GB2345696A - Stabilizer combinations for halogen-containing polymers - Google Patents

Abstract

A stabilizer combination for halogen-containing polymers comprises A) at least one organic zinc compound with a Zn-O bond and/or a Zn-S bond or an inorganic compound and B) at least one compound of the formula <EMI ID=1.1 HE=39 WI=88 LX=349 LY=518 TI=CF> <PC>in which the radicals and symbols have the following meanings:<BR> R<SB>1</SB> : H or C<SB>1</SB>-C<SB>8</SB>alkyl, C<SB>3</SB>-C<SB>8</SB>alkenyl, C<SB>7</SB>-C<SB>9</SB>phenylalkyl or C<SB>5</SB>-C<SB>8</SB>cycloalkyl;<BR> R<SB>5</SB> : H, C<SB>1</SB>-C<SB>8</SB>alkyl, C<SB>3</SB>-C<SB>8</SB>alkenyl, C<SB>5</SB>C<SB>8</SB>-cycloalkyl or G; <EMI ID=1.2 HE=24 WI=41 LX=237 LY=1277 TI=CF> <PC>A: -CO-, -(CH<SB>2</SB>)<SB>m</SB>-, -(CH<SB>2</SB>)<SB>d</SB>-CO- or -NH(CH<SB>2</SB>)<SB>n</SB>-CO-;<BR> m: 0 or 1; n: 2 to 12; p: 0 or 1; d: 1 to 8; r: 2 to 50;<BR> and, if p is 0, A: -CO-, (CH<SB>2</SB>)-<SB>m</SB>, -(CH<SB>2</SB>)<SB>d</SB>-CO- or -NH(CH<SB>2</SB>)<SB>n</SB>-CO-;<BR> if p is 1, A: (CH<SB>2</SB>)<SB>m</SB>.

Description

2345696 4-Acylamido-piperidine compounds in stabilizer combinations for

chlorine- containing polymers The invention relates to a stabilizer combination comprising an organozinc compound with an Zn-O and/or Zn-S bond, in particular a zinc carboxylate, and at least one compound of the formulae 1, 11, 111 and IV depicted below, which is suitable for stabilizing chlorinecontaining polymers, especially PVC.

PVC can be stabilized by a range of additives. Compounds of lead, of barium and of cadmium are particularly suitable for this purpose, but are nowadays controversial on ecological grounds (cf. "Taschenbuch der Kunststoffladditive", Eds. R. Gdchter and H. MbIler, Carl Hanser Verlag, 3rd Edition, 1989, pages 303-311, and Kunststoff Handbuch PVC, Volume 2/1, G.W.Becker, D.Braun, Carl Hanser Verlag 1985, pages 531-538). The search is therefore continuing for effective stabilizers and stabilizer combinations devoid of disadvantageous properties.

Sterically hindered amines have already been added to the PVC as light stabilizers. The thermal stability may also be favourably affected (cf. e. g. EP-A-366271 and EP-A-488951).

It has now been found that organozinc compounds, such as zinc carboxylates, can be combined advantageously with compounds of the formulae R 3-N-CX-R 2 (CH 0 R5 R 5 0 2n A I N A" N N' N (CH H 2), (C F RS - P R, N R, R 1 7 +C-CH 2 _S I R 5 (111) and/or uU 0 V) I L rY) (N) N-R, M M N q R, 0 4 in order to stabilize chlorine-containing polymers. In these formulae, the meanings of the radicals and symbols are as follows:

X: 0 or S; a: 0 to 8; b: 2 to 12; c: 1 or 2; k: 2 to 6; R1 H or Cl-C. alkyl, C 3-c.alkenyl, C7-C.phenylalkyl or C,-C.cycloalkyl; R C _C alkyl, -NH R NG-, R,-O-, [R -NG-C>q,.E-, 2 1 8 2' 3 3 (cl-c4alkyl N(CH phenyl or OH-, alkoxy- or alkyl-substituted phenyi, )2 2)k-CX-' C1_C4 C1_C4 G: N-RI R 3 H, C,-C.alkyl, C 3- C8 alkenyl, C.-C.cycloalkyl, R2-CX-NG-(CH 2) b' (C,-C,alkyl)2 N (CH 2)1- or G; R4: C1 -C4alkyl, cyclohexyl or benzyl; E: (CH 2)., 0-, a, -, -e-.

-CH=CH-, -CH(OH)-CH(OH)-, -CH2-CH(OH)- or -NH (CH 2)b NH-; A: -(CH 2)_111 ' >C01 _(CH2)d_CO_ or -NH(CH 2),_CO_' m: 0 or 1 -. n: 2 to 12; p: 0 or 1: d: 1 to 8; q: 1 or 2; r: 2 to 50; and, if p is 0, A: >CO, - (CH 2)-rn' _(CH2)C_CO_1 -NH(CH 2),-Co-; if p, is 1, A: -(CH 2)_M; the group L -CH -CHR,-, -(CH - -CH=CH., G-(N)-Y-N-C=:O 2 2) 3' M M -2 or IRS: H, Cl-C.alkyl, C3.c8alkenyl, C.-C cycloalkyl or G; RS:H, C1_C 12 alkyl; R7: H or CH' 3; Q: -0- or >NH; Y: -CH 2_CH(OH-CH 2-; and s: 3 to 60.

In the above formulae:

C1_C4aIkyI is methyl, ethyl, n-propyl, isopropyl, n-, i-, sec- or t-butyl.

C1_C8 alkyl arb the same radicals and, for example, n-pentyl, isopentyl, neopentyl, n-hexyl,.n-heptyl, 2-ethylhexyl, n-octyl or isooctyl.

C 5-C 8 cycloalkyl is, for example, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl. Cyclopentyl and, in particular, cyclohexyl are preferred.

C 3-C.alkenyl substituents can be branched or unbranched alkenyl, for example ally[, crotonyl, 2-methylallyl or hexenyl.

Cl-c4alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy or isobutoxy.

C7-C,phenylalkyl is, for example, benzyl, 1 - or 2-phenylethyl, 3phenylpropyl, alpha,alphadimethylbenzyl or 2-phenylisopropyl, preferably benzyl.

Preference is given in the stabilizer combination to compounds of the formulae I to IV, in which X 0 or S; a: 0 to 4; b: 2 to 6; c: 1 or 2; k: 2 or 3 1 R H or C,_C 8 alkyl; R 2 CI-C a alkyl, -NH 2' R3-NG-, [R -NG-CXI,,E- or (C,-C,alkyl)2 N(CH 2)k- CX-; R: H, C -C alkyl, R -CX-NG-(CH (C 1 -C4al kyl)2 N(CH) - or -G; 3 1 8 2 2)b 2% E -(CH 2)a-' -CH=CH- or -NH (CH 2) bNH-1- R H, C,-C alkyl or G; 8 A: -CO-, -(CH 2) -(CH 2)(1-Co- or -NH(CH 2),_C0_' m: 0 or 1; n: 2 to 6; p: 0 or 1;d: 1 to 4; q: 1 or 2; r: 2 to 50; and, if p is, 0, -CO-, -(CH 2) -(CH 2)d_C0_ or -NH(CH 2),-Co-; ifp is 1, A: -(CH 2)111 RS the group L: -CH -CHR,-, -(CH I - 0 or 2' 2) 3, G-(N)-Y-N C= M M I ': ja 12 R 6: H or C1_C,2 alkyl; Y: -CH 2-CH(OH)-CH 2R 7: H or CH 3; Q: -0- or >NH, and s: 3 to 60.

Particularly preferred compounds of the formulae I to IV are those in which X: 0; a: 0 to 4; b: 2 to 6; c: 1; Ri H or Cl-C.alkyl; R 2 [R 3-NG-CX]CE-; R3: H, C,-c,alkyl, R 2-CX-NG-(CH 2)11 or G; E: (C H A, or -NH-(CH 2) NH-; RS: G; A: -(CH 2) n_ m: 0 or 1; n: 2 to 6; p: 0; q: 1 or 2; r: 2 to 50', the group L: -CH 2-CHR,,-, -(CH 2)-'-' or -CH=CH--, R 6: H; Y: -CH _CH(OH)-CH 2 2 R 7: H 0: >NH: and s: 3 to 60.

