (RTM), MARK LA 63 (RTM), MARK LA 68 (RTM), UVASORB HA 88 (RTM), TINUVIN 622 (RTM), HOSTAVIN N 30 (RTM) and FERRO AM 806 (RTM).

The meanings of the terminal groups which saturate the free valences in the compounds of the formulae (B-1), (B-3), (B-4), (B-5), (B-6-.alpha.), (B-6-.gamma.), (B-6-.gamma.), (B-7), (B-8-b) and (B-10) 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 (B-1) are prepared by reacting a compound of the formula: ##STR40##

in which X is, for example, halogen, in particular chlorine, and R.sub.4 and R.sub.5 are as defined above, with a compound of the formula: ##STR41##

in which R.sub.1, R.sub.2 and R.sub.3 are as defined above, the terminal group bonded to the diamino radical is hydrogen or: ##STR42##

and the terminal group bonded to the triazine radical is X or ##STR43##

If X is halogen, it is advantageous to replace this, for example, by --OH or an amino group when the reaction is complete. Examples of amino groups which may be mentioned are pyrrolidin-1-yl, morpholino, --NH.sub.2, --N(C.sub.1 -C.sub.8)alkyl).sub.2 and --NR(C.sub.1 -C.sub.8 alkyl), in which R is hydrogen or a group of the formula (b-I).

The compounds of the formula (B-1) also cover compounds of the formula: ##STR44##

wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 and b.sub.1 are as defined above and R.sub.4 * has one of the meanings of R.sub.4 and R.sub.5 * has one of the meanings of R.sub.5.

One of the particularly preferred compounds of the formula (B-1) is: ##STR45##

The preparation of this compound is described in Example 10 of U.S. Pat. No. 6,046,304.

In the compounds of the formula (B-3), the terminal group bonded to the silicon atom can be, for example, (R.sub.14).sub.3 Si--O--, and the terminal group bonded to the oxygen can be, for example, --Si(R.sub.14).sub.3.

The compounds of the formula (B-3) can also be in the form of cyclic compounds if b.sub.2 is a number from 3 to 10, i.e. the free valences shown in the structural formula then form a direct bond.

In the compounds of the formula (B-4), the terminal group bonded to the 2,5-dioxopyrrolidine ring is, for example, hydrogen, and the terminal group bonded to the --C(R.sub.23)(R.sub.24)-- radical is, for example, ##STR46##

In the compounds of the formula (B-5), the terminal group bonded to the carbonyl radical is, for example, ##STR47##

and the terminal group bonded to the oxygen radical is, for example, ##STR48##

In the compounds of the formulae (B-6-.alpha.), (B-6-.beta.) and (B-6-.gamma.), the terminal group bonded to the triazine radical is, for example, Cl or a ##STR49##

group, and the terminal group bonded to the amino radical is, for example, hydrogen or a ##STR50##

group.

If the compounds of the formula (B-7) are prepared, for example, by reacting a compound of the formula: ##STR51##

in which A.sub.1 is hydrogen or methyl, with a dicarboxylic acid diester of the formula Y--OOC--A.sub.2 --COO--Y, in which Y is, for example, methyl, ethyl or propyl, and A.sub.2 is as defined above, the terminal group bonded to the 2,2,6,6-tetramethyl-4-oxypiperidin-1-yl radical is hydrogen or --CO--A.sub.2 --COO--Y, and the terminal group bonded to the diacyl radical is --O--Y or ##STR52##

In the compounds of the formula (B-8-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 ##STR53##

group.

In the compounds of the formula (B-8-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 (B-10), the end group bonded to the --CH.sub.2 -- residue can be, for for example, hydrogen and the end group bonded to the --CH(CO.sub.2 A.sub.7) residue can be, example, --CH.dbd.CH--COOA.sub.7.

E.sub.1, E.sub.8, E.sub.12, E.sub.13, E.sub.16, E.sub.18, E.sub.22, E.sub.23, E.sub.25, E.sub.29, R.sub.6, R.sub.13, R.sub.16, R.sub.18, R.sub.30 and R.sub.32 are preferably hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.10 alkoxy, cyclohexyloxy, allyl, benzyl or acetyl.

E.sub.1, E.sub.8, E.sub.12, E.sub.13, E.sub.16, E.sub.18, E.sub.22, E.sub.23, E.sub.25, E.sub.29, R.sub.6, R.sub.13, R.sub.16, R.sub.18, R.sub.30 and R.sub.32 are in particular hydrogen or methyl and E.sub.1 and R.sub.6 additionally are C.sub.1 -C.sub.8 alkoxy.

