AU766239B2 - Stabiliser combinations for chlorine-containing polymers - Google Patents

Description

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AUSTRALIA

Patents Act 1990

ORIGINAL

COMPLETE SPECIFICATION STANDARD PATENT Applicant(s): Crompton Vinyl Additives GmbH Chemiestrasse 22 D-68623 Lampertheim Germany DAVIES COLLISON CAVE Patent Trade Mark Attorneys Level 10, 10 Barrack Street SYDNEY NSW 2000 Address for Service: Invention Title: Stabiliser combinations for chlorine-containing polymers The following statement is a full description of this invention, including the best method of performing it known to me:- 5020 P:WPDOCSHUjw\Spccs 2\CROMPTON D3.doc-11/08/03 -1- STABILISER COMBINATIONS FOR CHLORINE-CONTAINING POLYMERS This application is a divisional of Australian patent application No. 58328/99.

The ensuing description is substantially identical to the description of the earliest "parent" application, No. 68041/96. The parent description has been fully readopted to facilitate identification of the parent/divisional relationship. The invention subject of this divisional application is as defined in the claims which follow.

The broad invention as described and exemplified herein relates to stabiliser combinations consisting of a compound of formula I shown below and at least one further substance from the following groups: the perchlorate compounds, glycidyl compounds, beta-diketones, beta-keto esters, dihydropyridines, polydihydropyridines, polyols, disaccharide alcohols, sterically hindered amines (tetraalkylpiperidine compounds), alkali aluminosilicates, hydrotalcites and alkali aluminocarbonates (dawsonites), alkali-(or alkaline earth-) carboxylates,- (bi)carbonates oder -hydroxides, antioxidants, lubricants or organotin compounds which are suitable for stabilising chlorine-containing polymers, especially PVC. PVC can be stabilised by a number of additives. Compounds of lead, barium and cadmium are especially suitable for the purpose but are controversial today for ecological reasons or owing to their heavy metal content (cf. "Kunstoffadditive" (Plastics additives), R. Gachter/-H. M.iller, Carl Hanser Verlag, 3 r d Edition, 1989, pages 303- 311, and "Kunststoff Handbuch PVC" (Plastics Handbook PVC), Volume 2/1, W.

Becker/D. Braun, Carl Hanser Verlag, 2 nd Edition, 1985, pages 531-538; and Kirk- Othmer: Encyclopedia of Chemical Technology", 4 t h Ed., 1994, Vol 12, Heat Stabilisers p. 1071-1091). Other effective stabilisers and stabiliser combinations that are free of lead, barium and cadmium are therefore sought. Compounds of formula I have already been described in DE-PS 1 694 873, EP 65 934 and EP 41 479 and can be prepared in one or several process step(s) by known methods.

P:\WPDOCS\HjwSpccs 2\CROMPTON D3.doc- 1/08/03 -2- It has now been found that A) compounds of formula I 0 R* 1 Y N NH 2

I

R*2 wherein R*i and R* 2 are each independently of the other C 1

-C

1 2 alkyl, C 3

C

6 alkenyl, Cs-Cscycloalkyl that is unsubstituted or substituted by from 1 to 3 C 1

C

4 alkyl, C 1

-C

4 alkoxy, Cs-Cscycloalkyl or hydroxy groups or chlorine atoms, or C 7

C

9 phenylalkyl that is unsubstituted or substituted at the phenyl ring by from 1 to 3

C

1

-C

4 alkyl, C 1

-C

4 alkoxy, Cs-C 8 cycloalkyl or hydroxy groups or chlorine atoms, and R*i and R* 2 may additionally be hydrogen and C 1

-C

12 alkyl, and Y is S or O, can be combined with B) at least one compound from the following group: perchorlate compounds and/or glycidyl compounds and/or beta-diketones, beta-keto esters and/or dihydropyridines, polydihydropyridines and/or polyols, disaccharide alcohols and/or 15 sterically hindered amines (tetraalkylpiperidine compounds) and/or alkali aluminosilicates (zeolites) and/or hydrotalcites and/or alkali aluminocarbonates (dawsonites) and/or, alkali- (or alkaline earth-) carboxylates,-(bi)carbonates oder -hydroxides, 20 and/or antioxidants and lubricants and/or organotin compounds for the purposes of stabilising chlorine-containing polymers, especially PVC.

*~e P:\WPDOCS\Hjw\Spes 2\CROMPTON D3.doc-I 1/08/03 -3- The present invention as claimed provides a stabiliser combination comprising A) at least one compound of formula I 0 R* I Y N NH 2

I

R*2 wherein and R* 2 are each independently of the other C 1 -C1 2 alkyl, C 3

-C

6 alkenyl, Cecycloalkyl that is unsubstituted or substituted by from 1 to 3 C 1

-C

4 alkyl, C 1

C

4 alkoxy, Cs-C 8 cycloalkyl or by hydroxy groups or chlorine atoms, or C 7 -Cgphenylalkyl that is unsubstituted or substituted at the phenyl ring by from 1 to 3 Cz-C 4 alkyl, Cz-

C

4 alkoxy, C 5

-C

8 cycloalkyl or by hydroxy groups or chlorine atoms, and R* 1 and R* 2 may additionally be hydrogen and C 1 -C1 2 alkyl, and Y is S or 0, and B) at least one alkali- (or alkaline earth-) carboxylate, -(bi)carbonate or -hydroxide compound.

For compounds of formula I:

C

1

-C

4 Alkyl is, for example: methyl, ethyl, n-propyl, isopropyl, iso-, sec- or 15 tert-butyl.

C

1

-C

1 2 Alkyl is, for example, in addition to the radicals just mentioned, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, isooctyl, decyl, nonyl, undecyl or dodecyl.

C

1

-C

4 Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy or isobutoxy.

Cs-C 8 Cycloalkyl is, for example, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

C

7 -CPhenylalkyl is, for example, benzyl, 1- or 2-phenylethyl, 3-phenylpropyl, a,adimethylbenzyl or 2-phenylisopropyl, preferably benzyl.

When the cycloalkyl groups or the phenyl group of the phenylalkyl radicals are substituted, then they are substituted preferably by two or one substituent and, of 25 the substituents, especially by CI, hydroxy, methyl or methoxy.

C

3

-C

6 Alkenyl is, for example, vinyl, allyl, methallyl, 1-butenyl or 1-hexenyl, preferably allyl.

Preference is given to compounds of formula I wherein R*1 and R*2 are each independently of the other C1-C4alkyl and hydrogen.

Especially preferably, either R*1 and R*2 are identical and are methyl, ethyl, propyl, butyl or allyl, or they are different and are ethyl and allyl.

To achieve stabilisation in a chlorine-containing polymer, the compounds of component A) are to be used in an amount of advantageously from 0.01 to 10 by weight, preferably from 0.05 to 5 by weight, and especially from 0.1 to 3 by weight.

The compounds of the groups mentioned under B) are illustrated as follows: Perchlorate compounds Examples are those of formula M(C104)n, wherein M is Li, Na, K, Mg, Ca, Sr, Zn, AI, La or Ce. According to the value of M, the index n is 1, 2 or 3. The perchlorate salts may be complexed with alcohols (polyols, cyclodextrins) or ether alcohols or ester alcohols. The ester alcohols include also the polyol partial esters. Also suitable in the case of polyhydric alcohols or polyols are their dimers, trimers, oligomers and polymers, such as di-, tri-, tetra- and polyglycols, and di-, tri- and tetra-pentaerythritol or polyvinyl alcohol in various degrees of polymerisation. The perchlorate salts can be introduced in various known forms, for example in the form of a salt or an aqueous solution applied to a substrate, such as PVC, calcium silicate, zeolites or hydrotalcites, or bound in a hydrotalcite by chemical reaction. Glycerol monoethers and glycerol monothioethers are preferred as polyol partial ethers. Other forms are described in EP 394 547, EP 457 471 and WO 94/24 200.

The perchlorates can be used in an amount of, for example, from 0.001 to advantageously from 0.01 to 3, especially from 0.01 to 2, parts by weight, based on 100 parts by weight PVC.

6lycidyl compounds o These contain the glycidyl group CH---CH,) n which is bonded

R,

1 R R 3 directly to carbon, oxygen, nitrogen or sulfur atoms and wherein either RI and R3 are both hydrogen, R2 is hydrogen or methyl and n=0, or R1 and R3 together are -CH2-CH2- or -CH2-CH2-CH2-, in which case R2 is hydrogen and n=0 or 1.

I) Glycidyl and b-methylglycidyl esters obtainable by reacting a compound having at least one carboxy group in the molecule with epichlorohydrin or glycerol dichlorohydrin or b-methyl-epichlorohydrin. The reaction is advantageously carried out in the presence of bases.

Aliphatic carboxylic acids may be used as compounds having at least one carboxy group in the molecule. Examples of those carboxylic acids are glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid or dimerised or trimerised linoleic acid, acrylic acid and methacrylic acid, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic i acid and pelargonic acid, and the acids mentioned in connection with the organic zinc compounds.

It is, however, also possible to use cycloaliphatic carboxylic acids, such as cyclohexanecarboxylic acid, tetrahydrophthalic acid, 4methyltetrahydrophthalic acid, hexahydrophthalic acid or 4methylhexahydrophthalic acid.

It is also possible to use aromatic carboxylic acids, such as benzoic acid, phthalic acid, isophthalic acid, trimellitic acid or pyromellitic acid.

Carboxy-terminated adducts, for example of trimellitic acid and polyols, such as glycerol or 2, 2 -bis(4-hydroxycyclohexyl)propane can also be used.

Other epoxide compounds that can be used within the scope of this invention are to be found in EP 0 506 617.

II) Glycidyl or (b-methylglycidyl) ethers obtainable by reacting a compound having at least one free alcoholic hydroxy group and/or phenolic hydroxy group and a suitably substituted epichlorohydrin under alkaline conditions, or in the presence of an acid catalyst with subsequent treatment with an alkali.

Ethers of that type are derived, for example, from acyclic alcohols, such as ethylene glycol, diethylene glycol and higher poly(oxyethylene) glycols, propane-1,2-diol, or poly(oxypropylene) glycols, propane-1,3-diol, butane-1,4diol, poly(oxytetramethylene) glycols, pentane-1,5-diol, hexane-1,6-diol, hexane-2,4,6-triol, glycerol, 1,1,1-trimethylolpropane, bistrimethylolpropane, pentaerythritol, sorbitol, and from polyepichlorohydrins, butanol, amyl alcohol, pentanol, and from monofunctional alcohols, such as isooctanol, 2ethyihexanol, isodecanol and C7-Cgalkanol anid C9-Cllalkanol mixtures.

They are, however, also derived, for exanple, from cycloaliphatic: alcohols, such as 1,3 or I ,4-di hydroxycyclohexane, bis(4-hydroxycyclohexyl)methane, 2,2-bis(4-hydroxycyclohexyl)propane or I ,1-bis(hydroxymethyl)cyclohex..3 ene, or they have aromatic nuclei, such as N,N-bis(2-hydroxyethyl)ani line or p,p'-bis(2 -hydroxyethylami no)diphenylmethrme.

The epoxide compounds can also be derived from mononuclear phenols, such as phenol, resorcinol or hydroquinone, or they are based on polynuclear phenols, such as bis(4-hydroxyphenyl)metharie, 2,2-bis(4hydroxyphenyl)propane, 2,2-bis(3 ,5-di bromo-4-hydroxyphenyl)propane, 4,4'dihydroxydiphenylsulfone, or on condensation products of phenols with formaldehyde obtained under acid conditions, such as phenol novolaks.

Other possible terminal epoxides are, for example: glycidyl-1-naphthyl ether, glycidyl- 2-phenylphenyl ether, 2-bi phenylglycidyl ether, N-(2 .3epoxypropyl) phthalimide and 2 3 -epoxypropyl-4-methoxyphenyl ether.

II) (N-Glycidyl) compounds obtainable by dlehydrochiorinating the reaction products of epichlorohydrin with amines containing at least one aminohydrogen atom. Those amines are, for example, aniline, N-methylani line, toluidine. n-butylamine, bis(4-aminophenyl)methane, m-xylylenediamine or bis(4-methylaninophenyl)methane, but also W,N,O-triglycidyl-m-aminophenol or NN,O-triglycidyl-p-aminophenol.

The (N-glycidyt) compounds also include, however, N,N-di-, N,N',N'-triand N,N4,N',N"'-tetra-gycidyl derivatives of cycloalkyleneureas, such as ethyleneurea or 1,3-propyleneurea. and NN'diglycidyl derivatives of hydantoins, such as 5,5-dimethylhydantoin or glycoluril and triglycidyl iso cyanurate.

IV) 5-Glycidyl compounds, such as di-S-glycidyl derivatives, that are derived from dithiols, such as ethane-1,2-dithiol or bis(4mercaptomethylphenyl) ether.

V) Epoxide compounds containing a radical of formula I wherein R1 and PR3 together are -CH2-CH2- and n is 0 are bis(2,3-epoxycyclopentyl) ether, 2,3-epoxycyclopentylglycidyl ether or 1,2-bis(2,3epoxycyclopentyloxy)ethane. An epoxy resin containing a radical of formula I wherein RI and R3 together are -CH2-CH2- and n is 1 is, for example, 3,4epoxy-6-methylcyclohexanecarboxylic acid (3',4'-epoxy-61methylcyclohexyl)-methyl ester.

Suitable terminal epoxides are, for example TM denotes®) a) liquid diglycidyl ethers of bisphenol A, such as AralditeTmGY 240.

AralditeTmGY 250, AralditeTmGY 260, AralditeTMAGY 266, AralditeTmGY 2600, AralditeTmMY 790; b) solid diglycidyl ethers of bisphenol A, such as ArolditeMT 6071, AralditeTmGT 7071, AralcliteTmGT 7072. AraiditeTMGT 6063, AralditeTmGT 7203, AralditeTm6T 6064, AralditeTMGT 7304, AralditeTMGT 7004, AralditeTmGT 6084, AralditeTmGT 1999, AralditeTMGT 7077, ArcilditeTMGT 6097, AralditeTm&r 7097, AralditeTMGT 7008, AralditeTmGT 6099, AralditeTmGT 6608, ArolditeTMGT 6609, ArcllditeTMGT 6610; c) liquid dliglycidyl ethers of bisphenol F, such as AralditeTMGY 281, AralditeTMPY 302, AralditeTAPY 306; d) solid polyglycidyl ethers of tetraphemylethane, such as CG7 Epoxy ResinTmOl63; e) solid and liquid polyglycidyl ethers of phenolformaldlehyde novolak, such as EPN 1138, EPN 1139, GY 1180, PY 307; solid and liquid polyglycidyl ethers of o-cresolformaldehyde novolak, such as ECN 1235, ECN 1273, ECN 1280, ECN 1299; 9) liquid glycidyl ethers of alcohols, such as 5hellTm glycidyl ether 162, AralditeTmtDY 0390, Aralclite llY 0391; h) liquid glycidyl ethers of carboxylic acids, such as ShellTmCardura E terephthalic acid ester, trimellitic acid ester, AralditeMPY 284; i) solid heterocyclic epoxy resins (triglycidyl isocyanurate), such as AralditeTm PT 810; j) liquid cycloaliphatic epoxy resins, such as AralditeMCY 179; k) liquid N,N,O-triglycidyl ethers of p-aminop henol, such as AraiditeTMY 0510; 1) tetraglycidyl-4,4'-methylenebenzamine or N,N,N,N'-tetraglycidyldiam inophenylmethane, such as AralditeTMMY 720, AralditeTMMY 721.

