AU2003203276B2 - Stabiliser combinations for chlorine-containing polymers - Google Patents

Description

Our Ref: 7776001 P/00/011 Regulation 3:2

AUSTRALIA

Patents Act 1990

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.WPDOCSijw\spec 2CROMPTON DS.do-27/0303 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. Gichter/-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 d 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:\WPDOCS\LMAwpec 2'CROMFMTN D. doc-271/03/ -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 Ci-Czzalkyl, C 3

C

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

C

4 alkyl, C1-C 4 alkoxy, C 5 -Cecycloalkyl or hydroxy groups or chlorine atoms, or C 7 Cgphenylalkyl that is unsubstituted or substituted at the phenyl ring by from 1 to 3 C1-C 4 alkyl, Ci-C 4 alkoxy, C 5 -Cscycloalkyl or hydroxy groups or chlorine atoms, and R*I and R* 2 may additionally be hydrogen and Ci-C 1 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.

PAVPDOCS\EqWSp-s 2\CROMPTON DS&doc-3II/O1S -3- The present invention as claimed provides a stabiliser combination comprising A) at least one compound of formula I 0 R*i Y N NH 2 R*2 wherein R*I and R* 2 are each independently of the other CI-CI 2 alkyl, Cs-C 6 alkenyl,

C

8 cycloalkyl that is unsubstituted or substituted by from 1 to 3 CI-C 4 alkyl, C 1

C

4 alkoxy, C5-Cscycloalkyl 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-Cecycloalkyl or by hydroxy groups or chlorine atoms, and R*1 and R* 2 may additionally be hydrogen and Cl-C1zalkyl, and Y is 0, and B) a glycidyl compound.

For compounds of formula I: C1-C 4 Alkyl is, for example: methyl, ethyl, n-propyl, isopropyl, iso-, sec- or tert-butyl.

C

1

-C

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

C1-C 4 Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy or isobutoxy.

C

5 -CBCycloalkyl is, for example, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

C

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

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

C

3

-C

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

Preference is given to compounds of formula I wherein R*1 and R*2 are each independently of the other C1-C4qlkyl and hydrogen.

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

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

The compounds of the groups mentioned under B) are illustrated as follows: Perchlorate compounds Examples are those of formula M(CIO4)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 -CH- CH) which is bonded dR, Rs R directly to carbon, oxygen, nitrogen or sulfur atoms and wherein either R1 and R3 ore both hydrogen, R2 is hydrogen or methyl and n=0, or RI and R3 together are -CH2-CH2- or -CH2-CH2-CH2-, in which case R2 is hydrogen and n=O 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 cyclooliphatic 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)propone 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,Z-diol, or poly(oxypropylene) glycols, propane-1,3-diol, butane-1,4diol, poly(oxytetramethylene) glycols, pentane-1,5-diol, hexane-l,6-diol, hexane-2,4,6-triol, glycerol, l.,-trimethylolpropane, bistrimethylolpropane, pentaerythritol, sorbitol, and from polyepichlorohydrins, butanol, amyl alcohol, pentanol, and from monofunctional alcohols, such as isooctanol 2ethylhexanol, isodecanoI and C7-C9olkanol and C9-Cj1alkanol 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 1,1I-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 pane, 2,2-bis(3.5-dibromo-4-hydroxyphenyl)propane, 4,4'dihydroxydiphenylsulfone, or on condensation products of phenols with formaldehyde obtained under acid conditions, such as phenol novolaks.

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

III) (N-Glycidyl) compounds obtainable by dehydroch lorinating 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)methone, m-xylylenediamine or bis(4-methylaminophenyl)methane, but also N,N,O-triglycidyl-m-aminopheno

I

or N,N,O-triglycidyl-p-ominophenol.

The (N-glycidyl) compounds also include, however, N,N',N"-triand N,N',N",N'"-tetr-glycidyl derivatives of cycloalkyleneureas, such as ethyleneureca or 1, 3 -propyleneurea, and NN'-diglycidyl derivatives of hydantains, 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 Rj 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 RI and R3 together are -CH2-CH2- and n is 1 is, for example, 3,4-.

epoxy-6-methylcyclohexanecarboxylic acid (3',4'-epoxy-6'methylcyclohexyl)-methyl ester.

Suitable terminal epoxides are, for example TM denotes a) liquid diglycidyl ethers of bisphenol A, such as AralditeTMGY 240, AralditeTMGY 250, AralditeTMGY 260, AralditeTMGY 266, AralditeTM"GY 2600, AralditemMY 790; b) solid diglycidyl ethers of bisphenol A, such as AralditeTM&T 6071, AralditeTMGT 7071, AralditeTMGT 7072, AralditeTMGT 6063, AralditeTMGT 7203, AralditeTMGT 6064, Araldite"MGT 7304, Araldite"GT 7004, AralditemGT 6084, AralditeTMGT 1999, AralditeTMGT 7077, AralditeTMGT 6097, AralditeTMGT 7097, AralditeTMGT 7008, AralditeTMGT 6099, AralditeMGT 6608, AralditeTmGT 6609, AmalditeTMGT 6610; c) liquid diglycidyl ethers of bisphenol F, such as AralditeTMGy 281, AralditeTPY 302, Araldite'"PY 306: d) solid polyglycidyl ethers of tetraphenylethane, such as CG Epoxy ResinT"0163; e) solid and liquid polyglycidyl ethers of phenolformaidehyde novolak, such as EPN 1138, EPN 1139, GY 1180, PY 307; f) solid and liquid polyglycidyl ethers of o-cresolformaldehyde novolak, such as ECN 1235, ECN 1273, ECN 1280, ECN 1299; g) liquid glycidyl ethers of alcohols, such as ShellTM glycidyl ether 162, AralditeTMbY 0390, AralditeTMbY 0391: h) liquid glycidyl ethers of carboxylic acids, such as ShellTM"Cardura E terephthalic acid ester, trimellitic acid ester, AralditeTmPV 284; i) solid heterocyclic epoxy resins (triglycidyl isocyanurate), such as AralditeTM PT 810: j) liquid cycloaliphatic epoxy resins, such as AralditeMCY 179; k) liquid N,N,O-triglycidyl ethers of p-aminophenol, such as AralditeMMY 0510; I) tetraglycidyl-4,4'-methylenebenzamine or N,N,N',N'-tetraglycidyldiaminophenylmethane, such as AralditerMMy 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 I 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'ICO CHR2'-COR'3 wherein R'1 is C1-C22alkyl, C5-Ciohydroxyalkyl, C2-Cl8alkenyl. phenyl, phenyl substituted by OH. C1-C4alkyl. C1-C4alkoxy or by halogen, C7-Clophenylalkyl, C5-Cl2cycloalkyl, C5-C12cycloalkyl substituted by CI-C4alkyl, or is a group S-R'6 or -R'5-0-R'6.

R'2 is hydrogen, C1-Csalkyl, 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 CI-C8alkoxy, R'4 is C1-C4alkyl or phenyl, is C1-Cl1alkylene and R'6 is CI-C12alkyl, phenyl, C7-C18alkylphenyl or CT-Clophenylalkyl.

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-Qaalkyl, such as methyl, ethyl, iipropyl, isopropyl, ri-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl or octadecyl.

R'j and R'3 as hydroxyalkyl are, especially,. mqroup -(CI-2)n-OH. wherein n is 6 or 7.

R'i and R'3 as alkenyl may be, for exampleyiryl, ailyl, methallyl, 1-butenyl, Ihexenyl or oleyl, preferably ailyl.

R' 1 and R'3 as phenyl substituted by OH, olkyl, alkoxy or halogen may be, for example, tolyl, xylyl, tert-butylphenyl, methoxyphenyl, ethoxyphenyl, hydroxyphenyl. ch lorophenyl or dichiorophenyl.

Ril and R'3 as phenylolkyl are especially benryl. R'2 and RP3 as cycloalkyl or alkylcyclocikyl are especially cyclohexyl or methylcyclohexyl.

R'2 as alkyl may be. especially, Ci-C4alkyl. RW2as C2-Cl2alkenyl may be, especially, allyl. R'2 as alkyiphenyl may be, especially, tolyl R2 as phenylolkyl may be, especially, berizyl. R'2 is preferably hydrogen. RP3'as alkoxy may be, for example, methoxy, ethoxy, butoxy, hexyloxy, octyloxy, dodecyloxy, tridecloxy, tetradecyloxy or octadecyloxy. R'5 as C1-Czoalkylene is especially C2- C4nlkylene- R'6 as alkyl is especially C4-C12a1kyl, such as butyl, hexyl, octyl, decyl or dodecyl. [V6 as alkylphenyl is especially tolyl. R'6 as phenylalkyl is especially benzyl.

Examples of 1,3-dicarbonyl compounds of the above formula aid their alkali metal, alkaline earth metal and zinc chelates are acetylacetone, butanoylacetone, heptanoylocetone, steoroylace-to ne, palm itoylaceto ne, lauroylaceto ne, 7-tert-no nylt hio-heptone-2 ,4-diorne, benzoylacetone, di berzoyl methane, lauroylbenzoylmethane, paliit'oyl-benzoylmethane- stearoylbenzoylmethane, isoo etyl benzoylmet hane, 5-hydroxycapronfl -berizoylmeithane, tri benzoylmethane, bis(4-methylbenzoyl~methane, benzoyl-pchlorobenzoylmethane, bis(2-hydroxybenzoyl)niethane, 4-methoxybeizoyl..

benzoylmethane, bisC4-methoxybenzoyl)methane, I-benzoyl-1--acetylnonane, benzoyl-acetylphenylmethane, stearoyl-4-methoxybenzoylmethane, b is(4-tertbutyrbenzoyl)methane, benzoyl-formylme-hone, benzoyl pheny lacetylm ethane, biscyc lohexanaylI-methane, di-pivoloyl-methane, 2 -acetylcyclopentanone, 2-benroylcyclopentanone, dliocetoacetic acid methyl, ethyl and oliyl 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, dodecyl or octadecyl ester, and propionyl- and butyryl-acetic acid ClCl8alkyl 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 CI-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 0 286 887 and EP 0 024.754.

