AU2003203242B2 - Stabiliser combinations for chlorine-containing polymers - Google Patents

Description

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ORIGINAL

COMPLETE SPECIFICATION STANDARD PATENT Applicant(s): Crompton Vinyl Additives GmbH Chemiestrasse 22 D-68623 Lampertheim Germany Address for Service: DAVIES COLLISON CAVE Patent Trade Mark Attorneys Level 10, 10 Barrack Street SYDNEY NSW 2000 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:\WFDOCS Itw'pc 2'CROMFTON D6 doc.27/3/03 -1- STABILISER COMBINATIONS FOR CHLORINE-CONTAINING POLYMERS This application is a divisional of Australian patent application No. 72572/00.

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. Gdchter/-H. Miiller, 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 th 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:WPDOCSHjrSpccM 2CROMFTON D6 doc-2h7033 -2- It has now been found that A) compounds of formula I 0

R*'

Y N NH 2

I

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

C

6 alkenyl, Cs-C 8 cycloalkyl that is unsubstituted or substituted by from 1 to 3 Cz-

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 Ci-C 4 alkyl, C 1

-C

4 alkoxy, Cs-Cacycloalkyl or hydroxy groups or chlorine atoms, and R*i and R*2 may additionally be hydrogen and Ci-Ci 2 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 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, and/or antioxidants and lubricants and/or organotin compounds for the purposes of stabilising chlorine-containing polymers, especially PVC.

P WPDOflaI. 7CROMPTON D6 do-17M0h0 -3- The present invention as claimed provides a stabiliser combination comprising A) at least one compound of formula I 0 R*1 Y N

NH

2 R*2 wherein R*I and R*z are each independently of the other CI-CI2alkyl, C3-Calkenyl, C 5 Ccycloalkyl that is unsubstituted or substituted by from 1 to 3 Cz-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 C 1

-C

4 alkyl, Cz-

C

4 alkoxy, C 5

-C

8 cycloalkyl or by hydroxy groups or chlorine atoms, and R*I and R* 2 may additionally be hydrogen and Ci-Ci 2 alkyl, and Y is S or 0, and B) at least one polyol or disaccharide alcohol.

For compounds of formula I:

C

1

-C

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

C-CI

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

Ci-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 -CgPhenylalkyl 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 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*I and R*2 are each independently of the other CI-C4alkyl and hydrogen.

Especially preferably, either R*i 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: Perch/orate compounds Examples are those of formula M(Cl04)n, wherein M is Li, Na. K; Mg, Ca, Sr, Zn, Al, 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.

Glycidyl compounds 0 These contain the glycidyl group which is bonded Rt, 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 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, 2ethylhexanol, isodecnol and C7-Cgalkanol and C9-Clalkanol mixtures.

They are, however, also derived, for exanple, from cycloaliphatic alcohols, such as 1,3- or 1,4-dihydroxycyclohexane, bis( 4 -hydroxycyclohexyl)methane, 2,2-bis(4-hydroxycyclohexyl)propane or 1,1-bis(hydroxymethyl)cyclohex-3ene, or they have aromatic nuclei, such as N,N-bis(2-hydroxyethyl)aniline or p,p'-bis(2-hydroxyethylamino)diphenylmethane.

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)methane, 2,2-bis(4hydroxyphenyl)pro pone, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 4,4'dihydroxydiphenylsuffone, 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-biphenylglycidyl ether, N-(2,3epoxypropyl) phthalimide and 2 3 -epoxypropyl-4-methoxyphenyl ether.

III) (N-Glycidyl) compounds obtainable by dehydrochlorinating the reaction products of epichlorohydrin with amines containing at least one aminohydrogen atom. Those amines are, for example, aniline, N-methylaniline, toluidine, n-butylamine, bis( 4 -aminophenyl)methane, m-xylylenediamine or bis(4-methylami nophenyl)methane, but also N.N.O-triglycidyl-m-aminopheno

I

or NN.O-triglycidyl-p-aminophena l The (N-glycidyl) compounds also include, however, N,N',N"-triand NN',N',N'"-tetra-glycidyl derivatives of cycloalkyleneureas, such as ethyleneurea or 1,3-propyleneurea, and N,N'-diglycidyl derivatives of hydantoins, such as 5,5-dimethylhydantoin or glycoluril and triglycidyl isocyanurate.

IV) S-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 RI and R3 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 R1 and R3 together are -CH2-CH2- and n is 1 is, for example, 3,4epoxy-6-methylcyclohexanecarboxylic acid (3',4'-epoxy-6'methyicyclohexyl)-methyl ester.

Suitable terminal epoxides are, for example TM denotes a) liquid diglycidyl ethers of bisphenol A, such as AralditeTMGY 240, Araldite'MGY 250, AralditeTMGY 260, AralditeTMGY 266, AralditeT"GY 2600, AralditeiMMY 790: b) solid diglycidyl ethers of bisphenol A,such as AralditeTMGT 6071, AralditeTMGT 7071, AralditeTMGT 7072, AralditeTMGT 6063, Araldite'TMGT 7203, AralditeTMGT 6064, AralditeTMGT 7304, AralditeTMGT 7004, AralditeTMeT 6084, AralditeTMGT 1999, AralditeTMGT 7077, Araldite"MGT 6097, AralditeTMGT 7097, AralditeTMGT 7008, AralditeT&T 6099, AralditeTMGT 6608, AralditerMGT 6609, AralditerMGT 6610; c) liquid diglycidyl ethers of bisphenol F, such as Araldite"GY 281, AralditeTMPY 302, AralditeTlPY 306: d) solid polyglycidyl ethers of tetraphenylethane, such as CG Epoxy ResinT"0163; e) solid and liquid polyglycidyl ethers of phenolformaldehyde novolak, such as EPN 1138, EPN 1139, GY 1180, PY 307; f) solid and liquid polyglycidyl ethers of o-cresolformldehyde novolak, such as ECN 1235, ECN 1273, ECN 1280, ECN 1299; g) liquid glycidyl ethers of alcohols, such as ShellTM glycidyl ether 162, AralditeTMDY 0390, ArolditeTMDY 0391; h) liquid glycidyl ethers of carboxylic acids, such as ShellT"Cardura E terephtholic acid. ester, trimellitic acid ester, Aroldite'TmPY 284; i) solid heterocyclic epoxy resins (triglycidyl isocyanurate), such as AralditeTM PT 810; j) liquid cycloaliphatic epoxy resins, such as AralditeTMCY 179; k) liquid N,N,O-triglycidyl ethers of p-aminophenol, such as Araldite"MY 0510; I) tetraglycidyl-4,4'-methylenebenzamine or N,N,N',N'-tetraglycidyldiaminophenylmethane, such as AralditeMMy 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(4-hydroxyphenyl)propane (bisphenol

A),

bis(4-hydroxyphenyl)-methane or mixtures of bis(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 1 to 25, parts by weight, based on 100 parts by weight PVC.

Beta-diketones, beta-keto esters 1,3-Dicarbonyl 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'1CO CHR2'-COR'3 wherein R'j is C1-C22alkyl, C5-Clohydroxyalkyl, C2-ClBalkenyl phenyl, phenyl substituted by OH, C1-C4alkyl. C1-C4alkoxy or by halogen, C7-ClOphenylalkyl, C5-C12cycloolkyl, C5-C12cycloalkyl substituted by CI-C4alkyl, or is a group S-R'6 or -R'5-O-R'6, R'2 is hydrogen, C1-C8alkyl, C2-Cl2alkenyl, 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 Ci-C4alkyl or phenyl, is C1-ClOalkylene and R'6 is C1-C12alkyl, phenyl, C7-C18alkylphenyl or C7-Ciophenylalkyl.

Those compounds include the hydroxy group-containing 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 US 4 339 383.

R'j and R'3 as alkyl may be, especially, CI-Ctlaakyl, such as methyl, ethyl, ivpropyl, isopropyl, n-bulyl, tert-butyl, pentyl, hexyl, heptyl, oct-yl, dlecyl, dodecyl or octadecyl.

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

R'i and R'3 as alkenyl may be, for example, uiryl, allyl, methaflyll. 1-burenyl, Ihexenyl or oleyl, preferably allyt.

RWi and R'3 as phenyl substituted by OH, alkyl, olkoxy or halogen may be, for example, to lyl, xylyl. tert-butyphenyl, metho-xyphenyl, ethoxyphenyl, hydroxyphenyl. chiorophenyl or dichiorophenyl.

PtI and R'3 as phenylalkyl are especially bemzyl. W'2 and R'3 as Cycloalkyl or alkylcycloalkyl are especially cyclohexyl or mettylcyclohexyl.

R'2 as alkyl may be, especially, CI-C4alkyl. A72 as C2-Cz20lkenyl may be, especially, alfyl- R'2 as aikyiphenyl may be, especially, tolyl RWa as phenylalkyl may be, especially, benzyl. W'2 is preferably hydrogen. R'3'as alkoxy may be, for example, methoxy. ethoxy, butoxy, hexyloxy, octyloxy. dodecyloxy, tridecyloxy, tetrudecyloxy or octodecyloxy. R'5 as Cb-Czoalkylene is especially C2- C4alkylene. R6 cis alkyl is especially C4-Cl2olkyI, such as butyl, hexyl, octyl; decyl or dodecyl. R'6 as alkyiphenyl is especially tolyl. R'6 as phtenylalkyl is especially benzyl.

Examples of 1,3-dicarbonyl compounds of the above formula and their alkali metal, alkaline earth metal and zinc chelates are acetylace-one, butanoylacetone, heptanoylacetone, stearoyloce-to ne, palmi toylaceto ne, lauroylaceto ne, 7-tert-no nylthio -heptane-2 ,4-dio ne, benzoylacetonie, di benzoylmretha ne, lauroylbenzoylmethane, pailritoyl-benzoylmnethane, stearoyl.

benzoylmethane, isooctylbenzoylmeI-hane, S-hyclroxycopronyl-benzoylmethahe, i-ribenzoylmethane, bis(4-methylbenzayl)metharie, benzoyl-pchlorobenzoylmethane, bis(2-hyd roxybenzoyl)niethane, 4-methoxybenzoyl..

berizoylmethane, bis(4-methoxyberizoyl)methane, l-benzoyil-ace-ylnonane, benzoyl-aicelylphenylmethane, stearoyl-4-merhoxybenzoylmethane, bis(4-tertbutylbenzoyl)methane, benzoyt-formylImet hane, benzoyl- pheny locelylmethane, bi scyclohexanoylI-methane, di-pivaloyl-methaie, 2 -acetylcyclopenranone, 2-benzoylcyclopentonhe, diacetoacel-ic acid methyl, ethyl and ollyl ester, benzoyl-, propionyl- and butyryl-acetoacetic acid methyl and ethyl ester, triacetylmethane, acetoacetic acid methyl, ethyl, hexyl, octyl, dodecyl or octadecyl ester, benzoylacetic acid methyl, ethyl, butyl. 2-ethylhexyl, dodecyi or octadecyl ester, and propionyl- and butyryl-acetic acid C1-CIalkyl ester.

Stearoylacetic acid ethyl, propyl, butyl, hexyl or octyl ester and polynuclear pketo 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'l is C1-C18alkyl, phenyl, phenyl substituted by OH, methyl or by methoxy, C7- Cl0phenylalkyl 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.