According to a preferred embodiment,

m.sub.1 is 1, 2 or 4,

if m.sub.1 is 1, E.sub.2 is C.sub.12 -C.sub.20 alkyl,

if m.sub.1 is 2, E.sub.2 is C.sub.2 -C.sub.10 alkylene or a group of the formula (a-I)

E.sub.3 is C.sub.1 -C.sub.4 alkyl,

E.sub.4 is C.sub.1 -C.sub.6 alkylene, and

E.sub.5 and E.sub.6 independently of one another are C.sub.1 -C.sub.4 alkyl, and

if m.sub.1 is 4, E.sub.2 is C.sub.4 -C.sub.8 alkanetetrayl;

two of the radicals E.sub.7 are --COO--(C.sub.10 -C.sub.15 alkyl), and

two of the radicals E.sub.7 are a group of the formula (a-II);

E.sub.9 and E.sub.10 together form C.sub.9 -C.sub.13 alkylene,

E.sub.11 is hydrogen or a group --Z.sub.1 --COO--Z.sub.2,

Z.sub.1 is C.sub.2 -C.sub.6 alkylene, and

Z.sub.2 is C.sub.10 -C.sub.16 alkyl;

E.sub.14 is hydrogen, and

E.sub.15 is C.sub.2 -C.sub.6 alkylene or C.sub.3 -C.sub.5 alkylidene;

E.sub.17 is C.sub.10 -C.sub.14 alkyl;

E.sub.24 is C.sub.1 -C.sub.4 alkoxy;

m.sub.2 is 1, 2 or 3,

when m.sub.2 is 1, E.sub.26 is a group ##STR54##

when m.sub.2 is 2, E.sub.26 is C.sub.2 -C.sub.6 alkylene, and

when m.sub.2 is 3, E.sub.26 is a group of the formula (a-IV)

the radicals E.sub.27 independently of one another are C.sub.2 -C.sub.6 alkylene, and

the radicals E.sub.28 independently of one another are C.sub.1 -C.sub.4 alkyl or C.sub.5 -C.sub.8 cycloalkyl; and

E.sub.30 is C.sub.2 -C.sub.8 alkylene;

R.sub.1 and R.sub.3 independently of one another are a group of the formula (b-I),

R.sub.2 is C.sub.2 -C.sub.8 alkylene,

R.sub.4 and R.sub.5 independently of one another are hydrogen, C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.8 cycloalkyl or a group of the formula (b-I), or the radicals R.sub.4 and R.sub.5, together with the nitrogen atom to which they are bonded, form a 5- to 10-membered heterocyclic ring, and b.sub.1 is a number from 2 to 25;

R.sub.7 and R.sub.11 independently of one another are hydrogen or C.sub.1 -C.sub.4 alkyl,

R.sub.8, R.sub.9 and R.sub.10 independently of one another are C.sub.2 -C.sub.4 alkylene, and

X.sub.1, X.sub.2, X.sub.3, X.sub.4, X.sub.5, X.sub.6, X.sub.7 and X.sub.8 independently of one another are a group of the formula (b-II),

R.sub.12 is hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.5 -C.sub.8 cycloalkyl or a group of the formula (b-I);

R.sub.14 is C.sub.1 -C.sub.4 alkyl,

R.sub.15 is C.sub.3 -C.sub.6 alkylene, and

b.sub.2 is a number from 2 to 25;

R.sub.17 and R.sub.21 independently of one another are a direct bond or a group --N(X.sub.9)--CO--X.sub.10 --CO--N(X.sub.11)--,

X.sub.9 and X.sub.11, independently of one another are hydrogen or C.sub.1 -C.sub.4 alkyl,

X.sub.10 is a direct bond,

R.sub.19 and R.sub.23 are C.sub.1 -C.sub.25 alkyl or phenyl,

R.sub.20 and R.sub.24 are hydrogen or C.sub.1 -C.sub.4 alkyl,

R.sub.22 is C.sub.1 -C.sub.25 alkyl or a group of the formula (b-I), and

b.sub.3 is a number from 1 to 25;

R.sub.25, R.sub.26, R.sub.27, R.sub.28 and R.sub.29 independently of one another are a direct bond or C.sub.1 -C.sub.4 alkylene, and

b.sub.4 is a number from 1 to 25;

b.sub.5 ', b.sub.5 " and b.sub.5 '" independently of one another are a number from 2 to 4, and

R.sub.31 is hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.5 -C.sub.8 cycloalkyl, phenyl or benzyl;

A.sub.1 is hydrogen or methyl,

A.sub.2 is a direct bond or C.sub.2 -C.sub.6 alkylene, and

n.sub.1 is a number from 2 to 25;

n.sub.2 and n.sub.2 * are a number from 2 to 25;

A.sub.3 and A.sub.4 independently of one another are hydrogen or C.sub.1 -C.sub.4 alkyl, or A.sub.3 and A.sub.4 together form a C.sub.9 -C.sub.13 alkylene group, and

the variables n.sub.3 independently of one another are a number from 1 to 25;

n.sub.4 is a number from 2 to 25,

A.sub.5 and A.sub.6 independently of one another are C.sub.1 -C.sub.4 alkyl, and

A.sub.7 is C.sub.1 -C.sub.4 alkyl or a group of the formula (b-I) with the proviso that at least 50% of the radicals A.sub.7 are a group of the formula (b-I).