Preference is given to those of the formula wherein Z is HC NH CH 3 COzCH 3 C0 2 CzH C02"C 2 zHz5or CO z C 4 Suitable polydihydropyridines are especially compounds of the following formula wherein T is CI-C22alkyl that is unsubstituted or substituted by Ci- C18alkoxy, CI-Cl1alkylthio, hydroxy, acryloyloxy, methacryloyloxy, halogen, phenyl or by naphthyl; that is unsubstituted or substituted by Cr-C1aalkyl, C1-C18alkoxy or by halogen and that may also be heterocyclic; CH3-CO-CH2-CO-OR-, CH3-CO-CH2-COO-R', CH3- C(NR'"2)zCH-COOR- or CH3-C(NR'"2)= CHCO-O L has the some meanings as T or is a tri- or poly-valent radical from an unsubstituted or CI-C12alkoxy-, C1-C12thioalkoxy-, C6-Caryl-, Cl- C12carboxy- or hydroxy-substituted straight-chained or branched alkyl group, m and n are numbers from 0 to k is 0 or 1, j is a number from 1 to 6 and the conditions j m n) 1 and m n O 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-C12thioalkoxy, C6- C-C12carboxy and hydroxy, p is from 2 to 18, t is from 0 to X is oxygen or sulfur, or, when k is O and j 1. R and R' together with L form a direct bond, R" is hydrogen, or Cl-Cl8alkyl, C2-Cl8alkoxycarbonyl or C6-ClOaryl each of which is unsubstituted or substituted by one or more C1-C12alkyl, C1-Calkoxy, halogen or N02 substituents, and the two radicals are identical or different and are hydrogen, Cj1- C18alkyl, Cl-C18-hydroxyalkyl or C-C1B8alkoxyalkyl 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.

Thiodiethylene-bis[5-methoxycarbonyl-2.6-dimethyl-1 ,4-di hydropyridi ne-3carboxylate] is especially preferred.

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

Polyols, disaccharide alcohols Exaimples of suitable compounds of that type are: pentaerythritol, dipentaerythritol. tripentaerythritol. bistrimethylopropane, bistrimethylo letharie, trismethylo Ipro pane, i nosite, p0 lyvi nylalco ho I, sorbito I, maltite, isomaltite, lactite, lycasin, mannitol. lactose, leucrose, tris(hydroxyethyl) isocyanurate, palati nite, tetomethylo lcycld'hexoa tetramethylo icyclopentano I, tetromethylo Icyclopyrano I, glycerol. diglycero I, polyglycerol. thiodiglycezrol or 1-O-a-I)-glycopyranosyl-C)mnrio dihydrate. Of those compounds, prefere.-ice is given to the disaccharide alcohols.

The polyols can be used in an amount of, for examnple, from 0.01 to advantageousl-,"from 0.1 to 20, and especially f rom 0. 1 to 10. parts by weight, based on 100 ports by weight PVC.

Ster1ically hindered am ines (tetraalcypiperidine compoundsv) The sterically hindered 'amines. especially piperidline compounds, that can be used according to the invention are known especially as light stabilisers. Those compounds contain one or more groups of the formula

H

3 C N CH 3 H 3C They Imay be cornpo-Urds of frelatively 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 te-tramethylpiperidine 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 "RI" in the descriptions.

a) Compounds of formula II H3C CH, R-F-N 0--R2 H3C CH3 n 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-C12aralkyl.

Cl-CBalkanoyl. C3-C5alkenoyl, glycidyl or a group -CH2CH(OH)-Z, wherein Z is hydrogen, methyl or phenyl, R being preferably C1-C4alkyl, allyl, benzyl, acetyl or acryloyl, and, when n isl. R 2 is hydrogen, Ci-C18alkyl that is uninterrupted or interrupted by one or more oxygen atoms, cyanoethyl, benzyl, glycidyl, a monovalent radical of an aliphatic, cycloaliphatic, aroliphatic, unsaturated or aromatic carboxylic acid, carbamic acid or phosphorus-containing acid or a monovalent silyl radical, preferably a radical of an aliphatic carboxylic acid having from 2 to 18 carbon atoms, a cycloaliphatic carboxylic acid having from 7 to 15 carbon atoms, an a.unsaturated carboxylic acid having from 3 to 5 carbon atoms or an aromatic carboxylic acid having from 7 to 15 carbon atoms, and, when n is 2, R 2 is C1-C12alkylene, C4-Cl2alkenylene, xylylene, a divalent radical of an aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid, dicarbamic acid or phosphorus-containing acid or a divalent silyl radical, preferably a radical of an aliphatic dicarboxylic acid having from 2 to 36 carbon atoms, a cycloaliphatic or aromatic dicarboxylic acid having from 8 to 14 carbon atoms or an aliphatic, cycloaliphatic or aromatic dicarbomic acid having from 8 to 14 carbon atoms, and, when n is 3, R 2 is a trivalent radical of an cliphatic, cycloaliphotic or aromatic tricarboxylic acid, an aromatic tricarbomic acid or a phosphoruscontaining acid or a trivalent silyl radical and, when n is 4, R2 is a tetravalent radical of an aliphotic cycloaliphatic or aromatic tetracarboxylic acid.

When any of the substituents are CJ-Cz2alkyl, 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 C-Calkyl, R2 may be, for example, the groups listed above and, in addition, for example, n-tridecyl, ni-tetradecyl, n-hexadecyl or noctadecyl.

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

P

1 as C3-C8alkynyl is preferably propargyl.

As C7-C12aralkyl R1 is especially phenethyl and more especially benzyl.

R1 as C1-C8alkanoyl is, for example, formyl, propionyl, butyryl, octanoyl, but preferably acetyl, and as C3-C5alkenoyl is especially acryloyL When R2 is a monovolent radical of a carboxylic acid, it is, for example, an acetic acid, caproic acid, stearic acid, acrylic acid, methacrylic acid, benzoic acid or B-(3.5-di-tert-butyl-4-hydroxyphenyl)-propionic acid radical.

When R2 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-butyi-4-hydroxybenzyl)-malonic acid or bicycloheptenedicarboxylic acid radical.

When R2 is a trivalent radical of a tricarboxylic acid, it is, for example, a trimellitic acid or nitrilotriacetic acid radical.

When R2 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 di carbomic acid, it is, for example, a hexamethylenedicarbamic acid or a 2 4 -foluylene-dicarximic acid radicl The following compounds are examples of polyalkylpiperidine compounds of that class: 1) 4-hydroxy- 2,2 .6,6-tetramethylpiperidi ve 2) 1 -al lyl-4- hydroxy- 2,2,6, 6 -tetromet hyIpiper idi ne 3) 1 -benzyl-4-hydroxy-2.

2 6 1 6 -tetroimethylpiperidine 4) 1 -(4-tert-bul-yl-2-bufenyl)-4-hydroxy.2 2,6 .6-tetraniethylpiperidinve 4 -stearoyloxy- 2 2 9 6.6-tetromethylpiperidine 6) 1-ethyl-4-solicyloyloxy-2 ,2 6 1 6 -tetraimethylpi peridine 7) 4-methacryloyloxy-1 .2,26.6-pentamerhylpi peridine 8) 1,,,,-etmtypprdn4y--35d-etbtl4hdoyhml propio note 9) di(l-benzyI-2.2.6.6-tetramethylpiperidin-.4-yI) malci note di(2 .2 6.6-tetrame-hylpiperidi n-4-yl) succina-te 11) di(2 .2 6.6-tetramethylpiperidi n-4-yl) glutorate 12) di(2,2.6,6-tetrmethylpiperidi n-4-yI) adipote 13) di(2,2.6,6-tetramethylpiperidin-4-yl) sebocate 14) di(1*2 ,2,6 .6-pentamethylpi peridi n-4-yl) sebacate d i(l 6-tetromethyl- 2, 6-d iethyl pipe ridi n-4-y1) sebacote 16) di(l-ohllyI-22.6.6-tetrmethylpiperidin-4-y) phthalote 17) l-propcrgyl-48-cyonoethyloxy-2 ,2 6 4 6 -tetramethylpiperidinve 18) l-ocetyl-2 .2,6 .6-tetramethylpiperidin-4-yI acetate 19) trimellitic acid tri(2.2.6.6-tetrmethylpiperidin-4-yI) ester l-ocryloyl-4-benzyloxy-2.26,64etramethylpipeidine 21) diethylmotonic acid di(2 ,2 ,6 6-f etromethylpiperidi n-4-yl) ester 22) dibutyimaooric acid diO ,2 .2,6 .6-pentotmethylpi peridi n-4-yl) ester 23) bul-yl-(3 .§-di-tert-buwl-4-hdroxybenzyl..moionic acid di(1.2,2,6,6pentamethylpiperidiri-4-yJ) ester 24) dibenzyl-malonic acid di (1,2.2, 6 6 pentamet hylpi per id in-4-yl) ester dibenzyl-malonic acid di(l,..J 6 -tetramethyl-2.&-diethyl-piperidin4-y) ester 26) hexane-1',6'-bis(4-ca.rbomoyloxy-z- n-bui-yl- 6 6 -tetramethy[.piperidi ne) 27) toluene-2,4-bis(4- carbamoyloxy-i n- pro pylI- 2,2 .6.6-fetramethylpiperidine) 28) di methyl- bis( 2 ,2,6,6-tetramethylpiperldi n4-oxy)si lane 29) phenyl -tri s(2,2, 6 6 -tetramethyl p iper id in-4_oxy)si lane tris(1-propyl-2 2 6 .6 tetramethylpiperdin.4-y1) phosphite 31) tris(1 -pro py 2 6 -tetramethylpi perid i n-4yi) phosphate 32) phenyl-[bis(I ,2.2 6 1 6 -pentamethylpiperidiv4.yl)] phospho note 33) 4-hydroxy-1 ,2,2 6 1 6 -pentornethyipiperidinE 34) 4-hydroxy-N-hydroxyethyl-2 ,2,6 6 -tetranethylpiperidine 4-hydroxy-N-(2-hydroxypropyQ)-2.2 6 1 6-tetramethylip eridi ne 36) l-glycidyl-4-hydroxy- 2,2 6 6 -tetrrnerhylpi peridine b) Compounds of formula (MI) Fb -i N R4 wherei n n is the number 1 or 2, Ris as defined for a), Ris hydrogen, C1-Cl2alkyI. CZ-C~hydroxyallcyl, C§-Cicycioalkyl, C7- Caaralkyl. C2..Cl8a1kanoyl, C3-Csulkenoyl or beazoyl. and, when n is 1. R4is hydrogen, Ci-CiBalkyl, C3-Csolkenyl, C5-C~ccloalkyl. Cj- C4alkyI substituted by a hydroxy, cyano, alkoxycarbonyl or carbamide group, glycidyl, a group of the formula -CHa-CH(OH)-Z or of the formula -CONH-z, wherein Z is hydrogen, methyl or phenyl: and, when n is R 4 is C2-Cl2cxlkylene, C6-Cl2arylene, xylylene, a -CH2--CH(OH)-cH 2 group or a group -CH2-CH(ouy.

CH2-O-O-O-. wherein D is C2-Czoalkylene, C6-Cl5arylene or C6- Cl2cycloalkylene, or, with the proviso that P 3 is not alkonoyl, alkenoyl or benzoyl,

R

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

When any of the substituents are CI-C2- or CI-Cis-alkyl, they are as already defined above under a).

When any of the substituents are C5-C7cyclocilkyl, they are especially cyclohexyl.

As Ci-Caaralkyl, R3 is especially phenylethyl or more especially benzyl. As R3 is especially 2-hydroxyethyl or 2-hydroxypropyl.