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

Preference is given to those of the formula wherein Z is HC NH CH 3

CO

2

CH

3 COzCzHt CO 2

"C

2

H

2 5 or CO z CzH 4 S"Ci 1 zHs.

Suitable polydihydropyridines are especially compounds of the following formula wherein T is C1-C22alkyl that is unsubstituted or substituted by Cj1- C18alkoxy, Cl-CtBalkylthio, hydroxy, acryloyloxy, methacryloyloxy, halogen, phenyl or by naphthyl; that is unsubstituted or substituted by C1-C1o8alkyl, C1-C18alkoxy or by halogen and that may also be heterocyclic: C3-C10alkenyl, CH3-CO-CH2-CO-OR-, CH3-CO-CH2-COO-R', CH3- C(NR'"2)-CH-COOR- or CH3-C(NR'"2)=CHCO-O L has the same meanings as T or is a tri- or poly-valent radical from an unsubstituted or C1-C12alkoxy-, C1-Cl2thioalkoxy-, C6-ClOaryl-, Cj- C12carboxy- or hydroxy-substituted straight-chained or branched alkyl group, m and n are numbers from 0 to k is 0 or 1, Sj is a number from 1 to 6 and the conditions j m n) 1 and n 0 are 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 unsubstituted or carries substituents from the series C1-C12alkoxy, C1-Cl2thionialkoxy, C6- ClOdaryl, C1-C12carboxy 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 C1-Cl8alkyl, C2-C18alkoxycarbonyl or C6-Claryl each of which is unsubstituted or substituted by one or more C1-Cj2alkyl, CI-C8alkoxy, halogen or N02 substituents, and the two radicals are identical or different and are hydrogen, Cj1- C18alkyl, C1-C18-hydroxyalkyl or C1-Cs8alkoxyalkyl or together are uninterrupted or O-interrupted or are straight-chained or branched C2-C22alkenyl.

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

CKI 12 Z Th odethylenebs[5methoxycarbony 2 6 dthl-1 4 -dihydropyridine-3-.

carboxylate] is especially preferred.

The (poly-)dihydropyridine compounds can be used in an amount from (i advantageously 0.001 to 5 parts, and especially from 0,005 to 1 parts by weight, C) based on 100 parts by weight ch lorine- containing polymer.

po/yo, disacchar-ide alcohols Examples of suitable compounds of that type are: pentaerylhritol, dipentaerythritol. tripentaerythritol, bistrirnethylolpropane bistrimethylolethane, trisme thyloipropane, inosite, polyvinylalco hol, sorbitol, maltite, isomaltite, lactite, lycasin, rnannitol1, lactose, leucrose, tris(hydroxyethyl) isocyanurate, palati nite, tetiamethylo lcyclohexanoll, tetramethylo Icyclopentano I. tetrarnethylo Icyclopyrano I, glycerol. diglycero

I,

polyglycerol, thiodiglycerol or 1-0aDb-glycopyranosyl-bmanritol di hydrate, Of those compounds, prefereirie is given to the disaccharide alcohols.

The polyols can be used in an amount of, for examnple, from 0.01 to advantageousl1y'from, 0.1 to 20, and especially from 0.1 to 10, parts by weight, based on 100 parts by weight

PVC.

Stel.ically hindered amInes (te tralA-y/j,4,eridine compounds) The sterically hindered amines, especially piperidine 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 CH 3 CH 3 H 3

CH

TheyAC

S

W Ir" WIi uiveiy 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 tetramethylpip-eridine 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 in the descriptions.

a) Compounds of formula II SHC

CH,

R- -N

O

R2 FHC CH 3 n (1) wherein n is a number from 1 to 4, preferably 1 or 2,

R

1 is hydrogen, oxy. C1-C12alkyl, C3-C8alkenyl, C3-C8alkynyl. C7-Cl2aralkyl, 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, Ci-Cs8alkyl that is uninterrupted or interrupted by one or more oxygen atoms, cyanoethyl, benzyl, glycidyl, a monovalent radical of an aliphotic, 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 acpunsaturated 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 CI-Cl2alkylene, C4-C12alkenylene, 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 dicarbamic acid having from 8 to 14 carbon atoms, and, when n is 3, R2 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 are CI-C12alkyl, 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 In the meaning of Cl-C8ealkyl, R 2 may be, for example, the groups listed above and, in addition, for example, n-tridecyl, n-tetradecyl, n-hexadecyf or noctadecyl.

When R 1 is C3-C8alkenyl, it may be, for example, 1-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl or 4 -tert-butyl-2-butenyl.

R

1 as C3-C8alkynyl is preferably propargyl.

As C7-Cl2aralkyl.

R

1 is especially phenethyl and more especially benzyl.

R

1 as C1-C8alkanoyl is, for example, formyl, propionyl, butyryl, octanoyl, but preferably acetyl, and as C3-C5alkenoyl is especially acryloyl.

When R 2 is 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 8-(3.5-di-tert-butyl-4-hydroxyphenyl)-propionic acid radical.

When R 2 is 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 bicycloheptenedicarboxylic 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-1.2.3,4-tetracarboxylic acid or of pyromellitic acid.

When R 2 is a divalent radical of a dicarbamic acid, it is, for example, a hexamethyleriedicarbamic acid or a 2 4 -toluylene-dicarbamic acid radical.

The following compounds are examples of polyalkylpiperidine compounds of that class: 1) 4-hydroxy-2 ,2 .6.6-tetramethylpi peridine 2) 1l-alIlyl-4- hydroxy- 2,2,6, 1 -tetramethyl piper idi ne 3) 2 -benzyl- 4 -hydroxy-2,2 4 6.6-tetramethylpiperidine 4) 1 -44-tert-butlI-2-butenyl)-4-hydroxy-2 ,2,6 6-tetramethylpiperidi ne 4-stearoyloxy-2.

2 .66-tetramethylpi per idine 6) 1-ethyl-4-salicyloyloxy-2 ,2 .6, 6 -tetramethylpi peridinve 7) 4-methacryloyloxy-1 ,2,2 6 1 6 -pentamethylpiperidine 8) 1 .2.2.6,6-pentamethylpiperidin-4-yl-B-(3 .5-di-tert-butyl-4-hydroxyphenyl) propioniate 9) di(l-benzyI-2.2 1 6.6-tetrimethylpiperidin-ev.yl) maleinate di(2 .2 .6.6-'tetramethylpiperidin-4-yI) succinate 11) di(2 ,2 ,6,6-tetramet hylpiperidi n-4-yI) glutarate 12) di(2 .6,6-tetraimethylpi peridin-4-yI) adipate 13) di(2,2 .6,6-tetramethylpiperidin-4-yl) sebacate 14) di(l.2,2,6.6-pentamethylpiperidin-4-yl) sebocare diU., 2 .3,6-tetramethyl-2,6-diethylpiperidin-4yl) sebacate 16) di(1-allyl-2 ,2,6 .6-tetramethylpiperidi n-4-yl) phthalore 17) 1l-proapargyl-48- cyanoethyloxy-2 22,.

6 6 -tetramethylpi peridi vie 28) 1-acelI-2.2.6.6-tetramel'hylpiperidin-4-y acetate 19) trimellitic acid triC 2 1 2 .6.6-tetraimethylpiperidinA..yI) ester l-acryloyl-4-benryloxy-2,2 6 -tetramethylpiperidine 21) diethylmalonic acid di(2 ,2 6 1 6 -tetramethylpiperidi n-4-yI) ester 22) dibutylmalonic acid di(l.

1 2 6 6-penratmethylpiperidin4-y) ester 23) butyl-(3 5 -di-tert-buyl-4-hydroxybenzyly-malonic acid di(l ,2,2 ,6,6pentamethylpiperidin-4-yl) ester 24) d ibenzyi-ma Ionic acid di(1,.2, 6 1 6 -PenromethylpiperidinA...yI) ester dibenzyl-maloni c acid di(1 ,2 3 6 -tetraimethvl-26-diethy.piperidin.4-y) ester 26) hexane-l',6'-bis(4-carbamoyloxy- 2-n-butyl- 2 5 2 5 6 6 -tetramethyl-piperidine) 27) toluene- 2 bis(4- carbamoyoxyI n- pro py1- 2,2,6 ,6 -tetrantethylpiperidine) 28) di met hyl- bis(2 .2 1 6 6 -tetra met hylpl1perid in-4oxy)si lone 29) phenyl-tris(2 ,2 ,6,6-tetramethylpiperidi n-4--oxy)si lane tris(1 -pro pyl- 2 ,2, 6 6 -tetramethylpi perid in-4-yI1) phosphite 31) tris(l -pro pyl 2,2,66-tetramet hylpperidi n4yj) phosphate 32) phenyl- [bis(1. 2 2 6 6 -Pentomethyl p iper idi n-4-yl)] phosphonate 33) 4-hydroxy-1 .2,2.6 6 -pentamethylpiperidire 34) 4-hydroxy-N-hydroxyethyl- 2,2,6 6 -tetranethylpi peridinie 4-hydroxy-N-(2 -hydroxypropyl)-2 .2,6 .6-tetramethylpi peridi ve 36) l-glycidyI- 4 -hydroxy-2,2,6.6-tetramethylpiprjdjne b) Compounds of formula (MI) n'n wherei n It is the number I or 2, Ris as defined for a), Ris hydrogen, C1-Cl2alkyl, C2-C5hydroxyolkyl, C5-Czcycloalkyl, Cy- Cearaikyl. C2-Clealkanoyl, C3-C5alkenoyl or benzoyl, and.

when n is 1, R 4 is hydrogen, CI-Cl8alkyl. C3-Caalkenyl, C5-C7cYcloalkyl,

CI-

C4alkyI substituted by a hydroxy, cyano, alkoxycarbonyl or corbamide group.

qlycidyl, 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-Cx2arylene. xylylene, a -CH2-CH(OH)-cH 2 group or a group -CH2-CH(oHy.

CH2-O-D-O-. wherein 0) is C2-Cboaikylene, C6-Cl5arylene or C6- Cl2cYcloalkylene, or, with the proviso that R3 is not alkanoyl, alkenoyl or bevizoyl,

P

4 may also be a divalent radical of an aliphatic, cycloaliphiatic or aromatic dicorboxylic acid or dicarbamic acid or also the group -CO- or, when n is 1, R 3 and k 4 together may be the divalent radical of an aliphatic, cycloaliphatic or aromatic 1,2- or ,3-dicarboxylic acid.

When any of the substituents are CI-C12- or C-Cia-alkyl, they are as already defined above under a).

When any of the substituents are C5-C7cycloalkyl, they are especiully cyclohexyl.

As C7-C8arolkyl.

R

3 is especially phenylethyl or more especially benryl. As R3 is especially 2-hydroxyithyl or 2-hydroxypropyl.

p 3 as C2-Clealkanoyl is, for example, propionyl. butyryl, actanoyl, dodecanoyl, hexadecanoyl, octadecanoyl, but preferably acetyl, and as C3is especially acryloyl.

When R 4 is C2-Ceolkenyl, then it is, for example, alfyl, methallyl. 2 -butenyl, 2-pentenyI, 2-hexenyl or 2-octenyl.