Examples of the p1peridine compounds of the formulae I to IV are:

01) N, N'-bis (2,2,6,6-tetram ethyl p1periclin -4 -yl) ethyie ne- 1, 2diacetamid e 02) N,N'-bis (2,2,6,6-tetramethyl:)Iperldin-4-yl) ethylene1,2-formamide 03) N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)adipamide 04) N,N'-bis(2,2, 6,6-tetramethylpiperidin-4-yl)oxamide 1 05) 4 - hyd roxybenzami do-2,2,6,6-tetram ethyl pi peridine FCH,-CO-N-(CH 2)T-N 06) H 0 0 07) HN NH-C C-NH- N FH I CH3-CO- N - (CH2)T-N -CO-CH3 08) H H 0 11 09) - N r4ri-C-CH 3 H H N N -CH2-CO N N N - p-t2- 6 r Nk N H H H H N N N HN-CO-NH 0 11 OH 12) H-N NH-U 13) N, N H 0 0 0 11 11 11 14) HN N rl - U-, M. 15) HN NH-C-C-NH (CH2)-N(i-Pr)2 2 CO-(CH2)1-Co -N-(CH2) N r 16) N N H H H3 C-CH-1 1 2 r 17) O=c NH 0 0 N-(CH 2):T-N-C-C-j 18) AN AN I I H H 0 0 11 11 7 N - (CH2)i--N-C-(CH -C 2)3 Ir N N 0 0 L N-(CH 2)6 N-C-NH-(CH 24-N 20) r N N H 21) (H-N NH)2C=S 0 0 11 -NH- N H 22) H-N NH-C C-NH 0 0 11 11 23) N Nrl-U- I H-, I H-U-NH-CN OH OH 0 0 24) H-N N-H C 4 H9 C,H 9 0 N if 0 (i-p')2 -CH;-CH 2 N-C-CH, 11 7 25) 26) [H - N> N-C CH kN' I N CHO I H C-N7,..N-H 0 27) 28) N-( N C:, N 0 CHS--C N il 29) 0 0 c 30) H-N N N N-H 0 0 0 0 31) IN CH 2 CH-CH 2 NH- N-H 32) H-N N-C-C-C,H9 OH C,H 9 0 0 OH H-N 33) NH-CHi-CH-CH-N N-CHTCH-CH=NH 2 N,H //- OH 0 0 0 0 1 35) C12H25 N 34) N N- I -( N-H 0 0 0 11 11 N (CH2):T- N - C - CHi- N (CH2)1- N - CHi- C T 36) N H H H H 0 0 37) N N - 38) N N I C I 0 0 0 C 11 0 4 Hi--N C__(D 40) IN-CN-H N 0 1 C2 H 5 0 0 it 11 -N (CH2) i--N-C-CH:T-N-CHF-CH 2-N-CHi--C_] P H H r 41) N H H 0 0 1\ 11 42) H / CH-N-(CH 2)i--N-C, H N H H The compounds of the formulae I to IV can be present in the chlorinecontaining polymer in proportions of from 0.005 to 5%, preferably from 0. 01 to 2% and, in particular, from 0.01 to 1 %.

Zinc compounds The organozinc compounds with a Zn-O bond comprise zinc enolates, zinc phenolates and/or zinc carboxylates. The latter are compounds from the series of the aliphatic saturated and unsatured Cl-C22carboxylates, the aliphatic saturated or unsaturated C2-C22carboxylates, which are substituted with at least one 01H group or whose chair, is interrupted by one or more 0 atoms (oxa acids), the cyclic and bicyclic carboxylates of 5-22 carbon atoms, the unsubstituted, monoor poly- 0 H -substituted and/or Cl.,r,alkyl-substituted pheny[carboxylates, thephenyl-C,., 6alkylcarboxylates, or the unsubstituted or Cl-,2alkyl-substituted phenolates, or of abietic acid. Examples of Zn-S compounds are Zn mercaptides, Zn mercaptocarboxyiates and Zn mercaptocarboxylic esters.

Mention may be made by name, as examples, of the zinc salts of monovalent carboxylic acids, such as acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, oenanthic acid, octanoic acid, neodecanoic acid, 2-ethylhexanoic acid, pelargonic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, myristylic acid, palmitic acid, lauric acid, isostearic acid, stearic acid, I 2-hydroxystearic acid, 9,1 0-dihydrcxystearic acid, oleic acid, ricinoleic acid, 3,6-dioxaheptanoic acid, 3,6,9-trioxadecanoic acid, behenic acid, benzoic acid, p-terLbutylbenzoic acid, dimethy(hyd,oxybenzoic acid, 3,5-cli-terlt-butyl4hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, n-propylbenzoic acid, salicylic acid, p-tert-octylsalicylic acid, and sorbic acid, cinnamic acid, mandelic acid, glycolic acid; zinc salts of divalent carboxylic acids and their monoesters, such as oxalic acid, malonic acid, succininic acid, glutaric acid, adipic acid, fumaric acid, pentane1,5-dicarboxylic acid, hexane-1,6-dicarboxylic acid, heptane-1,7dicarboxylic acid, octane1,8-dicarboxylic acid, 3.6,9-trioxadecane-1,10dicarboxylic acid, lactic acid, malonic acid, maleic acid, tartaric acid, malic acid, salicylic acid, poyglycclckarbcxylic acid (n=1 0-12), phthalic acid, isophthalic acid, terephthalic acid and nydroxypnthalic acid-, and the di- or triesters of tri- or tetravalent carboxylic acids, suci'-i as hemimeNitic acid, trimellitic acid, pyromellitic acid, citric acid and also so-called ove-baset zmc carboxylates, or zinc lauryl mercaptide, zinc thioglycolate, zinc thicisalicylate, zinc b Is - i-o.-- 'Lvlthiogi yco late, zinc mercaptopropionate, zinc thiolactate, zinc thlomalate, zinc bis-Cay1mercaptopmpionate, zinc bis-isooctylthiolactate and zinc bis-laurylthiomalate.

The zinc enolates preferably comprise enolates of acetylacetcne, of benzoylacetone, and of dibenzoy[methane and enolates of acetoacetic and benzoylacetic esters, and of dehydroacetic acid. It is also possible to employ inorganic zinc compounds such as zinc oxide, zinc hydroxide, zinc carbonate, basic zinc carbonate or zinc sulfide.

Preference is given to neutral or basic zinc carboxylates off a carboxylic acid having 2 to 22 carbon atoms (zinc soaps), for example benzoates or alkanoates, preferably Cealkancates, stearate, oleate, laurate, paimitate, behenate, Versatate, hydroxystearates and -oleates, di hyd roxystea rates, p-tert- butylbenzoate, or (iso)octanoate. ParLicular preference is given to stearate, oleate, Versatate, benzoate, p-tert-butylbenzoate and 2ethylhexanoate.

In addition to the abovementioned zinc compounds, (in)organic aluminiurn compounds having an AI-O bond are also suitable. The preferred aluminium compounds which can be used include, preferably, aluminium enolates and aluminium carboxylates. Examples of carboxylate and enolate radicals can be found correspondingly in the comments made regarding zinc above.

Examples of inorganic Al compounds are aluminiurn hydroxide and aluminjurn phosphates.

The described organozinc compounds and their mixtures can be employed in amounts of, for example, from 0.001 to 10 parts by weight, expediently from 0.01 to 5 parts by wiei.-ht preferably from 0.01 to 3 parts by weight, based on 100 parts by weight of chlo M'e-conLaining polymer.

They may also be present as mixed salts (coprecipftates).

The novel stabilizer combination can be used together withfurther additives which are customary for the processing and stabilization of chlorine-containing polym ers, examples being 1. Stabilizers:

Epoxides and epoxiclized fatty acid esters; phosphites; thiophosphites and thiciphosphates; polyols 1,3-dicarbonyl compounds; mercaptocarboxylic esters; dihydropyridines; antioxidants; light stabilizers and UV absorbers; alkali metal and alkaline earth metal compounds; perchlorate salts; zeolites; hydrotalcites: dawsonites; 2. F-jr-Lher common PVC additives, for example lubricants; plasticizers; impact modifiers; processing Paids, blowing agenzs, fillers; antistats, b(ocides; antifogging agents', pigments and dyes,- metal deactivattors: flarre.:)roofirg acents (cf. in this respect "Handbook of PVC Formulating", E. J. Wickson, J0rn Wiley & Sons, Ne,t/ York 1993).

12- Examples of such additives are known to the skilled worker and can be found in the technical literature. Without limitation, mention may be made here of some of the known additives and processing aids:

Phosphites: Organic phosphites are known co-stabilizers for chlorinecontaining polymers. Examples are trioctyl, tridecyl, triclodecyl, tritridecyl, tripentadecyl, trioieyl, tristearyl, triphenyi, tricresyl, trisnonylphenyl, tris-2,4-t-butylphenyl or tricyclohexyl phosphite.