Preference is given to the use of epoxide compounds having two functional groups. It is, however, also possible in principle to use epoxide compounds having one, three or more functional groups.

There are used predominantly epoxide compounds, especially diglycidyl compounds, having aromatic groups.

Where appropriate, a mixture of different epoxide compounds can also be used.

Especially preferred as terminal epoxide compounds are diglycidyl ethers based on bisphenols, such as 2 2 -bis(4Lhydroxyphenyl)propane (bisphenol A), bi s(4-hydroxyphenyl)-methane or mixtures of b is(ortho/parahydroxyphenyl)methane (bisphenol F).

The terminal epoxide compounds can be used in an amount of, preferably, at least 0.1 part, for example from 0.1 to 50, advantageously from 1 to 30, and especially from I to 25, parts by weight, based on 100 parts by weight PVC.

0ta-diketnes, beta-keto esters 1.3-[)icarbonyl compounds that can be used may be linear or cyclic dicarbonyl compounds. Preference is given to the use of dicarbonyl compounds of the following formula:.

R'iCO CHR2-COR'3 wherein 1 is C1-C22alkyl. C5-Clohydroxyalkyl, C2-Cl8alkenyl. phenyl, phenyl subsitued y O, C-C4al'kyl, C1-C4alkoxy or by halogen, C-Clophenylalkyl, 2cycloalkyl, C5-Cl2cycloalkyl substituted by CI-C4.alkyl. or is a group 5-R*6or -RS--R'6.

R2 is hydrogen, C1-C8alkyl, C2-CI201kenyl, phenyl, C7'-Cl2alkylphenyl. C7- Clophenylalkyl or a group -CO-R'4, R'3 has one of the meanings given for R'l or is Cl-Cl8alkoxy, R'4 is C1-C4alkyl or phenyl, is Ci-Cloalkylene and R'6 is Cl-Cl2alkyI, phenyl, C7-Cl8alkylphenyl or C7-Clophenylalkyl.

Those compounds include the hydroxy group- contai ni ng diketones of EP 346 279 and the oxa- and thia-diketones of EP 307 358, as well as the keto esters based on isocyanic acid of U5 4 339 383.

R'l and R'3 as alkyl may be, especially, CI-Ci~alkyl, such as methyl, ethyl, npropyl, isopropyl, n-butyl, tert-butyl. pentyl, hexyl, heptyl, octyl, decyl, dodecyl or octadecyl.

R'j and R'3 as hydroxyalkyl are, especially, a group -(CH2)n-OH, wherein n is 6 or 7.

Ril and R'3 as alkenyl may be, for example, vinyl, allyl, methallyl, 1-butenyl, Ihexenyl or oleyl, preferably allyl.

R'i and R'3 as phenyl substituted by OH, alkcyl, alkoxy or halogen may be, for example, tolyl, xylyl. tert-butyphenyl, methoxyphenyl, ethoxyphenyl, hydroxyphenyl, chlorophenyl or dichiorophenyl.

RI and R'3 as phenykilkyl are especially benizyl. R'2 and R'3 as cycloalkyl or alkylcycloalkyl are especially cyclohexyl or metluylcyclohexyl.

R'2 as alkyl may be, especially, CI-Cqalkyl. R*2 as C2-Cl2alkenyl- may be, especially, allyl. R'2 as alkylphenyl may be, especially, tolyl. R'2 as phenylalkyl may be, especially, benzyl. R'2 is preferably hydrogen. R'3'as alkoxy may be. for example, methoxy, ethoxy, butoxy, hexyloxy, octyloxy, dodecyloxy, tridecyloxy, tetrcidecyloxy or octadecyloxy. R.'5 as Ci-Cioalkylene is especially C2- C4alkylene. R'6 as alkyl is especially C4-Cl2alkyI., such as butyl, hexyl, octyl, decyl or dodecyl. R'6 as alkylphenyl is especially tolyl. R.6 as phenylalkyl is especially benzyl.

::Examples of 1,3-dicarbonyl compounds of the above formula and their alkali metal, alkaline earth metal and zinc chelates are acetylacetone, butanoylacetone, heptanoylacetone, -stearoylaceltone, palmitoylacetone, lauroylacetone, 7-tert-nonylthio-heptane-2 ,4-.io ne, benzoylacetone, di benzoylmethane, lauroylbenzoylmethane, palnitoyl-benzoylmethane, stearoylbenzoylmethane, isooctylbenzoylmethane, tribenzoylmethane, bis(4-methylbenzoyt)methane, benzoyl-pchlorobenzoylmethane, bis(2-hydroxybenzoyl)nieihane, 4-methoxybenzoylbenzoylmethane, bis(4-methoxybenzoyl)methane, 1 -benzoyl-l1-acet-ylno nane, benzoyl-acetyl phenylmethane, stearoyl-4-methoxybenzoylmethane, bis(4-tertbutyl benzoyl)methane, benzoyl-formylmethane, benzoyl-phenylacetylmethane, biscyclohexainoyl-methane, di -pivaloyl -methane, 2 -acetylcyclopentanone, 2-benzoylcyclopentainone, diacetoacetic acid methyl, ethyl and allyl ester, benzoyl-, propionyl- and butyryl-acetoacetic acid methyl and ethyl ester, triacetylmethane, acetoacetic acid methyl, ethyl, hexyl, octyl, dodlecyl or.

octadecyl ester, benzoylacetic acid methyl, ethyl, butyl, 2-ethylhexyl, dodecyl or octacdecyl ester, and propionyl- and butyryl-cicetic acid C1-Cl8alkyl ester.

Steoroylacetic acid ethyl, propyl, butyl, hexyl or octyl ester and polynuclear1keto esters as described in EP 433 230 and dehydroacetic acid and the zinc.

magnesium or alkali metal salts thereof.

Preference is given to 1,3-diketo compounds of the above formula wherein R'j is C1-Cl8alkyl, phenyl, phenyl substituted by OH, methyl or by methoxy, C7- Ciophenylalkyl or cyclohexyl, R'2 is hydrogen and R'3 has one of the meanings given for R'i.

The 1,3-diketo compounds can be used in an amount of, for example, from 0.01 to 10, advantageously from 0.01 to 3, and especially from 0.01 to 2, parts by weight, based on 100 parts by weight PVC.

bikydropyridies. polydihydropyridines Suitable monomeric, dihydropyridines are described, for example, in FR 20 39 496, EP 2007, EP 0 362 012, EP 0 286 887 and EP 0 024.754.

Preference is given -to those of the formula ,wherein Z is

H

3 CNHI

CH

3

CO

2

CH

3 C0 2

C

2

H

5 C0 2 nC 1 2

H

25 or COC 2

H

4 SnC 2

H

25 Suitable polydihydropyridines are especially compounds of the following formula wherein T is Cl-C22alkyl that is unsubstituted or substituted by Ci- Cl8alkoxy, Cl-Cl Balkylthio, hydroxy, acryloyloxy, methacryloyloxy, halogen, phenyl or by naphthyl; that is unsubstituted or substituted by CI-Ci~alkyl, CI-Cl8alkoxy or by halogen and that may also be heterocyclic; C3-Cloalkenyl, CH3-CO-CH2-CO-OR-. CH3-CO-CH2-COO-R', CH3- C(NR'2)--CH-COOR- or CH3-C(NR' '2)=CHCO-O l'I- L has the same meanings as T or is a tri- or poly-valent radical from an unsubstituted or Cl-Cl 2alkoxy-, Cl-Cl 2thioal koxy-, C6-Cl~arYl-. Cl- Cl2carboxy- or hydroxy-substituted straight-chained or branched alkyl group, m and n are numbers from 0 to k is 0 or 1, j is anumber fromi Ito 6and the conditions j(k- m +n)l>Iand m'+n 0are satisfied, R and R' are each independently of the other methylene. or phenylene or an alkylene group of the type -(-CpH2p-X-)t CpH2p- that is unsubslituted or carries substituents from the series Cl-Cl2alkoxy, C1-Cl2thioalkoxy, C6- Cloaryl, CI-Ci2carboxy and hydroxy, p is from 2 to 18, t is from 0 to X is oxygen or sulfur, or, when k is 0 and j 1. R and R' together with L form a direct bond, R" is hydrogen, or Cl-C18alkyl, C2-Cl8alkoxycarbonyl or C6-Cloaryl each of which is unsubstituted or substituted by one or more C1-Ci2alkyl, CI-C8alkoxy, halogen or N02 substituents, and the two R' radicals are identical or different and are hydrogen, Cj- C18alkyl, Cl-C18-hydroxyalkyl or CI-Cl~alkoxyalkyl or together are uninterrupted or 0-interrupted C3 or are straight-chained or branched C2-C22alkenyl.

Such compounds are described in more detail in EP 0 286 887.

Thiodiethylene- bis(5-methoxycarbonyl-2 ,6-dimethyl-1 ,4-di hydropyridi ne-3-.

carboxylate] is especially preferred.

Die (Poly-)bihydropyridine konnen im chiorholtigen Polymer zweckma~ig zu 0,001 bis 5 und insbesondere 0,005 bis I Gew.-Teilen, bezogen auf doas Polymer, angewcindt werden.

Polyols, disaccharide akcohols Examples of suitable compounds of that type are: pentaerythritol, dipentaerythritol, tripentaei-ythritol, bistrimethylo Ipropone, bistrimethylolethane, trismethyloipropane, i nosite, po lyvi nylalco hot, sorbitol, maltite, isomaltite, lactite, lycasin, mannitol, lactose, leucrose, S. OS tris(hydroxyethyl) isocyanurate, palatinite, tetramethylolcyclohexano

I,

tetramethylo Icyclopentano I, tetramethylolcyclopyrano I, glycerol, diglycerol, polyglycerol, thiodiglycerol or I-O-a-D-glycopyranosyl-tj-mannitol dihydrate. Of those compounds, preference is given to the disaccharide alcohols.

The polyols can be used in an amount of, for example, from 0.01 to 558555 advantageously from 0.1 to 20, and especially from 0.1 to 10, parts by weight, based on 100 parts by weight PVC.

Sterically hindered amines (te traalkylpiperidine compounds) The sterically hindered amines, especially piperidline compounds, that can be used according to the invention are known especially as light stabilisers. Those compounds contain one or more groups of the formula

H

3 C N

C

HCC

They may be compounds of relatively low molecular weight (<700) or of relatively high molecular weight. In the latter case they may be oligomeric or polymeric products. Preference is given to tetramethylpiperidine compounds having a molecular weight of more than 700 that contain no ester groups.

Especially important as stabilisers are the following classes of tel-ramethylpiperidline compounds.

In the following classes a) to substituents having subscript indices in their formula drawings correspond (for technical reasons) to the substituents having superscript indices in the description or definition belonging to the formula drawing in question. Thus, for example, the substituent "RI" in formula (II) corresponds to "R 1 in the descriptions.

a) Compounds of formula II

H

3 C cH 3

R

1 -N 0--R2 HC CH, n

(II),

wherein n is a number from 1 to 4, preferably 1 or 2, Rl is hydrogen, oxy. C1-C12alkyl, C3-C8alkenyl, C3-C8alkynyl, C7-C12aralkyl, C1-C8alkanoyl, C3-C5alkenoyl, glycidyl or a group -CH2CH(OH)-Z, wherein Z is hydrogen, methyl or phenyl, R 1 being preferably C1-C4alkyl, allyl, benzyl, acetyl or acryloyl, and, when n isl R 2 is hydrogen, C1-C18alkyl that is uninterrupted or interrupted by one or more oxygen atoms, cyanoethyl, benzyl, glycidyl, a monovalent radical of an aliphatic, cycloaliphatic, araliphatic, unsaturated or aromatic carboxylic acid, carbamic acid or phosphorus-containing acid or a monovalent silyl radical, preferably a radical of an aliphatic carboxylic acid having from 2 to 18 carbon atoms, a cycloaliphatic carboxylic acid having from 7 to 15 carbon atoms, an a,punsaturated carboxylic acid having from 3 to 5 carbon atoms or an aromatic carboxylic acid having from 7 to 15 carbon atoms, and, when n is 2, R 2 is C1-C12alkylene, C4-Cl2alkenylene, xylylene, a divalent radical of an aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid, dicarbamic acid or phosphorus-containing acid or a divalent silyl radical, preferably a radical of an aliphatic dicarboxylic acid having from 2 to 36 carbon atoms, a cycloaliphatic or aromatic dicarboxylic acid having from 8 to 14 carbon atoms or an aliphatic, cycloaliphatic or aromatic dicarbamnic acid having from 8 to 14 carbon atoms, and, when n is 3, PR 2 is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, an aromatic tricarbamic acid or a phosphoruscontaining acid or a trivalent silyl radical and, when n is 4, R 2 is a tetravalent radical of an aliphatic, cycloaliphatic: or aromatic tetracarboxylic acid.

When any of the substituents ore C1-C12alkyl, they are, for example, methyl, ethyl, n-propyl, n-butyl, sec-bulyl, tert-butyl, n-hexyl, n-oclyl, 2-ethyl-hexyl, nnonyl, n-decyl, n-undecyl or n-dodecyl.

In the meaning of Cl-Cl8olkyl, R 2 may be, for example, the groups listed above and, in addition, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or noctadlecyl.

When 11 1 is C3-C8ailkenyl, it may be, for example, 1-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl or 4-tea't-butyl-2-butenyl., Ras C3-C8alkynyl is preferably propargyl.

As C7'-Cl2aralky'l, R 1 is especi ally phenethyl and more especially benzyl.

*R as CI-C8alkanoyl is, for example, formyl, propionyl, butyryl, octanoyl, but preferably acetyl, and as C3-C5alkenoyl is especially acryloyl.

When Ris a monovalent radical of a carboxylic acid, it is, for example, an acetic acid. caproic acid, stearic: acid, acrylic acid, methacrylic acid, benzoic acid or 0-(3 .5-di-tert-butyl-4-hydroxyphenyl)-propio nic acid radical.

When Ris a divalent radical of a dicarboxylic acid, it is, for example, a malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, maleic acid, phthalic acid, dibutylmalonic acid, dibenzylmalonic acid, di -tert-butyl-4-hydroxybenzyl)-malonic acid or bicyclohepteiiedicarboxyli c acid radical.

When R 2 is a trivalent radical of a tricarboxylic acid, it is, for example, a trimellitic acid or nitrilotriacetic acid radical.

When R 2 is a tetravalent radical of a tetracarboxylic acid, it is, for example, the tetravalent radical of butane-l.,2,3,4-tetracor boxylIi c acid or of pyromellitic acid.

When R2is a divalent radical of a dicarbomic acid, it is, for example, a hexamethylenedicarbamic acid or a 2 ,4-toluylene-dicarbomic acid radical.