R

4 as CI-C4flkyl substituted by a hydroxy, cyano, alkoxycarbonyl or carbamide group may be, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2cyanoeihyl, methoxycarbonylmethyl, 2 -ethoxyccrbonylethyl, 2aminocorbonyipropyl or 2-(dimethylaminocarboftyl)-ethyl.

When any of the substituents are C2-Cl2alkylene they are. for example, ethylene, propylene. 2,2-dimethylpro pylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.

When any of the substituents ore C6-Cx5arylene. they are, for example, o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.

As C6-Cl2cycloalkylene, U is especially cyclohexylene.

The following compounds are examples of polyalkylpiperidine compounds of that class: 37) N,N'-bis(2,2 6 6 -tetramethylpiperidin-4-ylI hexamethylene-1 .6-diomine 38) N,N'-bis(2 6,6-tetramethylpiperidi n-4-yl)hexamethylene-1, 6 -diacetamide and 1,6-diformamide 39) l-acetyl- 4 -(N-cyclohexylacetamido)-2,2,6,6-tetrametylpiperjdine 4- benzoylamino-2,2.

6 6 -tetramethylpiperidine 41) N.N'-bis(2,2,66-tetramethylpiperidin-4- 42) N.N'-bi s(2,2,66 -tetromethylIp iperi[di n-4yl)yNN'd i cyohey...2 hydroxyprapylerie-1 .3-diomi ne 43) hJ,N'- bis(2 .2,6 .6-tetraime-hyl pi peridi n-4-yI)-p-xylylene-diami ie 44) N,N'-bis(2 ,2 .6 6-tetramethylpiperidi n-4-ylsuccine-diom ide

N-(

2 .2,6,6-tetramethy Ipiper id i n4yl-Omi ndi pro pioni c aicid di(2,2 ,6,6tetramethylpiperidin-4-yl) ester 46) the compound of the formula

CH

3 CH3CH 3

C

4

H

CH--N -N-C8 2

-CH(OH)-CH---O

C

3

CH

3 CHi--C-CH 3

CH

3 Cl- 3 [41 CHj- N N-H-C q)C j(

CH

3

CH

3 47) 44(bis-2-hydroxyethyl-amino)-1,2, 6 6 -pentomethylpiperidirne 48) 4-(3-methyI-4-hydroxy-5-tert-buwI...Inzoic acid amido)-2,2,6,6tetramethylpiperidine 49) 4 -methacrylamido-1,2,2,6,6-pentamethylpiperidje c) Compounds of formula (IV/) F- rN

(IV).

wherein n is the number I or 2, Ris as defined under a) and, when n1 is 1, is C2-Ceolkylenie or CZ-Cahydroxyalkylene or C4- C22acyloxyolkylene, and, when n is 2, R 5 is the group (-CH2)2C(CI-2-) 2 When P 5 is C2-Caoikylene or C2-Cahydroxyalkylene, it is, for example, ethylene, 1-methyl-ethylene, propylene, 2-ethyl-propylene or 2-ethyl- 2hydroxymethyipro pyfene.

As C4-C22ocyloxyalkylene,

R

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

The following compounds are exanples of polyalkylpiperidine com pounds of that class: 9-aza-8,8,10,1O-tetroamethyl-1 51) 9-aza- 8.8,1,1-tetramethyl-3 -ethyl-I ,5-d ioxaspi ro 52) 8 -oe- 2,77,8 .9,9-hexosnethyl-1I 4-dioxaspiro 53) 9 -aza- 3-hydroxynethyf-3 -ethyl 8891010 -pentameth>{.i 15 diaxaispira 54) 9 -aza- 3 -ethyl- 3 -acetoxymethl-9-cetyI...8lozo10tettamrethyij1.5 2.2,6,6-tetramethylpiperidine-4-spiro-.2' ,3 '-dioxone)-5 d) Compounds of formulae VA, V8 and VC \I

(VA)

H 3 G CH 3

T

13 N

HC'CH

3

H

H~ TI LR I -IZ R

(VC

7 n wherein ni is the number 1 or 2, Ris as def ined under a), R6is hydrogen, Ci-Cz2alkyI. ollyl, benryl, gqlycidyl or C2-C6alkoxyailkyl and, when n is 1, R7 is hydrogen, Cl-Cl 2alkyI, C3-C5alkenyl, C7-Cgaralkyl, C7cycloalkyI, C2-C4hydroxyalkyl. C2-C6alkoxyalkyl, C6-CloaryI, glycidyl or a group of the formula -(CI-2)p-COO-Q or of the formula -(CH2I)p-O-cO-Q, wherein p is I or 2 and Q is CI-C4alkyl or phenyl, and, when n is 2, R 1 7 is C2- Cl 2alkylene, C4-Cl 2alkenyiene, C6-C1 2aryiene, a group -CH2 -CHCOH)-CH 2 O-CH2-CH(OH)-CH2-. wherein b) is C2-Cloalkylene, C6.CI~arylene, C6- Ct2cycloaIlkylene. or a group -CH2CHOZYH2-CocH2cH(oz')c 2 wherein Z' is hydrogen, Cl-Claalkyl, allyl, benzyl, C2-ClZalkanoyl or benzoyl, Tj and T2 are each independently of the other hydrogen, Cl-Cl8alkyl, or unsubstituted or halo- or CI-C4a~kyl-substituted C6-Clo)aryl or C7-Cgaralkyf, or Ti and T2 together with the carbon atom that binds them form a C5-Cl2cycloalkane ring.

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

Any substituents having the definition of CI-Ciaalkyl may be, for example, the groups listed above and in addition, for example, n-tridecyl, n-tetradecyl, nhexadecyl or n-octodecyl.

When any of the substituents are C2-C6alkoxyalkyl, they are, for example, methoxymethyl, ethoxymethyl, prapoxymethyl, tert-butoxymethyl, ethoxyethy

I

ethoxypropyl, n-butoxyethyi, tert-butoxyethyl, isopropoxyethyl or pro poxypropyl.

When P7 is C3-C5alkenyl, it is, for example, I-propenyl, ally!, merhallyl, 2butenyl or 2-pentenyl.

As C7-Cgaralkyl. R7, T 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 R7 is C2-C4hydroxyalkyl, it is. for example, 2-hydroxyethyl, 2hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

As C6-ClOaryi, R 7 TI and T2 are especially phenyl, a- or 1-naphthyl, which are ursubstituted or substituted by halogen or by C1-C4alkyl.

When R7 is C2-Cl2alkylene, it is, for example, ethylene, propylene, 2,2dimethylpropylene. tetramethylene, hexanethylent, octamethylene, decamethylene or dodecamethylene.

As C4-Cl2alkenylene. R is especially 2 -butenylene, 2 -pentenylene or 3hexenylene.

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

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

0 (s C2-Cloalkylene. C6-Cl5arylere or C6-Cl2cycloalkylene is as defined under b).

The following compounds are examples of polyalkylpiperidine compounds of that class: 56) J-benzyl-l1,3,-triaza-7,7,99-tetramehylspiro[4.5]decane24dione 57) 3-n-octyl-1,3,8-triaa-7,7,9,9-tet d 58) 3-al lyl-l,3,8-trioaza-l 7 1 7 .9,9-pentamethylspira F4.5jdecane-2,4-dione 59) 3 -glyci1dylI- 1,3, 8-tr Iaza-17,7,8,,9 peritanlethylspi ro[(4.5jdecane- 24di one 1 ,3,7,7,B,9,9-heptamethyl-1,3 8 -triazaspiro[4.5]decane-Z ,4-dione 62) 2 .isopropyl-J.Z 9 9 tetramethyll-ox-3adroiza4oxo..spiro[4sw)ecane 62) 2,2 -dibufyl-? .7,9.9-tetramethyl -1-oxa-3 .S-diaza- 4 63) 2.2 ,4.4-tetranethyl-7-oxo-3 2 O-dioza-21-oxo-dispiror5i 1. 1 2 ]h-enicosane 64) 2-bulyl-7,7.9,9-tetramethyl-l -oxa-4,8-diaza- 3 -oxo-spirof 4 .S]decane 8-acetyl-3-dodecyl- 1, -triaza77j9.9-tet ramethylspirc45]deczne-2.4diane or the compounds of the following formulae: 01-3 OH 3

OH

3

OH

2 NH-C0O o=c Hi- N C--IN-OF- 3 CNCH 2

CH(OH)CH

2

ICOCH

2 CH(O)H)CH2]2 N- C 66) CH 3 0 0CM 3

CH,

67) OH 3

OH

3 Cl-I OH 3 C~-NNH-CTO 0 0

=-NH

C-N-(CH

2 6

-K

CH

3 OFH3 0H

O

3

OH

3 68) OH 3 OH 3 OH 3

OH

3 NH-C0 0C=N HN J

NH

CHP VOCH o C

(OH

2 69) HNI\- O-N-CH, OH 0000C1 H 2 2H 2

O

3 OH 3

U

e) Compounds of formula VI N N (VI), n wherein n is the number or 2 and 8 is a group of the formula N-f

CH,

3

CH

wherein R1 is as defined under a).

E is or -NR 1 1 A is C2-C6alkylene or -(CH2)3-O- and x is the number 0 or 1,

R

9 is identical to R 8 or is one of the groups -NR 11

R

12

-OR

1 3 -NHCH20R1 3 or -N(CH2OR 1 3 )2 when n 1, R 10 is identical to R 8 or R 9 and. when n 2. R 1 0 is a group -E-8wherein B is C2-C6alkylene that is uninterrupted or interrupted by -N(R 1 1

R

1 1 is C1-C12alkyl. cyclohexyl, benzyl or C1-C4hydroxyalkyl or a group of the formula RCH, CHR Rt 1 is CI-Cl2alkyI, cyclahexyl, benzyl, C1-C4hydroxyalkyl and ft 13 is hydrogen, C1-Cz2alkyi or phenyl, or

P

11 and R 12 together are C4-C5alkylene or C4-C5oxaolkylene, -CH CH or H C 2 for example -CH2CH2 are a group of the formula 0

N-R

-CH2C-f---\

N-F;

.or or alternatively

R

12 and R 12 are each a group of the formula

CH-

3 CH 3 TAH N MN N--r

HA

N tN

CH

3 CF-1 C4H -N CH3

ICH

3

CM

3 N4 Cl- 3 When any of the substii-uents are Cl-C 201kcyl, -they ore, for example, methyl, ethyl, n-propyl, n-buiyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2 -ethylhexyl. nnonyl, m-decyl, n-undecy! or n-dodecyl.

When any of the subst ituents ore Cl-C4hydroxyalkyl, they are, for example, 2 -hydroxyethyi, 2- hydroxypropyA. 3- hydroxypropyl, 2 -hydroxybu-yI or 4hydroxybutyl- When A is C2-C6alkylene, it is, for example, ethylene, propylene, 2,2dimethylpropylene, te 'tranethylene or hexamethylene.

When P1 and RP together are C4-C5alkylene or C4-C5axacilkylene, they are, for example, tetramethylene, pentamnethylene or 3 -oxapenlamethylene, The compounds of the following formulae are examples of polyolkylpiperfidine compounds of that class:.