Further suitable phosphites are variously mixed aryl dialkyl and alky diarylphosphites, such as phenyl dioctyl, phenyl didecyl, phenyl didodecyl, phenyl ditridecyl, phenyiditetradecyl, phenyl dipentadecyl, octyl diphenyl, decyl diphenyl, undecyl diphenyl, dodecy[diphenyl, tridecyl diphenyi, tetradecyl diphenyl, pentadecyl diphenyl, oley( diphenyl, stearyl diphenyl and dodecyl bis-2,4-di-t-butylphenyl phosphite, Furthermore, phosphites of various diols and polyols can also be used advantageously; examples are tetraphenyidipropylene glycol diphosphite, polyclipropylene glycol phenyl phosphite, tetramethyloicyclohexanol decyl diphosphite, Letramethyloicyclohexanol butoxyethoxyethyl diphosphite, tetramethyloicyclohexanol nonylphenyl diphosphite, bisnonylphenyl ditrimethylol propane diphosphite, bis-2-butoxyethyl di-trimethylol propane diphosphite, trishydroxyethyl isocyanurate hexadecyl triphosphite, did ecylpentaeryth ritol diphosphite, distearyl pentaerythritol diphosphite, bis-2,4-di-t-butylphenyl pentaerythritol diphosphite, and also mixtures of these phospites and aryl/alkyl phosphite mixtures of the statistical composition (H,gCg-CrH,,)Ol_sP (OC,2.l3H25.27)1.5 or [CeHj7-C6H,-0_12P[iCeHI701 Or (H,qCq-C6H.)Oj.sP (OCq,,jH,q.23),.5- The organic phosphites can be employed in an amcunt oi, for example, from 0.01 to 10 parts by weight, expediently from 0.05 to 5 parts by weicht and, in particular, from 0.1 to 3 parts by weight, based on 100 parls by weigt of PVC.

Polyols: Examples of suitable compounds ol this type are'. pentaerythritol, dipentaerythritol, tripentaerthritol, bistri methyiol propane, trimethylolethane, bistrimethylolethane, trimethylol propane, sorbitol, maltitol, isomaltitol, lactitol, lycasine, mannitol, lactose. leucrose, tris(hydroxyethyl) isocyanurate, palatinite, tetramethylolcyclohexanol (TMCH), tetramethyloicycloo,entanol, tetramethylolcyclopyranol, glycerol, dialycerol, polyglycerol, thiodialyceral, or 1-0-a-D-glycopyranosyl-D-mannitoI dihydrate, and also polyvinyl alcohol and cyclodextrins. Among these, TIVICH and the disaccharide alcohols are preferred.

The polyols can be employed in an amount of, for example, from 0.01 to 20 parts by weight, expediently from 0.1 to 20 parts by weight, and, in particular, from 0.1 to 10 parts by weight, based on 100 parts by weight of PVC.

1,3-Dicarbonyl compounds: Examples of 1,3-dicarbonyl compounds are acetylacetone, butanoylacetone, heptanoylacetone, stearoylacetone, palmitoylacetone, lauroylacetone, 7-tert-nonylthioheptane-2,4-dione, benzoylacetone, d i benz6yl methane, lauroylbenzoylmethane, palm itoylbenzoylmethane, stearoylbenzoylmethane, isoocty I benzoyl methane, 5hydroxycapronylbenzoylmethane, tribenzoylmethane, bis(4-methylbenzoyl) methane, benzoyi-p-chlorobenzoylmethane, bis (2-hydroxybenzoyl) methane, 4-methoxybenzoylbenzoylmethane, bis(4-methoxybenzoyl)methane, 1-benzoyi-lacetylnonane, benzoylacetylphenyl methane, stearoyl-4methoxybenzoy[methane, bis(4-tert-butylbenzoyl)me4Lhane, benzoylformylmethane, benzoylphenylacetylmethane, bis(cyclohexanoyl) methane, di(pivaloyl) methane, acetoacetic methyl, ethyl, hexyl, octyl, dodecyl or octadecyl ester, benzoylacetic ethyl, butyl, 2-ethylhexyl, dodecyl or octadecyl ester, stearoylacetic ethyl, propyl, butyl, hexyl or octyl ester and dehydroacetic acid, and the zinc, alkali metal, alkaline earth metal or aluminium salts thereof.

The 1,3-dicarbonyl compounds can be employed in an amount of, for example, from 0.01 to 10 parts by weight, expediently from 0.01 to 3 parts by weight and, in particular, from 0.01 to 2 parts by weight, based on 100 parts by weight of PVC.

Thiophosphites and thiophosphates: Thiophosphites and thiophosphates are compounds of the general type (RS)3P, (RS)3P=O and (RS)3P=S, as described in the patent documents DE 2809492, EP 090770 and EP 573394. Examples are: trithiohexyl phosphite, trithiooctyl PhosPhite, trithiolauryl phosphite, trithiobenzyl phosphite, tris(carboxy-l-octyloxy)methyl trithicphosphate, S,S,S-tris[carbo-i-octyloxy)methyI trithiophosphate, S, S,S-tris[carbo-2ethyl h exyloxy] methyl trithiophosphate, S,S,S,-tris-1 (carbohexyloxy] ethyl trithiophosphate, S,S,S-tris-1- [carbo-2ethylhexyloxy] ethyl trithiophosphate, S,S,S-tris-2-[carbo-2e'Lhyihexyloxy]ethy trithio phosphate.

The thiophosphites and thiophosphates can be present in the chlorinecontaining polymer expediently in proportions of from 0.01 to 20%, preferably from 0.1 to 5% and, in particular, from 0. 1 to 1 %.

Mercaptocarboxylic esters: Examples of these compounds are: esters of thioglycolic acid. thiomalic acid, mercaptopropionic acids, of mercaptobenzoic acids and of thiolactic acid, as are described in FR 2459816, EP 90748, FR 2552440 and EP 365483. The mercaptocarboxylic esters also embrace corresponding polyol esters and their partial esters.

They can be present in the chlorine-containing polymer expediently in proportions of from 0.01 to 10%, preferably from 0. 1 to 5% and, in particular, from 0. 1 to 1 %.

Epoxides and epoxidized fatty acid esters: The novel stabilizer combination may additionally comprise at least one epoxiclized fatty acid ester. Particularly suitable for zhis are esters of fatty acids from natural sources, such as soya oil or rapeseed oil.

The epoxy compounds are employed in amounts of, for example, upwards of 0. 1 part per 100 parts by weight of composition, expediently from 0.1 to 30 parts, preferably from 0.5 up to 25 parts by weight. Further examples are epoxidized polybutadiene, epoxidized linseed oil, epoxiclized fish oil, epoxiclized tallow, methylbutyl or 2-ethylhexyl epoxystearate, tris(epoxypropyl)isocyanurate, epoxiclized castor oil, epoxidized sunflower oil, 3-phenoxy-1,2epoxypropane, bisphenol A cliglycidyl ether, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide and 3,4epoxycyclohexylmethyi 3,4- epoxycyclo In exan ecarboxyl ate.

Also suitable as epoxides are derivatives of bisphenol A and of bisphenol F, as described, for example, in South African patent document ZA-2600/94.

Dihydropyridines and polydihydropyridines: Suitable monomeric dihydropyridines ae compounds as described, for example, in FR 2039496, EP 2007, EP 3620! 2 and EP 24754. Preference is given to those of the formula Z I H3CZnNHI CH 3 in which Z is C02CH3, C02C2H5, CO2"CI2H25 or -C02C,H,-S-'C,2H25- Particularly suitable polydihydropyriclines are compounds of the following formula 0 0 R 0 0 0 R' T -0 a 0 0 0 07L I 13 H 3C N CH H. C N CH H 3C N CH3 1 3 3 3 1 - 1 H Iml H n H k in which T is unsubstituted C,12alkyl, L is as defined for T, m and n are numbers from 0 to 20, k is 0 or 1, R and R' independently of one another are ethylene, propylene, butylene or an alkylene- or cycloalkylenebismethylene group of the type +CpH4-X-)tCpH2P-, p is from 2 to 8, t is from 0 to 10, and X is oxygen or sulfur.

Compounds of this kind are described in more detail in EP 0286887.

The (poly) dihydropyridines can be employed in the chlorine-containing polymer expediently in proportions of from 0.001 to 5 parts by weight and, in particular, from 0.005 to 1 part by weight, based on the polymer.

Particular preference is given to thiodiethylenebis[5-methoxycarbonyl-2,6dimethyl-1,4dihydropyridine-3-carboxylate].

Alkali metal and alkaline earth metal compounds: By these terms are meant principally the carboxylates of the above-described acids, or also corres, ponding oxides and hydroxides, carbonates or basic carbonates. Also suitable are mixtures thereof with organic acids. Examples are NaOH, KOH, CaO, Ca(OH2), M90, Mg(OH)2, CaCO3, MgCO3 dolomite, huntite, and also Na, K, Ca or Mg salts of fatty acids.

In the case of carboxylates of alkaline earth metals and of Zn, it is also possible to employ adducts thereof with MO or M(OH)2 (M = Ca, Mg. Sr or Zn), so-called overbased compounds.

16- Preference is given to the use, in addition to the novel stabilizer combination, of alkali metal, alkaline earth metal and/or aluminium carboxylates, for example Na, K, Ca or aluminium stearates.

Perchlorate salts: Examples are those of the formula M(CIO-), where M is Li, Na, K, Mg, Ca, Ba, Zn, Al, Ce or La. The index n is, in accordance with the valency of M, 1, 2 or 3. The perchlorate salts can be present as complexes with alcohols or ether alcohols. In this context, the respective perchlorate can be employed in various common forms in which it is supplied; for example as a salt or aqueous solution applied to a carrier material such as PVC, Ca silicate, zeolites or hydrotalcites, or obtained by chemical reaction of hydrotalcite with perchloric acid.