The following compounds are examples of polyalkylpiperidine compounds of that class: 1) 4-hydroxy-2,2,6,6-tetramethylpiperidine 2) 1 -aliyI-4-hydroxy-2 ,2 .6.6-tetramethylpi peridi ne 3) 1 -benzyl-4-hydroxy-2 ,2 .6,6-tetramethylpiperidi ne 4) 1 -(4-tert-bulyl-2-butenyl)-4-hydroxy-2 .2,6 .6-tetramethylpi peridi ne 4-stearoyloxy-2 .2.6 6-tetramethylpi peridine 6) 1 -ethyl-4-salicyloyloxy-2,2 .6.6-tetramethylpiperidine 7) 4-methacryloyloxy-1 .2,2,6 .6-pentamethylpiperidi ne 8) 1,2,2 .6,6-pentamethylpiperidin-4-yl-B-(3 .5-di -tert-buyl-4-hydroxyphenyl) propionate 9) di(1-benzyl-2,2,6,6-tetramethylpiperidin-!4-yl) maleinate di(2,2,6.6-tetramethylpiperidin-4-yl) succinate 11) di(2.2,6,6-tetramethylpiperidin-4-yI) glutcirate 12) di(2,2,6,6-tetramethylpiperidin-4-yl) adipcite 13) di(2,2,6,6-tetramethylpiperidin-4-yl) sebaccite 14) di(1.2,2,6,6-pentamethylpiperidin-4-yl) sebacate di(1 ,2 .3,6-tetrimethyl-2.6-diethylpiperidin-4-yl) sebacate di(1-olly-22,6.6-tetramethylpiperidin-4-yI) phthalate 17) l-propargyl-48-cyanoethyloxy-2 .2 .6.6-tetromethylpiperidi ne 18) 1 -ocetyl-2 .2,6 ,6-tetrimethylpi peridi n-4-yl acetate 19) trimellitic acid tri(2,2,6,6-tetramethylpiperidin-4-yI) ester 1-acryloyl-4-benzyloxy-2, 6,6-tetramethylpiperidine 21) diethylmalonic acid di(2 .2 .6,6-tetramethylpiperidin-4-yl) ester 22) dibutylmalonic acid di(1,2,2 .6,6-pentaimethylpiperidin-4-yl) ester 23) butyl-(3 ,5-di-tert-butyl-4-hydroxybenzyl)-mailo nic acid di(1 .2,2,6,6pentaniethylpiperidin-4-yl) ester 24) dibenzyl-malonic acid di(1 .2,2,6 .6-pentamethylpi peridin-4-yl) ester dibenzyl-malonic acid di(1.2 .3,6-tetramethyl-2,6-diethyl-piperidin-4-yl) ester 26) hexane-1',6'-bis(4-carbamoyloxy- 1-n- butyl- 2,2.6 .6-tetramethyl-piperidi ne) 27) toluene- 2' ,4'-bis (4-carbamoyloxy-1 -n-propyl- 2,2,6 .6-tetramethylpiperidine) 28) dimethyl-bis(2,2,6,6-tetrmethylpi perid n-4-oxy)si lane 29) phenyl-tris(2 .2.6,6-tetramethylpiperidi n-4--oxy)si lane tris(I -propyl-2.2 .6,6-tetramethylpi peridi n-4-yl) phosphite 31) tris(1-propyl-2 ,2 .6 6-tetramethylpi peridi n-4-yl) phosphate 32) phenyl-(bis(1.2.2 ,6,6-pentamethylpiperidin-4-yl)] phosphonate 33) 4-hydroxy-1 ,2,2,6 .6-pentamethylpiperidine 34) 4-hydroxy-N- hydroxyethyl- 2,2,6 .6-tetranethylpiperidi ne 4-hydroxy-N-(2-hydroxypropyl)-2,2 6,6-tetramethylpiperidine 36) 1-glIycidyl-4-hydroxy-2 ,2 .6,6-tetramethylpiperidine b) Compounds of formula (MI)

OH

3 *R 3 HC

OH

3 nrn wherein n is the number I r 2, *R is as defined for a), Ris hydrogen, C1-Cl20lkyl. C2-Cshydroxyolkyl, C5-C~ccloalkyl, C7- C8aralkyl, C2-Cl8c0lkanoyl, C3-Csalkenoyl or behzoyl, and, when n is 1, R4' is hydrogen, C1-Cl~alkyl, C3-C~alkenyl, C5-Clcycloalkyl, Cj- C4alkyl substituted by a hydroxy, cyano, alkoxycarbonyl or carbamide group, glycidyl, a group, of the formula -CH2-CH(OH)-Z or of the formula -CONH-Z, wherein Z is hydrogen, methyl or phenyl; and, when n is 2, R 4 is C2-Cl2alkylene, C6-Cl2arylene, xylylene, a -CH2--CH(OH)-CH2- group or a group -CH2-CH(OH)- CH2-O-D-O-, wherein D) is C2-Cloalkylene, C6-Cl5arylene or C6- C12cycloalkylene, or, with the proviso that PR 3 is not alkanoyl, alkenoyl or benzoyl, R4may also be a divalent radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid or also the group -CO- or.

when n is 1, R 3 and R4 together may be the divalent radical of an aliphatic, cycloaliphatic or aromatic 1,2- or 1,3-dicarboxylic acid.

When any of the substituents are C1-C12- or C1-C18-alkyl, they are as already def ined above under a).

When any of the substituents are C5-C7cycl-oalkyl, they are especially cyclohexyl.

As C7'-C8aralkyl, R 3 is especially phenylethylI or more especially benzyl. As

R

3 is especially 2-hydroxyetthyl or 2-hydroxypropyl.

R3as C2-Cl8alkanoyl is, for example, propiomyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl, octadecanoyl, but preferably acetyl, and as C3is especially acryloyl.

When R 4 is C2-C8alkenyl, then it is, for examnple, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl or 2-octenyl.

R

4 as CI-C4alkyl substituted by a hydroxy, cyano, alkoxycarbonyl or carbamide group may be, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2cyanoethyl, methoxycarbonylmethyl, 2-ethoxyccirbo nylethyl, 2aminocarbonyipropyl or 2-(dimethylaminocarboftyl)-ethyl.

When any of the substituents are C2-Cl2alkylene, they are, for example.

ethylene, propylene, 2 .2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene. decamethylene or dodecomethylene.

When any of the substituents are C6-Cl5arylene, they are, for example. o-, m- or p-phenylene, 1,4-naphthylene or 4,4!-diphenlene.

As C6-Cl2cycloalkylene, b) is especially cyclohexylene.

The following compounds are examples of polyalkylpiperidine compounds of that class: 37) N,N-bis(2 ,2,6 .6-tetramethylpiperid, n-4-yl )hexamethylene-1 ,6-diami ne 38) NN'-bis(2 ,2 ,6 6-tetramethylpiperidi n-4-yl )hexamethylene- 1.6-diacetamide and 1,6-diformamide 39) l-acetyl-4-(N-cyclohexylace-amido)-2 ,2 .6,6-tetramethy Ipiperidi ne 4- benzoylamino-2 ,2 ,6,6-tetramethylpi peridi ne 41) N,N'-bis(2 ,2 ,6,6-tetrmethylpiperidin-4-yl )-N,N'-dibul-yl-adipamide 42) N,N'-bis(2,2 .6,6-tetramethylpi peridi n-4-yl)-NN'-dicyclohexyl- 2hydroxypropylene-1 .3-diamine 43) N,N'-bis(2 .2 6,6-tetramethylpi peridi n-4-yI)-p-xylylene-diami ne 44) NN'-bis(2 ,2 .6 6-tetramethyl pi peridi n-4-yl)succi ne-diamide N-(2 ,2 .6,6-tetraniethylpiperidi n-4-yl)-3-ami nodipropioni c acid di (2,2.6,6tetramethylpiperidin-4-yl) ester 46) the compound of the formula

CH

3 CH3C

CH

3 N N-CH 2 -CH(OH)-CHj---0-

CH

3

CH

3

CH--C-CH

3

C

3

CH

3 CHg- N N-CH 2 -CH(OH)-CHI-0

CAH

CH

3

CH.

47) 4-(bis- 2-hydroxyethyl-ami no)-1 .2,2,6 .6-perntamethylpiperidi ne 48) 4-(3-methyI-4-hydroxy-5-tert- bulyl- beizo ic acid ainido)-2,2 .6,6tetramethylpiperidine 49) 4-methcicr-ylamido-1 pentamethylpiperidinte c) Compounds of formula (IV) [R-NZ K R (IV).

n wherein n is the number 1 or 2, Ris as defined under a) and, when n is 1, R5 is C2-C8alkylene or C2-C8hydroxyalkylene or C4- C22acyloxyalkylene. and, when n is 2, R 5 is the group (-CH2)2C(CH2-) 2 When R5is C2-C8alkylene or C2-C8hydroxyalkylene, it is, for example, ethylene, 1-methyl-ethylene, propylene, 2-ethyl-propylene or 2-ethyl-2- Iiydroxymethylpropylene.

As C4-C22acyloxyalkylene,

R

5 is. for example, 2-ethyl-2acetoxymethylpropylene.

The following compounds are examples of polyalkylpiperidine compounds of that class: 9-aza-8 ,8.10,1O-tetramelhyl-1 .5-dioxaspira 51) 9-aza-8 8, 1O.1-tetramethyl-3-ethyl-1 .5-dioxaspiro 52) 8-aza-2 ,l 7 7 8 9 ,9-hexaomethyl-1,4-dioxaspiro(4.5]lecane 53) 9 -aza- 3 -hydroX lmethyl- 3 -ethyl-8,8,9,1O,lo..penta.Tethyl15.

54) 9-aza-3- ethyl-3-acetoxymethyl-9-acetyl-.8,8 l,1O-tetramethyl-1 2,2 .6.6-tetramethylpiperidirne-4-spiro-2'-(1',3 '-dioxane)-5' .3"-dioxane)-2"-spiro-4'"-(2'" ,2'".6',6"'-tetramethylpiperidine).

d) Compounds of formulae VA, VB and VC C R1

HCH

3 1 6 F -Nj

\(VA)

H

3 C1 KRI-NF (Ve) H1 3 C CH 3

H

1- 3 C H4 R-N0- K O

T

2 C-1 R (C 1- 3 C CH 3 0 wherein n is the number 1 or 2, Pis as defined under ai), P6is hydrogen, CI-Cl2alkyl, allyl. benzyl, glycidyl or C2-C60:lkoxyalkyl and, when n is 1, R 7 is hydrogen. CI-Cl2alkyI. C3-C5alkenyl, C7'-Cgaralkyl, C§- C7cYcloalkyl, C2-C4hydroxyalkyl, C2-C6alkoxyalkyl, C6-C1QaryI. glycidyl or a group of the formula -(CH2)P-COO-Q or of the formula -(CH2)P-O-CO-Q, wherein p is 1 or 2 and Q is CI-C4alkyl or phenyl, and, when n is 2, R 7 is C2- Ci2alkylene, C4-Ci2alkenylene, C6-Cl2cxrylene, a group -CH2-CH(OH)-CH2-O-D- O-.CH2-CH(OH)-CH2-, wherein b is C2-Cloalkylene. C6-Cl5arylene, C6- C12cycloalkylene, or a group -CH2CH(OZE)CH2-(OCH2-CH(OZ7)CH 2 2 wherein Z' is hydrogen, CI-CiBalkyl, allyl, benzyl, C2-Claalkanoyl or benzoyl, Ti and T2 are each independently of the other hydrogen, Ci-Cialkyl, or unsubstituted or halo- or C1-C4alkyl-substituted C6-ClIaryl or C7-Cgaralkyl, or Ti and T2 together with the carbon atom that binds them form a C5-Cl2cycloalkane ring.

When any of the substituents are C1-Ci2alkyl, they are, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethyl-hexyl, nnonyl, n-decyl, n-undecyl or n-dodecyl.

Any substituents having the definition Of C1-Cl8alkyl may be, for example,.

the groups listed above and in addition, for example, n-tridecyl, n-tetradecyl, nhexadlecyl or n-octadecyl.

When any of the substituents are C2-C6alkoxyalkyl, they are, for example, methoxymethyl, ethoxymethyl, propoxymethyl, tert- butoxymethyl, ethoxyethyl, ethoxypro pyl, n- butoxyethyl, tert- butoxyethyl, isopropoxyethyl or propoxypropyl.

When R 7 is C3-C5alkenyl, it is, for example, I-propenyl, allyl, methallyl, 2butenyl or 2-pentenyl.

As C7-Cgaralkyl, R TI and T2 are especially phenethyl or more especially benzyl. When Ti and T2 together with the carbon atom form a cycloalkane ring, that ring may be, for example, a cyclopentane, cyclohexane, cyclooctane or cyclododecane ring.

When R 7 is C2-C4hydroxyalkyl, it is, for example, 2-hydroxyethyl, 2hydro~cypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

As C6-Cloaryl, R Ti and T2 are especially phenyl, a- or B-naphthyl, which are unsubstituted or substituted by halogen or by C1-C4alkyl.

When R 7 is C2-Ci2alkylene, it is, for example, ethylene, propylene, 2.2di methylpropylene, tetramethylene, hexamethylene, octamethylene, decamrethylene or dodecamethylene.

As C4-C1201kenylene,

R

7 is especially 2-bulenylene, 2-pentenylene or 3hexenylene.

When R 7 is C6-Cl2arylene, it is, for example, m- or p-phenylene, 1,4naphthylene or 4,4'-diphenylene.

When Z is C2-Cl2alkanoyl, it is, for example, propionyl, butyryl, octanoyl, dodecainoyl, but preferably acetyl.

D Gs C2-Cloalkylene. C6-Cl5arylene or C6-Cl2cycloalkylene is as def ined under b).

The following compounds are examples of polyalkylpiperidine compounds of that class: 56) 3-benzyl-l ,3,8-triaza-7,7,9 9 -tetramethylspiro[4.5]decne24-dione 57) 3-n-octyl-i,3 8 -triaza- 7 7 9 9 -tetramethylspiro[4.5]decane-2,4-dione 58) 3-allyl- 1,3 ,8-triaza-1 17,7,9 .9-pentamethylspiro [4.5]decane-2 ,4-dione 59) 3-gfycidyl-1.3 ,8-triaza-7,7,8.9 ,9-pentamethylspiro[4.5]decane-2,4-dione 1,3,7,7,8,9 .9-heptamethyl-1.3 ,8-triazaspiro[4.5]decane-2 ,4-dione 61) 2 -isopropyl-7,7,9,9-tetramethyl- 1-oxa-3 ,8-diaza-4-oxo-spiro 62) 2 ,2-dibutyl-7,7,9,9-tetramethyl-l-oxci-3 .8-diaza-4-oxo-spiro(4.5]decane 63) 2,2 ,4,4-tetramehyl-7-oxa-3 ,20-diaza-21-oxo-dispiro5.1.1 1.2]henicosane 64) 2 -butyl-7,7,9,9-tetramethyl-1-oxa-4,8-diaza-3-oxo-spiro[4.5]decane 8-acelyl-3-dodecyl-1 ,3 8 -triaza-7,7,9,9-tetramethylspiro[4.5]decan...2,4.

dio ne or the compounds of the following formulae:

OH

3

OH

3

OH

3

OH

3 CH-N II

N-OH

3 CN -CH 2

H(OH)CH

2 -[0H 2

-H(OH)CH

2 2

N-C

0C 3 67) CH~ O H 3 OH 3

OH

3 *NH-0 0O-NH **CH-N j j I-N- (CH 2

-KCOH

O

3

OH

3 0OH

O

3 68) OH 3 OH 3 OH 3

OH

3 HN NH0

NH

0 O H 2 -0 -N-

OH

3

OH

3 0

OCH

3

OH

HO O H3 0-C (OH 2 11 69) HN 1- P 1 1

H

2 0H 2 00002

OH

3

OH

3 0 e) Compounds of formula VI N N (VI), n wherein n is the number 1 or 2 and P8is a group of the formula

CH

3

CH

3 -E(A N-R1

CH

3

CH

3 wherein RI is as defined under a), E is -0-or -NP 1 A is C2-C6alkylene or -(CH2)3-O- and x is the number 0 or 1, Pis identical to R8or is one of the groups -NP.