CH 3 HC I CH-3 HC N H C q OH 3

N-C

4

H~

(CH 3

CH

2 2 N N N(CH 2 CH 3 2 N (0H H, 2

WAI

RJ N

H

3 C CH 3 -NH-CH 2

CH

2 CH/3 N-OH 3 H 3 C) CH 2 wherein R

CH

3

CH

2

-CH

2

I

73) 74)

CH

3

ICH

3

CH

3 PM, N rp cC,

C

4

M*-N

CA

CHc, CHn CH, N j C H R 7 R-NH-(CHJ,-N N-(C8 2 ),-NH-i

CH

3 CH 3 ,wherein R is

CH

3 CH 3

CH

3 76)

WNHCH

2 3 N (C H 2 3

NH-R

CH

3 wherein R

NI,

N, N

C

4

H

9

N

CH I 3 CH 3 CH 3 N OH 3 OH 3 77)

H

3 R H CH3 CH 3 OH 3 N I -I N N-CH 3 N N wherein P C= OH OH CH 3 '-HO t Ho a 6 H'3 E aHO z HO-OH (6L 'Ho, r HO'HO HO

CH

2

-CH=CH

2 3 N CH,

H

3 C

CH,

N-C

4

,H

CH

3 N N CH CH, C=HC-HC-N N N N

N-CH.-CCH

C

4 H,

CH

H

3 C CH 3

CH

3

CH,

f) Oligomeric or polymeric compounds, the structural repeating unit of which contains one or more 2,2,6, 6 -tetraalkylpiperidin e radicals of formula especially polyesters, polyethers, polyamides, polyamines, polyurethanes, polyureas, polyaminotriazines, poly(meth)acrylates, polysiloxanes, 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.

CH, CH, 0 0 II 11 81) f C-CH-CH,C-O-CH,-CH,-N CH 3 CH3 CH, CH, 0 m, CH, iiII0 0 82) CM,*CH,-N 0 C-CCH,), C 0 N-CM,-CH,.o CH, CH, CM, CH, 83) 84) m CH 3 86) CH 3 CH CH 3 0 C 4

H,)

if I Hi *0-C C -a Im

CH

3 8 7 N 4 H 9 C -1 1 3 H H OH/ HlI 3OH 3

OH

3 CH OH Ol H 3 C j 3 H 3

-C

88) NH 2

O

2 0C(C 2 4

-C

OH

3

OH

3 CH- CH 3 m 0 2HS 0 OH -O 3 89) fC C1 2 -N0 CH 3S

OH

3

CH

3 043 C 3

I

0 N-CH-

CH-

9)CH CH, m C 6 H 13 -N

N-CM

3

NN

m

OHI

3 OH 3 CH,

OH

3 cl, N

CM

3 OHC

H

3 H

H

L~

(H

2 6 NC 93) CH1 OH H 3 O6 1H 3

OH

3 H OH 3 C, N~ 014, 0 N-C-C2 94) OH,\ CH, CH3

CH,

CH3

IJ

96) wherein Rt H or CH3 Hg1C 4

(RI)N

(CH

2 3 _j N(f) 4 H,

N

:N-J

'N

HC

4 (R)NZ<N'

N(A)C

4

H.

H

3 C -CH 3 wherein R=: N .N F-1C4(R)N N N(R) C 4

A

and R'= or H (obtainable by reacting the reaction product of trichlorotrizmne and NH2- (CR2)3 -NH-(CR2)2-(CH2)3-N-I with 4-N-butyl- 2,2,6 6 -tetranlethylpiperidine; Of those classes, classes c) and f) are especially suitable, especially those tetralkylpiperidine compounds that contain s-triazine groups. Also especially suitable are compounds 74, 76, St, 87, 92, 95 ad 96.

The preparation of the N-piperidinyI-triazims is known fromi the literature for example, Hlouben-Weyl 'Mtoe der organischen Chemie", Vol. VIII, p. 233-237. *d Ed., Thieme Verlag Stuttgart 1971). There may be used as starting material for the reaction with various 14piperidylamines cyanuric chloride, diarnino-chloro-1 .3 .5-triazine or variouslY substituted bisdialkylamino..

chlor'o-1, 5-triozines or dielkylomino- or olkylaruino-dichloro-1z Technically important exampWe of tetra- and pentoalkylpiperidine compounds are: bis(2 ,2,6'.6.-tetramethyl-pi peridyl) sebaxte, bis(2 ,2,6.6 tetromethyl-pi peridyl) succinate, bIs(1,22.

6 1 6 -pentamethylpipe.idyl) sebacate, n- butyl -3 .5-di-tert-betylA-hyd fxyb~anwtl-malorjic acid bis~i,2 pentaniethylpiperidyl) ester,. the condensation product of l-hydroxyethyl.

2,2.6.6-tetramethyl-4-hydroxy-ppeiine, and soccinic acid, the. condensation product of NN"-bis(2 .2.6.6 -tetramnepthyl-4-pi peridyl)-hexaimethyenogji 0 ni ne and 4-tert-o ctylzri no- 2.6-dick bra- 1,3.5 -s-triaizi ne, *tis(2 .2,6 6 -tetramrhyl.4.

pi peridyl )nitri botriucetate, tetrakis(2 .2,6 .6-tetrarethyl-4-pi peridyl)-1 .2,3,4butanetetraoate, 1 .2-cthcauwiyj)-bis(3 .3 .S.-tetramethyi-piperazi none), 4benzoyl- 2 2 .66tetrmylipmridivm. 4 -ulearylcxy- 2,2,6,6tetramethylpiperidine, bi!S(1.V ,20 t6 .pe.ntamethylpi perldyl)- 2- n-butyl-2-(2 hydroxy-3 .5-di-tert-buty lbe)nl) onate, 3- n-octyl-7,7,9.9 -tetramethyl- I ,3,8-triazspiro4.5cdecane.2,4-d-lone, bis(1-oclyloxy-2.2,6 .6tetramethylpiperidyl) sebczcate, biglI-octyloxy-2,2 6,6 -tetromethylpiperidyl) succiriate, the condensaton product of N.N'r-bis(2,2 6.6-tetramelhyl-4piperidyl)hexamethylenedlanine and 4 -morpholino)-2,6-dihoro135triazire the condensation product -of 2-chlormo-4,6-di4.n-butylami no-2 .2,6,6tetramethylpiperidyl)-l ,S.5-triazine and 11,2 -b is(3 -amino pro pyloamino)et hone, the condensation product of 2 -chloro-4.6-di(4-n..],ujylacino-i ,2 .2,6,6pentamethylpiperidyl)-1,3,!5-tr'io-tjp* ad l.Z-bis( 3 -aminopropylamino)ethane, 8ccetyl-3-dodecvl-7.7.9.F9-tetramethyl.1,3,8 -triazaspiro 4 .5]decane-2 .4-dio ne, 3-dodecyl-1 6 -tetramethyl-4-pipridyl)pyrro lidi ne-2 .5-dione, 3 -dodecyl- 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.

Hydrotalcites and alkali (alkaline earth) aluminosilicates (zeolites) 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 vn M2+l-x M3*x(OH)2 (Ab-)x/b d H20 (VII) wherein

M

2 one or more of the metals from the group Mg, Ca, Sr, Zn or Sn,

M

3 Al, or B, An is an anion having the valency n, b is a number from I to 2, 0 <x 0.5, and m is a number from 0 to Preferably,

A

n OH-, C104-, HC03-, CH3COO-, C6H5COO-, C03 2 (CHOHCOO)22-, (CH2COO)2 2 CH3CHOHCOO- HPO3 or HP04 2 Examples of hydrotalcites are Al2O36M 9 O.C02.12H20 W1, M 9 4 5A12(OH)13CO335H 2 0 (ii), 4Mg.Al203.WO2.9H20 (iii), 4MgO-Al203.COZ.6H20, ZnO.3M 9 0O.Al 2 o 3 C02.l- 914z0 and Zn0.3Mg0.AI2O3.co2.5-6w 2 o. Special preference is given to t-ypes i, ii and iii.

Zeolites (alkali and alkalfine ear-th alum ifasificares) These can be described by _general formula (VII) Mx/n((A102)xC5i2)yi-wH 2 o (VII) 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, Ca, Sr or Ba; y:x is a number from 0.8 to 15. preferaby from 0.8 to 1.2; anid w is a number from 0 to 300. preferably from 0.5 to Examples of zeolites are sodium aluminosilicates of the formulae NaU1A 1125112048 27 H20 [zeolite Na6Al6Si602q 2 NoX. 7-5 X= OH, halogen, C104 [sodalite]; Na6Al6Si300n 24 H20: K08A18S 4 0 0 9 6 24 H-20: Na16Al165i240o. 1I6 H20; N01k6A11 6 i 3 2

O

9 6 16 NO6AI565i1360 3 8 4 250 H20 [zeolite Noe6Ala6Silo 6

O

3 8 4 264 1-20 (zeohite X]j 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)1OAI~oS2 2 0 6 4 20 H-20; CG4.5Nos[(A0 2 1 2 (5io 2 )12J. 30 K9NQ [(Al02)12(iOsz) 12 1. 27 Preferred zeolites correspond to the formulae NaU~A125iq 2

O

4 8 27 H20 (zeolite A], Na6Al6i602 4 2NaX 7.5 H-20, X 0OH, Cl, C104, 1/2C03 [sodalIite] Na6Al65i300 7 2 24 Nc8Al8S54 0 096-24 N0[16A116S12 4 0 89 16 Na16Alx65i32O 9 6 -16 Na56A156S11360384. 250 H20 (zeoliteY] N086A1865il060384. 264 H20 [zeolite X] and zeolites of the X od Y type possessing an Al/Si ratio of about 1:1, or the zeolites that can be formed by partial or complete replacement of the Na atoms by Li, K, Mg, Ca, Sr, Bo or Zn atoms, such as (Na,K)1OAIIOSi22064 20 Ca4,5No3[(AIO2)12(Si2)12]. 30 K9Na3[(Al02)12(SiO2)12]. 27 The zeolites listed may also have a lower water content or may be anhydrous.

Other suitable zeolites are: Na20-A1203-(2 to 5) Si0 2 to 10) H-20 [zeolite PJ Na20-A1203-2 Si02-(3.5-0)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,No.,KH)Al1oS5i2206 4 20

K

9 Na3(AlO2)12(SiO2)12 2 7

K

4 A1 4 5i4016-6 H20 [zeolite K-F] Na 8 A1 8 5i400 9 6.24 H20 zeolite D, as described in Barrer et a. J. Chem.

Soc. 1952, 1561-1571, and in US 2 950 952: The following zeolites are also suitable: potassium offretite, as described in EP-A-400 961; zeolite R, as described in 68 841 812: zeolite LZ-217, as described in US 4 503 023; Co-free zeolite LZ-218, as described in US 4 333 859; zeolite T, zeolite LZ-220, as described in US 4 503 023; Na3K6Al95i27072.21 H 2 0 [zeolite L]; zeolite LZ-211, as described in US 4 503 023; zeolite LZ-212, as described in US 4 503 023; zeolite 0, zeolite LZ-217, as described in US 4 503 023; zeolite LZ-219, as described in US 4 503 023: zeolite Rho, zeolite LZ-214, as described in US 4 503 023; zeolite ZK-19, as described in Am. Mineral. 54 1607 (1969); zeolite W as described in Barrer et J. Chem. Soc. 1956, 2882; Na 3 0 Al30Si 6 6 019 2 98 H20 [zeolite ZK-5, zeolite QJ.