The perchlorates can be employed in an amount of, for example, from 0.001 to 5 parts by weight, expediently from 0.01 to 3 parts by weight and, with particular preference, from 0.01 to 2 parts by weight, based on 100 parts by weight of PVC.

Hydrotalcites and zeolites: The chemical composition of these compounds is known to the skilled worker, for example from the patent documents DE 3843581, US 4000100, EP 062813, WO 93/20135.

Compounds from the series of the hydrotalcites can be described by the general formula VI m 2+ M'. - (0 H)2 ' (A') j,- mH20 (VI) in which M 2. = one or more metals from the group consisting of Mg, Ca, Sr, Zn and Sn, M 3. = Al or B, A"' is an anion having the valency n, n is a number from 1-2, 0 < x -. 0.5, and 11r, is a number f= 0-20.

Coo I A" is preferably = OH', CIO,', HCO3', CH3COO-, C6H5COO-, CO,2, SO, Coo-, COO)22-, 2 2 po.2.

(CHOH (CH2COO)2 CH3CHOHCOO-, HP03 or H Examples of hydrotalcites are A1203.6MgO.C02-121-120, Mg., 5A12(OH),3.C03- 3-5H20, 4M90 Al-203=2 91H20, 4MgO.A:2O1.CO2.6H20, ZnO.3MgO.AI203.CO2 8- 9H20 and ZnO.3MgOA120' C02-5-6H20 Compounds from the series of the zeolites (alkali metal and/or alkaline earth metal aluminosilicates) can be described by the general formula (VIII) lVl,j,[(Al02),, (Si02)y1.wH20 (VIII) in which n is the charge of the cation M; M is an element from the first or second main group, such as Li, Na, K, Mq-, Ca, Sr or Ba, or Zn, y:x is a number from 0.8 to 15, preferably from 0.8 to 1.2; and w is a number from 0 to 300, preferably from 0.5 to 30.

Structures can be found, for example, in the Atlas of Zeolite" by W.M. Meier and D.H. Olson, Butterworth-Heinemann, 3rd ed. 1992.

Examples of zeolites are sodium alumosilicates of the formulae Nal2AI12Si, 20,18. 27 H20 [zeolite A], NarA16Si6024. 2 NaX. 7.5 H20, X= OH, halogen, CIO, (sodalite]; Na,,,Al6Si3OO72. 24 H20; Na&A18Si,00qr,. 24 H20; Na, rAllrSi2lO8O. 16 H20; Nal6AI16Si320915 - 16 H20; Nas6AI56Si,360384. 250 H20 [zeolite Y], NaL8A86Si106O384 - 264 H20 [zeolite)q; or the zeolites which can be prepared by partial or complete exchange of the Na atoms by Li, K, Mg, Ca, Sr or Zn atoms, such as (Na, K 10 A110&2206,. 20 H20; Ca,,.sNa3 P10012 (Si02)121. 30 H20; K9Na3 [(AI02)12 (Si02)121 27 H20Other suitable zeolites are: Na20'AI203(2 to 5) Si02'(3.5 to 10) H20 (zeolite P] Na20'AI203-2 Si02'(3.5-1 0)H20 (zeclite MAP) or the zeoiites which can be prepared by partial or complete exchange of the Na atoms by Li, K or H atoms, such as (Li,Na,K,H)j0 AI10Si2206-. 20 H20, K9Na3 [(AI02)12 (Si02)121. 27 H20, KAISi,:O,6-6H2O [zeolite K-F], Na8AIeSioO96. 24 H20 zeolite D, as described in Barrer et al., J. Chem. Soc. 1952, 156171, and in US 2,950,952; Also suitable are the following zeolites: K off retite, as described in EP-A-400,961', zeolite R, as described in G 6 841.812- zeolite LZ-217, as describpd in US 4,503,023,- Ca-free zeolite LZ-218, as described in Us 4,333,859; zeolite T, zeolite LZ-220, as described in US 4,503,023; Na3KrAI9Si27072.21 H20 [zeolite L]; zeolite LZ-21 1, as described in US 4, 503,023; zeolite LZ-212 as described in US 4,503,023; zeolite 0, zeolite LZ-217 as described in US 4,503,023; zeolite LZ-219, as described in US 4, 503,023: zeolite rho, zeolite LZ-214, as described in US 4,503,023; zeolite ZK-1 9, as described in Am. Mineral. 54 1607 (1969); zeolite W (K- M), as clescl ibed in Barrer et al., J. Chem. Soc. 1956, 2882; and Na--, AIKSiC,60192. 98 H20 [zeolite ZK-5, zeolite Q].

Particular preference is given to the use of zeolite P types of the formula VII in which x is 2 to 5 and y is 3.5 to 10, especially zeolite MAP of the formula V1 I in which x is 2 and y is 3.5 to 10. The substance concerned is, in particular, zeolite Na-P, i.e. M is Na. This zeolite occurs generally in the variants Na-P-1, NaP-2 and Na-P-3, which differ in their cubic, tetragonal or crthorhomblc structure (R.M.Barrer, B.M. Munday, J.Chem.Soc. A 1971, 290914). The literature reference just mentioned also describes the preparation of zeolite P-1 and P-2. Zeolite P-3 is accordingly very rare and therefore of virtually no practical interest. The structure of zeolite P-1 corresponds to the gismondite structure known from the abovementioned Atlas of Zeolite Structures. In more recent literature (EP-A-384 070) a distinction is made between cubic (zeolite B or Pc) and tLetragonal (zeolite Pl) zeolite of the P type. Also mentioned therein are more recent zeolites of the P type with Si:Al ratios below 1.07:1. These are zeolites bearing the designation MAP or MAP, for Maximum Aluminiurn P. Depending on the preparation process, zeolite P may include small fractions of other zeolites. Highly pure zeolite P has been described in WO 94/26662.

In the context of the invention it is also possible to use those finely divided, water-insoluble sodium alumosilicates which have been precipitated in the presence of water-soiuble inorganic or organic dispersants and crystallized. These can be introduced in the reaction mixture in any desired manner, prior to or during the precipitation or crystallization.

P, eference is civen to Na-zeolite A and Na-zeolite P.

The hydrotalcites and zeolites can be naturally occurring minerals or synthetically preDaired compounds.

The hydrotalcites and/or zeolites can be employed in amounts of, for example from 0.11 to 50 parts by weight, expediently from 0. 1 to 10 parts by weight and, in particular, from 0. 1 to 5 parls by weight, based on 100 parls by weight of halogen -containing polymer.

Alkali metal aluMocarbonates (dawsonites): These compounds can be represented by the formula {(M20),,.(Al203).Z..pH20j (V), in which M is H, Li, Na, K, Mg,/2, Ca,/2, Sr,/2 or Zn,/2; Z is C02, S02, (C1207)1/2, 13, 06, S202 (th iosulfate) or C202 (oxalate); m, if M is M91/2 or Ca,/2, is a number between 1 and 2. in all other cases a number between 1 and 3; n is a number between 1 and 4; o is a number between 2 and 4; and p is a number between 0 and 30.

The alumo salt compounds of the formula (V) which can be used can be naturally occurring minerals or synthetically prepared compounds. The metals can be partially substituted by one another. The abovementioned alumo salt compounds are crystalline, partially crystalline or amorphous or can be present in the form of a dried gel. The alumo salt compounds can also be present in rarer, crystalline modifications. A process for preparing such compounds is specified in EP 394670. Examples of naturally occurring alumo salt compounds are indigirite, tunisite, al umo hyd rocal cite, para-alumohydrocalcite, stro nti od resse rite and hydrostrontiodresserite. Further examples of alumo salt compounds are potassium alumocarbonate (1<20).(A1203MC02)2.21-120b sodium alumothiosulfate f(Na20),(A1203).(S202)2.2H201, potassium alumosulfite f(K20).(Al203)-(S02)2.2H201, calcium alumooxalate f(Ca0).(Al203).(C202)2. 5H201, magnesium al umotetrabo rate f(MgO).(AI203)-(B,06)2.5H20l,i([MgO. 2NaO.6120).(AI203)-(CO2)2.4.lH201, MM90.2Nao.612 0)-(Al203)-(C02)2.4. 3H20j and f([MgO.3Nac).,1120)-(AI203)-(CO2)2.2.4.9H201- The mixed alumo salt compounds can be obtained in accordance with methods known per se by cationic exchange, preferably from the alkali metal alumo salt compounds, or by combined precipitation (see for example US 5,055, 284).

Preferred alumo salt compounds are those of the above formula in which M is Na or K; Z is C02, S02 Or (C1207)1/2: M is 1-3; n is 1-4: o is 2-4 and p Is 0-20. Z is particularly preferably C02- Also preferred are compounds which can be represented by the following formulae: M20.AI203-(CO2)2. pl-120 (la), (M20)2-(AI203)2-(CO2)2 - pl-120 (lb), M20.(A]203)2.(CO2)2. pl-120 00 N in which M is a metal such as Na, K, Mg,12, Cal/2, Sr,12 or Zn,12 and p is a number from 0 to 12.