11

R

12

-OR

13 -NHCH2OR 13 or -N(CH20R 13 )2, *when n 1, i is identical to R 8 or R 9 and, whenn Rio is a group -E-8wherein B is C2-C6Glkylene that is uninterrupted or interrupted by -N(R 11

)Y-

R 11is C1-C12olkyl. cyclohexyl, benzyl or C1-C4hydroxyalkyl or a group of the formula R CH 3

CH

2

R

N-R

N

CH

2

R

R12 is C1-Cl2alkyl, cyclohexyl, benzyl, C1-C4hydroxyalkyl and R13 is hydrogen, CI-Cl2alkyl or phenyl, or

R

11 and P 12 together are C4-C5alkylene or C4-C5oxaolkylene, for example C 2 H 2 0 o r C 2. N Ro r -CH 4

CHC

are a group of the formula -C 2H* o r

C

H C 2 N -R 1 -CH2~r

-/-CH

2

CH--/

or alternaitively R11 an 1 are each a group of the formula C H 3

OH

3

N

:HN N ljfv -NH-A- CH1 3

OH

3 OH3

OH

3

**O

3 N OH 3

H

When any of the substituents are Cl-Cl2alkyl, they ame, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, nnonyl, n-decyl, n-undecyl or n-dodeeyl.

When any of the substituents ore Cl-C4hydroxyalkyl. they are, for example, 2 -hydroxyethyl, 2 -hydroxypropyl1, 3 -hydroxypropyl, 2-hydroxybutyl or 4hydroxybutyl.

When A is C2-C6alkylene, it is, for example, ethylene, propylene, 2,2d imethylpropylene, tetramethylene or hexamethylene.

.When R1and R12 together are C4-C5alkylene or C4-C50xcialkylene, they are, for example, tetramethylene, pentamethylene or 3 -oxapentomethylene.

The compounds of the following formulae are examples of polyalkylpiperidin~e compounds of that class:

OH

3 H C I CH3 3 N H3Cq C3 N-C

H

9

(CH

3

CH

2 2 N) N NC2H)

N(C

4

H

9 2 H3 CH 3 NC

H

3

OH

3 71)

I

C

2

H

5 -N

N-C

2

H

C

2

H

5

CAH

CH

3

H

3 C O 3 *R

H

3 C CH 72) N whemin R -NH-CH 2 CH 2 CNI0J

N-CH

3 .9 R O3 H3

CH

3 CIA 3

CH

2

-CH

2

NH

73) CH 3 CH 3 NJH CH 3

H

3 CH( H 3 HN 0H 2

-CH

2 -NH I N)2-C2 NH

CHI

3

CH

3 CHKCH 3

CHCHN

CHC

4

H,-N

C IH N N CA C* N N~

CHOH

2

CM,

R-mH-NCHH2-Nc-CH. CH. N-(H 2 )N NH- :a CH NCHH.C 3

C.C.'

R R -I.vH)i 1N-NI 2MI-NH 76)

R-NH(C

2 (CH 2 2 3

H-R

wherein R

S

S

S.

SS

S S

S

S

S

55 I S

S

S.

S S

S

OFH

3 77 CH O H 3

OH

3 H

CH

N I N NNOH wherein Ry OH 3

OH

3

K

CH

ICH

3

OH

3 ,0 3 CHN

NH

NH CN H 3 78) CBHi-N N: <NH(CH2)3 CH1 3 CH 3

OH

3 NJ OH3

H

2

CH

2

CH

2

OH

CH N C3

H

3

OH

3 79)

N-C

4

H

9 C H 3 OH3 NkN 5 S -4HCHj-N N N- *ee. 4I"S OH;"

OH

3 OH 3 ICH 3

CH

2

-CH=CH,

H 3 C N H 3 N-C H9 H COH 3 N YN CH 3

OH

3 H 2 C=HC-H 2 0-N N N 1 1'N -HC H2

COH

H3C O 3 OH 3

OH

3 f) Oligomeric or polymeric compounds, the structural repeating unit of which contains one or more 2 2 6 ,6-tetrcilkylpiperidine radicals of formula especially polyesters, polyethers, polyamides, polyamin es, polyurethanes, ~polyureas, po lyami noiriazi nes, p0 ly(meth)aicrylates, po lysi loxanes, poly(meth)acrylamides and the copolymers thereof that contain such radicals.

Examples of 2,2,6.6-polyalkylpiperidine light stabilisers of that class are the compounds of the following formulae wherein m is a number from 2 to approximately 200.

OH

3 OH 3 0 0 81) Cf- -H 2 -CH-C-0-H 2 -CH--N

OH

3 CH 3 CH, CIA, 0 0 CH, CH, 00 0 82) -f--CH,-C~i4-N 0 -(cH 2 4 c -C-H-0 CI-C,.C CHI, CH, CHI, CHi, ,CA1I 83) 84) m 85)

CH

3 1

,CH

3 Ty CH3

H

86) 0 C 4

H

9 0 11 1 11 -c c

I

4 9 87) a a 0 11 88) 89)

OH

3

CH

3 91)

CH

3 FI I CH 3 OH m OH-N3 3

OH

3

CH

3

S

S

S.

92)

CH

3 93) 94) CH3

(CH

2 3 9 wherein R =Hor CH3

OH

3

CH

3

HSC

4

(R)N

96)

H

3

C-

CH

3 wherein R= HAC(R)N N'jN(R)C 4 H 9 and R'= or H (obtainable by reacting the reaction product of trichiorotriazine and NI-12- (CH2)3-NH-(CH2)2-(CH2)3-NH2 with 4-N-butyl-2 .2,6 .6-tetramethylpiperidi ne) Of those classes, classes e) and f) are especially suitable, especially those tetraalkylpiperidline compounds that contain s-triozine groups. Also especially suitable are compounds 74, 76, 84, 87, 92, 95 arid 96.

The preparation of the N-poperidinyl-triazines is known from the literature for example, Houben-Weyl *Methoden der' organischen Chemieu, Vol. VII, p. 233-237, Yd~Ed.. Thiemne Verlag Stuttgart 1971). There may be used as starting material for the reaction with various 1-piperidylamines cyanuric chloride, diamino-chloro-l .3 5-triazine or variously substituted bisdialkylami noch loro- 1,3 ,5-triazines or dlelkyloMino- or alkylam ino-dichloro-! .3 Technically important exampI~s of tetra' and penta-alkylpiperidine compounds are: bis(2,2.664tetramethyl-piperidyll) sebacate, bis(2.2,6.6tetromethyl-piperidyl) succlnate, bis( 2,2.6 .6-pentamethylpi peridyl) sebacate.

n- bulyl-3 .5-di-tert-butylA4,hy i'b eybe.ytmalovnic Gacid bis(1 .2,2,6.6pentamethylpiperidyl) esteir, the condensation product of 1-kydroxyethyl- 2,2,6,6-tetramethyl-4-hydroxy-piperldine and succinic acid, the. condensation product of N.N'Y-bis( 2 2 6 6 -tetramthyl-4-piperidyl)-hexamethylenediamine and 4-tert-octylami no-2 .6-dichloro- 1,3 .5-s-t-riazi ne, -tris(2.2 .6,6-tetramethyl-4piperidyl)nitrilotriacetate, tet-rakis(2,2 .6.6-tetraenethyl-4-pi peridyl)-1 butanetetrooakte, 1 .3,r>.5-tetramethyl-piperazinone), 4benzoyl-2 ,2 .6.6-tetrwiic4iipellnsi.-.H 4t'ea'ylogy-2,6,6tetramethylpiperidine, bis(t ;22.6, &pentamnethylpi peridyl)- 2-n-butyl-2-(2hydroxy-3 .5-di-tert-buybezy) mhl1onate. 3-n-octyl-7,7,9,9-tetromethyl- 1,3 .8-triazaspiro[4.5jdecone.2.4-done, bis(1-octylxy-2 .2,6,6tetramethylpiperidyl)-sebacate, bis(1-octyloxy-2,2 .6,6-tetraniethylpiperidyl) succinate. the condensation product of N.N'-bis(2.2.6.6-tetramethyl-4piperidyl)hexamethyleredidminet and 4-morpholino-.2 6-dichloro-1 .3 the condensation product *of 2-chloro-4,6-di(4-n-butylamino-226,6 tetramethylpiperidyl)-1 .3,5-triazine and.tl, 2 -bis(3-aminopropylamino)ethaine, the condensation product of 2-chloro-4,6-di(4-n-butylami no-I ,2,2 .6,6pentamethylpiperidyl)-1,3,5 4 -1rlzn n 1 2 -bis(3-aminopropylamino)ethane, 8acetyl-3-dodecyl-7.7.9.9O-fttcmethyl -1,3,8 -triazaspiro (4.5]decane-2 ,4-dio ne, 3-dodecyl- 1-(2 2 ,6,6-tetramethyl-4-piperidyl)pyrro lidi ne-2 .5-dione, 3 -dodecyl- 1-(1 ,2,2,6,6 -pentaimethyl-4-piperidyl)-pyrro lidine- Instead of a single sterically hindered amine, it is possible within the scope.

of the present invention also to use a mixture of different sterically hindered amines.

The amount of sterically hindered amine added depends on the desired degree of stabilisation. In general, from 0.01 to 0.5 by weight, especially from 0.05 to 0.5 by weight, based on the polymer, is added.

/-fdoakites and alkali (alkaline earth) aluniinosihicates (zeoites) The chemical composition of these compounds is known to a person skilled in the art. for example from patent specifications DE 38 43 581, US 40 00 100, EP 062 813, WO 93/20135.

Compounds from the hydrotalcite series can be described by general formula Vii M 1-X M 3 x(OH)2 (Ab- )x/b d H20 (Ma) wherein 2+ M =one or more of the metals from the group Mg, Ca, Sr, Zn or

M

3 Al,orB8, An is an anion having the valency n.

b is anumber from Ito 2, 0Ocx 1E 0.5, and m is a number from 0 to Preferably, An 0H-, C104-, HC03-, CH3COO-, C6HS1COO-, C03 2 (CHOHCOO)2, (CH2CQO)2 2 CH3CHOHCOO ,HP03 or HP04 2 Examples of hydrotcilcites are A1203.6MgO.C02.12H-20 Mg4.5A2(OH)3.co3.3.5H 2 0 (ii).

4MgO.A203.C02.9H20 (iii), 4MgO.A 1203.CO2.6H20, ZIIO.3M.A20 3 .C0 2 .8 9H-20 and ZnO.3MgO.A203.W2.5-6H 2 0- Special preference is given to types i, ii and iii.

Zeoites (alkali and alkaline earth aluminosiicates) These can be described by general formula (Vn~j) Mx/n[(AI02)x(5i02)y].wH2O

(VIII)

wherein n is the charge of the cation M: M is an element of Group I or Group 171, such as Li, Na. K, Mg, Co. Sr or Ba; 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 Examples of zeolites are sodium aluminosilicates of the formulae N I12A12S112O48 27 H20 (zeolite N06Al6Si6O2 4 2 NaX. 7.5 SX= OH, halogen, C104 (socialite]; Na6Al6Si300 7 2. 24 H20; Na8Al8Si4009 6 24 H20; Kk16Al16Si24080. 16-H20; N4al6All6Si32Og 6 16 :Na56A156Si136038 4 2501H20 (zeolite N86Al86Sil0 6

O

3 84 264 (zeolite X]; or the zeolites that can be formed by partial or complete replacement of the Na atoms by Li, K, Mg, Ca, Sr or Zn atoms, such as (Na,K)10A11OSi22O64. 20 H20; Ca4.5Na3[(A102) 12 (Si0 2 121 30 K9Na3[(AI02)12(5i02)12]. 27 Preferred zeolites correspond to the formulae Na,12AI 1 2

S

12

O

4 8 27 H 2 0 (zeolite A], Na6Al65i6O24. 2NaX. 7.5 H20, X OH, Cl, C104, 1/2C03 [sodalIite] Na6Al6Si300l2. 24 Na'8A854009 6 24 Na16AlI65i24O080 16 Na16AI165i32O9 6 16 N056A156S136O384. 2501-H20 [zeoliteY] NaW1A8654l06O384.2641-120 [zeoliteX] and zeolites of the X od Y type possessing orn Al/Si ratio of about 1:1, or the zeolites that can be formed by partial or complete replacement of the No atoms by Li, K, Mg, Ca, Sr. Ba or Zn atoms, such as (NaK)10AI0Si22O064. 20 Ca4,5Na'3[(A102)12(5i02)1 30 K9NOa3(A02)12(i02)12]. 27 The zeolites listed may also have a lower water content or may be anhydrous.

Other suitable zeolites are: Na2O-AI203-(2 to 5) Si0 2 to 10) H20 (zeolite P] Na 2 O-Al203-2 Si02-(3.5-I)H 2 0 (zeolite MAP) or the zeolites that can be formed by partial or complete replacement of the Na atoms by Li. K or H atoms, such as (Li.NaK.H)jOA1 1 Si2 2

O

64 20 H 2 0 KNa 3 [(AlO2)12(SiO2) 12 27

K

4 A14Si4O1 6 *6 H 2 0 (zeolite K-F] Na8A 18540096.24 H 2 0 zeolite D, as described in Barrer etal, JI. Chemn.

Soc. 1952,.1561-1571, and in US 2 950 952; sops The following zeolites are also suitable; potassium offretite, ais described in EP-A-400 961; zeolite R. as described in GB 841 812; zeolite LZ-217, as described 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; Na3K 6 A1 9 Si 27

O

7 2 .21 H20 [zeolite L]; zeolite LZ-2 i, ais 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-2 14, as described in US 4 503 023; zeolite ZK-19, as described in Am. Mineral. 54 1607 (1969); zeolite W as described in Barrer etal, J. Chem. Soc. 1956, 2882; Na 30 A1 30 Si 6 6 0 19 2 98 H20 [zeolite ZK-5, zeolite Q].

Special preference is given to the use of zeolite P types of formula I wherein x is from 2 to 5 and y is from 3.5 to 10, especial ly zeolite MAP of formula I wherein x is 2 and y is from 3.5 to 10, and very especially zeolite Na-P, that is to say M is Na. That zeolite generally occurs in variants Na-P-1, Na-P-2 and Na-P- 3, which are differentiated by their cubic, tetragonal or orthorhombic structure Barrer, B.M. Munday, J.Chem.Soc. A 1971, 2909-2914). The literature just mentioned also describes the preparation of zeolite P-1 and P-2.

According to that publication, zeolite P-3 is very rare and is therefore of little practical interest. The structure of zeolite P-1 corresponds to the gismondite structure known from the above-mentioned Atlas of Zeolite Structures. In more recent literature (EP-A 384 070) a distinction is made between cubic (zeolite B or Pc) and tetragonal (zeolite P 1 zeolites of the P type. That publication also mentions relatively new zeolites of the P type having Si:AI ratios of less than 1.07:1. Those are zeolites designated MAP or MA-P for "Maximum Aluminium P".

Depending upon the preparation process, zeolite P may contain small quantities S. of other zeolites. Very pure zeolite P has been described in WO 94/26662.

Within the scope of the invention it is also possible to use finely particulate, water-insoluble sodium aluminosilicates which have been precipitated and crystallised in the presence of water-soluble inorganic or organic dispersants.