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. especially 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 (reolite P 1 zeolites of the P type. That publication also mentions relatively new zeolites of the P type having Si:Al 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 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, Sri/2 or Zni/2; Z is CO2, S02, (C1207)1/2. 8406, 5202 (thiosulfate) or C20 2 (oxalate); m is a number from 1 to 2 when M is Mg1/2 or Cal/2. and in all other cases is a number from 1 to 3: n is a number from 1 to 4; a is a number from 2 to 4: and p is a number from 0 to The alumino salt compounds of formula that con be used according to the invention may be naturally occurring minerals or synthetically prepared compounds. The metals may partlli reiplace 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 alumina 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 alumina salt compounds are indigirite; tunisite, aluminohydroclcite, paro-aluinohydrocalcite strontiodresserite and hydrostrontiodresserite. Other edimples of alumina salt compounds are potassium aluminocorbonote ((K20)(Aa203).(C2)2.2H20), sodium alumi nthosulfate ((Nq2O).(AIOlO($202)2.2H20) potassium aluminosulfite 1203).(502)2HZO). caliitfn aluminoxalate 1203)(C202)2.5H20), magnesium aluminotetraborate ((MgO).(A1203).(B406)2.5l20), (((Mg90 .2hO.62 1203).(C2)2.41 (([MgO.2 NaO.6]20).(A 1203).(CO2)2.4. 3 H20) and N0.4120).(A 20 3 ).(CO2)2.2.4.9H20).

The mixed alumino salt compoundc can be obtained in accordance with processes known per se by catio.nitdtp9 e. preferably from the alkali alumino salt compounds or by combine pS atio n (see, for example, US 5 055 284) Preference is given to alumina salt compounds of the above formula wherein M is Na or K Z is C02, 502 or (C207)1/2; m is 1-3; n is 1-4; a is 2-4 and p is 0-20. Z is especially C02.

Preference is given also to compounds that can be represented by the following formulae: M20.A1203.(CO2)2 pH20 (1a) (M20)2.(A1203)2.(CO2)2 pH20 (Ib) M20.(A1203)2.(CO2)2 PH20 (Ic) wherein M is a metal, such as Na. K, M91/2, 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 with further additives that are customary for the processing and stabilisation of chlorine-containing polymers, such as: Zinc compounds 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, phenylcarboxylates that are unsubstituted, substituted by at least one OH group and/or Cl-C16alkyl-substituted, phenyl-Cl-Cl6alkylcarboxylates, 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-octylslicylic 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, heptane-1,7-dicarboxylic acid, octane-1,8-dicarboxylic acid, 3 6 9 -trioxadecane-1,10-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, benzoylacetone or dibenroylmethane and enolates of acetoacetates and benzoyl acetates and of dehydroacetic acid. In addition, inorganic zinc compounds, such as zinc oxide, zinc hydroxide, zinc sulfide or zinc carbonate, can 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 CBalkanoates, stearate, oleate, laurate, palmitate, behenate, versatate, hydroxystearotes, 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 enolates.

The metal soaps described and mixtures thereof can be used in amounts of, for example, from 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 propellants, and antifogging agents (cf. "Handbook of PVC Formulating" by E. J. Wickson, John Wiley Sons, New York 1993).

In a non-limiting manner, some of the known additives and processing auxiliaries are mentioned here: Alli metal and alkaoine earth metal compound.

These are to be understood to include especially the carboxylates of the acids described above, but also corresponding oxides or hydroxides or Cbi)arkonates. Mixtures thereof with organic acids are also suitable. Examples are NOH. Na-stearate, NoHCOl s KOH, K-stearate, KHCOs, LiOH, LizcO3, Listeorate, COO, C(OH02), MgO. Mg(OH)2. Mg-stearate, CaCO3, MgC03 as well as dolomite, huntit. chalk, basic Mg-carbonate and other Na- and K-salts of fatty acids.

NoOH. KOH, CoO, Co(OH2), MgO, 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)a (M Ca, Mg, Sr or Zn), so-called "overbased" compounds, to be used.

Preference is given to alkali metal, alkaline earth metal and/or aluminium carboxylotes in addition to the stabiliser combination according to the invention Other Metal Stabilisers Special mention has to be made of organotin stabilisers, carboxylates, mercoptides and Sulfides being preferred. Examples of suitable compounds may be found in US 4,743,640.

G/idan ts(L UBRICAN

TS)

Suitable glidants are, for example: Montan wax, fatty acid esters, PE waxes, amide waxes, chloroparaffins glycerol esters or alkaline earth metal soaps. Suitable glidants are also described in "Kunststoffadditive" (Plastics additives), R. Scichter/H. Miller, Carl Hanser Verlag, 3 Ed., 1989, pages 478-488. Mention may also be made of fatty ketones (as described in DE 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, diisotridecyl, dicyclohexyl, dimethylcyclohexyl, dimethylglycol, dibutylglycol, benzybuty and diphenyl phthalate and mixtures of phthalates, such as C7-C9- and C9- CII-alkyl phthalates from predominantly linear alcohols. C6-CIO-n-alkyl phthalates and CB-C10-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 phtholates. Special preference is given to di-2-ethythexyl diisononyl and diisodecyl phthalate, which are also known by the customory abbreviations DOP (dioctyl phthalate, di-2-ethylhexyl phthalate), bINP (diisononyl phthalate), DIP (diisodecyl phthalate).

B) Esters of aliphotic dicarboxylic acids, especially esters of adipic, azelaic and sebacic acid: Examples of such plasticisers are di-2-ethylhexyl adipate, diisooctyl odipate (mixture), diisononyl adipate (mixture), diisodecyl adipate (mixture).

benzylbutyl adipate, benzyloctyl adipate, di-2-ethylhexyl arelate, di-2ethylhexyl sebacate and diisodecyl sebacate (mixture). Di-2-ethylhexyl adipate and diisooctyl adipate ore preferred.

C) Trimellitic acidesters, for example tri-2-ethylhexyl trimellitate, triisodecyl trimellitate (mixture), triisotridecyl trimellitate, triisooctyl trimellitate (mixture) and tri-C6-C8alkyI, tri-C6-CloaIkyl, tri-C7.C9alkyl and tri-C9-CllclkyI trimellirtte. The last-mentioned trimellitates are formed by esterifying trimelirtic acid with the appropriate alkanol mixtures. Preferred trimellitates ore tri-2-ethyihexyl trimellitate and the mentioned trimellitates from alkanol mixtures. Customary abbreviatlions are TOTM (trioctyl trimellitate, tri-2-ethylhexyl trimelfitate), flOTM (triisadecyl trimellitare) and TrDT (triisotridecyl trimellitote).

Epoxide plasticisers These are mainly epoxidised unsaturated fatty acids, such as epoxidised soybean oil.

E) Polymer placticisers A definition of thtse p'kirticfsers and examples thereof are given in wKurststroffodditivt (Plastics additives), kt Gtchter/-L Miller, Curl Hcrnser Verlag 9 3r Ed., 1989. Chapter 5.9,6. pgs412-415, and in "PVC rechnology".

W.V. flow, 4 *s Ed.. Elsev1fetAbl. 1984. pages 165-170. The most commonly used starting materials for tbc 'preparation of polyester'plasticisers are: dicorboxylic acids, suchas adipic, phthalic, ozelaic and sebacic acid; dials, such as 1.2-propanedil. 1,3-butanediol, 1.4-butanediol, 1,6-hexaniediol, neopentyl glycol and diethylene -glycol.

F) Phosphoric acid esters A definition of those g0ters- is to be found in the above-mentionedj 'Taschenbuch der Kimtftodd~ailive" (Handbook of Plastics Additives), pp.48 4942. Exampes of such phosphoric acid esters are tributyl phosphate, tri-2-e-hylbutyl phosph ate, tri-2-ethylhexyl phosphate, trichioroethyl phosphate.LZ-ethyl-hexyl-diphenyl phosphate, cresyl diphenyl phosphate, triphenyl phosphate, tricresyl phosphate and trixcylenyl phosphate. Tri'-2-elhylhexyl phosphate and WmReofos 50 and 95 (Ciba-Geigy) are preferred.

G) Chlorinated hydrocarbons (paraffins) H) HydrocarbonsI I) Morsoesters, e.g. butyl oleate, phenoxyethyl oleute, terrahydrofurfuy o leate and -alkylsulfi a.c-6c idO ester s.

J) Glycol esters., e.g. digl ycol benzoates.

Definitions and examples of plasticisers of groups G) to J) are to be found in the following handbooks: "Kunststoffadditive" (Plastics Additives), R. GCchter/H. MUller, Carl Hanser Verlag, 3 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, 4t 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 J).

It is also possible to use mixtures of different plasticisers.

The plasticisers 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 person skilled in the art. Examples of inorganic pigments are TiOz. carbon black, Fe 2

O

3 5bzO3. (Ti,Ba.Sb)O 2 .CrzO 3 spinels, such as cobalt blue and cobalt green, Cd(S,Se), ultramarine blue. Organic pigments are, for example, azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, diketo-pyrrolopyrrole pigments and anthroquinone pigments. Preference is also given to TiOz in micronised form.

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

Fillers Fillers (HANDBOOK OF PVC FORMULATING, E.J.Wickson John Wiley Sons, Inc., 1993 pp. 393-449) and reinforcing agents (TASCHENBUCH der KA'e (HANDBOOK of Plastics Additives), R.Gichter H.Muller, Carl Hanser, 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 phasphites, phenyl dialkyl phosphites, tris-(nonylphenyl) phosphite, trilnuryl phosphite, Itrioctadecyl phosphite, distearyl-pentaeryhrito I diphosphite, tris( 2 ,4-di-ert-btuwphenu) phosphite. diisodecylpentqerythritos diphosphite, bis(2 .4-di-tertbutyl phenyl)pentaerythrito I di phosp hite, bis(2.6-di -tert-buyk-4methylphenyl)pentaeryihritol diphosphite, bis- isodecyloxy-pentaierythritoI diphosphite.

bi(,-itr-utl6mtypeylpn rtrtI diphosphire, bis(2.4,6.tri-.

tet- bulylpheuiyl)pentaerythrito 1 di phosphi te, tristearyl-sorb ito I triphosph ite, bis(2,A-di-1ert-buyl- 6 -methylphenyl)mnethyI phosphite, bis(2 ,4-di-terr- butyl-6.

methylphenyl)ethyl phosphite.

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

trioleyl, triphenyl-, tricresyl, tris-p-nonypheny; or tricyclohexyl phosphite and special preference is given to the aryl-dialkyl and alkyl-diaryl phosphires, such as'phenyldidecyl phosphite. (2 ,4-di -tert- butylphenyl)-di-dodeqI phosph ite. (2,6di-rtert-buylphev1>.-di..dodecyI phosphite -and to the dialkyl 7and diurylpentoerythriro I di phosphiwes, such as disteorylpenraierythritolIdiphosphite, and non-stachiomerric triaryl phosphures. for exanple those having the composition (H19C96H4)1§r(ocl2l1 3

H

2 5.