Particular preference is given to sodium alumodihydroxycarbonate (DASC) and the homologous potassium compound (DAPC). The dawsonites can be employed in an amount of, for example, from 0.01 to

50 parts by weight, expediently from 0.1 to 10 parts by weight, particularly preferably from 0.1 to 5 parts by weight, based on 100 parts by weight of halogen-containing polymer.

The novel stabilizer combination can be used together with further additives which are customary for the processing and stabilizing of chlorine-containing polymers, examples being: Antioxidants: Suitable examples are:

1. Alkylated monophenols, for example 2,6-di -tert-butyi -4- m ethyl ph e no 1, 2-butyl4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethyl phenol, 2,6-ditert- b utyl-4-n-butyl phenol, 2,6-ditert-buty 1-4 -iso butyl phenol, 2,6dicyclopentyl-4-methyl phenol, 2-(a-methylcyclohexyl)4,6-dimethyl phenol, 2,6-d i octaclecyl -4-m ethyl phenol, 2,4,6-tricyclohexylphenol, 2,6-ditertbutyl-4-methoxymethylphenol, 2,6-dinonyl-4-methylphenol, 2,4-dimethyl6-(l'-methylundecl'-yl)-phenol, 2,4-dimethyl-6-(l'-methylheptadec-l'-yi) phenol, 2,4-d i methyl-6- (1'- m ethyl tridec-l'-yl)phenoi and mixtures thereof.

2. A]kVithiomethylphenols, for example 2,4-diocythiomethyl-6-tertbutylphenol, 2,4-dioctylth io m ethyl-6-m ethyl phenol, 2,4-d ioctylthiomethyl -6-ethyl phenol, 2,6-didodecylthiomethyl-4-nonyl phenol.

3. Hvdroauinones and alkylated hydroquinones. for example 2,6-di-ter-tbutyl4-methoxyphenol, 2,5-di-terL-butylhydroquinone, 2,5-di-=-r,.amvlhydroo.ulnone, 2,6-diphenyl4-ac'Ladecyloxyphenol, 2,6-di-ter-lbutylhydroc.uinone, 2,S-di-,Leri-butyl-4-hydroxyarisole, 3,5-di-ter'Lbutyl-4-hydroxyanisole, 3,5-d'i-ter-butyl-4-hydroxyphenyI stearate, bis(3, 5-di-terlbutyl-4-hydroxyphenyl) adipate.

4. Tocopherols, for example a-tocophero!, b-tocophercl, c -Loco pherol, ctocopherol and mixtures thereof (vitamin E).

5. Hydroxylated thiodiphenyl ethers, for example 2,2'-th io bis (6-te rtbutyl -4-m ethyl -ph eno 1), 2,2'-thiobi s(4-octyl phenol), 4,4'-thiobis (6-tert-butyl-3-methyl phenol), 4,4'-thiobis-(6-tert-butyl2-methyl phenol), 4,4'-thiobis(3,6-di-sec-amylphenol), 4,4'-bis(2,6-dimethyl-4hydroxyphenyl) disulfide.

6. Alkylidenebisphenols, for example 2,2'-methylen e bis (6-tert- butyl 4-m ethyl ph e no 1), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'methylenebis[4-methyl-6-(a-methylcyclohexyl) phenol], 2,2'-methylenebis(4methyl-6-cyclohexylphenol), 2,2'-methylenebis(6- nonyl-4- methyl phenol), 2,2'- methyl enebis (4,6-d i-tert-butyl phenol), 2,2'-ethylidenebis(4,6di-tert-butyl phenol), 2,2'-ethylidenebis(6-tert-buy-4-isobutylphenol), 2, 2'-methylenebis[6-(a-methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-(a, a-dimethylbenzyl)-4-nonylphenol), 4,4'-methylenebis (2,6-d i-tert-butyl phenol), 4,4'-methylen ebis(6-terI-butyl-2-methylphenol), 1,1-bis(5-tertbutyl-4-hydroxy-2-methylphenyl) butane, 2,6-b is (3-te rt- butyl -5- m ethyl2-hydroxybenzyl)-4-methylphenol, 1, 1,3-tris(5-tert-butyl-4-hydroxy2-methylphenyl) butane, 1, 1 -bis(5-tert-butyl-4-hydroxy-2-methylphenyl)3-n-dodecy[mercaptobutane, ethylene glycol bis[3,3-bis(3'-tert-butyl-4'hydroxyphenyl)butyrate], bis (3-tert- butyl-4-hydroxy-5-m ethylphenyl)dicyclopentadiene, bis[2-(3'-tert-butyl-2'-hydroxy-5'methylbenzyl)-6-tert-butyl4-methylphenyl] terephthalate, 1, 1 -bis(3,5dimethyl-2-hydroxyphenyl) butane, 2,2-bis(3,5-dite rt- butyl-4-h ydroxyph enyl) propane, 2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4ndodecy[mercaptobutane, 1, 1,5,5-tetra- (5-tert-butyl-4-hydroxy-2-m ethyl p henyl) pentane.

7. 0-, N- and S-benzvl compounds, for example 3,5,3',5'-tetra-tert-butyl4,4'-dihydroxydibenzyl ether, octadecyl 4-hydroxy-3,5dimethylbenzyimercaptoace'Late, tris(3,5-ditert-butyl-4hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6dimethylbenzyI)dithioterephthalate, bis(3,5-di-tert-butyl-4hydroxybenzyl) sulfide, isooctyl 3,5-di-tert-butyl4hydroxybenzylmercaptoacetate.

8. HydroxVbenzVlated malonates, for example dioctadecyl 2,2-bis(3,5-ditert-butyl2-hydroxybenzyl)malonate, clioctadecyl 2-(3-tert-butyl-4hydroxy-5-methylbenzvi)malonaLe, didodecyl mercaptoethyl-2,2-bis(3,5-diter-t-butyl-4-hydroxvbenzyl)malonate, di(4 - (1,1,3,3 -tetram ethyl butyl) ph en yl] 2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

9. Aromatic hydroxvbenzvl compound, for example 1,3,5-trIs(3,5-di-terLbutyl4 - hyd roxybenzy 1) -2.4,6-tri methyl benzene, 1,4-bis(3,5-di-tertbutyl-4-hydroxybenzyl)2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tertbutyl-4-hydroxybenzyl) phenol.

10. Triazine compounds, for example 2,4-bisoctylmercapto-6-(3,5-di-tertbutyl4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-ditert-butyl-4-hydroxyanilino)1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5di-tert-buLyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-tris(3,5-di-tertbutyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris(3,5-di-tert-butyl4hydroxybenzyi) isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6dimethylbenzyl) isocyanurate, 2,4,6-Lris (3,5-d i-tert-butyl-4-hyd roxyph enyl ethyl) - 1, 3, 5-triazin e, 1,3,5-tris(3,5di-tert-butyl-4hydroxyphenylpropionyl)hexahydro-1,3,5-triazin e, 1,3,5-tris(3,5dicyclohexyl4-hydroxybenzyl) isocyanurate.

11. BenzVlphosphonates, for example dimethyl 2,5-di-tert-butyl-4hydroxybenzylphosphonate, diethyl 3, 5-d i -tert-b utyl -4- hyd roxybe nzyl ph as phonate, dioctaclecyl 3,5-di-tertbutyl-4hydroxybenzylphosphcnate, dioctaclecyl 5-te rt- butyl-4-hyd roxy-3 - m ethyl benzyl phosphonate, the calcium salt of the monoethyl ester of 3,5di-ter-butyl-4-hydroxybenzylphosphonic acid.

12. Acyiar-inophenols, for example 4-hydroxylau rani lid e, 4hydroxystearanilide, octyl N-(3,5-di-ter-L-butyl-4hydroxyphenyl)carbamate.

13. Esters of b-(3,5-di-tert-butyl-4-hydroxyphenVI)proDionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanoi, octaclecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) Isocyanurate, N, N'-bis(hydroxyethyi)oxalamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, tri methylol propane, 4-hydroxymethyl-l-phospha-2,6, 7-trioxabicyclo [2.2.2] octane.

14. Esters cf b-(S-eri-butvl-4-hydroxv-3-methvip,enyl)oroc)ionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol. octanol, octadecanal, 1,6-hexanediol, ',,9nonane-dic, ethylene glycol, 1,2propanediol, neoPentyl glycol, thiodiethylene glycol. diethylene giycol, 'riethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N, N'bis(hydroxyethyl)cxalamide, 3-thiaundecanol, 3-Ithiapentadecanol, trimethylhexanedici, tnmethylol-propane, 4-hydroxymeLhyl-l-phospha-2,6,7trioxab'tcyclo[2.2.2]octane.

1S. Esters of b-(3,5-dicyclohexyl-4-hydroxyphenyl)proc)ionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octaclecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol. 1,2propanediol, neopenty! alycol. thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl', isocyanurate, N, N'-bIs(hyd-cxy2thyl)- oxalamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylol propane, 4-hydroxymethyl-1 -phospha-2,6,7-trioxabicyclo[2.2. 2]octane.