The two different sterically hindered amine compounds of component (I) are preferably selected from the group consisting of the compounds of the formulae (A-1-a), (A-1-b), (A-1-c), (A-1-d), (A-2-a), (A-3-a), (A-3-b), (A-4-a), (A-4-b), (A-5), (A-6-a), (A-7), (A-8-a), (A-9-a), (A-9-b), (A-9-c), (A-10-a), (B-1-a), (B-1-b), (B-1-c), (B-1-d), (B-2-a), (B-3-a), (A-4-a), (B-4-b) and (B-4-c), a product (B-6-a) and the compounds of the formulae (B-7-a), (B-8-a), (B-8-b), (B-9-a) and (B-10-a); ##STR55##

wherein E.sub.1 is hydrogen, C.sub.1 -C.sub.8 alkyl, O.sup.-, --OH, --CH.sub.2 CN, C.sub.1 -C.sub.18 alkoxy, C.sub.5 -C.sub.12 cycloalkoxy, C.sub.3 -C.sub.6 alkenyl, C.sub.7 -C.sub.9 phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C.sub.1 -C.sub.4 alkyl; or C.sub.1 -C.sub.8 acyl; ##STR56##

in which two of the radicals E.sub.7 are --COO--C.sub.13 H.sub.27 and two of the radicals E.sub.7 are ##STR57##

and E.sub.8 has one of the meanings of E.sub.1 ; ##STR58##

wherein E.sub.12 has one of the meanings of E.sub.1 ; ##STR59##

wherein E.sub.13 has one of the meanings of E.sub.1 ; ##STR60##

wherein E.sub.16 has one of the meanings of E.sub.1 ; ##STR61##

wherein E.sub.18 has one of the meanings of E.sub.1 ; ##STR62##

in which E.sub.19, E.sub.20 and E.sub.21 independently of one another are a group of the formula (a-III) ##STR63##

wherein E.sub.22 has one of the meanings of E.sub.1 ; ##STR64##

wherein E.sub.23 has one of the meanings of E.sub.1 ; ##STR65##

wherein E.sub.25 has one of the meanings of E.sub.1 ; ##STR66##

wherein E.sub.29 has one of the meanings of E.sub.1 ; ##STR67##

wherein b.sub.1 is a number from 2 to 20 and R.sub.6 is hydrogen, C.sub.1 -C.sub.8 alkyl, O.sup.-, --OH, --CH.sub.2 CN, C.sub.1 -C.sub.18 alkoxy, C.sub.5 -C.sub.12 cycloalkoxy, C.sub.3 -C.sub.6 alkenyl, C.sub.7 -C.sub.9 phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C.sub.1 -C.sub.4 alkyl; or C.sub.1 -C.sub.8 acyl; ##STR68##

wherein R.sub.13 has one of the meanings of R.sub.6, ##STR69##

wherein b.sub.2 is a number from 2 to 20 and R.sub.16 has one of the meanings of R.sub.6 ; ##STR70##

wherein b.sub.3 is a number from 1 to 20 and R.sub.18 has one of the meanings of R.sub.6 ; ##STR71##

wherein b.sub.4 is a number from 1 to 20 and R.sub.30 has one of the meanings of R.sub.6 ;

a product (B-6-a) obtainable by reacting a product, obtained by reaction of a polyamine of the formula (B-6-1-a) with cyanuric chloride, with a compound of the formula (B-6-2-a): ##STR72##

in which R.sub.32 has one of the meanings of R.sub.6 ; ##STR73##

wherein n.sub.1 is a number from 2 to 20; ##STR74##

wherein n.sub.2 and n.sub.2 * are a number from 2 to 20; ##STR75##

wherein the variables n.sub.3 independently of one another are a number from 1 to 20; ##STR76##

wherein n.sub.4 is a number from 2 to 20, and

at least 50% of the radicals A.sub.7 are a group of the formula (b-I): ##STR77##

wherein R.sub.6 is hydrogen, C.sub.1 -C.sub.8 alkyl, O.sup.-, --OH, --CH.sub.2 CN, C.sub.1 -C.sub.18 alkoxy, C.sub.5 -C.sub.12 cycloalkoxy, C.sub.3 -C.sub.6 alkenyl, C.sub.7 -C.sub.9 phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C.sub.1 -C.sub.4 alkyl; or C.sub.1 -C.sub.8 acyl,

and the remaining radicals A.sub.7 are ethyl.