Those compounds can be introduced into the reaction mixture in any desired manner before or during the precipitation and/or the crystallisation.

Sodium zeolite A and sodium zeolite P are very especially preferred.

The hydrotalcites and/or zeolites can be used in amounts of, for example, from 0.1 to 20, advantageously from 0.1 to 10, and especially from 0.1 to 5, parts by weight, based on 100 parts by weight of halogen-containing polymer.

Alkali aluminocarbonates (dawsonites) These are compounds of the formula ((M20)m.(A1203)n.Zo.pH20}, wherein M is H, Li, Na, K, Mgl/2, Cal/2, Srlf2 or Zn1/2; Z is CO2, 502, (C1207)1/2, B406, 5202 (thiosulfate) or C20 2 (oxalate); m is a number from 1 to 2 when M is M91/2 or Cal/2, and in all other cases is a number from 1 to 3; n is a number from 1 to 4; o is a number from 2 to 4; and p is a number from 0 to The alumino salt compounds of formula that can be used according to the invention may be naturally occurring minerals or synthetically prepared compounds. The metals may partially replace one another. The mentioned alumino salt compounds are crystalline'. partially crystalline or amorphous or may be present in the form of a dried gel. The alumino salt compounds may also be present in relatively rare crystalline modifications. A process for the preparation of such compounds Is described in EP 394 670. Examples of naturally occurring alumino salt como n are indigirite- tunisite.

cluminohydrocalcite, pam aluhftnohydrocalclte. strontiodresserite and hydrostrontiodresserit. Other acdmples of alumino salt compounds are potassium alumihocarbolhate ((K20)(1203).C02)2.2H-20). sodium aluminbthiosulfate 1 '0(A~~(a24.2420), Potassium aluminosulfit ((CaO).(A203).(C202)2.5H20). magn esium alum inotetraborate 1203).(B406)2.5H20.), (MgO.2NabO.6]20)-(A 1203 ).(C02)2.4.l H201, (((M9o.2Nao0.6j20).(A 1203).(C02)2.4.3H20) and (((Mgci3NO.4]20).(A1203).(C02)2.2.4.9H20) The mixed alumino salt compounc4 can be obtained in accordance with processes known per se by cto da9.perblfomhelkiaumina salt compounds or by comb idpre n see, for example, US 5 055 284).

Preference is given-to Olumino salt compounds of the above formula wherein M is NoorK.V, .02 S02or (41207)1/2;m is i C-3 nis 1-4; ois 2-4and pis 0-20. Z is especially C02.

Preference is given also to compounds that can be represented by the following formulae: M20.Al203.(C02)2 PH20 (Ia) (M20)2.(A1203)2.(C02)2 pH20 (Ib) M20.(AI203)2.(C02)2 pH20 (Ic) wherein M is a metal, such as Na, K, Mgl/2, Cal/2, Srl/2 or Znl/2 and p is a number from 0 to 12.

Special preference is given to sodium aluminodihydroxycarbonate (DASC) and to the homologous potassium compound (DAPC).

Dawsonites may also be substituted by lithiumalumohydroxycarbonates or lithium-magnesium-alumohydroxycarbonates, as described in EP 549,340 and DE 4,425,266.

The dawsonites can be used in an amount of, for example, from 0.01 to advantageously from 0.1 to 3, especially from 0.1 to 2, parts by weight, based on 100 parts by weight of halogen-containing polymer.

The stabiliser combination preferably comprises component A) and, as component at least one substance from the following groups: perchlorate compounds, glycidyl compounds, or dihydropyridines and polydihydropyridines.

The stabiliser combination according to the invention can be used together S with further additives that are customary for the processing and stabilisation :i of chlorine-containing polymers, such as: Zinc compound The organic zinc compounds having a Zn-O bond are zinc enolates and/or zinc carboxylates. The latter are, for example, compounds from the series of aliphatic saturated C2-C22carboxylates, aliphatic unsaturated C3- C22carboxylates, aliphatic C2-C22carboxylates that are substituted by at least one OH group or the chain of which is interrupted at least by one oxygen atom (oxa acids), cyclic and bicyclic carboxylates having from 5 to 22 carbon atoms, *o phenylcarboxylates that are unsubstituted, substituted by at least one OH group and/or C1-C16alkyl-substituted, phenyl-Cl-C16alkylcarboxylates, or phenolates that are unsubstituted or C1-C12alkyl-substituted, or abietic acid.

There may be mentioned specifically, as examples, 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, 2ethylhexanoic acid, pelargonic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, myristic acid, palmitic acid, lauric acid, isostearic acid, stearic acid, 12-hydroxystearic acid, 9,10-dihydroxystearic acid, oleic acid. 3,6dioxaheptanoic acid, 3,6,9-trioxadecanoic acid, behenic acid, benzoic acid, ptert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3 ,5-di -tert-butyl-4hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, npropylbenzoic acid, salicylic acid, p-tert-octylsolicylic acid, and sorbic acid; zinc salts of divalent carboxylic acids or the monoesters thereof, such as oxalic acid..

malonic acid, succinic acid, glutaric: acid, adipic acid, fumaric acid, dicarboxylic acid, hexane-1.6-dicarboxylic acid, lheptahe-1,7-dicarboxylic acid, octane-I ,8-dicarboxylic acid, 3 6 9 -trioxadecane-,1O-dicarboxylic acid, lactic acid, malonic acid, maleic acid, tartaric acid, -cinnamic acid, mandelic acid, malic acid, glycolic acid, oxalic acid, salicylic acid, polyglycol-dicarboxylic acid 12), phthalic acid, isophthalic acid, terephthalic acid and hydroxyphthalic acid; and the di-- or tri-esters of tri- or tetra-valent carboxylic, acids, such as hemimellitic acid, trimellitic acid, pyromellitic acid, citric acid and also so-called overbased zinc carboxylates.

The zinc enolates are preferably enolates of acetylacetone, benzoylacetoe.

or dibenzoylmethane and enolates of acetopcetates and benzoyl acetates and of dehydroacetic acid. In addition,' inorganic zinc com~pounds, such as zinc oxide, zinc hydroxide, zinc sulfide or zinc carbonate, camn also be used.

Preference is given to zinc carboxylates of a carboxylic acid having from 7 to carbon atoms (zinc soaps), such as benzoates or alkanoates, preferably C~alkanoates, stearote, oleate, laurate, palmitate, behenate, versatate, hydroxystearates, dihydroxystearates, P-tert-butylbenzoate, or (iso)octanoate.

Preference is given especially to stearate, oleate, versatate, benzoate, p-tertbutylbenzoate and 2-ethylhexanoate- Also suitable in addition to the mentioned zinc compounds are organic aluminium, cerium or lanthanum compounds having a metal-O bond. The aluminium compounds that can be used and that are preferred include carboxylates and eno lates.

The metal soaps described and mixtures thereof can be used in amounts of, for example, f rom 0.001 to 10, advantageously from *0.01 to 5, preferably from 0.01 to 3, parts by weight, based on 100 parts by weight of chlorine-containing polymer.

The stabiliser combination can be provided with further stabilisers, auxiliaries and processing agents, such as alkali metal and alkaline earth metal compounds, glidants, plasticisers, pigments, fillers, phosphites, thiophosphites.

and thiophosphates, mercaptocarboxylic acid esters, epoxidised fatty acid.

esters, antioxidants, UV absorbers and light stabilisers, optical brighteners.

impact strength modifiers and -processing aids, gelling agents. antistatic agents, biocides, metal deactivators, fireproofing agents and propellaynts, and antifogging'agents (cf. "Hakndbook of PVC Formulating" by E. J. Wickson, John Wiley Ai Sons. New York 1993).

'in a non-limiting manner, so me of the known additives and processing auxiliaries ame mentioned here: Akali metal and alkaline earth metal These ame to be understood to include especially the carboxylates of the acids describied above, but also corresponding oxides or hydroxides or (bi)Carltonates. Mixtures thereof with organic acids are also suitable. Examples are NhOH, Na-stearate, N aHCO 3 KOH, K-stearate. KHCOs, Li 2

CO

3 Listewrae, COO. Ca(0H2). Mg0. Mg(OH)2. Mg-stearate. CQC03, 0.C3 nwell as dolomite, huntit. chalk, basic Mg-carbonate and other Na- and K-salts of fatty acids- NaOH. KOH, CaO. Ca(0H2). MgOj Mg(OH)2. CaCO3 and MgCO3 and also fatty acid sodium and potassium salts.

~:In the case of alkaline earth metal and zinc carboxylates, it is also possible for their adducts with MO or M(OH)z (M =Ca, Mg. Sr or Zn), so-called Noverbased" compounds, to be used.

Preference is given to alkali metal, alkaline earth metal and/or aluminium carboxylates in addition to the stabiliser combination according to the invention, Other Mletal Stabilisers S pecial mention has to be made of organolin stabilisers, carboxylates, rnercaptides and Sulf ides being preferred. Examples of suitable compounds may be found in US 4,743,640.

Glidants(LURIRICANTS) Suitable glidants are, for example: Monlan wax, fatty acid esters, PE waxes, amide waxes, chioroparaffins.

glycerol esters or alkaline earth metal soaps. Suitable glidaiits are also described in "Kurnststoffadditive" (Plastics additives), R. Gdchter/H. Wuller, Carl )4anser Verlag. Yd Ed., 1989, pages 478-488. Mention may also be made of fatty ketones (as described in D)E 42 04 887) and of silicone-based glidants (as described in EP 225 261) or combinations thereof, as listed in EP 259 783.

Plasticisers Suitable organic plasticisers are, for example, those of the following groups: A) Phthalic acid esters: Examples of such plasticisers are dimethyl, diethyl, dibutyl, dihexyl, di-2ethylhexyl, di-n-octyl, diisooctyl, diisononyl, diisodecyl, dilsotridecyl, dicyclohexyl, dimethylcyclohexyl, dimethylglycol, dibutylglycol, benzylbutyl and diphenyl phthalate and mixtures of phthalates, such as C7-C9- and c9- CII-alkyl phthalates from predominantly linear alcohols, C6-Clo-n..alkyl phthalates andl C8-ClO-n-alkyl phthalates. Of those compounds, preference is given to dibutyl. dihexyl, di-2-ethylhexyl, di-n-octyl, diisooctyl, diisononyl, diisodecyl, diisotridecyl and benzylbutyl phthalate, and to the mentioned mixtures of alkyl phthalates. Special preference is given to di-2-ethylhexyl, diisononyl and diisodecyl phtha late, which are also known by the customary abbreviations I)OP (dioctyl phthalate, di-2-ethylhexyl phthalate), OINP :>(diisononyl phthalate), [)IDP (diisodecyl phthalate).

B) Esters of aliphatic dicarboxylic acids, especially esters of adipic, azelaic and sebacic acid: Examples of such plasicisers are di-2-ethylhexyl adipate, diisooctyl adipote (mixture), diisononyl adipate (mixture), diisodecyl adipate (mixture), benzylbutyl adipate, benzyloctyl adipate, di-2-ethylhexyl azelate, di-2ethylhexyl sebacate and diisodecyl sebacate (mixture). bi-2-ethylhexyl adipate and diisooctyl adipate are preferred.

C) Trimellitic acid-esters, for example tri-2-ethylhexyl trimellitate, triisodecyl trimellitate (mixture), triisotridecyl trimellitate, tri isooclyl trimellitate (mixture) and tri-C6-C8alkyl, tri-C6-Cloalkyl, tri-C7-.C9alkcyl and tri-C9-Cilalkyl trimellitate. The last-mentioned trimellitates are formed by esterifying trimreflitic acid with the appropriate alkanol mixtures. Preferred trimellitates are tri-2-ethylhexyl trimellitate and the mentioned trimellitates from alkanol mixtures. Customary abbreviations are TOTM (trioctyl trimellitate, iri-2-ethylhexyl trimellllote)i TIM)M (triisodecyl trimellitate) and TITC)TM (tri isotridecyl trimellitate).

0) Epoxide plasticisers These are mainly epoxidised unsaturated fatly acids, such as epoxidised soybean oil.

E) Polymer plasticisers A -definition of tee phlaiclsers and examples thereof are given'in nlunststoffadditiVea (Plastics additives), kt Gdchter/H. M~jller, Carl Hlanser Verlag, 3rd Ed., 19.89, Chapter!S59,6. aes412-415, and in "PVC Technology", T itow, 4 tb Ed., ELse fbL 1984 pages 165-10 h otcmol used starting materials for the peatinof polyester'plasticisers are: dicarboxylic acids, such' asodipic, phthalic, azelaic and sebacic acid; diols, such as 1,2-propanediol. l,3--'bitanediol, 1.4-bUtanediol, 1,6-hexanediol.

neopentyl glycol and diethylene glycol.

F) Phosphoric acid esters.

Adefinition of tho c.*pr Ist efudi h bv-mentioned 'Taschetibuch der Km*adtie(abok of Plastics Additives), Chapter 5.9.5. p.p. 4 amesosuhphosphoric acid esters are tri butyl phosphate, tri-Z*ethylbutyl phosphate, tri-2-ethylhexyl phosphate, trichioroethyl phosphate. 2-e.thyl-hexyl-diphenyl phosphate, cresyl diphenyl phosphate, triphenyl phosphate, tricresyl phosphate and trixylenyl phosphate. Tri-2-ethylhexyl phosphate andT*Reofos 50 and 95 (Ciba-Geigy) are preferred.

6) Chlorinated hydrocarbons (paraff ins) H) Hydrocarbons I) Monoesters,. eig. butyl oleate, phenoxyethyl oleate, tetrahydrofurfuryl oleate and -alkylsulf f 6ic id' eters.

JT) Glycol esters-, e.g. diglycol benzoates.

Definitions and examples of plasticisers of groups G) to J) are to be found .in the following handbooks: "Kunststoffadditive" (Plastics Additives), R. Gdchter/H. Muller, Carl Hanser Verlag, 3Y Ed., 1989, Chapter 5.9.14.2, p.p. 422-425 (group and Chapter 5.9.14.1, p. 422 (group H).

"PVC Technology", W.V. Titow. 4$ Ed., Elsevier Publishers, 1984, Chapter 6.10.2. pages 171-173. (group Chapter 6.10.5, page 174 (group Chapter 6.10.3, page 173, (group I) and Chapter 6.10.4, pages 173-174 (group 3).

It is also possible to use mixtures of differerit plasticisers.

The pkasticisers can be used in an amount of, for example, from 5 to 120, advantageously from 10 to 100, and especially from 20 to 70, parts by Weight, based on 100 parts by weight PVC.

Pigments Suitable substances are known to the persoo -skilled in the art. Examples of inorgaNic pigments are 1i0O 2 carbon black, Fe 2

O

3 5b 2 0 3 (Ti,8a.Sb)O 2 .Cr 2

O

3 spinels, such as cobalt blue and cobalt green, Cd(SSe), ultramarine blue. Organic pigments are, for example, azo pigments, phthalocyanine pigments, quinacridlone pigments, perylene pigments, diketo-pyrrolopyrrole pigments and anthroquinone pigments. Preference is also given to T10 2 iin micronised form.

Definitions and further descriptions are to be found in the "Handbook of PVC Formulating", E.J.Wickson, John Wiley &Sons. Jew York 1993.