16. Esters of 3,5-di-tert-butVI-4-hydroxvDhenvI 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 (hyd roxyethyl) oxal amid e, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1 -phospha-2,6,7trioxabicyclo[2.2.2]octane.

17. Amides of b- (3,5 -d i-te rt- butyl-4-hyd roxyPh enyl) pro Q ionic acid, for example N,N'-bis(3,5di-tert-butyl-4hydroxyphenylpropionyl)hexam'ethylenediamine, N,N'-bis(3,5-di-tert-butyl4hyd roxyphen yl pro pionyl)tri m ethylenediamin e, N,N'-bis(3,5-di-tertbutyl-4-hydroxyphenylpropionyl)hydrazine. If desired it is also possible to employ a mixture of antioxiclants differing in structure.

The antioxiclants can be employed in an amount of, for example, from 0.01 to 10 parts by weight, expediently from 0.05 to 10 parts by weight and, in particular, from 0.05 to 5 parLs by weight, based on 100 parts by weight of PVC.

UV absorbers and light stabilizers: examples of these are:

1. 2-(2'-Hydroxyphenvl)benzotriazoles, for example 2-(2'-hydroxy-S'methylphenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-(1,1,3,3tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di-terl-butyl-2'hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl2'-hydroxy-5'methylphenyl)-S-chlorobenzotriazole, 2-(3'-sec-butyl-5'-terL-butyl2'hydroxyphenyl)-benzotriazole, 2-(2'-hydroxy-4'octoxyphenyl)benzotriazole, 2-(3',5'-di-tertamyl-2'-hydroxyphenyl)benzotriazole, 2- (3', 5'-bis (a,a-dim ethyl benzyl) -2'-hyd roxyph en yl) benzotriazole, a mixture of 2-(3'-tert-butyl-2'-hydroxy-5'(2-octyloxycarbonylethyl)pheny!)-5chlorobenzo-triazole, 2-(3'-tert-butyl5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxvphenyl)5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonyI ethyl) phenyl)-5chlorobenzo-triazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2metho xycar bon ylet h y 1) phen yl) benzotriazo le, 2-(3'-teri-butyl-2'hydroxy-S'-(2octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl5'-[2-(2ethvlhexyloxy)carbonylethyl]-2'-hydroxyphenyl)ben zotriazole, 2(3'-dodecyl-2'-hydroxy-5'- m ethyl ph e nyl) benzotriazol e, and 2-(3'-tert-butyl-2'-hydroxy-S'-(2- isooctyloxyca rbo nyl ethyl) ph enyl benzotriazo I e, 2,2'-methylenebis[4(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol]; the transesterification product of 2-[3'-tert-butyl-5'-(2methoxycarbonylethyl) -2'-hydroxyphenyl] benzotriazo le with polyethylene glycol 300; COO(CH - IRCH 2 CH 2 2)3 +2 where R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-yl,ohenyl.

2. 2-Hydroxvbenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecylo)(y, 4-benzyloxy, 4,2',4'-trihydroxy and 2'hydroxy-4,4'-dimethoxy derivative.

3. Esters of substituted or unsubstituted benzoic acids, for example 4tert-butyl-phenyl salicylate, pheny! salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis(4-tertbutylbenzoyl)resorcinol, benzoylresorcinoi, 2,4-d'i-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-terL-buy-,-,T-hydroxybenzoa"Le, octaclecyl 3,5-di-tert-buy4hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyI 3,5-di-tert-butyl-4hydroxybenzoale.

4. Acrylates, for example ethyl a-cyano-b,b-diphenylacrylate or isooctyl a-cyanoP,P-diphenylacr-ylate, methyl a-carbomethoxycinnamate, methyl acyano-b-methylp-methoxycinnamate or butyl a-cyano-p-methyl-pmethoxycinnamate, methyl a-carbomethoxy-p-methoxycinnamate and N-(bcarbomethoxy-b-cyanovinyl)-2-methylindoline.

5. Nickel compounds, for example nickel complexes of 2,2'-th io- bi s [4(1,1,3,3 -tetramethylbutyl) phenol], such as the 1:1 or 1:2 complex, with or without additional ligands such as n-butylamine, triethanolamine or Ncyclohexyidiethanolamine, nickel dibuty1dithiccartamate, nickel salts of monoalkyl esters, such as of the methyl or ethyl ester, of 4-hydro)(y-3,5di-tert-butylbenzylphcsphonic acid, nickel complexes of ketoximes, such as of 2-hydroxy-4-metlylphenyl undecy! ketoxime, nickel complexes of 1 phenyl-4-lauroyi5-hydroxypy-azole, with or without additional ligands.

6. StericalIv hindered amines, for example bis(2,2,6,6tetramethylpiperidyl) sebacate. bis(2,2,6,6-tetrametLiylplperidyl) succinate, bis(l 2,2,6,6-pentamethylpio,eridyl) sebacate, bis(1,2,2,6,6centamethylpiperidyl) n-butyl 3,5-di-teri-butyl-4-hydroxybenzylmalonate, tne condensate of 1 -hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the condensate of N,N'-bis(2,2,6,6-tetramethyl-4-p'ipe, ,Idyl)hexamethylenediamine and 4-tertoctylamiro-2.6-cich!,oro-1,3,5-striazine, tr-s(2,2.6,6-tetramethyl-4-piperidy1) nitmotriacetate, tetra ki s (2,2,6,6-tetramethyl -4 - pi peri dyl) 1,2,3,4-butanetetraoate, 1,1'-(1,2-ethanediyl)bis (3,3,5,5-tetra -n ethyl p i perazi none), 4benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy2,2,6,6-tetram ethyl piperidine, bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy3,5di-tert-butylbenzyl) malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8triazaspiro[4.5]decan2,4-dione, b is (1 -octyl oxy- 2,2,6,6-tetram ethyl pi peri dyl) sebacate, bis(l-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, the condensate of N,N'-bis(2,2,6,6-tetramethyl-4piperidyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5triazine, the condensate of 2-chloro4,6-di(4-n-butylamino-2,2,6,6tetramethylpiperidyl)-1,3,5-triazine and 1,2-bis(3aminopropylamino)ethane, the condensate of 2-chloro-4,6-di-(4-nbutylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazine and 1,2-bis (3aminopropylamino) ethane, 8-acetyl-3-dodecyl7,7,9,9-tetram ethyl- 1, 3,8 triazas pi ro [4.5] decan e-2,4-d i one, 3-dodecyl-l-(2,2,6,6tetrameLhyl4-piperidyl)pyrrolidine-2,5-dione, 3-dodecyl-l-(1,2,2,6,6pentamethyl-4-piperidyl)pyrrolidine2,5-dione.

7. Oxalamides, for example 4,4'-dioctyloxyoxanilide, 2,2'diethoxyoxanilide, 2,2'-dioctyloxy5,5'-di-tert-butyloxanilide, 2,2'didodecyloxy-5,5'-di-tert-butyloxanilide, 2-ethoxy-2'ethyloxanilide, N,N'bis(3-dimethylaminopropyl)oxalamide, 2-ethoxy-5-tert-butyl-2% ethyloxanilicle and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tertbutyloxanilide and mixtures of o- and p-methoxy and of o- and p-ethoxydisubstituted oxanilides.

8. 2-(2-Hydroxvohenvi)-1,3,5-triazines, for example 2,4,6-tris(2-hydroxy4-octyloxyphenyl)1,3,5-triazine, 2- (2- hydroxy-4-octyloxyphenyl) -4,6bis (2,4-dim ethyl ph enyl) - 1, 3,5-tri azi ne, 2-(2,4-dihydroxyphenyl)4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy4propyloxyphenyl)-6-(2,4-dimethylphenyt)-1,3,5-triazine, 2-(2-hydroxy-4octyloxyphenyl)4,6-bis(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2hydroxy-4-(2-hydroxy-3-butyloxypropyloxy)-phenylj4,6-bis(2,4dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3octyloxyprolc)cxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

The novel stabilizer mixture is preferred with alkali metal or alkaline ear-th metal carboxylates, especially calcium carboxylates, with aluminium carboxylates, with 1,3-dicarbonyl compounds, with dihydropyridines, with phosphites or with combinations 04, these substances.

Plasticizers: Examples of suitable organic plasticizers are those from the following groups:

A) Phthalic esters: Examples of such plasticizers are dimethyl, diethyl, dibutyl, dihexyl, di-2-ethylhexyl, di-noctyl, di-isooctyl, di-isononyl, di-isodecyl, di-isotridecyl, dicyclohexyl, di-methylcyclohexyl, dimethylglycol, clibutylglycol, benzyl butyl and diphenyl phthalate, and also mixtures of phthalates, such as C7-9- and Cq-11alkyl phthalates from predominantly linear alcohols, C6_10n-alkyl phthalates and C,3,c-n-alkyl phthalates. Among these, preference is given to dibutyl. dihexyl, di-2ethylhexyl, di-n-oct, di-isooctyl, di-isononyl, di-isodecyl, diisotridecyi and benzyl butyl phthalate and to the above rrentio ned mixtures of alkyl phthalates. Particular preference is given to di-2ethylhexyl, cli-isononyl and di-isodecyl phthalate, which are also known under the common abbreviations DOP (dioctyl phthalate, di-2-ethylhexyl phthalate), DINP (diisononyl phthalate), and DIDP (diisoclecyl phthalate).