According to a preferred embodiment,

the two different sterically hindered amine compounds of component (I) are

1) a compound of the formula (A-1-b) wherein E.sub.1 is hydrogen, and a compound of the formula (B-1-a) wherein R.sub.6 is hydrogen;

2) a compound of the formula (B-1-a) wherein R.sub.6 is hydrogen, and a compound of the formula (B-7-a); or

3) a compound of the formula (B-2-a) wherein R.sub.13 is methyl, and a compound of the formula (B-7-a).

The organic salt of zinc or magnesium defined in component (II) is preferably a compound of the formula MeL.sub.2 in which Me is zinc or magnesium and L is an anion of an organic acid or of an enol. The organic acid can, for example, be a sulfonic acid, sulfinic acid, phosphonic acid or phosphinic acid, but is preferably a carboxylic acid. The acid can be aliphatic, aromatic, araliphatic or cycloaliphatic; it can be linear or branched; it can be substituted by hydroxyl or alkoxy groups; it can be saturated or unsaturated and it preferably contains 1 to 24 carbon atoms.

Examples of carboxylic acids of this type are formic, acetic, propionic, butyric, isobutyric, caprioic, 2-ethylcaproic, caprylic, capric, lauric, palmitic, stearic, behenic, oleic, lactic, ricinoleic, 2-ethoxypropionic, benzoic, salicylic, 4-butylbenzoic, toluic, 4-dodecylbenzoic, phenylacetic, naphthylacetic, cyclohexanecarboxylic, 4-butylcyclohexanecarboxylic or cyclohexylacetic acid. The carboxylic acid can also be a technical mixture of carboxylic acids, for example technical mixtures of fatty acids or mixtures of alkylated benzoic acids.

Examples of organic acids containing sulfur or phosphorus are methanesulfonic, ethanesulfonic, .alpha.,.alpha.-dimethylethanesulfonic, n-butanesulfonic, n-dodecanesulfonic, benzenesulfonic, toluenesulfonic, 4-nonylbenzenesulfonic, 4-dodecylbenzenesulfonic or cyclohexanesulfonic acid, dodecanesulfinic, benzenesulfinic or naphthalenesulfinic acid, butylphosphonic acid, phenylphosphonic acid, monomethyl or monoethyl phenylphosphonate, monobutyl benzylphosphonate, dibutylphosphinic acid or diphenylphosphinic acid.

If L is an enolate anion, it is preferably an anion of a .beta.-dicarbonyl compound or of an o-acylphenol. Examples of .beta.-dicarbonyl compounds are acetylacetone, benzoylacetone, dibenzoylmethane, ethyl acetoacetate, butyl acetoacetate, lauryl acetoacetate or .alpha.-acetylcyclohexanone. Examples of o-acylphenols are 2-acetylphenol, 2-butyroylphenol, 2-acetyl-1-naphthol, 2-benzoylphenol or salicylaldehyde. The enolate is preferably the anion of a .beta.-dicarbonyl compound having 5 to 20 carbon atoms.

Organic salts of zinc or magnesium are preferably an acetylacetonate or an aliphatic monocarboxylate having, for example, 1 to 24 carbon atoms. Magnesium acetate, laurate and stearate, zinc formate, acetate, oenanthate, laurate and stearate as well as zinc acetylacetonate and magnesium acetylacetonate are some of the particular preferred examples.

Zinc stearate, magnesium stearate, zinc acetylacetonate, magnesium acetylacetonate, zinc acetate and magnesium acetate are of special interest.

The inorganic salt of zinc or magnesium is for example a carbonate containing compound such as

Zn-hydroxide-carbonate, Mg-hydroxide-carbonate, dolomite, e.g a Ca/Mg carbonate such as Microdol Super (RTM) from Micro Minerals (RTM); or

a natural or synthetic hydrotalcite.

The natural hydrotalcite is held to possess a structure Mg.sub.6 Al.sub.2 (OH).sub.16 CO.sub.3.4H.sub.2 O. A typical empirical formula of a synthetic hydrotalcite is

Examples of the synthetic product include:

Preferred synthetic hydrotalcites are L-55R II (RTM) from REHEIS (RTM) as well as ZHT-4A (RTM) and DHT-4A (RTM)