R3as C2-Clalkanoyl is, for example, propionyl. butyryl, octanoyl, dodecaoyl, hexodecanoyl. octodecanoyl, but preferably acetyl, and as C3is especially acryloyl.

When R 4 is C2-C8alkenyl, then it is, for example, allyl, nethallyl, 2-butenyl, 2-pentenyl, 2-hexenyi or 2-octenyl.

P

4 as CI-C4alkyl substituted by a hydroxy, cyano, alkoxycorbonyl or carbomide group may be, for example, 2-hydrocyethyl, 2-hydroxypropyl, 2cyanoethyl, methoxycarbonylmethyl, 2 -ethoxycorbonylethyl. 2aminocarbonylpropyl or 2-(dimethylcuinocarbonyl)-ethyl.

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

ethylene, propylene, 2,2-di methyl propylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.

When any of the substituents are C6-Cz5arylene, they are, for example, o-, m- or p-phenylene, 1,4-nophthylene or 4,4'-daphenylene.

As C6-Cl2cycloalkylene, 0 is especially cyclohexylene.

The following compounds are examples of polyalkylpiperidine compounds of that class: 37) N,N'-bis(2,2 .6.6-tetramethylpiperidin-4-yl )hexamethylene-1,6-diamine 38) N,N-bis(2,2 ,6, 6 -tetramethylpiperidin-4-yl)hexamethylene 6 -diacetamide and 1,6-diformamide 39) l-acetyl- 4 -(N-cyclohexylacetamido)- 2,a6,6-tetramethylpperidine 4- benzoylamnino-2,2 6 1 6-tetramethylpiperidine 41) NN'-bis(2,2 6,-tetrmethylpiperidin-4-y )-NN'-dibutyl-cdipamide 42) N.N'-is( 2 2 6 6 etrmethylpiPeridin-4-yi}4NN-dicycloht<.yl-2 hydroxypropylene-! .3-diami ne 43) N.N'-bis(2.2,6,6-tetramethylpiperidi n- 4 -yl)-p-xylylene-diamine 44) bis(2 ,2,6 .6-tetramethylpiperidi n-4-yi)succine-diom ide N-(2,266tt ehlieiin4y)Baioirpoi acid di (2,2,6,6tetramethylpi peridi n-4-yI) ester 46) the compound of the formula

OH

3 OH 3C CHj-- N N-CH2-CH(OH)-CH--O

CH

3

CH

3

CH--C-OH

3 CH 3

OH

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

CAH

CH 3

CH

3 47) 4-(bis-2-hydroxyethyl-ami .2,2 .6.

6 -pentarrethylpiperidine 48) 4-(3-methyl-4-hydroxy-5-tert-bulyl.benzo ic acid oamido)-2 ,2 .6,6tetramethylpiperidirne 49) 4-methocryamido-1 ,2*2 6 6 -pentamethylpiperidirne c) Compounds of formula (IV) wherein ni is the number I or 2.

Pis as defined under a) and, when n is 1, P.

5 is C2-Cealkylene or C2-Cehydroxyalkyiene or C4- C22acyloxyolkylene, and, when n is 2, P 5 is the group (-CH2)2C(CH2-) 2 When R5is C2-C8olkylene or C2-C8hydroxyalkylene. it is, for example, ethylene, 1 -methyl-ethylene, propylene, 2 -ethyl-propylene. or 2-ethyl-2 hydroxymethyipro pylene.

As C4-C22acyloxyulkylene, R5 is. for example, 2-ethyl-2acetoxymethylpro pylene.

The following compounds are examples of poryalkylpiperidine compounds of that class: 9 -amc- 8,8 ,lO,1-tetrwnethyl-1I.5-dioxaspiro (5.5 N ndecane 51) 9 -aza- 8, 8J0,lO-etramethyl-3-ethyl-z 1,5-d ioxaspi ro 52) 8-aza-2 .7.7.5.9.9-hexnethyl-1,4-ioxxspiro4.5]gecone 53) 9 -aza- 3 -hvdroxymethyl-3-ethyl-8.8.9lozo10pentmethyl..z§..

54) 9-arc- 3-ethyI-3-ocetoxymethy-9-ceyla 8 ,lO.10-tetramethyl.15.- 2, 6,6-tetramethylpiperidine-4-spiro.2 ,3 -dioxane)-5' (l".,3"-dioxane)-2"-spiro--4' "2 ".6"'-tetromethylpiperidiMe).

d) Compounds of formulae VA, VB and V/C

(VA)

H 3 C CH 3

T

P-N C- 1T 2 N-C0O

H

3 C 'CH 3

H

-CT

KA-

(V.C)

11 7 H3C CH 3 0 n wherein ni is the number 1 or 2, Pisos defined under a), Ris hydrogen, C1-Cl2alkyl, allyl, benzyl, glycidyl or C2-C6alkoxyalky I and, when n is 1. R 1 7 is hydrogen. C1-Ci2alkyl. C3tC5alkenyl, C7'-Cgaralkyl, C7c)'Cloalkyl, C2-C4hydroxyalkyl, CZ-C6alkoxcyaikyl, C6-Cloaryt, gqlycidyl or a group of the formula -(CH2)p-COO-Q or of the formula -(CH2)p-O-CO-Q, wherein p is 1 or 2 and Q is CI-C4alkyl or phenyl, and, when n is 2 R 7 is C2- Cl2alkylene, C4-Cl2alkenylene. C6-Cl2aryiene. a group -CH2-CH(OH)-CH20ob O-CH2-CH(OH)-CN2-. wherein D is C2-Czoailkylene, C6-Ci5ar-yIene, C6- Cj 2cYcloalkylene, or a group -CH2CH(Or7)CH2-(OCH2-CH(Or7)CH 2 )2 wherein Z' is hydrogen, Ci-Cioalkyl, allyl, benzyl, C2-ClzalkanoyI or.benzoyl, Tx and T2 are each independently of the other hydrogen, C[.Cxsolkyl. or unsubstituted or halo- or Cl-C4alkyI-substituted C6-ClOaryl or C7-Cgaralkyl, or Ty and T2 together with the carbon atom that binds them form a C5-Cl2cycloalkane ring9.

When any of the substituents are Cl-Cx 2alkyl, they are, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-bu-yl, n-hexyl, n-octyl, 2-ethyl-hexyl, nnonyl, n-decyl, n-undecyl or n-doclecyl.

Any substituents having the definition of Cl-CI8alkyl 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, propoxymethyl, tert-butoxymethyl, ethoxyethyI.

ethoxypropyl, n-butoxyethyl, tert-butoxyethyl, isopropoxyethyl or propoxypropyl.

When R7 is C3-C5alkenyl, it is, for example, 1-propenyl, allyl, methallyl, 2butenyl or 2-pentenyl.

As C7-C9oralkyl, R7, T1 and T2 are especially phenethyl or more especially benryL 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-Cl0oaryl, R T1 and T2 are especially phenyl, a- or -naphthyl, which are unsubstituted or substituted by halogen or by C1-C4alkyl.

When R 7 is C2-CI2akylene it is, for example, ethylene, propylene. 2,2dimethylpropylene, tetramethylene, hexcmethylene, octamethylene, decamethylene or dodecamethylene.

As C4-C12alkenylene, R is especially 2 -butenylene, 2 -pentenylene or 3hexenylene.

When R 7 is C6-C12arylene, it is, for example, m- or p-phenylene, 1,4naphthylene or 4,4'-diphenylene.

When Z' is C2-C12alkanoyl, it is, for example, propionyl, butyryl, octanoyl, dodecanoyl, but preferably acetyl.

D as C2-C10lkylene, C6-CI5arylene or C6-C12cycloalkylene is as defined under b).

The following compounds are examples of polyalkylpiperidine compounds of that class: 56) 3-benzyl-1,3,8-triaz-7,7,9,9-tetramethylspiro[4.5]decane-24-dione 57) 3-n-octyl-1,3,8-triaza-7,7,9,9-tet thyspiro[4.5]decae-2,4-dione 58) J-alyl-l.

3 5 -triaza- 1 0 117 9 9-pentamet hyspiro4s51decne2,4dione 59) 3 -glycidyl 1,3 ,8-triczo-7,7,8 9 9 -pentcmethylspiro[4.5]decane.2,4-dione 1 .3,7,7,8,9,9-heptamet hyl-1 .3 triozaspiro[4.Sjdecane-2 ,4-dione 61) 2- isopropyl-7 1 7,99-tetramethyl- 1-oxa- 3,8 -diazo-4-axo-spiro( 4 62) 2 2 -dibutl-7,7,9.9-tetramethyl-boxo.3,8diazo-4oxo-spiror4.

5 wecne 63) 2 .2,4,4-tetramethylI-7-oxa- 3, 2 -dia za -2 I-oxo-dispi ro [5.l1.11.

2 ]hen icosane.

64) 2-butyl-7,7,9,9-tetramethyl- IOXa- 4 i8-dioza-3-oxo-spiro[45Necane 8-ocelyl-3-dodecyl- 1.3 .S-triazu-7.7,99-tetrmethylspiro (4.5]decone-2 4diane or the compounds of the following formulae:

CH

3

CH

3

CH-

3

CH-I

N H C 0 O 0 0 CHr-N I I

N-CM

3 3C-N

-CH

2 OH(0Il)

CH

2 -[0C8 2 -CH(QH)CHJ,- N -C CH, C HO OCH,

OH

3 66) 67) a-i H3CH

CM,

O~-NNM-C=Q 0 0C-NH

N-OH,

OH, OH 3 0 CH-I3 OH, 68) OH, OH3 OH 3 CH3 NH-00O 0=C-NH HNN N

NH

OH, OH,3 0

OCH

3 OH,3 H, C,

(OH

2 11 69) HN K-" C-N-CH 2 CH 2 00 OCZH2

CHI

OH

OH,

e) Compounds of formula VI N'k N (VI), Rio wherein n is the number I or 2 and R 8 is a group of the formula

CH

2

CH

3 wherein R 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 1 1

R

1 2

-OR

13 -NHCH20R1 3 or -N(CH2OR13)2.

when n 1, R 10 is identical to R 8 or R 9 and, when n 2, R 10 is a group -E-Bwherein B is C2-C6alkylene that is uninterrupted or interrupted by -N(R 11

R

11 is C1-C12alkyl. cyclohexyl, benzyl or C1-C4hydroxyalkyl or a group of the formula

RCH

3

CHR

N-

R

CH

3

CHR

12 is CJ-Cl2alkyl, cyclohexyl, benzyl, Cl-C4hydroxynlkyt and- 1is hydrogen, CZ-Cl2alkyl or phenyl, or PfI anid R 12 together are C4-C~alkylene or C4-C~oxaalkylene, for example -CH2 r_ -wl

-CH

2 CHr--J are a group of the formula 0

-CH

2

CH--/

2

N-R

-CH CH-I -CHaCHl----\ -CHCH-- N-R 1 2 or or alternatively ft 11 and Rt 12 are each a group of the formula Cl- 3

CH,

CH~

ICH3 When any of the substituents are Cl-Cl 2alkyl, 'they are, for example, methyl, ethyl, n-propyl, ri-bulyl' sec-butyl, tert-butyl, n-hexyl, n-octyl, 2 -ethylheyul nnonyl, n-decyl, n-undecyl or ri-dodecyl.