B) Esters of aliphatic dicarboxylic acids, especially esters oil adipic, azelaic and sebacic acid Examples of such plasticizers are cli-2ethylhexyl adipate, di-isooctyl adipate (mixture), diisononyl adipate (mixture), di-isodecyl adipate (mixture), benzyl butyl adipate, benzyl octyl adipate, di-2-ethylhexyl azelate, di-2-ethylhexyl sebacate and diisodecyl sebacate (mixture). Preference is given to di-2-ethylhexyl adipate and di-isooctyl adipate.

C) Trimellitic esters, for example tri-2-ethylhexyl trimeHitate, triisodecyl trimellitate (mixture), tri-isotridecyl trimellitate, triisooctyl trimellitate (mixture) and also tri-CIS.,,alkyl, tri-Cs.,Oalkyl, tri-C7-galkyl and tri-Cq,alkyl trimellitates. The latter trimellitates are formed by esterification of trimellitic acid with the corresponding mixtures of alkanols. Preferred trimellitates are tri-2-ethylhexyl trimellitate and the abovementioned trimellitates from alkanol mixtures. Common abbreviations are TOTM (trioctyl trimellitate, tri-2-ethylhexyi trimellitate), TIDTM (trilisoclecyl trimellitate) and TITDTM (triisotridecyl trimellitate).

0) Epoxy plasticizers These are principally epoxidizec unsat-irated fatty acids sic',, as epoxidized soybean oil.

E) Polymer plasticizers The most common star,ing materials for the preparation of the polyester plasticizers are] dicarboxylic acids such as adipic, phthalic, azelaic and sebacic acid-, and diols such as 1,2propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, necper', tylglycol and diethylene glycol.

F) Phosphoric esters Examples of suZh phosphoric esters are tributyl phosphate, tri-2-ethylbutyl phosphate, tri-2ethylhexyl phosphate, trichloroethyl phosphate, 2-ethylhexyl diphenyl phosphate, cresyl diphenyl phosphate, triphenyl phosphate, tricresyl phosphate and trixylenyl phosphate. Preference is given to tri-2-ethylhexyl phosphate and to 0 Reofos 50 and 95 (from FMC). G) Chlorinated hydrocarbons (paraffin) H) Hydrocarbons 1) Monciesters, for example butyl oleate, phenoxyethyl oleate, tetrahydrofurfuryl oleate and alkylsulfonic esters. J) Glycol esters, for example diglycol benzoates.

Definitions and examples of plasticizers from groups A) to J) can be found in the following handbooks:

"Taschenbuch der Kunststoffadditive", eds. R. Gcchter and H. Moller, Carl Hanser Verlag, 1989, Chapter 5, pp. 341-442.

"PVC Technology", ed. W.V. Titow, 4th. Ed., Elsevier Publishers, 1984, Chapter 6, pages 147-180.

It is also possible to employ mixtures of different plasticizers.

The plasticizers can be employed in an amount of, for example, from 5 to 120 parls by weight, expediently from 10 to 100 parts by weight, based on 100 parts by weight of PVC.

Examples of suitable lubricants are.- montan wax, fatty acid esters, PE waxes, amide waxes, chlorinated paraffins, glycerol esters or alkaline earth metals soaps, and siliconebased lubricants as described in EP 225261. Lubricants which can be used are also described in "Taschenbuch der Kunststoffadditive", eds. R. Gccnter and H. Mcille,, Carl Hanser Verlag, 3rd edition, 1989, pages 478-488.

Fillers: Examples of possible fillers ("Handbook of PVC-Formulating" by E. J. Wickson, John Wiley & Sons, New York 1993, pp. 393-449) and reinforcing agents ("Taschenbuch der Kunststoffadditive", eds. R. Gcchter and H. Moller, Carl Hanser Verlag, 3rd edition. 1989, pages 549-615) are: calcium carbonate, dolomite, wollastonite, magnesium oxide, magnesium hydroxide, silicates, glass fibres, talc, kaolin, chalk, mica, metal oxides and metal hydroxides, carbon black or graphite), preference being given to chalk.

Pigments: Suitable substances are known to the skilled worker. Examples of inorganic pigments are Ti02, carbon black, Fe203, Sb203, (Ti,Ba,Sb)02, Cr203, spinels such as cobalt blue and cobalt green, Cd(S,Se), ultramarine blue. Preference is given to Ti02, including its micronized form. Examples of organic pigments are azo pigments, phthalocyanine pigments, quinacriclone pigments, perylene pigments, pyrrolopyrrole pigments and anthraquinone pigments. Further details are to be found in "Handbook of PVC Formulating", E.J. Wickson, John Wiley & Sons, New York 1993, pp. 449 - 474.

Examples of the chlorine-containing polymers to be stabilized or their recyclates are: polymers of vinyl chloride, vinyl resins containing vinyl chloride units in their structure, such as copolymers of vinyl chloride and vinyl esters of aliphatic acids, especially vinyl acetate, copolymers ofvinyl chloride with esters of acrylic and methacrylic acid and with acrylonitrile, copolymers of vinyl chloride with cliene compounds and unsaturated dicarboxylic acids or their anhydrides, such as copolymers of vinyl chloride with diethyl maleate, cliethyl fumarate or maleic anhydride, post-chlorinated polymers and copolymers of vinyl chloride, copolymers of vinyl chloride and vinylidene chloride with unsaturated aldehydes, ketones and others, such as acrolein, crotonalclehyde, vinyl methyl ketone, vinyl methyl ether, vinyl isobutyl ether and the like-, polymers of vinylidene chloride and copolymers thereof wit"ir vinyl chloride and other polymerizable compounds-, polymers of vinyl chloroacetate and clichlorodivinyl ether; chlorinated polymers of vinyl acetate, chlorinated polymeric esters of acrylic acid and of alphasubstituted, acrylic acid; polymers of chlorinated styrenes, for example dichlorostyrene-, chlorirated rubbers-, chlorinated polymers of ethylene-, polymers and pcst-chioinated polymers cf crlorobutladiene and - copolymers thereof witl, vinyl chloride, c.1-flornated natural and sy- nthetic rubbers, and mixtures of 'the abovementioned polymers witl, each other or with other polymerizab'ie compounds.

In the conte)ct of this invention the 'erm PVC also i,-icludes copolymers with polymerizable compounds such as acrvionitrile, viry. acetate cr ABS, which can be susoensicn, bulk or emulsion polymers, Preference is given to PVC ncmcpolymer, alone or in combina'lon with polyacrylates.

Also included are 'the graft polymers of PVC wit EVA, ABS and MBS Other preferrecl substrates are mixures of 'he above-entionecl 1-1omc- and copolyme,s. especially. viryl chloride homopolymers, with other thermoplastic and/or elastomeric polymers, especially blends with ABS, iBS, NBR, SAN, EVA, CPE, MBAS, PMA, PMMA, EPDM and polylactones.

Preference is given to suspension polymers and bulk polymers, and to emulsion polymers.

A particularly preferred chlorine-containing polymer is polyvinyl chloride, especially as suspension polymer and bulk polymer.

For stabilization in the context of this invention, further suitable polymers are, in particular, recyclates ofchlorine-containing polymers, these polymers being the polymers described in more detail above that have undergone damage through processing, use or storage. PVC recyclate is particularly preferred. The recyclates may also include small amounts of extraneous substances, for example paper, pigments, adhesives, which are often difficult to remove. These extraneous substances may also arise from contact with various materials in the course of use or of reprocessing, examples being residues of fuel, fractions of coating material, traces of metal and residues of initiator.

The stabilizer mixture is employed in a manner familiar to the skilled worker.

It is also possible, for instance, for the stabilizer mixture to be processed together with conventional additives, prior to the actual use, by shaping it into, for example, granules or extruclate or a paste.

The present invention additionally provides for the use of the abovedescribed stabilizer mixture - as granules, extruclate or paste and/or in conjunction with lubricants (so-called one-pack formulations) - for stabilizing a halogen-containing polymer or polymer recyclate. For the individual stabilizers and for the halooen-containing polymer itself, the preferences expressed above apply; similarly, one of the above-described additional constituents can be employed.