2 7 1 Preferred organic phosphites 'are distearyt-pentoeurthritolI diphosphite, trisnonyiphenyl phosphite and phenyldidecyl phosphite-.

The organic phosphiwes 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.

Tioqphosphites and thiophosp hates There are to be understood by thiophosphiwes and thiophosphates compounds of the general type:

(RS)

3 P= or (RS) 3 P=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. trithioocryi phosphite. trithialauryl phosphite, trithobenzyl phosphite, trithiophosphorous acid tris(carboisooctyloxy)ethyl ester, trithiophosphorous acid tris(carbotrimethylcyclo hexyloxy)methyl ester, trithiophosphoric acid 5,5,5tris(corboisooctyloxy)methyl ester, trithiophosphoric acid 5,5,5-tris(carbo-2ethylhexyloxy)methyl ester, trithiophosphoric acid (carbohexyloxy)-ethyl ester, trithiophosphoric acid SS,5-tris-1-(wGrbo-2ethylhexyloxy)-ethyl ester, trithiophosphoric acid S5.5-tris-2-(carbo-2ethylhexyloxy)-ethyl ester.

Mercaptocarbocylic acid esters Examples of these compounds are: esters of the thioglycolic acid, thiomalic acid, mercaptopropionic acid, mercaptobenzoic acids or thialactic 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.

Epoxidised fatty acid esters The stabiliser combination according to the invention may additionally comprise preferably at least one epoxidised fatly acid ester. Especially suitable are esters of fatly 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.

Anti oxidants Suitable antioxidants are, for example: 1. A Ikylated monophenols. for example 2 6 -di-tert-butyl-4-methylphenol 2-tert-butyl-4,6-dimethylpheno1, 2,6-di-tert-butylA-ethylphenoI, 2,6-ditert-butyl-4-n-butylpheno 2 6 -di-tert-buyl-4-isobutylphenol, 2,6dicyclopentyl-4-methylphenol, 2 -(a-methylcyclohexyl)-4,6 -dimethylpheno

I,

2,6-dioctadecyl-4-methylphenol, 2 4 1 6-tricyclohexylphenolD 2.6-di-tertbutyl-4-nethoxymethylphenol, 2,6-di-nonyl-4-methyfphenol, 2.4-dimethyl-6- (l'-methyl-undec-'-yI)phenol, 2 .4-dimethyl-6-('-methyl-heptadec- yl)phenol, 2.4-dimethyl-6-O'-methyl-tridec-'-yl)phenol, octylphenol, nonyiphenol, dodecylphenol and mixtures thereof.

2. Alkylthiome'rhylphenols. for example 2 4 -di-octylthiomethyl..6.tert.

butyiphenol, 2 9 4 -di-octvylthiomethyl-6-methylphenoI, 2 4 -di-octylthiomethyl- 6-ethyiphenol, 2 6 -di-dodecylthiomehyl-4-nonylphenol.

3. AflaMI4hydrouinones. for example 2,6-di-tert-butyl-4mnethoxyphenol, 2 5 -di-tert-butyl-hdroquinoone, 2 hydroquinone, 2, 6 -diphenyl-4-octdecyloxypheno I. 2,6-di-tert-bu-ylhydroquinone, 2 .§-di-tert-butyl-4-hydroxyo'nisole. 3 ,5-dli-tert-butyl-4hydroxyoniso Is, 3 ,5-di -tat- butyl-4- hydroxyphenystearcote, bis(3 ,5-di -terpbutyl-4-hydroxyphenyI) adipate.

4. R*4!Q~yjgjsdthiodiphenfIethers- for example 2.2'-thio-bis(6-teet-.

butyl-4-vnethylpheno 2, 2-thic- bis(4-octylpheno 4,4'-thio--bis(6 -tertbut-3-methylphena Ix 4 ,4'-thiO-big(6-tert-buy-2-rmethylpheno 4,44k hiobis(3 .6-di -sec-omyipheno Ii, 4.4'-bis(2 .6-dimethyl-4-hydroxyphertI) disulfide.

A lkylidene bisphenols. for example 2.2'-methylene- bis(6-tert- butyI-4methyipheac 2 ,2'-methylene- bis(6 -tefl-buwl-4-ethylpheno 2,2'methylene-bis(4-methyl- 6 -(a-methylcyclohexyl)phenol J, 2.2'-methylensbis(4-me-thyl-6-cyclohexylpheno

Z.

2 -methylene-bis6-'nnyI-4 rnethylphenol), 2 .2'-methylene-bis(46-di-tert.butylphenolI, 2.2'-ethylidene.

bis(4.6-di-tert-butylpheno IX 2.

2 '-ethylidene-bis(6trp bul-yl-4isobutylphertolIX 2 .2'-methyiene-bis 6 -(oi-methylbenzyl )-4-nonyipheno] i, 2'mpethylene-bis6-(.a-dimethylbenyl--ype,npj) 4,4-methylenemethylpkenol), 1,1 -bis(5-tert-buty-4-hydr.xy.2-methylphenyl~ftata 2.6bis(3-tert-butyl-5-methyl-2 hdroxybenzyl)-4-rmethyp.eno I, 1.1.3 ter-t-bul-4-hydroxy- 2-methylphenyl)butone, I.1-bis(5-tert-butyl.4hydroxy- 2-methyiphenyf 3- n-dodecylmercapto butane, ethylene glycolIbis[3.3-bis(3'-tert-butyl-4'- hydroxyphenyl) butyrote). bis(3 -tert-butyl.4.

di cyc lopentodiene, bis(2 -(3-tert- butyl-2'-hydroxy.

5'-methyl-benzylY-6-tert-buwI-4-methylphenyI] terephthalate, 1 ,1-bis(3,5-.

dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3 .5-dli--ert-bui-yl-4hydroxyphenyl)propane, 2 2 bis(4- hydroxyphenyl)propane, 2 b~utyI- 4 -hvdroxy-Z-methypheny}..4.n.dodeqylmercaptobut.an 0 2,1,5,5butyl-4- hydroxy-2 rmethylphenyi)pentane.

6. Benryl compounds, for example 3 ,5,3',5-tetra-tert-butyl-4,4'dihydroxydibenzyl ether, octadecyl-4-hydraxy-3 mercaptoacetal-e, tris(3 .5-di-tert-butyl4-hydroxybenzy)am 1 ne, bis(4-tert.

bu-tyl-3-hydroxy-2,6-dimethylbenzyl) dit h ioterephi ha late, bis(3 bufyi-4-hydroxybenzyl) sulfide, isooctyl- 3,5-di -tert-bulyl-4- hydroxybenryl mercaptoacetate.

7. Ijvdroxybenzvlate-d inolonotes. for example dioctadecyl-2.2-bis(3,5-.

di-tert- butyl- 2-hydroxybenzyl) malonote, di-octadecyl- 2-(3 -tert- butyl-4- :ilonoat. dIdodecylmercaptoethyl -2,2 -bis(3 tert-butyl-4-hydroxybenzyl) malonate, di-(4-(1 ,1,3,3terome-thylbulyl)phenyl .2-bis(3 .5-di -tert-butyl-4-hydroybe-nzl) maonate.

a. Hydr2eyk~nxL gonmgicsmmgmagsL for example 1,3,5-tris(3.5-diter-butyl-4-hydroxybeny)-2.46--rimehyftbenzene, 1 .4-bis(3,5-di-terrbutyl-4-hyxr~ybny)-2.36-tetramethylbenzeis, 2,4.6-ris(35-di-tr..

butyl-4-hydroxybenryl)phenol.

9- Triazins cOMMWn*. for example Z.

4 tetbtl4hd)ynln)-,:-raie 2 -octylmercapto-4.6-bis(3§...dI.

tcrt-butyl-4-lydroxyn'lrl 3 5triezine 2 oylmerapto.6-bIs(35di.

tert-butyl-4-hydroxyphenoxy .3 .5-trlazire, 2 1 4,6-tris(3 .5-di--teut-buyl.4.

bydroxyphenoxy)-l ,2,3-trlozlne. 1,3 .5-tris(3.-di -tert-butyl -4- Iuydroxybenzyl) isocyarsurte, I 3 ,5 i(-a--uy--hdo 6dimethylbenzyl) isocyanurate. 2.4.6-tris(3,5di-te-bt-.hydroxyphenyletbyl}.1.3,5-triozine. 1 1 3 1 5-tilt3.5-di-ten-btyl-4hydroxyphunylproplonylhqw hydro-1.3,5-triazlng, 2 .3.5-tris(3,5dicyclohexyl-4-hydronybenz ylJ leDcyanrt.

Phosphonates o aft"~p.$e. for exampl butyl-4-hydroxybenryt -pfwsphonote, clisthykS .5-di-tert-buty-4-.

hydroxybenzyl phosphonate. dictiey-,-itr-uy--yrxbny phosphonote, dioctadecyt.-5-Stert-butyl-4-hydroxy- 3-methylbenzyl phosphonate, calcium salt of S.§'dI-;er-bul-4hydroxybenylpyjsphonj acid monoethyl ester, tetrakis(2 .4-d i-tert- butlphentyl).-4.4'-.biphenylene diphosphonite, 6-isooclyloxy-2,4.

4 1 .I-tetro--terr-buiyI-1 2H-dibenzo[d,!gJ.

2 ,3,2-dioxaphosphocine, 6-f luoro-2 ,4.8 .lO-tetro-tert-butyl-12-methhy[ dibenzo(d,gJ-1 .3 .2-dioxaphosphocine.

11.4 thm 91j for example 4-hydroxy-louric acid anilide, 4hydroxystearic acid 'i Aide, N-(3 ,5-cfl -tert-butyl-4-hydroxyphenyl )-carbomi c acid octyl ester.

12. Esters of b-( 3 .S-di-tert-buyl-4-hyrox<yphenyI)proponjc acid with mono- or poly-hydric alcohols, such as methanol, ethanol, octonol,octadecanol1, 1,6 -hexanediol1, l,9-nonanediol, ethylene glycol, l.

2 -propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythrito I, dipentaerythrito I, tris(hydroxyethy I) isocyonurate,

!N,N-

bis( hydroxyethyl)oxali c acid diamide, 3-thicundecanol, 3-tb ;apentadeconol, tri metbylhexanedioi, trimethylo ipropane, di-trimethylo Ipropane. 4hydroxymethyl- 1-phospha-2 6 1 7-trioxcabicyc lo[2.2.Zjoctone.

13. Esters of b-(§-tert-butvl-4-hvdrox J-methlphenyl)pro ionic acid with mono- or poly-hydric alcohols, such as methanol, ethanol, octanolj' octadeconol, I ,6-hexanedio I. 1 .9-nononediol, ethylene glycal, l,Z-prcponeJiol, neopentyl _glycol, thiodiethylene glycol, diethylne _glycol, triethylene glycol, pentoerythritol, tris(hydroxy)ethyl isocyonurote,

N,N'-

bis(hydroxyethyl)oxoli c acid diauniide, S -thiouridecanol, 3 -thiapentadeconol.

triniethylhexcanedio I, trimethylo Ipropane, 4- hydroxynmethyl-l1rphospha- 2.6,7-.

trioxobicyclo(2.2J2octana.