When any of the substituents are CZ-C4hydroxyalkyl, they are, for example, 2 -hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl or 4hydroxybutyl- When A is C2-C6alkylene, it is, for example, ethylene, propylene, 2,2dimethyipropylene, tetramethylene or hexamethylene.

When R1 and R1 together are C4-C5alkylenve or C4-C5oxaalkylene, they are, for example, tetramethylene, pentamethylene or 3 -oxapentamethylene.

The compounds of the following formulae are examples of polyalkyipiperfdine compounds of that class; clI

HGC

H3 ICH 3 1CH 3 70)1 N-C H 9

AN"

(CH

3

CH

2 2 N"LN::tNCH) N N(CH 2

CH

3 CH 3 71) C 2

H

6 -N N

N

CH

3

CH

3

C

2 5 C L 2 1 72)

R

H

3 C CH 3 -NH-CH 2

CH

2 CFI-o )-CH 3

H

3 C CH 3 wherein R 73) 74) CH 3

CH

3 CH 3

OH

3

C.H,

C' N N'

I

CH, 04,l CHNJCH. CH N~CH,

II,

H C.X

H

R-NH IHJ- N -(0H 2 3

-NH-R

OH

3 CH- 3 ,wherein R is

CH

3

O

3 CH 3

CH-

76) R R R-NH -(CH 2 0H)--N-(CH 2 3

-NH-R

CH

3 IC 3 wherein R

OH

3

OH

3 7) Cl- 3 R

CH,

R-N-(FIj-N(H)- N H 2 13N

,CH

3 0 4

H,

wherein PR

CH

3 OH 3 78) 79)

CH

3

CH

3 ICH 3

CAH

OH

3

CH~'

CH

2

-CH=CH,

CH

ICH,

H

3

C

f 4"' HtC CH, N"kN CH,

CH

3 2

C=HC-H

2 C-N N "N N

N-CH,-CH=CH,

C

4 H

CHI

H

3 C CH 3

CH

3

CH

3 f) Oligomeric or polymeric compounds, the structural repeating unit of which contains one or more 2 ,2,6, 6 -tetraalkylpiperidine 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.

OH

3 C H 3 o o II 11 81) -CH,-CH, C-O- CH-CH-- N

O

m

CH

3 CH, CH, 0 0 82) 0f--CM,-CM,-NC- I CH~ CH,

C

NH-(CNH-

83) C C 2

H

0 0 C-ICH2j,-- c 84) rn CH 3

CH

3 86) CH 3 I H 3 0 C 4 H 9 11 1I1 0-C c

C

4

H"

9 CH/"

CH

3

H

CH 3 87) cI-

CI-

58) 89) 0 0 -0)-C-(CH 2 4

-C-

m 0 CH' CH 3 CH I 3 1 CH 3 91CH CH m

C

6 H 13 N N-OH,3 92) NW N H2g' 01 OH 3

OH

3 CH-,

OH

3 N

OH

3 OH, N CH 3 H

H

N (OH 2 6 93) OH' 3 OH 3

OH

3

OH,

OH

3 AN OH 3 OH,

CH

3 H

H

0 0 94) CH 31

OH,

wherein PR H or CR3

CH.,-

CH

3

CH

3 96) Is

NH

NJ. N HBC(R)NX< N J N(R)C 4

H,

wherein R= H 3 C CH 3 -wii-HC 4 (R)N N N(R)C 4 H,9 anO K or H (obtainable by reacting the reaction product of trichiorotriozine and NI-2- (CH2)3 -NH-(CH2)2-(CH2)a-NH2 with 4-N-butyl- 2,2,6 6 -tetramethylpiperidirq) Of those classes, classes e) and f) are especially suitable, especially those tetroalkylpiperidine compounds that contain S-triazine groups. Also especially suitable are compounds 74, 76, 84, 87, 92, 95 and 96.

The preparation of the N-piperidinyl-triazirs is known from the literature Ifor example, Hlouben-Weyl 'Methoden der organischen Chemie', Vol. I/rn p. 233-237, Ed., Thieme Verlag Stuttgart 1971). There may be used as starting material for the reaction with various l 4 -piperidylamines cyanuric chloride, diamino-chloro-1 ,3,5-triazine or variously substituted bisdialkyamino-.

chioro- 13,5-triozines or dialkyloinino- or alkylamino-dgchloro-1 3 rechnicaIly important examples of tetra- and penta-alkylpipeu'idin.

compounds are: bis(2 6-tetrwnethyll-pi peridyl) sebacate, bis(2,2,6,6 tetromethyl-pi peridyl) succinct., bis(1 ,2,2,6 6 -pentamethylpipericiyl) sebocate, n- butyl-3 .5-di-tert-bUtyk14-hv'dro)x ybfyl-mlomic acid bis(1 .2,2,6.6pentarnethylpipericiyl) ester, tihe condensation product of 1-hydroxyethyl..

2,2 6 1 6 -tetramethyl-4-hydroxy-piperine and sliccinic acid, the, condensation product of NN"-bis(2 ,2,6 ,6-ttaehy--ieidl-eamtyeeiomime and 4-tert--octylamino- 2,6 -dichloro- 1,3 .S-s-triaui,2. lris(2 ,2 .6 6-tetromethy-4pi peridyl)nitrilotroacetate, tetrokis(?2 6 t 6 -tetrmme "thyl-4-piperidy).1 .2.3,4butnnetetraoate 4 l.l'-(t.2-etha iyl)-:bist(3 .3 5 -tetrametyl-piperaz none), 4benzoyl-2.2.6.6-tetramtbvlhpipp jl "e 4 -stearykexy-2,.z6,6.

tetramethylpiperidimi, bis(t: ',22,6 'pentnethylpipesidyl)-2-n- bulyl-2-(2hydroxy-3 .5-di-tert-butylbuzl) Malonate, 3 -fl-acty-77,9.9-tetromethyl.

1,3 ,8-triazaspiro(4.5Jcdecanz-2,4-cglort bis(l-octyloxy.2 ,2,6,6tetraimethylpiperklyl) sebacate, bis(1-octyloxy-2.2 6 6 -tetramethyl pi peridyl) succinate, the condensation product of NNt-bis(2.2,6,6-tetramthyl.4-.

piperidyl)hexomethylenediojnine and 4-rnorpho lino- 2,6-dick loro-1.3 ,S-triazine, the condensation product of 2-chloro -4,6-di(4-n- butylariino-2 ,2 .6,6tetramethylpiperidyl}-1 ,3,5.rtriazine and .1 2 bis( 3 -aminopropylamino)ethane, the condensation product of 2 -chlor-46-di(4nbutylami,-,,226 6 pentamethylpiperidyl-3 §-triotjW uhd I,2- bis(3 -aminlopro pylomirlo)ethane, 8acetyl -3-dodecyl-7.7.9,9,LAetram 'ethyl-.1,3,8 -triaras piro [4.5 decane- 2,4-dio ve, 3 -dodeyl 2 2 6 6 -tetramethy-4pper idyl)pyrro Ilidi ne- 2.5-d io ne, J-dodecy[- 1-(I,2,2.66pn ehl4pprdy)proiie25doe 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) aluminosihcates (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

M

2 l-x M 3 +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 4 Al, or B,

A

n 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-, CO32- (CHOHCOO)22-, (CH2COO) 2 CH3CHOHCOO, HPO3-or HPO4 2 Examples of hydrotalcites are A1203.6MgO.C02.12H 2 0 M 9 4 5A2(OH)13-C3.335H 2 o (ii), 4M90.A1203C,2.9H2o (iii), 4M90.A1203coa.6H 2 o, ZnO.3MgO.A12o 3 CJ2 9H20 and ZnO.3MgO.A1203.co2.§.6H 2 0. Special preference is given to types i, ii and iii.

Zeoites (alkali and alkaine earth aluminosb1cates) These can be described by general formula (Vm) Mx/n((A 1 O2)x(5102)yiwH2O

(VII)

wherein n is the charge of the cation M: M is an element of Group I or Group II, such as Li, Na, K, Mg. Ca, 5r or Ea.

y:x is a number from 0.8 to 15, preferably from 0.8 to 1.2; and w is a number from 0 to 300, preferably from 0.5 to Examples of zeolites are sodium aluminosilicates of the formulae N012A1125i12O48. 27 H20 (reolite N06A16Si 6

O

2 4 2 NaX. 7.5 H2O X= OH, halogen, C104 [sodalite]; N6A16S1 3 0 0 7 2 24 H20: No8Alasi 4 00 96 24 H2O; Na16Alz65i2 4 80. 161120; Na6A1165i 3 2 96 16 Na56A565il3 6 a38. 250 120 (zeolite No86AI86Sio 6 0 3 a 4 264 H2o [zeoite Xj or the zeolites that can be formed by partial or complete replacement of the No atoms by Li, K, Mg. Ca, 5r or Zn atoms, such as (Na,K)lOAosi220 6 4 20 1120; C04.5N03 [(A102) 12 (Sio 2 1 2 30 H,2; K9N3[(AlO2)12(5i0 2 1 2 J. 27 Preferred zeolites correspond to the formulae Na12AIl2SI 2 0 4 8 27 H20 [zeolite A], Na6Al656024 2NaX. 7.5 H20, X OH, Cl, Cl04, 1/2C03 [sodalite] Na6Al6Si300 n. 24 NaBA13i40 9 6 24 NOI6AII6Si2 4 0O 16 Na16A1165i320 9 6 16 N056A156Si1360384. 250 H20 (zeolite Y] N86A186S0160384. 264 H20 [zeoliteX] and zeolites of the X ad 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, Ba or Zn atoms, such as (NS,K)IOAIOSi22064. 20 Ca4,5Na3[(A102)12(5i02)12] 30 K9NO3[(AIO2)12(5i02)121. 27 The zeolites listed may also have a lower water content or may be anhydrous.