Fillers Fillers (HANDBOOK OF PVC FORMULATING. E.J.Wickson John Wiley Sons, Inc., 1993 pp. 393-449) and reinforcing agents (TASCHENBUCH der KAe (HANDBOOK of Plastics Additives), R.Gdichter H.MUller, Carl 1-anser, 1990, pp. 549-615) (such as calcium carbonate, dolomite, wollastonite, magnesium oxide, magnesium hydroxide, silicates, glass fibres, talc, kaolin, chalk, mica, metal oxides and hydroxides, carbon black or graphite).

Chalk is preferred.

Phosphites Examples are triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris-(nonylphenyl) phosphite. trilauryl phosph ite, 'trio ctadecyl phosphite. distearyl-pentaerythrito I diphosphite, tris(2,4-di-tert-butylphenyl) phosphite. diisodecylpentqerythritol diphosphite, bis(2,4-di-tert- .butylphenyl)pentaerythritol diphosphite, bis(2 .6-di -tert-b utyl-4-methylphenyl).

pentaerythritol diphosphite, bis- isodecyloxy-pentaierythritol diphosphite.

bis(2 4 -di-tert-butyl-6-methylphenyl)pentaerylthrito I diphosphite, bis(2 ,4,6-tritert-butylphenyl)pentczerythrito I diphosphite. tristearyl-sorbito I triphosph ite, bis( 2 4 -di-tert-bul.6methylphenyl)mnethyI phuosphite, bis(2 .4-di-tert-butyl-6-.

methylphenyl)ethyl phosphite.

Especially suitable are trioctyl, tridecyl, tridodecyl,. tritetradecyl. tristearyl.

trioleyl, triphenyl-, tricresyl, tris-p-nonylphenyl or t ricyclohexcyI phosphite and special preference is given to the aryl-dialkyl anid alkyl-dioryl phosphites, such as .phenyldidecyl phosphite. 2 4 -di-tert-buylpueny)-di-dodecyl phosphite, (2,6penlatertbutley)d-ocI phosphite -and to the dialkyl- and diaaylpenaerthrtoldiphosphites, such as distearylpentaerythritol diphosphite. and non-stoichiometric triaryl phosphil-es. for example those having the composition- (HI9C9-C6H4)O1.5P(C12 13 25 27 Preferred organic phosphites are distearyl-pentaierythrgtol diphosphite, trisnonylphenvyl phosphite and phenyldidecyl phosphite-.

The organic phosphites can be used in an amount of, for example, from 0.01 to 10, advantageously from 0.05 to 5, and especially from 0.1 to 3. parts by weight, based on 100 parts by weight PVC.

Thiophosphites and thiophosphates There are to be understood by thiophosphites and thiophosphates compounds of the general type:

(RS)

3 P, (RS) 3 P=-O or (RS)aP=5, which are described in patent specifications DE 28 09 492, EP 090 770 and EP 573 394.

Examples of those compounds are: trithiohexyl phosphite. 1rithiooctyl phosphite, trithio lauryl phosphite, trithio benzyl phosphite, tri thio phosphorous acid tris(carboisooctyloxy)methyl ester, trith io phosphorous acid tris(carbotrimethylcyclohexyloxy)methyl ester, trithiophosphoric acid 5,5,5tris(corboisooclyloxy)niethyl ester, trithiophosphoric acid 5,S,5-tris(carbo-2ethylhexyloxy)methyl ester, trithiophosphor,c acid S,SS-tris-1- (carbohexyloxy)-ethyl ester, trithiophosphoric acid S,S,S-tris-1-(carbo-2..

elhylhexyloxy)-ethyl ester, trithiophosphori c acid 5,5.-iris- 2-(carbo-2 ethylhexyloxy)-ethyl ester.

MercaptocarboxyiC acid esters Examples of these compounds are: esters of the thioglycolic acid, thiomalic acid, mercaptopropionic acid, mercaptobenzoic acids or thiolactic acid that are described in patents FR 2 459 816, EP 90 748, FR 2 552 440 and EP 365 483.

The mentioned mercaptocarboxylic acid esters also include polyol esters and the partial esters thereof.

too* Epoxidised fatty acid esters :The stabiliser combination according to the invention may additionally comprise preferably at least one epoxidised fatl acid ester. Especially suitable are esters of fatt acids from natural sources (fatty acid glycerides), such as soya oil or rape oil. It is, however, also possible to use synthetic products, such as epoxidised butyl oleate.

Antioxidants Suitable antioxidants are, for example: 1. Alk5ylated monophenols. for example 2 6 -di-tert-butyl-4-methylphenol, 2-tert-buyl-4,6-dimethylpheno 1, 2 ,6-di-tert-buyl-4-ethylpherol, 2 ,6-ditert-butyl-4-n-butylpheno I, 2 .6-di -tert-buyl-4-isobutylphenol, 2,6di cyclopentyl-4-methylphenol, 2 -(a-methylcyclo hexyl)-4,6 -dimethyipheno I, 2 ,6-dioctaidecyl-4-methylpheno I, 2 ,4,6-tricyclohexylphenol, 2 ,6-di-tertbutyl-4-methoxymethylpheno I, 2 ,6-di -nonyl-4-methylphenol, 2 ,4-dimethyl-6 (1'-methyl-undec-IV-yl)phenol, 2 ,4-dimethyl-6-(1'-methyl-heptadec- 1'yl)phenol, 2 ,4-dimethyl-6-(l'-methyl-tridec-1-yl)phenol, octylpheno I, nonylphenol, dodecylphenol and mixtures thereof.

2. Alkylthiomethyphenols. for example 2 4-di-oclylthiomethyl-6-tertbutylphenol. 2 ,4-di-octyllhiomelhyl-6-methylpheno I, 2 ,4-di -octyithiomethyl- 6-ethylphenol, 2 ,6-di-dodecylthiomethyl-4-nonylphenol.

3. Alkylqted hydroguinones. for example 2,6-di-tert-butyl-4methoxypheno I. 2 ,5-di -tert- butyl-hydroquinone, 2 hydroqui none, 2 .6-diphenyl-4-ocadecyloxyphenol. 2 ,6-di -tert-butylhydroquinone, 2 .5-di-tert-butyl-4- hydroxyoisole, 3 .5-di -tert-butyl-4hydroxyanisole. 3 .5-di-tert-buyl-4-hydroxyphenylstearate, bis(3 .5-di -lertbutyl-4-hydroxyphenyl) adipate.

4. 1-lydoxlated thiodiphenyl ethers-, for example 2,2'-thio-bis(6-tertbutyl-4-methylpheno 2 .2'-thio-bis(4-octylpheno 4,4'-thio-bis(6-terbutyl-3-methylphenol), 4 4 '-thio-bis(6-tert-bul-2-methylphenol), 4,4'-tb obis(3 .6-di-sec-amylphenol), 4,4'-bis(2,6-dimethyl-4-hydroxyphenwyl) disulfide.

Alkylidene bisphenols. for example 2 ,2'-methylene-bis(6-tert-butyl.4methyiphenol), 2.

2 '-methylene-bis(6-ter-buyl-i4-ehylphenol),* 2,2'methylene-bis[4-methyl6-(a-methylcyclohexyl)phenioj], 2,2'-niethylenebis(4-nmethyl-6-cyclohexylpheno 2.2'-methylene-bis(6-nonyl-4-.

methylphenol). 2.

2 '-methylene-bis(4,6-di-tert-butylphenol). 2 ,2-el-hylidenebis(4,6-di-tert-butylpheno 2,2'-ethylidene-bis(6-tert-butyl-4.

isobutylphenol), 2 .Z'-methylene-'bis(6-(a-methylbenzl.4-nonylphenol], 2.2'methylcne-bis(6-(a~a-dimethylbenzyl)-4-norylphwoi]. 4,4!-mewthylene- *bis(2.6-di-tert-buylphenol). 4.4'-methylene-bis(6-tert-bu-tyl-2- ***meihyiphenot), ll-bis(5-tert-butyl-4-hydroy-2-methylphenvyl)butarwe 2.6bis(3-tert-butyl-5-methyl-2-hydybenzyl)4-methyphenol, 1,1,3 tert-butyl-4-hydroxy- 2-methylphenyl)butane. 1 .1-bis(5-terl-bulyl-4hydroxy-2-methylphenyl)- 3-n-dodeeylmerccptobutane. ethylene. glycolIbis[3 .3-bis(3'-tert-butyl-4-hydroxyphenwyl) butyrote], bis(3-tert-buyl-4di cyclopentodiene, bis(2-(3'-tert-butyl-2'-hydroxy.

5'-methyl-benzyl)-6-ter-butyl-4-mehylphenyl] terephtha late, 1,1 -bis(3 di methyl- 2-hydroxyphenyl)butane. 2,2- bis(3 .5-di -tert- bulyl-4hydroxyphenyl)propane, 2,2- bis(4- hydroxypIhenyl)propane, 2 butyl- 4 -hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane, 1,1,5.5tetra(5-tert-butyl-4-hydroxy-2-methlphenyl)pentane.

6. Benzyl compounds. for example 3 .53',5-tetra-tert-butyl-4,4'di hydroxydi benzyl ether, octadecyl-4-hydroxy-3 mercaptoacetate, tris(3 .5-di-tert- butyl-4- hydroxybenzyl )ami ne, bis(4-tertbutyl-3-hydroxy-2 ,6-dimethylbenzyl) dithioterephthalcite, bis(3 butyl-4-hydroxybenzyl) sulfide, isooctyl- 3 5-di -tert-butyl-4- hydr-oxybenzyI mercoptoacetate.

7. Hydroxbenzylaied malonottes. for exomple dioctodecyl-2.2-bis(3,5di-tert-butyl-2-hydroxybonzyl) malonate, di-octadecyl-2-(3 -tert-bu-tyl-4- M*Iorit., dldodecylmercaptoethy-2,2-bis(3.5.di..

tert-butyl-4-hydroxybenz .yl) malonate, di-[4-(1 .1,3,3tetraniethylbutyl)phenyl]-2,2-bis(3 .5-di-tert-butyl-4-hydroxybenzyl) malonate.

8. Hvdroxybeny grotic comboUnds. for example 1,.3,5-tris(3,5-ditert-butyl-4-hydroxybenzyl)-2.4.6-trimethylbenzene, 1 ,4-bis(3,5-di-tergbuty-4-hydroxyb~y)-2L3A.6-tetrnsthylbenzens, 2 .4.6-tris(3 butyl-4-hydrxybPnzyl)pht~ol.

Triazine oftoo for example 2.4-bis-octlmecapto-6-{3.5.ditert-butyl-4-hydquj.*Ino)-la,.-triozgne, 2-octylmercapto-4,6-bis(3,5-ditert-buty-4-hyroyhocy)l,3-,5-.trlozirne,'2,4,6-tris(3 .5-dl-tert-burtyl-4hyroxypheroxy)-1,2,3-trorlne, 1,3 ,5-tris(3,5-di-tert-butyl-4hydroxybenzyl) isocyaNuorate, 1,3 ,5-tris(4-tet-butyl-3-hydroxy-2 .6dimethylbenzyl) isocyanurate, 2,4,6-tris(3,.5-di-tert-butyl-4hydroxypheriylethyl)-1.3 ,5-triazine, I .3,5-tris(3,5-di-tert-butyl-4hydroxyphe~lpropIonyIlhpwq yro-1 ,3.5-1triauine, 1.3 .5-trls(3 dicyclohexyI-4-hydroxybroyJ I POP.yauat.

Ptosphonoe an h butyl-4-hydroxybenzyl. phosphonate, dlethylk3,"-i-tert-butyl-4- *hydroxybenzyl phosphonate, diF tlr e phospho nate, dioci ode eyti 5 tertbutyi-4hydroxy-3-methylbenzyI phosphonote. calciwn salt of 3 5 -di-1tert-butly-4-hydroxybenzylphosphonic acid monoethyl ester, tetrac~kis(2 4 -di-tert-utylpheyl).4,4'-biphenylerne diphosphonite, 6-isooctyloxy-2 ,4.8 ,l0-tetra--er-buyl-1 2H-dibenzo (d,gJ- 1,3,2 -dioxaphosphocine, 6kf luoro-2 14.8 ,IO-tetra-tert-butyl-12-methyldi benzo~d,g]-1,.2-dioxa~phosphoci he.

11. Acvlarii-opeor fri-exam~ple 4-hydroxy-louric acid anilide, 4hydroxystearic oc'Idon'"ilice, N-(3 .S-di-tert-butyl-4-hydroxyphenyl)-carbmi c acid octyt ester.

12. Esters of b-(3 .5-di-tert-buvl-4-hydroyhenyl)-propionic acid with mono- or poly-hydric alcohols, such as methaznol, ethanol, octanol, oclcidecanol, 1,6-hexanediol, 1,9-nontanediol, ethylene glycol, l.2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pemtaerythrito I, dlipentaerythritol, tris(hydroxyethyl) isocyanurate, NUN'bis( hydroxyethyl)oxali c acid diamide, 3-thioundecano I, 3-thiapentacdecano

I,

tri methyihexanediol, trimethylo Ipropane, di-Itrimethylo Ipropane, 4hydroxymethyl-1-phospha-2 .6,7-trioxabicyc Io[ 2 .2.2]octane.

13. Esters of b-(5-tert-buyl-4-hdroy-3-methylhevl).propi-onic acid with mono- or poly-hydric alcohols, such as nethanol, ethanol, oclanol.' octadecanol, 1,6-hexanediol, 1 .9-nonianediol, ethylene glycol, 1 2 -propanediol.

neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxy)ethyl isocyanurate, N,N'bis(hydroxyethyl)oxalic acid dicimide, 31-thicurmdecanol, 3-thiapentadecanol, ~.trimethylhexanediol, trimiethylo Ipropane, 44uhydroxymethyl-1-phospha-.6 .7trmioaicycio[;.2. ]octn.

14. Esters of b-( 3 .5-digyclohexyl-4-hydroxyphepyl)propionic acid with mono- or poly-hydric alcohols. such as methanol, ethanol, oc-tanol, octadecanol, 1,6-hexanediol, 1.9-nonaned iol, ethylene glycol, l.

2 -propanediol, neopentyl- glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxy)ethyl isocyanurate, NN'bis- (hydroxyethyl)oxalic acid dianiide. 3-thiciuncecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl- l-phospha-2 .6,7trioxabicyclo[2.2.2 ]octane.

Esters of 3.5-di-tert-bulyl-4-hdroyhenyacetic acid with mono- or poly-hydric alcohols, such as methanol, ethanol, octanol, octadecanol, 1.6hexanediol, 1.9-nonane-diol, ethylene glycol, 1,2-propanediol, neopenlyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxy)ethyl isocyanurate, N.N-bis(hydroxyethyl)oxalic acid diamide, 3-thiciundecainol, 3-thiapentadlecanol, trimethyhexanediol, trimethylolpropane, 4-hydroxymethyl-l -phospha-2 ,6,7-trioxabicyclo(2.2.2]octane.

16. Amides of b-( 3 di-tert-buyl-4-hydroyphenyl)-propioni-c acid, such as N.N-bis(3,5-di-tert-butyl-4hydroxyphenylpropionyl)hexamethylenediamine, N,N'bis(3 .5-di-tert- butyl-4hydroxyphenylpropionyl)trimethylenediami ne, N,N'-bis(3 .5-di-tert-butyl-4.

hydroxyphenylpropionyl) hydrazine.

Preference is given to antioxidants: of groups I to 5, 10 and 12, especially 2,2bis(4- hydroxyphenyl)propcine, esters of 3 .5-di -tert- butyl-4hydroxyphenyipropionic acid with octanol, octadecanol or pentaerythritol or tris(2.4-di-tert-butyphenyl) phosphite.