14. Esters of b-(3 4 5 _-digyclohf= l-4-hydroxphnyl~poionic acid with mono- or poly-hydric alcohols, such os methanol, ethanol, oc-tanol, octadeconol, I ,6-bexanediol, 1 .9-nonanediol, ethylene glycol, 2 -propanediolneopenlyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythrito I, tris(hydroxy)ethyl isocyonurote, N.N'-bis- (hydroxyethyl)oxalic acid diarnide, S-thiaundecano 1. 3-tb iapentadecanal.

trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl- 1-phospha-z,6 ,7trioxobicyclo(2.2.2]octane.

Esters of 3,5-di-tert-buly1-4-hdro phenlacetic acid with mono- or poly-hydric alcohols, such as methanol, ethanol, octanol, octodecanof, 1,6hexanediol, 1,9-nononediol ethylene glycol, 1,2-proponediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triet hylene glycol. pentoerythritol, tris(hydroxy)ethyl iso cyanurate, NNf-bi s(hydroxyethyl )oxalic acid diam ide, 3-thioundecanol. 3-thiapentadecanol. trirnethyihexonediol, trimnethyl o [propane, 4-hydroxyrnethyl- -'phosphot-2 6 ,7-trioxabicyclo octane.

.16. Amides of b-(3 .5-di -tert- butyl-4- hvdraxvphenyl )-probioriic acid, such as NN-bis(3,5-di-tert-butyl-47 hydroxyphenylpropionyl)hexanethylenedj 0 mijp, NN-bis(3 .5-di-tert-buty-4hydroxyphenylpropionyfltrimethylenediami ne, hydroxyphenyiproplonfl hydrazi ne.

Preference is given to antioxidants of groups I to 5, 10 and 12, especially 2,2bis(4- hydroxyphenyl)propare, esters of 3,5-di-tert- butl-y-4hydroxyphenylpropionic acid with octanol, octadecanol or pentoerythritol or tris(2 ,4-di -tert-butlyphenyl) phosphkite.

Where appropriate, it is also possible to use a mixture of antioxidants having different structures.

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

UV absorbers and light stabilisers Examples ore;.

1. '2-;(2-ydoxphevl)-benzotrizzol la, such as 2-(2-hydroxy-5'methylphenryl)-benzotriazo Ic, 2- -tert-butyl--hydroxcyphenyl)y.

benzotriazo le, 2 -(5'-tert-butyl- 2'-hydroxyphenyl )-benzotriazole, 2- hydro6xy-5'-(1,1,3,3 -tetramethylbu-yl)ph 'enyl)-benzotriizo le, 2 butyl-2'-hydroxyphenl )-5-chloro- benzotriazo Ia, 2 -(3'-tert-butyl- 2- 5-chloro-benzotriazole. 2-(3'-sec-bu-5-ter..

butyl-2'-hydroxyphenyl)-benzotriazole, 2 -(2'-hydroxy-4-octoxyphery).

benzotriazole, 2- (3.5'-di-tert-myl-2'-hydroxyphenyI)-benzotriozo Ia, 2methyl benzyl}- hydroxyphenyly. benzotriazo Is, a mixture of 2 -(31-tert-butyl- 2'-hydroxy-5'-(2 -octyloxycorbo benzotriozo Ic, 2 -(3-tert- butyl-5'- (2 -ethyl hexyloxy)-cctr bonylethyl]- 2'- Ic, 2-(3'-tert-butyl-2'-hydroxy-5st(2methoxycarbo nylethyl)phenyl)- 5- ch lora -ben zatriazo le, 2-(3 -tert-buiy[-2'.

hydroxy-5'-(2-methoxycarbonylethyl)phenyly. benzatriazo Ic, 2 -(3'-tert- butylhydroxy-5'- (2-o ctyboxycorba nylethylphenyl)- benzotrio zo le, 2-(3-et butyl-5'-(2-(2-ethylhexyloxy)carbonylethylp-2'..hydroxyphenyl)benzotriazole, 2 dodecyl 2 %-hydro xy-5'-niethyl ph enyI)- be nzotria 0 bo e, and 2-(3'-tert-butyb- 2'-hydroxy-5'-(2 -isooctyloxycarbonylethyl)phenyl beizotriazole, 2 ,2'-methylene-bis[4-(1 11,3 ,3-tetromethylbutyl)-6benzotriazol-2-ylphenol]; the transesterif icat ion product of Z-[3-tert--z butyl-5'-(2-methoxycarbonylethyl)- 2'-hydroxy-phenyl]- benizotriazo le with polyethylene glycol 300; wherein 3'-tert-butyl-4'-hydroxy-5'.2j.

benzotriazol-2-ylphenyl.

2. 2-ydroxybeozophenones such as the 4-hydroxy-, 4-mnethoxy-, 4ocayloxy-, 4-decyloxy-, 4-dodecyloxy-, 4-beinzyloxy-, 4,2 ,4'-tri hydroxy- or 2'-hydroxy-4,4'-dimethoxy derivative.

3. Esters of unsubstituted or substituted benzoie acids, such as 4-tertbutyl-phenyl salicykite, phenyl solicylate, octyiphenyt solicylote, di benzoylresorcinol, bis(4-tert- bulylbenzoyl )resorci not, benzoylresorcii, 3 ,5-di -tert-butyl-4-hydroxybenzoic acid 2 .4-di-tert-butylphenyl ester, di-tert-butyl-4-hydroxybenzoic acid hexodecyl ester, 3,5-di-tert-butyl4.

hydroxybenzoic acid octodecyl ester, 3 5 -di-tert-btrtyl-4-hyciroxybenzojc acid 2-methyl-4,6-di-tert-butylphenyl ester.

4. Acrylotes, such as a-cyono-b,b-diphenylocerylic acid ethyl ester orisooctyl ester. o-corbomethoxy-cinnamic acid methyl ester, o-cyono-bmethyl-p-methoxy-cinnomic acid methyl ester or butyl ester, acarbomrethoxy-.p-methoxy- cinnami c acid methyl ester, t"-(b-'corbomnethoxy.

b-cyanovinyl)-2-methyl-i ndo line.

Nickel compounds, such as nickel comnplexes of 2.2'-thio-bis(4..{lz ,3.3 tetramethylbutyl)phenolJ. such as the 1:1 or -the 1:2 complex, where appropriate with. additional ligands, such as it-butylamine, triethnokamiie~ or N-cyclohexyl diethanolomine, nickel dlibutyl dithiocorbomote. nickel salts of 4- hydroxy- 3 5-di-tert- butylbenzylphosphoni c acid monoalkyl esters, such as methyl or ethyl ester, nickel complexes of ketoxirnines, such as 2-hydroxy-...

methylphenyl-undecylketoxime, nickel complexes of hydroxy-pyrozole, where appropriate with additional ligands.

6-4 ticgl~hindeedomims such as bis(2 12,6,6-tetramerhyl- pi peridyl) sebocate, bis(2,2 6 6 -tetrmethyl-piperidyl) succinate, bis(l .2,2,6,6pentaimerhylpiperidyl) sebacate, n-butyl-3 5 -di-tert-butyl-4.hydroxybenzyjmalonic acid bis(1 ,2 pentavnethylpiperidyl) ester, the condensation product of l-hydroxyethyl-2,26,6-retromethyl4-hydroxqpjperjdjne and succi nic acid, the condensation product of N, N'-bis(2 ,2 .6 6 -tetramerhyl.4piperidyl)hexomethyle-ediamine and 4 -tert-octyamino-2,6-dichloro-.j 3,5-5triazine, tris(2 ,2,6 6 -tetramethyl-4-piperidyl)nitrilotracetate, ethanediyl)-bis(3 3 5 1 §-tetramethyi-piperazinoe), 4-benzoyl-2.26,6-z tetrwnethylpiperidine. 4-stearyloxy-22 6 6 -tetrarnefhylpiperidine, bis(I .Z.

2 6 1 6 -pentamethYlriperidvi)-2-n-butyI-2-c2-hydroxy-3.5-di-tertbulylbenryl) malonote, 3 -h-octy-7,7.9,9-tetromethyl-1,3 8triazaspiro(4.5deoane24-dione, biS(1 -ocyxy-2 ,2,6,6 tetrwnethylpiperid$) Ssba#.ts. bis(l-octyoxy-2,2 1 6 6 -tetramefliylpipcridyl) succinote, the COfld fl'oflbtrduct of NJt 4 -bis(2.2.66-tetrwpcthyl.4.

piperidyl)-hexamiethyksneiomine and 4 -morpholino-2,6..dichlomo-l triazinie, the condenation product of Z-chloro-4,6-d(4-n-butywnuno-.

2,2,6,6-tetramthyprdyI)-1.,5-triozint a 'nd 1 ,2-b is(3aininoprowlomino)*thane. the condensation product of 2-chkmr-4.6-di-(4-n.

butylomino-1,*.2,6,l1 et1whliprd$ -1.3 .5-triazine and 1.2- bis(3 amhtopropylominc*M ne 8 1I 3 -dodecyI-7J.,9.9-tetramethyl-x,3&.triazospiro[4.§.ite-2.,-done, 3 -dodec$i.lI-(2,2,6,6.tetrmet>l4-.

3-dodecyl 66-penlamthyl-4.

piperidyl)aOdi~e 4 4~ an*-A *;vd C4hlmossrb 966.

7. Oxal1c acidgiqajd4-" such as 4 9 4 '-di-oclylxy-oxanifide. 2.2'-i oxohIde, 2 oxani lide, 2-ethoxy-2-ethyl oxani lid., NXN-bis(3 -dimethylarninoprcpyl) oxaiwnide, 2-ethoxy-5-tert-butyl-Z-cthyl oxanilide and a mixtuft thereof with 2-ethoxv-2'-ethy-5,4'.dio-teirt-butyl oranilide, mixtures of a- and pmethoxy- and a- adpthIydubntnned oaoilides.

8. 2~24d &kP@#~,such as 2,4,6-tr~g24rydroyA..

OctylXyphnyl)-13.5 ukjin, (.hrXY-c~oyhWY,-bt24 dime-thylphenl)-l ,3.5-triazine, Z-(2,4-dihydroxyphenyl}-.46..bjs(2 .4dirnethylphenyl)- 1,3,5-wiozinp. 2.4- bis(2- hydoxy-4-prpykxyphenyly.6.

(2 .4-dimethylpheny)l33.5triiine, Z-(Z-hydroxy-4-octyIoxypheal)-4 6bis(4-mnethylphevl-) -43,5-tri mn 2 -(2-hydmoxy-44dodey~pheny4,6 bis(2 .4-dimnethylphti)- 1y,3 ,5-friori tie, 2- 2-hydroxy-4-(2-hydroxy-3 butyloxy-propyloxy)phenyly-4,6- bis(2 .4-di methylphenyiy-.3,5-trzin, 2- [2hydroxy-4-(2-hydiroxy3 -otyoxypro pyloxy)phenyl]-4,6 -bis(2 .4dimethylphenryi)-,.354. riczne.- Propellants Propellants are organic 020 and hydrazo compounds, tetrozoles, 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.Miller, Carl Hanser Verlag, 3" 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 A) That method is suitable especially for the in situ preparation of calcium acetyi 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 methocrylic 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 copolymers 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 potylactones.