Other suitable zeolites are: Na20-A1203-(2 to 5) 51i02-(3.5 to 10) H20 [zeolite PJ Na20-AI203-2 Si0 2 -(3.5-10)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,K,H) 10 AlO 0 Si 2 2 0 6 4 20 K9Na 3 1(A10 2 12 (Si0 2 12 J. 27 H 2 0

K

4 AL4Si4016-6 H 2 0. (zeolite K-F] NagAI8i40096.24 H20 zeolite D, as described in Barrer etal, J. Chem.

Soc. 1952, 1561-1571, and in US 2 950 952; The following zeolites are also suitable: potossium offretite, as described in EP-A-400 961; zeolite R, as described in GB 841 812; zeolite LZ-217, as described in US 4 503 023; Ca-free zeolite LZ-218, as described in US 4 333 859; zeolite T, zeolite LZ-220, as described in US 4 503 023; Na3K 6 A195i27072.21 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 O, 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 U5 4 503 023: zeolite ZK-19 as described in Am. Mineral. 54 1607 (1969); zeolite W as described in Barrer etal, J. Chem. Soc. 1956, 2882; Na 3 0 A1 3 0 Si 6 6 01 9 2 98 H20 [zeolite ZK-5, zeolite Q].

Special preference is given to the use of zeolite P types of formula I wherein x is from 2 to 5 and y is from 3.5 to 10, 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 (zeolite Pj) 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 203)n.Zo.pH20) wherein M is H, Li, No, K, M91/2, Cai/2, Srlf2 or Zn1/2; Z is C02, 502, (C1207)1/2, 8406, 5202 (thiosulfate) or C202 (oxalate); m is a number from 1 to 2 when M is Mg91/2 or Cal/2, and in all other cases is a number from 1 to 3: n is a number from 1 to 4: o is a number from 2 to 4; and p is a number from 0 to The alumino salt compounds of formula that can be used according to the invention may be naturally occurring minerals or synthetically prepared compounds. The metals may partially replace one another. The mentioned alumino salt compounds are crystalline, partially crystalline or amorphous or may be present in the form of a dried gel. The alumino salt compounds may also be present in relatively rare crystalline modifications. A process for the preparation of such compounds is described in EP 394 670. Examples of naturally occurring alumino salt omponds ae indigirite, tunisite, aluminohydrocalcite, para-alumlnhydrocalcite. strontiodresserite and hydrostrontiodresserite. Otheri examples of alumino salt compounds are potassium aluminocarbonate ((K2O(Al203).(CO2)2.2H20), sodium aluminothiosulfate lzO O2)2.2H20), potassium aluminosulfite 1203).(502)2. H20). cldwni aluminoaxalate 1203).(C202)2.5H20). magnesium aluminotetraborate I203).(8406)2.5H20), ((MgO.2taO.6J20).(A 1203).(C2)2.4.1 (([Mg90.2NoO.6]20).(A203).(CO2)2-4.3H20) and (([M90.3NaO.4]20).(A 1203).(CO2)2.2.4.9H20).

The mixed alumino salt compounds can be obtained in accordance with processes known per s by cotlo d e preferably from the alkali alumino salt compounds or by combid tation (see, for example, US 5 055 284).

Preference is given to alumino salt compounds of the above formula wherein M is No or K- Z is C02. 502 or (Cl207)1/2; min is 1-3; n is 1-4; o 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.A203.(C2)2 pH20 (19) (M20)2.(A1203)2.(CO2)2 pHZO0 (Ib) M20O.(AI1203)2.(CO2)2 pH20 (1c) wherein M is a metal, such as No, K, Mg1/2, Cal/2, Sr1/2 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-Cl6alkyl-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 monovolent 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, 1 2 -hydroxystearic acid, 9 ,10-dihydroxystearic acid, oleic acid, 3,6dioxaheptanoic acid, 3,6,9-trioxadecanoic acid, behenic acid, benzoic acid, ptert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-di-tert-butyl-4hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, npropylbenzoic acid, salicylic acid, p-tert-octylsolicylic acid, and sorbic acid; zinc salts of divalent carboxylic acids or the monoesters thereof, such as oxalic acid malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, dicarboxylic acid, hexane-1.6-dicarboxylic acid, heptane-1,7-dicarboxylic acid, octane-1,8-dicarboxylic acid, 3, 6 9 -trioxadecane-l,1O-dicarboxylic acid. lactic acid, malonic acid, maleic acid. tartaric acid,cinnamic acid, mandelic acid, malic acid, glycolic acid, oxalic acid, salicylic acid, polyglycol-dicarboxylic acid 12), phthalic acid, isophthalic acid, terephthalic acid and hydroxyphthalic acid; and the di-- or tri-esters of tri- or tetra-valent carboxylic acids, such as hemimellitic acid, trimellitic acid, pyromellitic acid, citric acid and also so-called overbased zinc carboxylates.

The zinc enolates are preferably enolates of acetylacetone, benzoylacetone or dibenzoylmethane 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, con 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 C8alkanoates, steorate, oleate, laurate, palmitate, behenate, versatate, hydroxystearates, dihydroxystearates, p-tert-butylbenzoate, or (iso)octanoate.

Preference is given especially to stearate, oleate, versatate, benzoate, p-tertbutylbenzoate and 2-ethylhexanoate.

Also suitable in addition to the mentioned zinc compounds are organic aluminium, cerium or lanthanum compounds having a metal-O bond. The aluminium compounds that can be used and that are preferred include carboxylates and enalates.

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 ports by weight of chlorine-containining 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 A Sons, New York 1993).

In a non-limiting manner, some of the known additives and processing auxiliaries are mentioned here: Alkali metal and alkaline earth metal compounds These are to be understood to include especially the carboxykltes of the acids described above, but also corresponding oxides or hydroxides or (bi)carbonates_ Mixtures thereof with organic acids are also suitable. Examples are NaoH. Na-sterate. NaHCO,. KOH, K-stearate, KHCO 3 LiOH, LiCO3. Listearate, CoO. Ca(OH2). MgO, Mg(OH)2. Mg-steorate, CaCO3, MgCO3 as well as dolomite, huntit, chalk, basic Mg-carbonate and other Na- and K-salts of fatty acids.

NaOH, KOH, CoO, Co(OH2), MgO, Mg(OH)2. CC03 and MgCO3 and also fatty acid sodium and potassium salts.

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

Preference is given to alkali metal, alkaline earth metal and/or aluminium carboxylates in addition to the stabiliser combination according to the invention.

Other Metal Stabilisers Special mention has to be made of organotin stabilisers, carboxylates, mercaptides and Sulfides being preferred. Examples of suitable compounds may be found in US 4,743,640.

6/idan ts(L /BRICANTS) Suitable glidants are, for example: Monton 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. Giichter/H. Miller, Carl Hanser Verlag, 3 rd 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-2ethyhexyl, di-n-octyl, diisooctyl, diisononyl, diisodecyl diisotridecyl.

dicycloaxyl, dimethylcyclohexyl, dimethylglycol, dibutylglycol, benzylbutyl and diphenyl phthalate and mixtures of phthalates, such as 7-Cg- and C9- C1ii-alkyl phthalates from predominantly linear alcohols, C6-C1-n-alkyl phthalates and C8-Clo-n-olkyl phthalates. Of those compounds, preference is given to dibutyl, dihexyl, di-2-ethylhexyl, di-n-octyl, diisooctyl, diisononyl, diisodecyl, diisotridecyl and benzylburyl phthalate and to the mentioned mixtures of alkyl phthalotes. Special preference is given to di-2-ethylhexyl diisononyl and diisodecyl phthalate, which are also known by the customary abbreviations DOP (dioctyl phthalate, di-2-ethylhexyl phthalate)

DINP

(diisononyl phthalate), DIbP (diisodecyl phthalate).

B) Esters of oliphatic dicarboxylic acids, especially esters of adipic, azelaic and sebacic acid: Examples of such plasticisers are di-2-ethylhexyl adipate, diisooctyi adipate (mixture), diisononyl adipate (mixture). diisodecyl adipate (mixture) benzylbutyl adipate, benryloctyl adipate, di-2-ethylhexyl azelate, di-2ethylhexyl sebacate and diisodecyl sebacte (mixture). Di-2-ethylhexyl adipate and diisooctyl adipate are preferred.

C) Trimellitic acid esters, for example tri-2-ethylhexyl trimellitate, triisodecyl trimellitate (mixture), triisotridecyl trimellitate, triisooctyl trimellitate (mixture) and tri-C6-C8alkyl, tri-C6-Cloolkyl, tri-C7-C9alkyl and tri-C9-CIjalkyl trimellitate. The last-mentioned trimellitates are formed by esterifying trimellitic acid with the appropriate alkanol mixtures. Preferred trimellitates ore tri-2-ethylhexyl trimellitate and the mentioned trimellitates from oalkanol mixtures. Customary abbreviations are TOTM (trioctyl trimellitate, tri-2-ethylhexyl trimellitate), TIOTM (triisodecyl trimellitate) and TITDrMTM (triisotridecyl trimellitate).

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

E) Polymer plasticisers A definition of these plasticisers and examples thereof are given in "Kunstoaffadditive (Plastics additives), R gtchter/H. Miller, Carl Hanser Verlag, 3" Ed., 1989, Chapter 5,9,6. pages 412-415, and in "PVC Technology" W.V. Titow, Ed., Elti ilflbl 1984, pages 165-170. The most commonly used starting materials for the preparation of polyester plasticisers are: dicarboxylic acids, such as odipic, phthalic, ozelaic and sebacic acid; diols, such as l.2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol neopentyl glycol and diethylene glycol.

F) Phosphoric acid esters A definition of those rters Is to be found in the above-mentioned "Taschenbuch der ffof ive" (Handbook of Plastics Additives), Chapter 5.9.5, p.p. 40842. mples of such phosphoric acid esters are tributyl phosphate, tri-2-ethylbutyl phosphote, tri-2-ethylhexyl phosphate, trichloroethyl phosphate Z-ethyl-hexyl-diphenyl phosphate, cresyl diphenyl phosphate, triphenyl phosphate, tricresyl phosphate and trixylenyl phosphate. Tri-2-ethylhexyl phosphote and "'eofos 50 and 95 (Ciba-Geigy) are preferred.

6) Chlorinated hydrocarbons (paraffins) H) Hydrocarbons I) Monoesters, eig. butyl oleate, phenoxyethyl oleate, tetrahydrofurfuryi oleate and alkylsulforl!ic acid kters.

J) Glycol esters, e.g. diglycol benzoates.

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

"PVC Technology". W.V. Titow, 4 *h 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 TiO2, carbon black, FezO 3 Sb203. (Ti,Ba.Sb)Oz.CrzO, 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.Gdchter H.Miiller, 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.

Phosphiltes Examples are triphienyl phosphite, diphentyl alkyl phosphites, phenyl dialkyl phosph ites, tris-(nonylphenyl) phosph ite, tri lauryl phasphite, triactadec,,, phosphite, distearyl-pentaerythnitoj diphasphite, trisc 2 4 -di-ertuywlIphelyl) phosphite, diisodecylpentqerythrito I diphosphite, bis(2 .4-di-tertbutyl phenyl)pentoert'nrita I di phosph ite, bis(2 ,6-di -tert-b uty1-4-methylp henyiypentcieryrhritol diphosphite, bis-isodecyloxy-pentaeryhrt 0 diphosphite.

bi(.-itr-utl6mtypeylpnartrtI diphosphite. bis(2,4,6tr...

tert- butylphenyl)pentaerythrito I di phosphite, tristearyi-sarb ito I triphosph 'te, bis( 2 4 i-ert-butL-6-.methylphenyl~wethyI phosph ite, bis(2 .4-di -ter-t- bu-y-6methyiphenylethyl phosphite.