Where appropriate, it is also possible to use a mixture of antioxidants havingq different structures.' The antioxidants can be used in an amount of, for example, from 0.01 to advantageously from 0.1 to 10, and especially from 0.1 to 5, parts by weight, based on 100 parts by weight PVC.

Ulabsorber-s and light stabilisers Examples are:.

1. 2--(2'-HdoxyhnyF..benzotriazo le, such as 2-(2'-hydroxy-5'methylphenyl)-.benzotriazo le, -tert- butyl-2 -hydroxyphenyl)-.

benzotriazole, 2 -(5S-tert-butyl-2-hydroxyphenyl)-benzotriozole, hydroxy-5!-(1 ,1,3 3 -tetr-amethylbutyl)phenyl)-benzotriazole, 2-(3,5-di-tert- 2-(3'-tert-butyl-2@- 2 buty-2'-hydroxyphenyl)-benzotriazole, 2-(2'-hydroxy-4!-octoxyphenyl).

benzotriazole, 2-(3'.5!-di-tert-amyl-2-hydroxcyphenyl)-benzotriazo le, 2- (3',5'-bis(a,a-dimethylbenzyl)-2'- hydroxyphenyl)-benzotriazole, a mixture of 2 -(3'-tert-butyl-2-hydroxy-5'-(2 benzotriazole, 2 -(3'-tert-butyl-5'-[2 -(2-ethyl hexyloxy)-carbonylethyl]- 2'- 2 -(3'-tert-butyl-2'-hydroxy-5-(z..

methoxycarbo nylethyl)phenyl)-5- ch loro- benzotriazo le, 2 -tert- butyl- 2'hydroxy-5'-(2-methoxycrbonylethyl)pheny)-.benzotriazo le, 2 -(3'-tert-butyl- 2 '-hydroxy-5-(2-octyloxycarbonylethyl)phenyl)-benzotriazole, 2-(31-tert- 2-(2-ethyl hexyloxy)carbonylethyl]-2'- hydroxyphenyl)benzotriazole, 2 -(3'-dodecyl 2 -hydroxy-5-methylphenyl)-benzotriazo le, and 2-(3'-tert-butyl- 2'-hydroxy-5'-(2 -isooctyloxycarbonylethyl)phenylbenzolriazole, 2 ,2'-methylene-bis(4-(1,1,3,3 -tetramethylbutyl)-6benzotriazol-2-yphenol]; the transesterif ication product of 2 -[3'-tertbutyl-5'-(2-methoxyccirbonylethyl)-2'-hydro xy-phenyl]-benzotriazole with polyethylene glycol 300; wherein R 3'-tert-butyl-4'-hydr-oxy-5'-2Hbenzotriazol- 2-ylphenyl.

2. 2±Hyroxvbenzophenones, such as the 4-hydroxy-, 4-methoxy-, 4octyloxy-, 4-decyloxy-, 4-dodecyloxy-, 4-be nzyloxy-, 4.2'4-trihydroxy- or 2-hydroxy-4.4'-dimethoxy derivative.

3. Esters of unsubstituted or substituted benzoic acids, such as 4-tertbutyl-phenyl sal icykite, phenyl sali cylale. octyiphenyl salicylate, di benzoylresorcinol, bis(4-tert-buylbenzoyl )resorcino I, benzoylresorcinolI 3 .5-di -tert-butyl-4-hydroxybenzoic acid 2 .4-di-tert-butylphenyl ester, di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester, 3'.5-di-tert-bu-tyl-4hydroxybenzoic acid octadecyl ester, 3.5-di-tert-butyl-4-hydroxybenzoic acid 2-methyl-4,6-di-tert-butylphenyl ester.

4. Acrylates, such as a-cyano-b,b-dipherwylacrylic acid ethyl ester or isooctyl ester, a-carbomnethoxy-cinnamic acid methyl ester, a-cyano-bmethyl-p-mrethoxy-cinnamic acid methyl ester or butyl ester, acarbomethoxy-p-methoxy-cinnamic acid methyl ester, N-(b-carboniethoxyb-cyainovinyl)-2-methyl-irmdoline.

Nickel comDound such as nickel complexes of 2.2'-thio-bis[4-(1,1,3.3tetramrethylbuyl)phenol], such as the 1:1 or -the 1:2 complex, where .appropriate with 'additional ligonds, such as vn-butylamine, triethanolamine or N-cyclohexyl diethanoloinine, nickel dibutyl dithiocorbamte. nickel salts of 4-hydroxy-3.5-di-tert-butylbenzylphosphonic acid monoalkyl esters, such as :::.methyl or ethyl ester, nickel complexes of ketoximines, such as 2-hydroxy-4methylphenyl-undecylketoxime, nickel complexes of 1-phenyl-4-louroyl-5hydroxy-*pyrazole. where appropriate with additional ligands.

6. Sterically hindered amines, such as bis(2,2.6.6-tetraniethyl-piperidyl) sebacate, bis(2 ,2 ,6,6-tetramethyl-piperidyl) succinate, bis( ,2 ,2 ,6,6pentamethylpiperidyl) sebacate, n- butyl-3 ,5-di -tert-butyl-4-hydroxybenzylmalonic acid bis(1 .2,2 .6.6-pentamethylpiperidyl) ester, the condensation product of 1-hydroxyethyl-2 ,2 .6,6-tetramet hyl-4-hydroxypiperidi ne and succinic acid, the condensation product of N.N'-bis(2,2,6,6-tetramethyl-4piperidyl)hexamethylenediami ne and 4-tert-octylami no- 2,6-di ch loro-1 3 triazine, tris(2 .2,6 .6-tetramethyl-4-piperidyl)nitri lotriacetate, tetraki s(2,.2,6 ,6 -tetramethyl -4-pi peridyl)- 1,2,3,4- butane tetraoate, 1 ethanediyl)-bis(3.3 .5,5-tetramethyl-piperaz inone), 4-benzoyl-2 .2,6,6tetranethylpiperidine, 4-stearyloxy-2 ,2,6,6 -tetrmethylpiperidi ne, bis(1.2,2,6,6- pentanmethylpiperidyI)-2-n-butyl-2-(2-hydroxy-3 .5-di -lertbutylbenzyl) malonate, 3-n-ocly-7,7,9,9-tetrmethyl-1 .3.8triazospiro[4.5jdecane-2,4-dione, bis(1-octyoxy-2 .2,6,6tetranethylpiperlyl) este~ bis(l-octyloxy-2,2,6,6-tetramnethylpipe.,dyl) succinate, the cohdenstionproduct of NM?1bis(2.2,6,6-tetromethiyI-4 piperidyl)-hexamnethynedlatnine and 4-morpholino-2.6-dichloro-l triazine, the condensation product of 2-chloro-4,6-di(4-n-butylamino- 2,2,6 .6-tetramthylporyl)-1.3,.5-triazine and 1 .2-bis(3aminopropykunino.)6thaft 1 the condensation product of 2-chloro-4.6-di-(4-nbulylaniino-1,*_!O ,WApetth ip dy)1, 5-triazine. and I .2-bis(3amifopromyui)#Me S-1-'I-3-odcy-7.79.9-tetrmethyl.38-.

_*~,4d0we 3-dodecyl -I-(2,2,6,6-tetramethyl-4- ~pipeidyl)pyrrotld inei..4op 3-dd l-1-(l .2.

2 6.6-pentamthy-4-.

pipeidyI)pyrr 5 dClassorb96 7. OxqlISci d' j-such as 4.4-di-Octyloxy-oxanitide, 2,21-dloctyloxy-!5.5-d14.';- ty W~ieIide, 2,2'-didodecyloxy-5.5'-di-trt-buyl oxani lide, 2-ethoxy-2'-ethyt oxeaniide, N.-bis(3-dimethylaminkopropyl) oxalamide, 2-ethuxy-5-tert-butyl-2-ethyl oxanilide ond a mixture thereof with 2-ethoxy-2'-ethyIo.4d-1tortbutyI oeanitide, mixtures of o- and pmethoxy- and o- ard pohMbsIies xanifides.

8. WPO*y~ OW4raxnssuhas 2.4k6-trIg24ydroxy-4_ t .(2'hydroxy-4-octyloxyphenyI)A.6- bis(2 4-.

dimethylphenyl)-1 ,3.5O-triazine, 2-(2 .4-dihydroxyphenyl)-4,6-bis(2 .4dimethylphenvyI)-I,3..'rkizia 2.4 -bis(.2-hydroxy-4-propyoxyphenyy..6 (2 .4-dimethylphenyf)-13,5S -riine, 2-(2-hydroxy-4-octyloxypheny)-.4,6bis(4-methylphenyI).4s3.5-trioine, 2-(2-hydroxy-4-dodecyloxyphenyI)-4 6bis(2 .4-dimethylIpht-3.54r~laziine, 2-(2-hydroxy-4-(2-hydroxy-3bulyloxy-propyloxy)phenyl].4,6-bis(2 .4-dimethylphenyl)-l .3,5-triazi ne, 2-[2hydroxy-4-(2-hydroxy-3-octIoxypropyloxy)phenyI]-4,6bis(2 .4dimethylphenyl)- 1 3,8!5-trjiciin.

Propellants Propellants are organic azo and hydrazo compounds, tetrazoles, oxazines, isatoic anhydride, and sodium carbonate and sodium hydrogen carbonate.

Preference is given to azodicarbonamide and sodium hydrogen carbonate and mixtures thereof.

Definitions and examples of impact strength modifiers and processing aids, gelling agents, antistatic agents, biocides, metal deactivators, optical brighteners, fire-proofing agents and antifogging agents are described in "Kunststoffadditive" (Plastics Additives), R.Gichter/H.Muiller, Carl Hanser Verlag, 3 d Ed.. 1989, and "Handbook of Polyvinyl Chloride Formulating", E.J.Wilson, J.Wiley Sons, 1993. Impact strength modifiers are also extensively described in "Impact Modifiers for PVC', J.T.Lutz/D.LDunkelberger, John Wiley Sons, 1992.

The stabiliser combination can be prepared not only by mixing the components in apparatus suitable for the purpose, but also by preparing some of the additional components in situ in a melt of glidants and/or metal soaps before adding component That method is suitable especially for the in situ preparation of calcium acetyl acetonate (cf. EP 336 289) Examples of chlorine-containing polymers to be stabilised or of the recyclates thereof 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 of vinyl chloride with esters of acrylic and methacrylic acid and with acrylonitrile, copolymers of vinyl chloride with diene compounds and unsaturated dicarboxylic acids or the anhydrides thereof, such as copolymers of vinyl chloride with diethyl maleate, diethyl fumarate or maleic acid anhydride, post-chlorinated polymers and copolyners of vinyl chloride, copolymers of vinyl chloride and vinylidene chloride with unsaturated aldehydes, ketones and others, such as acrolein, crotonaldehyde, vinyl methyl ketone, vinyl methyl ether, vinyl isobutyl ether and the like; polymers of vinylidene chloride and copolymers thereof with vinyl chloride and other polymerisable compounds; polymers of vinyl chloroacetate and dichlorodivinyl ether; chlorinated polymers of vinyl acetate, chlorinated polymeric esters of acrylic acid and alpha-substituted acrylic acid; polymers of chlorinated styrenes, for example dichlorostyrene; chlorinated gum; chlorinated polymers of ethylene, polymers and post-chlorinated polymers of chlorobutadiene and the copolymers thereof with vinyl chloride, gum hydrochloride and chlorinated gum hydrochloride; and mixtures of the mentioned polymers with one another or with other polymerisable compounds.

Also included are the graft polymers of PVC with EVA, ABS and MBS.

Preferred substrates are also mixtures of the above-mentioned homo- and copolymers, especially vinyl chloride homopolymers, with other thermoplastic and/or elastomeric polymers, especially blends with ABS, MBS, NBR, SAN, EVA, CPE, MBAS, PMA, PMMA, EPDM and polylactones.

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

Polyvinyl chloride is especially preferred as the chlorine-containing polymer, especially in the form of a suspension polymer and of a bulk polymer.

Within the scope of this invention, PVC is also to be understood to include copolymers or graft polymers of PVC with polymerisable compounds such as acrylonitrile, vinyl acetate or ABS, which may be suspension, bulk or emulsion polymers. Preference is given to PVC homopolyners also in combination with polyacrylates.

Also suitable for stabilisation within the scope of this invention are especially recyclates of chlorine-containing polymers, the polymers being those described in detail above, which have been damaged as a result of processing, use or storage. PVC recyclate is especially preferred. The recyclates may also contain small amounts of foreign substances, such as paper, pigments and adhesives, which are often difficult to remove. Those foreign substances may also originate from contact with various substances during use or working-up, such as propellant residues, traces of lacquer, traces of metal, and initiator radicals.

The invention relates also to a process for stabilising chlorine-containing polymers, which comprises adding to the polymers a stabiliser combination 9* according to claim 1 and homogeneously mixing the components in apparatus suitable for the purpose.

Advantageously, the stabilisers can be incorporated using the following methods: Sin the form of an emulsion or dispersion (one possibility is, for example, as a paste-like mixture). An advantage of the combination according to the invention in the case of that form of introduction is the stability of the paste); in the form of a dry mixture during the mixing of additive components or polymer mixtures; by direct addition to the processing apparatus (for example a calender, mixer, kneader, extruder or the like) or in the form of a solution or melt.

Stabilised PVC according to the invention, to which the invention also relates, can be prepared in a manner known per se, the stabiliser combination according to the invention and, where appropriate, any further additives being mixed with the PVC using apparatus known per si, such as the processing apparatus mentioned above. In that procedure, the stabilisers can be added individually or as mixtures or alternatively in the form of master batches.

The invention thus also relates to a process for the preparation of stabilised S. PVC, which comprises mixing components and described hereinbefore and, where appropriate, any further additives with the PVC using apparatus, such as calenders, mixers, kneaders, extruders and the like.

PVC stabilised in accordance with the present invention can be brought into the desired form by known methods. Those methods are, for example, grinding, calendering, extrusion, injection moulding, sintering or spinning, also blow S extrusion or processing by the plastisol method. The stabilised PVC can also be processed to form foams. When azodicarbonamide is used as propellant it is advantageous not additionally to use 1,3-diketones.

Stabilised PVC according to the invention is suitable, for example, for semirigid and soft formulations, especially as soft formulations for wire sheathing, crash pad sheeting (automobiles) and cable insulation, which is especially preferred. In the form of semirigid formulations, the PVC according to the invention is suitable especially for decorative sheeting, foams, agricultural sheeting, hoses, sealing profiles and office film.

In the form of rigid formulations, the stabilised PVC according to the invention is suitable especially for hollow bodies (bottles), packaging sheets (thermoforming sheets), blown sheets, pipes, foams, heavy-duty profiles (window frames), transparent wall profiles, building profiles, sidings, fittings, office sheeting and equipment housing (for computers, household appliances).

Examples of the use of the PVC according to the invention as plastisol are synthetic leathers, floor coverings, textile coatings, wallpapers, coil coatings and underseal for motor vehicles.

Examples of sintered PVC applications for the stabilised PVC according to the invention are slush, slush mould and coil coatings.

Preference is given to PVC rigid foam mouldings and PVC pipes, such as those for drinking water or waste water, pressure pipes, gas pipes, cable conduits and cable-protection pipes, pipes for industrial pipelines, drain pipes, waste pipes, guttering and drainage pipes. For more detailed information see "Kunststoffhandbuch PVC" (PVC Plastics Handbook), Volume 2/2, W.Becker/H.Braun, 2 nd Ed., 1985, Carl Hanser Verlag, pages 1236-1277.