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 polynerisable compounds such as acrylonitrile, vinyl acetate or ABS, which may be suspension, bulk or emulsion polymers. Preference is given to PVC homopolymers 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 according to claim I 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 s, 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 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 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, officesheeting 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" Ed., 1985. Carl Hanser Verlag, pages 1236-1277.

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

Example I: 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 YI 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 1900C (rolled for 5 min at 190 0

C)

Mixture 11 12 13 Solvic 268 PC (S-PVC K value 68) 100 100 100 Omyalite 30 T' 3.0 Ca stearate 0.6 0.6 0.6 Hostalub H42) 1.0 1.0 Hostalub H12 0.2 0.2 0.2 CH 300') 0.4 0.4 0.4 Mark 6045 ACM 4 '0.3 0.3 0.3 0.2 0.2 0.2 NaCIO4 0.05 YI YI VI 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) 4Glidant supplied by Hoechst (polar ethylene wax) 'Phenylisodecyl phosphite 4 Mixture of 9 NaCI04, 45% CaCO 3 40%. CaSiO, 6% H2O '6-Aino-1,3-dimethyl-uracil It is found that the use of small amounts of perchlorate compound as component 8 in mixtures II and 13 according to the invention results in considerably better stabilisation than without component B.

Table II: Static heat test at 190 0 C (rolled for 5 min at 170 0

C)

Mixture Evipol SH 6030 (PVC K value 60) CH 3003) Wax E 6 Epox. soya oil Araldite GY 25071 Araldite PT 810O) Stabiliser 15) Stabiliser 2 9 Stabiliser 3 0) II II2 II3 14 II5 1I6 17 18 119 100 0.8 0.4 5.0 1.0 100 100 0.8 0.8 0.4 0.4 5.0 5.0 1.0 1.0 100 0.8 0.4 5.0 1.0 100 100 0.8 0.8 0.4 0.4 5.0 5.0 1.0 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 I YI YI YI YV YI Y1 YI yI Minutes 17.4 17.3 15.6 23.2 33.7 29.5 33.6 54.9 46.3 13.4 17.8 23.5 11.8 12.5 18.5 17.7 29.9 27.8 14.8 21.2 27.2 16.2 17.1 24.4 24.0 33.6 30.8 )Phenylisodecyl phosphite )Ester wax (based on: montanic acid) )Diglycidyl ether of bisphenol A (liquid epoxide) Solid heterocyclic epoxy resin (triglycidyl isocyanurate) )6-Amino-1.3-di-n-butyluracil o )6-Amino-1.3-di-ethyl-thiouracil The stabiliser combination (II4 to 119)of glycidyl and aminouracil compound according to the invention is found to be superior.

Table III: Static heat test at 190 0 C (rolled for 5 min at 170*C) Mixture Evipol SH 6030 (PVC K value 60) CH 3003 Wax E') Epox. soya oil Rhodiastab 501) Ca steorate Zn steorate Alkamizer I3 Stabiliser 15) Stabiliser 2') Stabiliser 30) MII II21II3 1114 I15 I16 100 0.8 0.4 5.0 0.2 0.3 0.5 1.0 100 0.8 0.4 5.0 0.2 0.3 0.5 1.0 100 0.8 0.4 5.0 0.2 0.3 0.5 1.0

VI

100 0.8 0.4 5.0 0.2 0.3 0.5 1.0 1.0

YI

VI

100 100 0.8 0.8 0.4 0.4 5.0 5.0 0.2 0.2 0.3 0.3 0.5 0.5 III7 III8 III9 200 100 100 0.8 0.8 0.8 0.4 0.4 0.4 5.0 5.0 0.2 0.2 0.2 0.3 0.3 0.3 0.5 0.5 1.0 1.0 1.0 1.0 YI VI YI 1.0

I.

1.0

YI

1.0 1.0

VI

YI YT Minutes 15.2 31.4 57.2 22.7 37.4 66.9 12.9 10.6 16.1 20.6 22.5 26.5 34.0 49-1 41.8 10.0 10.2 12.4 16.3 17.0 18.8 24.1 29.7 26.5 "'Steoroyl-benzoy-methane supplied by RHONE-POULENC ')Dihydroxyaluminium sodium carbonate (DASC) ")'Htydrotalcite supplied by KVOWA (Japan) The addition of dowsonite and the addition of hydrotolcite both increase the stability.

Table IV: Static heat test at 190*C (rolled for 5 min at 170"C) Mixture Evipol SH 6030 (PVC K value 60) CH 3003 Wax E 6 Epox. soya oil Rhodiastab 50") Chimassorb 9444) Molbit CR (maltite) Dipentaerythritot Stabiliser 1 5 Stabiliser 29) Stabiliser 3' 9 IVI IV2 IV3 IV4 IV5 IV6 IV7 IV8 IV9 IV10IV11 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 0.8 0.4 2.0 0.2 0.15 1.0 100 0.8 0.4 2.0 0.2 0.15 1.0 100 100 0.8 0.8 0.4 0.4 2.0 2.0 0.2 0.2 0.15 0.5 100 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 0.5 1,0 100 0.8 0.4 2.0 0.2 0.5 1.0 100 0.8 0.4 0.2 1.0 Y: YI I YVI YI I YI VI YIr y YI Yr Y Minutes 6.0 10.1 24.2 6.6 12.7 10.3 18.7 6.6 7.8 5.8 7.7 9.0 5.8 11.1 7.3 6.2 7.2 9.4 19.5 8.1 10.4 11.1 16.1 5.4 6.7 11.7 21.9 5.8 10.0 9.9 11.2 20.1 15.7 48.0 25.2 29.5 47.9 13.8 10.6 15.4 8.9 59.9 >70 >60 29.1 32.1 24.8 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.

Table V: Static heat test at 190 0 C (rolled for 5 min at 170°C) Mixture Evipol SH 6030 (PVC K value 60) CH 3003) Wax E') Epox. soya oil Rhodiastab 50" Ca steorate Zn steorate Wessalite P' 5 Zeolite p'6) Stabiliser 15) Stabiliser 29) Stabiliser 310) VI V2 V3 V4 V5 V6 V7 V8 V9 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 1.0

VI

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 1.0 1.0

YI

100 0.8 0.4 2.0 0.2 0.3 0.5 1.0 1.0 yI S100 0.8 0.4 2.0 0.2 0.3 0.5 1.0 1.0

YI

100 0.8 0.4 2.0 0.2 0.3 0.5 1.0 1.0 yi 100 0.8 0.4 2.0 0.2 0.3 0.5 1.0 1.0 VyI 100 0.8 0.4 0.2 0.3 yr Minutes 10.3 19.6 41.1 12.3 15.4 34.7 28.6 29.5 58.8 8.8 12.4 21.0 10.6 14.2 16.8 19.5 32.5 30.5 9.3 9.4 13.3 15.3 25.0 29.2 15.7 22.6 34.8 5 Na zeolite A supplied by DEGUSSA "Nol zeolite P supplied by DEGUSSA The stabiliser combination comprising hydrotalcite and zeolites is found to give better results.

Table VI: Static heat test at 190°C (rolled VI3 VI4 for 5 minutes at 170°C) Mixture Evipol EH 6030 (PVC K value 60) Wax E' CH 300 3 Epox. soya oil Ca stearate Zn stearate Rhodiastab 50" D-26-155'~ 7 Stabiliser 1 Stabiliser 2) VII VI2 100 100 0.4 0.4 0.8 0.8 5.0 5.0 0.55 0.55 0.25 0.25 1.0 1.0 yf y- 100 100 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 YI YI Minutes 18.5 9.7 36.518.8 103 33.3 11.4 15.6 21.9 28.3 46.0 59.2 Ot Y, ,V.

ON o y "'-keto ester of the formula Y (CH 2 2

-O-CO-CH

2

-CO-CH

3 It can be seen that combinations comprising B-diketone or 8-keto ester give good results.

Table VII: Static heat test at 190C (rolled for 5 min at 170 0

C)

Mixture VTl V112 Vr13 VII4 VI5 VL16 VII7 VII8 Evipol SH 6030 (PVC K value 60) CH 3003) Wax E6) Epox. soya oil Ca stearate Zn steorate Synesal M6) Stavinor D 507" Stabiliser 15 Stabiliser 29) Stabiliser 330) 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 0.25 100 0.8 100 0.8 100 0,8 0.4 04 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 /1 100 100 0.8 0.8 0.4 0.4 5.0 0.55 0.55 0.25 0.25 0.2 0.2 1.0 1./ 1.0 1.0 1.0 Minutes VI VI VI YI yr YI vI vI 0 5.4 4.8 6.3 2.9 3.9 2.3 2.9 4.4 6.4 4.7 6.7 3.5 4.1 2.3 3.7 4.9 6.7 5.5 7.0 4.4 5.3 3.5 4.5 6.7 7.3 7.6 8.3 5.4 7.5 5.4 6.3 8.2 10.8 12.3 12.5 8.9 13.9 9.3 11.3 11.9 19.9 28.5 22.9 18.0 27.2 17.5 23.8 21.3 33.7 65.8 45.1 31.8 64.2 32.3 62.6 38.4 8 Thiodiethylene-bis(5-methoxy-carbonyl-2 .6-dimethyl-1,4-dihydro-pyridine)-3carboxylate supplied by LAGOR 9)3-bisdodecyloxycarbonyl-2 .6-dimethyl-1,4dihydropyridine supplied by ATOCHEM The test shows that stabiliser combinations comprising dihydropyridines (VIT4 to VIT8) have improved initial colour and colour maintenance (mean colour).

P:WPDOCSHtjiK'a ZCROMPTON D6.-27/0303 65 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.

Claims (10)

1. A stabiliser combination for chlorine-containing polymers comprising A) at least one compound of formula I 0 R* Y N NH 2 R*2 wherein R* and R* 2 are each independently of the other Ci-C 12 alkyl, C 3 -C 6 alkenyl, Cs- Cscycloalkyl that is unsubstituted or substituted by from 1 to 3 Ci-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 Ci-C 4 alkyl, C 1 C 4 alkoxy, Cs-C 8 cycloalkyl or by hydroxy groups or chlorine atoms, and R*I and R* 2 may additionally be hydrogen and C 1 -C 12 alkyl, and Y is 5 or 0, and B) at least one polyol or disaccharide alcohol.

2. A stabiliser combination according to claim 1, wherein R*i and R* 2 are each independently of the other H and CI-C 4 alkyl or C-C 4 alkyl.

3. A stabiliser combination according to claim 1, wherein the compound of component A) is 6-amino-1,3-dimethyl-uracil, 6-amino-1,3-di-n-propyl-uracil, 6-amino- 1,3-di-n-butyl-uracil, 6-amino-1,3-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. 2CROMPTON D6.do.27/033 -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. 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.

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. PAWPD0CSXHj~spems 2\CROMPTON D6.doc-29/IO/04 -68- Z 13. A stabiliser combination of claim 1, or a polymer containing the same 0 ~substantially as hereinbef ore described with reference to the Examples. DATED~ this 29th day of October 2004 CROMPTON VINYL ADDITIVES GMBH By its Patent Attorneys DAVIES COLLISON CAVE