Especially suitable ore trioctyl, tridecyl. tridodecyl,' tritetradecyl, tristenryl.

trioleyl. triphenyl-, trieresyl, tris-p-nonylphenyl or tricyclohexyl phosphite and special preference is given to the aryl-dialkyl oftd alkyl-dicwyl phosphites. such as phenyldiecyl phosplute. 2 4 -di-1tert-butylphenyly-i-i..dcI phosphite. (2.6di-tert-butylphenyi-dodecyr -phosphite and to the dialkyl1- and diairylpentaerythriioi di phosp hites, such as distearylpenraerythrito Udiphosphite. and non-si-aichiometric trioryl phosphites, for example those having the composition (Hz 9C9-C61- 4 )Ol !5PCOCI2.23 H25.2f1.5.

Preferred organic phosphites are distearyl-pcntoerythritoI diphosphite, trisnonyiphenyl phosphite and phenyldidecyl phosphite-.

The organic phosphites can be used in an amount of, for example, from 0.01 to 10, advantageously from 0.05 to 5. and especially from 0.1 to 3,prsb weight, based on 100 parts by weight PVC. .prsb Thiophosphites arid thiophosp hates There are to be understood by thiophosphites and thiophosphutes compounds of the general type:

(PS)

3 P, (RS) 3 P=-O 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 phasphite, trithicoctyl phosphite, trithiolauryl phosphite, trifhiobenzyl phosphite, trithio phosphorous acid tris(corboisoocyloxy)nethyf ester trith i phosphorous acid= tris(carbotrirnethylcyclohexyloxy)methyl ester, tri'thiophosphori c acid 5,5,5tris(corbo isooctyloxy)methyl ester, trithiophosphoric acid 5,5,S-tris(carbo-2-.

ethylhexyloxy)methyl ester, trit hiophosphoric acid 5.,55-tris-l (corboliexyloxy)-ethyl ester, trithiophosphoric acid S,5,5-tris-1-(carbo-2z ethylhexyloxy)-ethyl ester, trith io phosphoric acid S.S.5-tris-2-(corbo,..z ethylhexyloxy)-ethyl ester.

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

The mentioned mercaptocarboxylic acid esters also include polyol esters and the partial esters thereof- Epoxidised ftny acidF ester-s The stobiliser combination according to the invention may additionally comprise preferably at least one epoxidised fat-ty acid ester. Especially suitable are esters of fatty 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 oleote.

Anioxidants Suitable antioxidanits oire, for example: l15!istemowOhenls for example Z, 6 -di-tert-buVyl4rnethylphenol, 2-tert-butyl-4,6-dimethylphenol, 2 6 -di-tert-but-yl-4.ethylphenol, 2 ,6-diiert-bu-yl-4-n-butylphenol, 2,6-di -tert-buyl-4-isobuitylphewil, 2.6dicyclopentyl-4-methylphenol, 2 -(cz-methylcyclohexyl)-4.6 -dimethyiphenol, 2,6-dioctadecyl-4-methylphenol, 2 4 1 6-tricyclohexylpheno I. 2,6-di-mertbulyl-4-rnethoxymethylphenol, 2 .6-di-nonyl-4-merhylphenol, 2.4-dimethyl-6 (1'-methyl-undec-1'-yl)phenol, 2 0 4-dimnethyl-6-(l -methyl-heptadec-1'yl)phenol, 2 ,4-dimethyl-6-('-methyl-tridec-l'-yl)pheno I, octyipheno I, nonylphenol, dodecyiphenol and mixtures thereof.

2. Alkylthiomethylphenols. for example 2 4 -di-oclylthiomethy6tert.

butlphenol,

Z,

4 -di-octthomethyl-6-methylphenoI, 2 4 -di-ociylthiomethyl.

6-ethyipheno I, 2 ,6-di -dodecylthiomethyl-4-nonyupheno

I.

3. Alkyated Iwdroguinones. for example 2 1 6-di-tert-butyl-4-.

methoxyphenol I. Z 5 -di-tert-buyl-hydroquiwn, 2 hydroquinone, 2 6 -diphenyl-4-octadecyloxypheno I, 2 .6-di-tert-buwI...

hydroqui none. 2 ,5-di-tert- butyf -4-hydroxyarilso Ic, 3 .5-di -tert-butyl -4hydroxyonisole, 3 .5-di -tet- but-yl- 4 -hydroqyphenylstearate, bis(3 ,5-di -tertbulyl-4-hydroxyphenyl) adipote.

4. Hycfroxylcted thiodiphenyl ethers, for example 2.2-thio-bis(6-tertbutyl-4--methylpheno 2,2'-thio- bis(4-octypheno 4.4'-thio-bis(6 -tertbutyl- 3-methyiphano I, 4 9 4 -thio-bis(6atcrt.buwI..2.methye phenol), 4,4'-thiobis(3 .6-di-sec-amylphenol), bis(2 ,6-dimethyl-4- hydroxyphenwyl) disulfide.

Alkylidene. bispbheols. for example 2 2 -mnethylene-bis(6.tert-uwg..4methyiphano 2 2 '-methyene-bis(6-tert-buity[.4-ethylphenog), 2,2'methylen-bis(4-methyl- 6 -(a-methylcyclohcxyl)phenoij, 2.

2 '-:methylenebis(4-methyl-6-cyclohexylpheno 2 2 '-methylene--bis(6-'nonyl-4mnethylphenol), 2.2'-methylene-bis(4.6-di-terp -butyipheno 2 ,2-ethylidene.

bis(4,6-di-tert-butylpheno 1)1 2, Z' cthylidene-bis(6-tert- butyl-4isobu-tylphenoQ, 2, 2'-methylene- bis(6-(a-methylbenzyly..4 nonyipherto 2,2'methylene-bis(6 -(a.a-dimethyl benryl)-4-niornyiphenoIl] 4 5 4*-rnethylenebis(2.6-di-tert-butyphenol), 4 1 4 V-methylcerw-bis(6-tert..butjplz.

niethylphenol), 1,1 -bis(5-tert-butyl-4-hydrocy.

2 -methylpkcrvy)butatne 2,6bis(3 -tert-butyl-5-mnethyl-2 -hydrmxybenzyl)-4-rnethylphen, 13 tert-butyl-4-hydroxy- 2-methy lphenylbutane, 1,1 -bis(5-tert- butl -4hydroxy- 2-methylphenyl)- 3- n-dodecylmercapto butane, ethylene, g lycolIbis[3 ,3 -bis(3'-terl--butyl-4!-hydroxyphenyl) butyrcate], bi s(3 -tert-butlk4 di cyclopentadiene, bis[2- (3'-tert- butyl-2-hydroxy.

5§-methyl-benzyI)-6-tertbutyl-4.methylphenyI] terephthalxte, 1 ,1-bis(3,5..

diniethyl- 2 -hydroxyphenyl)butane, 2.2-bis(3 .5-di-tert-butyl-4hydroxyphenyl)pro pane, 2 2 -bis(4-hydroxyphenyl)propone, 2 2 bu1y- 4 hvdroxy-2- methylphenyIY-4.n-dodecy, lmercopto butane, 2,1,5,5butyl-4- hydroxy-2 methyip henyl)pentane.

6. Benryl comrounds. for example 3,.

3 ,5'-tetra-tert- butyl-4,4'dihydroxydibenzyl ether, octadecyl-4-hydroxy.3 5 -dimethylbeizyl mercaptoacetate, tris( 3 5 -di-tert-but-yl.4-hydroxybenzyl)aniine, bis(4-ter-tbutyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis(3 butyl-4-hydroxybenzyl) sulfide, isooctyl- 3,5-di -tert-butyl-4- hydroxybenzy; mercoptoacetate.

7. )-tydroxybenzylatedrMlonotes. for example dioctodecyl-2.2-bis(3,5.

di-lert- butyl-2-hydraxybenzyi) moalonote, di-octodecyl- 2- (3-teft- butyl-4tklonate, dldodecylmercaprocthyg 2-bis(3*b-i tert-butyl-4-tydroxybenz'yl) malonate, di-(4-(1,1.3,3tetramelthylbutyl)phenlY]-Z 2 -bi(3.5-di-tert-bu-yl-4-hydrcoxybenzyl) mhalnate.

S. EWktMSMfflEYL IgfllSS ff~ndL. for 'example 1.3,5-tris(3.5-ditert-butyl-4-hydrbezl)-2.4.6-trimethyuiez~s 1.4-bis(3 butyl-4-hydlroxvbeeqy-2,3.5 ,6-tenosnehylbcenreps Z.4.6-tris(3,5-3i-.ta.tbutyl-4-hydlroxybenz l)phehol.

9. Triain cg*rWpo, for example 2 .4-bis-ocymercapto-6-.{54 1 trert-butyI-4.'hydroxiaIlino)-l.3i0-mriuzie. 2-ocylnrcapto-4,6bs(3,5..i.

ien-tyl-_4-drkalvl ,Sj 'wene, 2-*ctylmercapto-4.6-bls(3,5-di..

tefl-butyl-4-hydroxypoxy ,3 ,S5-trazine, Z.

4 6 hydroxypheraow)l.2,3 -trlozine, tris(3.5-ditt-buty-4hydroxybenzyl) isocyanirate, 1,3 .5-tris(4-tert-bn)3-hroa 6dimethylbenzyl) isocycinurate. Z.

4 6 -trif(3.-di-tert-butyl...hydrox-ypheutylethyl)-1 ,3,54.riazine. 1 .3,5-ts35ditertbudI-4-q hydroxypheulprOPlonyl~h~odo-13,riun, l.5-trls(3,5dicyckohexyl-4-hydroxybeO l iocgmoe Popooe*udpspoete.for exam*pl buty-4-hydroxybenryl phosphonote, hydroxybenzyl phosphonate, dibctdecyi3.5-dirteu wI...4.hrxybezI phosphonate, di tr.btl4hdoy3mtybny phosphonate, calciwm salt of -3,-itr-uy--yrxbnypopoi acid monoethyl ester, tetroakis(2 ,4-di-tert- butylphenl)-4,4'-biphenyiene diphosphonite. 6-isooetyloxy-2 4 9 8 1 l-telro-tert-buiyl-1 2H-dibenzo~d,g..

1,3 .2-dioxaphosphocine, 6-f luoro-2,4,8 .IO-tetro-tert-butyl-12-methyl.

di benzo(d,_g]-1.3,2-dioxapho-spho cine.

11. f A mp ,fr eaple 4-hydroxy-louric acid orulide, 4hydroxystearic aci 'aonide, N-(3 .§-dI-tert-butyl4-hysroxyphenyl)-crlymi c acid octyl ester.