The Examples that follow illustrate the invention further without, however, S limiting the invention. Unless otherwise indicated, parts and percentages relate to the weight, as in the remainder of the description.

Example 1: Static heat test The mixtures according to the following Tables are each plasticised for minutes at 190*C and 170°C in a roll mill. Test strips are cut from the resulting sheets (which are 0.3 mm thick) and subjected to heating in a Mathis Thermo- Takter at 190'C for the period indicated below in the Tables. Then the Yellowness Index (YI) according to ASTM-1925-70 is determined.

The lower the VI value found, the more effectively the stabiliser system prevents yellowing and thus. damage to the material. The long-term thermostability of the stabilised polymer can also be determined from the sudden appearance of discolouration throughout the polymer.

The longer that that discolouration when subjected to heating is delayed, or the lower the initial discolouration and the better the colour maintenance (low mean discolouration), the more effective is the stabiliser.

Table I: Static heat test at l90*C (rolled for 5 min at 190 0

C)

Mixture 11 12 13 Solvic 268 RC KC value 68) 100 100 100 Omyalite 30 Ca stearate, 0.6 0.6 0.6 Hostalub HO 2 1.0 1.0 1.01 Hlostalub H1220) 0.2 0.2 0.2 CH 3003) 0.4 0.4 0.4 Mark 6045 ACM 4 0.3 0.3 0.3 Stabiliser!* 0.2 0.2 0.2 NaCIO./ 0.05 Minutes 20.7- 29.9 22.2 28.4 66.6 29.1 40.2 108.4 39.2 ')Chalk 2 )Glidant supplied by Hoechst (paraffin wax) '41Gldant supplied by Hoechst (polar ethylene wax) 3 )Phenylisodecyl phosphite 4) Mixture of 9%

NWCO

4 6 457. CaCO3, 407. CaSiO 3 6% HzO 3)6-Amino-1.3-dimethyl-uracil It is found that the use, of tmnall amnounts of perchiorate compound as component B in mixtures II and 13 accordling to the invention results in considerably better stabi lisation* than without component B.

Table II: Static heat test at 190*C (rolled for 5 min at 170*C) Mixture Evipol SH 6030 (PVC K value 60) CH 3W3)~ Wax E6) Epox. soya oil Araldite GY 250@ Araldite PT 8108) Stabiliser 15) Stabiliser 21 Stabiliser 3'0) 111 112 113 114 175 116 117 118 119 100 100 0.8 0.8 0.4 0.4 5.0 5.0 1.0 1.0 100 0.8 0.4 1.0 100 0.8 0.4 5.0- 1.0 100 100 0.8 0.8 0.4 0.4 5.0 1.0 1.0 100 0.8 0.4 5.0 100 0.8 0.4 5.0 100 0.8 0.4

'U

i 4. 4.

4 Minutes 20 30 VI YI YI 17.4 17.3 15.6 23.2 33.7 29.5 33.6 54.9 46.3 YI VIVYI 13.4 11.8 12.5 17.8 18.5 17.7 23.5 29.9 27.8 VIV Y1 Y 14.8 21.2 27.2 16.2 17.1 24.4 24.0 33.6 30.8 3 )Phe nyisodecyl phosphite ")Ester wax (based on: montanic acid) 7)biglycidyl ether of bisphenol A (liquid epoxide) 8) Solid heterocyclic epoxy resin (triglycidyl isocyanurate) 9)6-Amino-1 ,3-di-n-butyluraci I 1 0 6-Amino-1,3-di-ethyl-thiouraci I The stabiliser combination (I14 to 119). of glycidyl and aminouracil compound according to the invention is found to be superior.

Table MI: Static heat test at 190*C (rolled for 5 min at 170*C) Mixture Evipol SH 6030 (PVC K value 60) CH 300O3) Wax E') Epox. soya oil Rhodiastab 5011) Ca stecrate Zn stearate

DASC'

2 Alkamnizer 113) Stabiliser l Stabiliser 29) Stabiliser 3'0) 1111 M121113 M141r15116 111711U8II19 100 0.8 0.4 5.0 0.2 0.3 0.5 1.0

YI

100 0.8 0.4 5.0 0.2 0.3 0.5 1.0

YI

100 0.8 0.4 5.0 0.2 0.3 0.5 100 0.8 0.4 5.0 0.2 0.3 0.5 1.0 100 0.B 0.4 5.o 0.2 0.3 0.5 1.0 100 0.8 0.4 5.0 0.2 0.3 0.5 100 0.8 0.4 5.0 0.2 0.3 0.5 1.

1 100 0.8 0.4.

5.0 0.2 0.3 0.5

YI

100 0.8 0.4 0.2 0.3 1.

YI

a. a 1.0 YI YI Minutes 15.2 31.4 57.2 22.7 37.4 66.9 a *Oa a a, a, 12.9 10.6 16.1 20.6 22.5 26.5 34.0 49.1 41.8 by RHONE-POULENC 10.0 16.3 24.1 10.2 12.4 17.0 18.8 29.7 26.5 ")Stearoyl-benzoyl-methane supplied 1 "lbihydroxyaluminium sodium carbonate (PA SC) 3 )HYdrotalcite supplied by KYOWA (Japan) The addition of dawsonite and the addition of hydrotalcite both increase the stabi lity.

Table IV: 5tatic heat test at 190 0 *C (rolled for 5 min at 170 0

C)

Mixture Evipol 5H 6030 (PVC K value 60) CH 3W30 Wax E'6) Epox. soya oil Rhodiastab 5011) Chimassorb, 94414) Malbit CR (maltite) W~pentaerythritol Stabiliser 15) Stabiliser 29 Stabiliser .319) IVI 1V2 IV3 1V4 1V5 1V6 1V7 1V8 1V9 IVIVIl IV12 100 0.8 0.4 2.0 0.2 1.0 100 0.8 0.4 2.0 0.2 1.0 100 0.8 0.4 2.0 0.2 1.0 100 100 0.8 0.8 0.4 0.4 2.0 2.0 0.2 0.2 0.15 0.15 1.0/ 1.0 100 0.8 0.4 2.0 0.2 0.15 100 0.8 0.4 2.0 0.2 0.5 1.0 100 0.8 0.4 2-0 0.2 0.5 1.0 100 0.8 0.4 2.0 0.2 1.0 100 0.8 0.4 2.0 0.2 0.5 100 0.8.

0.4 2.0 0.2 0.5 100 0.8- 0.4 0.2 a a

C

a. ~YI w nI YI WI nI nI n I n Minuites 10 15 6.0 10.1 6.6 12.7 10.3 18.7 6.6 7.8 5.8 7.7 10.6 32.1 9.0 5.8 11.1 7.3 6.2 8.1 7.2 10.4 9.4 11.1 19.5 16.1 5.4 6.7 11.7 21.9 5.8 9.9 20.1 48.0 10.0 11.2 15.7 25.2 24.2 29.5 47.9 13.8 59.9 >70 >60 29.1 15.4 24.8 8.9 11.1.

4 )sterically hindered amine, supplied by CIBA-GEIGY AG (HALS) The stabiliser combinations according to the invention (IV4 to IV12) are found to give improved stabiliser activity.

C C Table V: 5tatic heat test at 190 0 C (rolled for 5 min at 170 0

C)

Mixture Evipol 5H 6030 (PVC K value 60) CH 3003) Wax E6) Epox. soya oil Rhodiastab 50) Ca stearcile Zn steorate Wessalite, P1 5 Zeolite pi6) Stabiliser P) Stabiliser 29) Stabiliser 310) Minutes 20 30 VI V2 V3 V/4 V5 V6 V7V8 V9 100 0.8 0.4 2.0 0.2 0.3 0.5 1.0

YI

10.3 19.6 41.1 100 0.8 0.4 2.0 0.2 0.3 0.5

YI

100 0.8 0.4 2.0 0.2 0.3 0.5 1.0 Y1 100 0.8 0.4 2.0 0.2 0.3 0.5 1.0 1.0 yr 8.8 12.4 21.0 100 0.8 0.4 2.0 0.2 0.3 0.5 1I.0

YI

100 0.8 0.4 2.0 0.2 0.3 0.5 1.0

YI

100 0.8 0.4 2.0 0.2 0.3 0.5 1.

100 0.8 0.4 2.0.

0.2 0.3 0.5 1.

1 100 0.8 0.4 0.2 0.3

YI

15.7 22.6 34.8

C

S. Ce

C

(C

C

C,

12.3 15.4 34.7 28.6 29.5 58.8 10.6 14.2 16.8 19.5 32.530.5 9.3 9.4 13.3 15.3 25.0 29.2 zeolite A supplied by DEGUSSA "~azeolite P su pplied by I)EGUSSA The stabiliser combination comprising hydrotalcite and zeolites is found to give better results.

Table VI: Static heat test at 190*C (rolledfo5miueat70C for 5 minutes at 1700C) Mixture Evipol EH 6030 (PVC K value 60) Wax E') CH 3003) Epox. soya oil Ca stearate Zn stearate Rhodiastab 50") Sta-26e157 Stabiliser VI1 V12 V13 VI4 100 100 0.4 0.4 0.8 0.8 5.0 5.0 0.55 0.55 0.25 0.25 11.0 VI Y3 100 t00 0.4 0.4 0.8 0.8 5.0 0.55 0.55 0.25 0.25 0.3 0.3 /0.3 1.0 YE Y1 e

S

a 55

S

S

Minutes 20 18.5 9.7 36.5 18,8 30 103 33.3 1 'N-keto ester of the formula 11.4 15.6 21.9 28.3 46.0 59.2 0 Y (CH 2 2 -0.CO-CH 2

-GO-CH

3 It can be seen that combinations comprising O-diketone or O-keto ester give good results.

Table VII: Static heat test at 190 0 C (rolled for 5 min at 170*C) Mixture VIII VII2 VnI3 VII4 VII5 VII6 VII7 VII8 Evipol SH 6030 (PVC K value 60) CH 3003) Wax E 6 Epox. soya oil Ca stearate Zn stearate Synesol M' 8 Stavinor D 50719) Stabiliser 1 5 Stabiliser 29) Stabiliser 310) 4* V V *r 100 100 100 0.8 0.8 0.8 0.4 0.4 0.4 5.0 5.0 5.0 0.55 0.55 0.55 0.25 0.25 0.25 1.0 1.0 1.0 YI VI YI 5.4 4.8 6.3 6.4 4.7 6.7 6.7 5.5 7.0 7.3 7.6 8.3 10.8 12.3 12.5 19.9 28.5 22.9 33.7 65.8 45.1 100 100 100 0.8 0.8 0,8 0.4 0.4 0.4 5.0 5.0 5.0 0.55 0.55 0.55 0.25 0.25 0.25 0.2 0.2 0.2 1.0 1.0 1.0 100 100 0.8 0.8 0.4 0.4 5.0 0.55 0.55 0.25 0.25 0.2 0.2 1.0 YI YI 2.9 4.4 3.7 4.9 4.5 6.7 6.3 8.2 11.3 11.9 23.8 21.3 62.6 38.4 Minutes 0 10 15

YI

2.9 3.5 4.4 5.4 8.9 18.0 31.8 YI YI 3.9 2.3 4.1 2.3 5.3 3.5 7.5 5.4 13.9 9.3 27.2 17.5 64.2 32.3 'l Thiodiethylene-bis(5-methoxy-carbonyl-2,6-dimethyl-1,4-dihydro-pyridine)-3carboxylate supplied by LAGOR 1 9 3-bisdodecyloxycarbonyl-.26-dimethyl-l,4dihydropyridine supplied by ATOCHEM The test shows that stabiliser combinations comprising dihydropyridines (VI4 to VII8) have improved initial colour and colour maintenance (mean colour).

P:\WPDOCS\HjwSpm 2CROMPTON D3.doc11/08103 Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", and variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.

The reference to any prior art in this specification is not, and should not be taken as, an acknowledgment or any form of suggestion that that prior art forms part of the common general knowledge in Australia.

e *ooe

Claims (2)

1. 8-03; 1:57 20-8-0; 612 93645173 4/ 1.AW~OCSlilS 25MWTON DAw,-2CNJU
2. 66- The claims defining the invention are as follows: 1. A stabiliser combination for chlorine-containing polymers comprising A) at least one compound of formula I 0 Y N INH 2 wherein R*1 and R*2 are each independently of the other C 1 -Ct 2 alkyl, C 3 -C 6 alkenyl. C 5 Cacycloalkyl that is unsubstituted or substituted by from 1 to 3 Cl-C. .lkyl, C 1 .C 4 alkoxy, Cii-C 8 cycloalkyl or by hydroxy groups or chlorine atoms, or C 7 -Cgphenylalkyl that is unsubstituted or substituted *at the phenyl ring ~by from 1 to 3 Ci-C 4 alkyl, Cr- C 4 alkoxy, C 5 ,-C 8 cycloalkyl or by hydroxy groups or chlorine atoms, and and R*2 may additionally be hydrogen and CI-C, 2 alkyI, and Y is S or 0, and 8) at least one alkali- (or alkaline earth-) carboxylate, -(bi)carbonate or -hydroxide compound. V,. 2. A stabiliser combination according to claim 1, wherein and l*2 are each independently of the other H and C,-C 4 alkyl or C 1 -C 4 alkyl. 3. A stabiliser combination according to claim 1, wherein the compound of component A) is 6-aimino-l,3-dimethyl-uracil, 6-amino- 1,3-di-n-propyl-uracil, 6-amino- l,3-di-n-butyl-uracil, 6-amino-I .3-diethyl-thiouracil or 6-amino-1,3-di-n-butyl- thiouracil. 4. A stabiliser combination according to any one of claims 1 to 3, which additionally comprises at least one epoxidised fatty acid ester. COMS ID No: SMBI-00384241 Received by IP Australia: Time 14:35 Date 2003-08-20 P;\WPDOCS\Ij.\Sp-s 2\CROMPTON D3.do.-I 1/09/03 -67- A stabiliser combination according to any one of claims 1 to 4, which additionally comprises zinc and/or alkali metal and/or alkaline earth metal carboxylates or aluminium carboxylates. 6. A stabiliser combination according to any one of claims 1 to 5, which additionally comprises at least one further substance from the groups of the phosphites; antioxidants, beta-dicarbonyl compounds, plasticisers, fillers, glidants and pigments. 7. A stabiliser combination according to claim 6, wherein the filler is chalk. 8. A stabiliser combination according to claim 6, wherein the glidant is calcium stearate. 9. A stabiliser combination according to claim 6, wherein titanium dioxide is used as the pigment. 10. A composition comprising a chlorine-containing polymer and a stabiliser combination according to any one of claims 1 to 9. 11. A composition according to claim 10, wherein PVC is used as the chlorine- containing polymer. S 12. A method of stabilising chlorine-containing polymers, which comprises incorporating into the chlorine-containing polymers a stabiliser combination according to any one of claims 1 to 9. P:\WPDOCSIj.'Spo- 2\CROMPTON D3.dow-I 1/08103 68 13. A stabiliser combination of claim 1, or a polymer containing the same substantially as hereinbef ore described with reference to the Examples. bATEb this 1 1 1h day of August 2003. CROMPTON VINYL AbbITIVES GmbH By its Patent Attorneys bAVIES COLLISON CAVE