The stabilizer mixture can be added to the polymer in a known manner, the abovementioned stabilizers and, if desired, further additives being mixed witi the halogencontaining polymer using known devices such as mixers, compounders, ex-truders, mills and the like. In this context the stabilizers can be added individually or as a mixture or else in the form of so-called masterbatches. The invention consequently also provides a process for stabilizing halogen-containing polymer, which comprises mixing the stabilizer components and, if desired, further additives with the PVC using devices suc.'i as calenders, mixers, compounders, extruders and the like.

t The invention also relates to the polymer compositions stabilized in this way comprising the novel stabilizer mixture. They can be brought into the desired form by known methods. Examples of such methods are calendering, extrusion, injection moulding, sintering or spinning, and also extrusion blow moulding or processing by the plastisol process. The polymer compositions can also be processed to foams.

The invention also relates to the use ol the stabilized Polymer compositions for preparing mouldings which can be prepared from halogencontaining polymer. The novel polymer compositions are suitable for semirigid and flexible formulations, for example for flexible formulations for wire sheathing and cable insulation. In the form of semirigid formulations, the novel polymer compositions are suitable for decorative films, foams, agricultural films, hoses, sealing profiles, office films, extruded profiles and sheets, flooring films and sheets, coated products and synthetic leathers, and also crashpad sheets (for use in the automotive sector).

In the form of rigid formulations, the novel Polymer compositions are suitable for hollow articles (bottles), packaging films (thermoform films), blown films, crashpad sheets (cars), pipes, foams, heavy profiles (window frames), transparent wall profiles, construction profiles, sidings, fittings and apparatus enclosures (computers, domestic appliances) and also other injection-moulded articles.

Examples of the use of the polymer compositions stabilized in accordance with the invention as plastisol are artificial leathers, flooring, textile coatings, wallpapers, coil coatings and underbody protection for motor vehicles.

Examples of sinter applications of the polymer compositions stabilized in accordance with the invention are slush, slush mould and coil coatings.

The preparation of the N-piperldinyltriazines is known from tne literature (-,f- e.c. HCUtenWeyl "Methoden der organischen Chemie" Vol. Vill, pp. 233-237, SAUERSTOFFVERBINDUNGEN III, 3rd Ed., Thieme Verlaq Stuttgarl, 1952). As starting material lor the reaction with var'ous Npiperidinylamines it, is pcssibie i3 ernlpio"" -,,,,,anur!C chloride, dlamino-c,Ioro-l 3,S-t,,iazine or variously substituted bisdialkylaminochloro-1,3,5triazines or dialkylamino- and,lor al',Kvlamino-dichloro-1,3, 5-tr;azines.

The examples which follow illustrate the invention!n more detail withoi restricti,7- it. As in the remainder of the cescription, pars and percentages are t)y weigh- unless otherwise.

Example 1: N,N'-tDis[2.2,6,6-te,am--ivi.cipe,,idin-4-yl]oxamide 156.3 g (0.8 mol) of 4-amino-2,2,6,6-tetramethylpiperidine are added slowly with stirring to 56.1 g (0.4 mol). oi diethyl oxalate, arninolysis taking place with severe evolution of heat. The temperature rises to about 1 OOOC. Following the addition of 150 ml of xylene, ethanol is distilled off at 88-137"C over the course of 18.5 hours. The batch is subsequently taken up in 1500 ml of xylene, filtered while hot, and cooled. The precipitated crystals are filtered off with suction and recrystallized from xylene.

Yield 120g (82% of theory) m.p. 225-231C.

The following products (Examples 2 - 8) were prepared by reacting 4-amino2,2,6,6tetram ethyl piperid in e with the corresponding acid chlorides or by reacting bis-2,2,6,6tetram ethyl pi peridi nyl- 1, 6-hexan ediam i ne with acetic anhydride:

0 0 2: HN NH-C NH m.p. 273'C decomp., Z 3: HN > NH-CO-CH 2 CH 2)2 m.p. 217'C; N 4: ( H > NH-CO-CH 2 CH 2 CH 2-CH 2)2 m.p. 145OC; r C-CO-N-CH LH3 212 5: m. P. 11 97-1 99'C; tNj H [n-C H,,-CO-N-(CH S 2)312 6: HK rn.p. 79-81 "C' -32 NH NH.-C 0 NH 7: C NH, m.p. > 300'C NHNH ' -C C) N-CO-CH,8: H Nixt- 12 1 m.p. 140-1430C.

Example 9: For preparing the stabilizers I and 11, a Zn/Ca stearate mixture is mixed intensively with a commercial beta-diketc-ne (stab. 1) and also with the piperidine compound 5 in a ratio of 8.-2.-1.5 (stab. 11) in a tumble mixer for a period of 1.5 hours. Of these stabilizermixtures, portions of 1.0 part (stab. 1) or 1.15 parts (stab. 11) are each mixed with 100 parts of S-PVC (K value 70) and 21 pa,-ts of a mixture of dicictyl phthalate/epoxidized soya oil and with a commercial liquid aryl-alkyl phosphite, and the mixture is plasticated on mixing rollers at 1 900C for 5 minutes. Test specimens are cut from the resulting sheets (thickness 0.2 mm) and are subjected to thermal stress in a Mathis Thermotakter at 180'C for the period indicated in Table I below. Subsequently the Yellowness Index (YI) is determined in accordance with ASTM-1925-70.

The lower the YI value found, the more effective the prevention by the stabilizer system of yellowing anc -herefore of damage to tne material. The long-term the,,mal stability of the stabilized polymer is evident from the sudder onset of massive discolouration. A stabilizer is all the more effective the!oncer th,s disc--IoLraticn is delayed under t1r,ermal stress conditions.

Heat test: YJ of tes7t specimens at 1800C Table 1

Stabilizer Coadditive Test duratlon [min] Inlerrupted 0 6 12 24 48 at time [min] 5.1 5.4 5.3 black black 17 Com pd. 5 5.7 6.0 6.5 7.9 12.8 70

Claims (14)

WHAT IS CLAIMED IS:

1. A stabilizer combination for halogen-containing polymers, comprising A) at least one organic zinc compound with a Zn-O bond and/or a Zn-S bond B) at least one compound of the formula 0 R C (C H') I 1 1 1 N N N H,% H R, in which the radicals and symbols have the following meanings:

R,: H or Cj-C8alkyl, C3-C8alkenyl, C7-Cqphenylalkyl or C-C8cycloalkyl-, R,5- H, C.,-C8alkyl, C3-Cealkenyl, C5CS-CYCloalkyl or G; G: N A: -CO-, -(CH2)1-, -(CH2)d-CO- or -NH(CH2),-CO-; m: 0 or 1 -, n:

2 to 12; p: 0 or 1; d: 1 to 8; r: 2 to 50-1 and, if p is 0, A: -CO-, -(CH2)-,, - (CH2)d-COor -NH(CH2),-C0-.1 if p is 1, A: (CH2)1- 2. A stabilizer combination according to caim 11 in.%,hich the radicals and symbos have the following meanings:

R.,: H, or Cl-C8alkyl-, R5: H, C.-Cealkyl or G-, A- _C0_. -(CH2).-, -(CH2)d-CO- or -NH(CH2),-CO-., m-. 0 or 1 1 n: 2 to 6: p: 0 or 1", d: 1 to 4, r: 2 to 501 and, if p is 0, A: -CO-, -(CH2)-m, - (CH2)d-CO- Or -NH(CH2)n-CO--, if p is 1, A: (CH2)rl-

3. A stabilizer combination according to claim 1, in which the radicals and symbols have the following meanings:

R, H or Cl-CBalkyl; R5 G; A: -(CH2)m-; and m: 0 or 1; n: 2 to 6; p: 0; r'. 2 to 50.

4. A stabilizer combination according to claim 1 in which the organic zinc compound has a Zn-0 bond.

5. A stabilizer combination according to claim 1 in which the organic zinc compound is a zinc carboxylate.

6. A stabilizer combination according to any preceding claim which additionally comprises alkali metal compounds and/or alkaline earth metal compounds and/or aluminium compounds.

7. A stabilizer combination according to any preceding claim which additionally comprises calcium carboxylates.

8. A stabilizer combination according to any preceding claim which additionally comprises aluminiurn carboxylates.

9. A stabilizer combination according to any preceding claim which additionally comprises at least one further substance from the group consisting of the epoxides and epoxidised fatty acid esters, phosphites, thiophosphites and thiophosphates, polyols, 1,3carbonyl compounds, mercaptocarboxylic esters, dihydropyridines, antioxidants, light stabilizers and UV absorbers, alkali metal compounds and alkaline earth metal compounds, perchlorate salts, zeolites, hydrotalcites and dawsonites.

10. A stabilizer combination according to any one of the preceding claims in which the combination further comprises an inorganic zinc compound.

11. A stabilizer combination for halogen-containing polymers, comprising:

a) at least one inorganic zinc compound b) at least one compound B) as defined claim 1.

12. A composition comprising a halogen-containing polymer and a stabilizer combination according to any one of the preceding claims.

13. A process for stabilizing halogen-containing polymers, which comprises adding to them a stabilizer combination according to any one of claims 1 to 11.

14. A stabilizer combination according to claim I comprising one or more compounds substantially as hereinbefore described.