12. Esters of b-( 3 5 -di-tert-bwl 4hydroxfphenyl)-prapionic acid With mono- or poly-hydric alcohols, such as methanol, ethanol, octonol, octadecanol, 1,6-hexanediol, 1 9 -nonanediol, ethylene glycol, l.

2 -propaneiiol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritolI di pentaerythrito I, tris(hydroxyethyl) isocyonurate,

NN-

bis( hydroxyethyl)oxaic acid diamidle, 3-thioundecano I, 3-th iapentadecanal, tri methylhexianecjiol, trimethylolpropane, di-1trimerhylolpropane, 4hydroxymethyl- l-phospha-2 .6 .7-triaxabi cyc lo[2.2.2 ]octacne.

13. Esters of b-5tr-bt 4hvr:y 3 -methylphenyl)-pr-opionic acid with mono- or poly-hydric alcohols, such as methanol, ethanol, octonol,' octadecanol, 1 ,6-hexonediol, 1 .9-noncinediol. ethylene glycol, l,Z-proanedio

I.

neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, penraeryrhritol, tris(hydroxy)ethyl isocyanairae,

N.N'-

bis(hydroxyetihyl)oxaiic acid diamride, 3 -thicundecano1, 3 -thiapen-acecan, trimethylhexanedio I, trimerhylo Ipro pane, 4-;hydroxymethy... -phospho- 2.6,7,trioxobicyclo(2.2.2 Joctana 14. Esters of b(-iccoey4hvrcvhnIppon acid with mono- or poly-hydric alcohols, such as methanol, ethanol, octanol, octadecanol, 1 .6-hexanediol, l,9-nonanediol, ethylene glycol I. I.

2 -propanediof; neopentyl glycol, thiodiethylene glycol. diethylene glycol, triethylene glycol, pentaerythrito I, tris(hydroxy~ethyl isocyanarate, NNt-bis- (hydroxyethyt)oxaiic acid dianiide, 3 -thiotundecano I. 3 -thiapentodecano

I,

triniethylhexanediol, trimethylo Ipropone, 4 -luydroxyrnethyr. l-phospha-2 .6,7trioxabicyc Ic 2.22 ]actane- Esters of 3.5-di-tert-buty1-4-hydry hen acetic acid with mono- or poly-hydric alcohols, such as methanol, ethanol, octanol, octadecanol, 1,6hexanediol, 1,9-nonanediol, ethylene glycol, l.2-propanediol, neopentyl glycol, thi odiethylene g lycolI, di ethylene glycot, triethylene g lycolI. pentaerylhriyo

I,

tris(hydroxy)ethyl iso cyonurate, N34T-bi s(hydroxyethyl)oxa lie acid diamide.

3 -thioundeconol, 3-thiopentodecanol. trimelhyihexonedio

I,

trimethylo Ipropane, 4- hydroxymeihyl-! -phospho-2 ,6 7 -trioxabicyc Ia 2.2.2]octane- 16. Amide~s of b-(3.5-di-tert-bu 1l-4-hydrox henyI -propionic acid, such as N,N'-bis(35-di-tert-butyl.4 hyrxpeypoinl~eaehlmdaie NXN-bis(3,5-di-tert.but-4hydroxyp henylIpropio nyi)tri methy lened iami ne, hydroxyphenyipropionyl) hydrazine.

Preference is given to antioxidants of gqroups I to 5, 10 and 12, especiaily 2.2bis(4-hydroxyphenyl)propane, esters of 3 .5-di-tert- butyl-4hydroxyphenyipropionic acid with octonol, octadecanol or pentoerythril-ol or tris(2 ,4-di -tert-butyl phenyl) phosp hite.

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, from 0.01 to advantageously from 0.1 to 10, and'especially from 0.1 to 5, parts by weight, based on 100 parts by weight PVC- U V absorbers and IAghtr stabilis'ers Examples are: 1. 2(Z-ydroyphnyl-benol-ioles, sch as 2-(2'-hydroxy-5t.

methylphenyl-benrotriazolec 2- (3.5'-di -tent-butyI-2'-hydroxypheny)-.

benzotriozole, 2-(5'-tert-butyl- 2'-hydroxyph 'enyl)- benzotriazo Ic, hydro6xy-5'-(1 ,1,3,3 -tetramethylbul)phenyl)- benzotriazo le, 2 butyl-2'- -methylphenyl)-5-chloro -benzotriazo It, 2-(3'-sec-butyI-5'-terbutyl-2'-hydroxyphenyl)- benzotriazole, 2- (2-hydroxy-4'-octoxyphenyl).

benzotriazole, 2-(3',5'-di-tert-amyl- 2 -hydroxyphenyl)-benzotriazo It, 2- (3',5'-bis(a,o-dimethylbenzyl)-2'- hydroxyphenyl)-benzotriazole, a mixture of 2-(3'-tert- butyl-2'-hydroxy-5'-(2 -octyloxycarbo nylethylphenyl)-5-ch lorobenzotriazo Ic, 2 -(3'-tert- butyl-5'- (2 -(2-ethylhcxyloxy)-.car barylethyl]- 2'loro- beniotria zo Ic, 2 -(3'-tert- butyl-2'-hydroxy-'- (2methoxycarbo nylethyl)phenyi)- 5- ch lora- ben zotriazo le, 2-(3-tert- butyl-athydroxy-5'-(2- methoxycarbonylethyl )p henyl)- benzotriozo be, 2-(3 '-tert- butyb- 2'-hydroxy-5'-(2 -octyloxycorbo nylethyl)pheny}- benzatrio zo Ic, 2-(3'-tert- 2 2 -ethyhexylox)corbonylethyl-2'-hydroxyphenyl).

benzotriazole, 2-(3'-dodecyl 2 '-hydroxy-5'-niethylphenyl)-benzotraol;. and 2-(3'-tert-bulyl- 2'-hydroxy-5'-(2 -isooctyloxycarbo nylethyl)phenyibenzotriazole, 2,2'-methylene-bis[4-(l,1,3 ,3-tetramethylbutyl)-6benzotriozol-2-ylphenol]; the transesterification product of 2..[Y.tert.2 butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxy-phenylJ- benzotriazo le with polyethylene glycol 300; wherein RZ 3-etbtl4-yr~y5-H benzotriaroI- 2-y Iphenyl.

2. 2-htvd'oxvbkenzophenones, such as the, 4-hydroxy-, 4-methoxy-, 4octy loxy-, 4-decyloxy-, 4-dodecyloxy-, 4-ben zyloxy-, 4 2 ,W-tri hydroxy- or 2'-hydroxy-4,4'-dimethoxy derivative.

3. Esters of unsubstiruted or substituted benzoic acids, such as 4-tentbutyl-phenyl solicylote, phenyl solicylate, octyiphenyl solicylote, di benzoylresorciriol, bis(4-tert-buylbenzoyl )resorci nol benzoylresorcinol, 3 ,5-di -tert-butyl-4-hydroxybenzo ic acid 2 ,4-di-tert-butyphenyl ester, di-tert-butyl-4-hydroxybenzoic acid hexodecyl ester, 3 1 5-di-1ert-bety;-4-.

hydroxybenzoic acid octadecyl ester, 3.-itr- 14hdoyeri acid 2-metlhyl-4,6-di-tert-butylphenyl ester.

4. Acrylts scasacyano.bb-diphrylac.>lic acid ethyl ester or isooctyl ester, a-carbomethoxy-cinnamic add methyl ester, a-cyarno-bmethyl-p- 'methoxy-cinnamic acid methyl ester or butyl ester, acarbomethoxy-p-methoxy.cinnamnic acid methyl ester, N.(b-carbomethoxrb-cyanovinyl)-2-methyl-indo line.

Nickel compounds, such as nickel complexes of 2.2'-thio-bis[C(1.13 3..

tetramethybutyl)phenolj, such as the 1: or -the 1:2 complex. where appropriate with 'additio 'nal ligonds 4 such as ri-butyloinine, triethonolomine or N-cyciohexyl diethonolamine, nickel dibutyl dithiocarbamnate, nickel saits of 4- hydroxy- 3.5-di-tert-butylbenzyphosphoni c acid monoalkyl esters, such as methy or ethyl ester, nickel complexes of ketoximines, such as Z-hydroxy.4.

msthylphenyl-u ndecylketoxime, nickel cornplexes of I-phenyi-4-kauroy...s hydroxy-pyrozole, where appropriate with additional ligands.

6. Sterically hindered. amines, such as bis( 2 Z2 6 i 6 -tetrmethylpipridy) sebocote, bis(2.2 6 ,6-tetramethyl-piperidy) succinote, bis(1 ,2 .2,6,6pentamnethylpiperidyl) sebacote. n.-butyl-3 5 -di -tert-buty-4..hydroxybnzy..

mnalonic acid bis(l.

2 2 6 6 -pentomethylpiperidyl) ester, the condensation product of l-hvdroxyethyl-2.2,6.6-tetromethyl-4hdroxyppe.jdjne and succinic acid, the condensation product of N.N'-bis(2.2.6,6-tetramethyi-4.

pi peridyl)hexomet hylenediami ne and 4 -tert-octylam ino- 2,6-di chora-I triozine, tris(2,2,6 6 -tetramethyl-4-piperidyi)nitri botriacewrzte, tetra ki S(2,2, 6 6 tetramet hyl- 4-p iperidylyl 12,3,4 -butane tetraoate, ethonediyl)-bis(3,3 ,S.S-tetramethyl-piperazinone), 4-benzoyl-226,6tetramethylpiperidine, 4-stearyloxy- 2.2.6 6 -tetramethylpiperidirie, bis(1 ,2,2 .6.6-PentoanethvIPiPeridvI)-2-n-buty-2-(2.hydroxy-3 butylbenryl) malonute, 3 -fl-octyl-7,7.9.9-tetrmethyl-.i,3,8triazospiro (4.5jdeane-2 .4-diane. bis(1 -ocyoxy-2 ,2,6 ,6tetramethypiperldyf)'bsi~at 0 bis(l-octyloxy-2 ,2.

6 6 -tetrmetyIpiperidyi) succinate, the conidenstt product of N3 4 Y-bis(2,2,6.6-tetr~lethyls...

piperidyl)-hexwnethyncdkqvnine and 4-morpholinio-2,6-dichloro-z.3 triazine, the condensation product of 2-chloro-4,6-di(4-nbutylamino 2,2,6 ,6ttanehlfsrdl-.3.5-triaz in. a 'nd 1.2-b is(3 aminopropylamino)etume, the condensation product of 2-chkmr-4,6-di-(4-nbutyamio-Z2 ,*40jgwatashy~ipsrldy y1 3 .5-triozine and I .2-bis(3 omninopropylamn)i*In S-n'ky3-odec4e77.99-tetrehy.-1 ,3,6 triozaspiro4.§fln aiw4,4-done, 3-dodec-l--(2,2.6,6.tetrm 8 th,,e4-.

piprid~pyrotdies~i~-Io* 3-dodecyl-1-(i .2,2 6.6-pentamftyl-4piperidyI)-pyrrhldliie4.,41 Ons ad dimassrb%96.

7. Oxallc- acid.4diqai4 such as 4 4 '-di-octyloxy-o xan'ilide, 2,.-di- .o-cAnIIds, 2,2 oxoni ids, 2-ethory-2-ethy0Ioxani tide, NNt-bis3-dimethylairopropwI) oxalamide, 2-etfhoxy-5-tert-butyl-2'-ethyl oxanilide and a mixture thereof with 2-ethoxv-2'-ethyl.!5.4-!.di*tert-butyl oxanilide, mixtures of o- and pmethoxy- and adpthiydIsbtur oxenhlides.

16i~ cia such asZ,4 6 4r~f(24ydroxcyA..

octyloxyphey)-1,35 4kti14, 2 (ZhvroxY-44OcYyxphvl)4A6 .bi(24 dimethylphentyl)-l1 3.5-'triazine, 24(2.4-dihydroxyphenyI)-4.6-bis(z .4dimethylphenyI)-l,3,,-triaiip, 2 -bis(-hdy-4-propyxyphejyy..6-.

(2 .4-dimethylpheny4)I.3,5-rrictine. 2 2 -hydroxy-4-octyoxypeny,)I4 6bis(4-methylphsnyl)-1,3,5-tri-ozine, 2 -(2-hydroxy-4-dodecybxp vnyl>-4,6bis(2 .4-dimethytpheny-*-l ,3 ,5-fri~azinve, 2 -(2-bydroxy-4-(2. hydroxY-3 bu-tyloxy-propyloxy)phenyl]-4,6 -bis(2 .4-dimethyiphenyl)- 1, 3,5-triuz inve, 2- [2hydroxy-4-(2 -hydroxy43-octyloxypro pyloxy)phenyl bisC2 .4dimethylphenyl)- 1.3 ,S.riorine,.- Propellants Propellants are org 'anic azo and hydrazo compounds, tetrozoles, oxazines, isatoic anhydride, and sodium carbonate and sodium hydrogen carbonote- Preference is given to ozodicarbonamide 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.Gdchter/H.MUiler, 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 acetyl acetonate (cf. EP 336 289).

Examples of chlorine-containing polymers to be stabilised or of the recyclates thereof are: polymers of vinyl chloride, vinyl resins containing vinyl chloride units in their structure, such as copolymers of vinyl chloride and vinyl esters of aliphatic acids, especially vinyl acetate, copolymers of vinyl chloride with esters of acrylic and methacrylic acid and with acrylonitrile, copolymers of vinyl chloride with diene compounds and unsaturated dicarboxylic acids or the anhydrides thereof, such as copolymers of vinyl chloride with diethyl maleate, diethyl fumarate or maleic acid anhydride, post-chlorinated polymers and 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 polylactones.

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

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

Within the scope of this invention, PVC is also to be understood to include copolymers or graft polymers of PVC with polymerisable compounds such as acrylonitrile, vinyl acetate or ABS, which may be suspension, bulk or emulsion polymers. Preference is given to PVC 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 1 and homogeneously mixing the components in apparatus suitable for the purpose.

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

Stabilised PVC according to the invention, to which the invention also relates.

can be prepared in a manner known per se, the stabiliser combination according to the invention and, where appropriate, any further additives being mixed with the PVC using apparatus known per se, 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 Honser 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 1: Static heat test The mixtures according to the following Tables are each plasticised for minutes at 190°C and 170°C in a roll mill. Test strips are cut from the resulting sheets (which are 0.3 mm thick) and subjected to heating in a Mathis Thermo- Takter at 190'C for the period indicated below in the Tables. Then the Yellowness Index (YI) according to ASTM-1925-70 is determined.

The lower the 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 190 0 C (rolled for 5 min at 190C) Mixture II 12 13 Solvic 268 RC (S-PVC K value 68) 100 100 100 Omyalite 30 T 3.0 Ca stearate 0.6 0.6 0.6 Hostalub H4) 1.0 1.0 Hostalub H12 0 0.2 0.2 0.2 CH 3003 0.4 0.4 0.4 Mark 6045 ACM 4 0.3 0.3 0.3 Stabiliser 0.2 0.2 0.2 NaCIO 4 0.05 YI YI YI Minutes 20.7 29.9 22.2 28.4 666. 29.1 40.2 108.4 39.2 *Chalk 2 )Glidant supplied by Hoechst (paraffin wax) 2Glidant supplied by Hoechst (polar ethylene wax) ')Phenylisodecyl phosphite 4) Mixture of 9% NaC104. 45% CaCOs, 40% CaSiO3. 6% HEO 5)6-Amino-l.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°C (rolled for 5 min at 170°C) Mixture Evipol SH 6030 (PVC K value 60) CH 300 3 Wax EL Epox. soya oil Araldite GY 2507 Araldite PT 810 1 Stabiliser 15) Stabiliser 29) Stabiliser 310) 1 II 2 II3 14 II5 I6 ~17 fI8 19 100 0.8 0.4 5.0 1.0 100 0.8 0.4 5.0 1.0 100 0.8 0.4 5.0 1.0 100 0.8 0.4 5.0 1.0 100 0.8 0.4 5.0 1.0 100 0.8 0.4 5.0 1.0 100 0.8 0.4 5.0 1.0 100 0.8 0.4 5.0 1.0 100 0.8 0.4 Minutes YI YI YI 17.4 17.3 15.6 23.2 33.7 29.5 33.6 54.9 46.3 YI YI YI 13.4 11.8 12.5 17.8 18.5 17.7 23.5 29.9 27.8 Yr YI yI 14.8 16.2 17.1 21.2 24.4 24.0 27.2 33.6 30.8 )Phenylisodecyl phosphite )Ester wax ether of bisphenol A (liquid epoxide) B) (based on: montanic acid) 7Diglycidyl Solid heterocyclic epoxy resin (triglycidyl isocyanurate) )6-Amino-1.3-di-n-butyluracil 10 )6-Amino-l.3-di-ethyl-thiouraci The stabiliser combination (II4 to 119)of glycidyl and aminouracil compound according to the invention is found to be superior.

Table I: Static heat test at 190 0 C (rolled for 5 min at 170"C) Mixture Evipol SH 6030 (PVC K value 60) CH 300 3 Wax E' Epox. soya oil Rhodiastab 50") Cao stearate Zn stecrate CiDASC' 0 Alkamizer I' 3 Stabiliser 10 Stabiliser 29) Stabiliser 310) III III2II13 1114 I5 III6 I7 II8 I119 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 0.5 100 0.8 0.4 5.0 0.2 0.3 0.5 100 0.8 0.4 5.0 0.2 0.3 0.5 1.0 1.0 1.0 100 100 0.8 0.8 0.4 0.4 5.0 5.0 0.2 0.2 0.3 0.3 0.5 0.5 1.0 1.0 100 0.8 0.4 5.0 0.2 0.3 0.5 /.0 Y1.0

VI

100 0.8 0.4 5.0 0.2 0.3 0.5 1.0 1.0 yr 100 0.8 0.4 0.2 0.3 yI 1.0 1.0 YI Y1 1.0 fl YI 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 by RHONE-POjLENC 10.0 16.3 24.1 10.2 12.4 17.0 18.8 29.7 26.5 ")Stearoyl-benzoyl-methane supplied 2 Dihydroxyaluminium sodium carbonate (DASC) 'Hydrotalcite supplied by KYOWA (Japan) The addition of dawsonite and the addition of hydrotalcite both increase the stability.

Table IV: 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 Rhodiastab 501) Chimassorb 94414) Molbit CR (maltite) Dipentaerythritol Stabiliser 1 Stabiliser 29) Stabiliser 39) IV! IV2 IV3 IV4 IV5 IV6 IV7 IV8 IV9 IVIOIVII 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 1.0 100 100 100 100 0.8 0.8 0.8 0.8 0.4 0.4 0.4 0.4 2.0 2.0 2.0 2.0 0.2 0.2 0.2 0.2 0.15 0.15 0.5 0.5 1.0 1.0 1.0 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 YI VI -YI YI YI YI YI Y VYI I y yI Minutes 6.0 10.1 6.6 12.7 10.3 18.7 6.6 5.8 7.8 7.7 9.0 5.8 11.1 7.3 15.4 8.9 24.8 11.1 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 24.2 29.5 47.913.8 59.9>70 >60 29.1 10.6 32.1 '"stericalty hindered amine supplied by CIBA-6EIGY 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 6 Epox. soya oil Rhodiastab 50" Co steorate Zn stearate Wessalite P") Zeolite p6') Stabiliser 15i 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 yr 100 0.8 0.4 2.0 0.2 0.3 0.5 1.0 1.0

VI

10C 0.8 0.4 2.0 0.2 0.3 0.5 1.0 1.0 VyI )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 Vt I100 0.8 0.4 2.0 0.2 0.3 0.5 1.0 1.0 yI 100 0.8 0.4 0.2 0.3

YI

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 aIa zeolite A supplied by DEGUSSA "'Na 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 0

C)

Mixture Evipol EH 6030 (PVC K value 60) Wax E' CH 3003) Epox. soya oil Ca stearate Zn stearate Rhodiostab 50') D-26-155' 7 Stabiliser 1 5 Stabiliser 29) 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 YI YI 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 36.5 18.8 103 33.3 'L-keto ester of the formula 11.4 15.6 21.9 28.3 46.0 59.2 0

ONA

y Y (CH 2 2

-O-CO-CH

2

-COCH

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

Table VII: Static heat test at 190C (rolled for 5 min at 170"C) Mixture VIII VII2 V113 VI14 VII5 VI16 VI17 V1I8 Evipol SH 6030 (PVC K value 60) CH 3003) Wax E6) Epox. soya oil Ca stearate Zn stearate Synesal M') Stavinor 0 507'9) Stabiliser 1" Stabiliser 29) Stabiliser 3 100 100 100 0.8 0.8 0.8 0.4 0.4 0.4 5.0 5.0 5.0 0.55 0.55 0.55 0.25 0.25 0.25 1.0 1.0 1.0 VI YI YI 5.4 4.8 6.3 6.4 4.7 6.7 6.7 5.5 7.0 7.3 7.6 8.3 10.8 12.3 12.5 19.9 28.5 22.9 100 100 100 0.8 0.8 0,8 0.4 0.4 0.4 5.0 5.0 5.0 0.55 0.55 0.55 0.25 0.25 0.25 0.2 0.2 0.2 .1.0 1.0 100 100 0.8 0.8 0.4 0.4 5.0 0.55 0.55 0.25 0.25 0.2 0.2 /.0 1.Q Minutes 0 yI 2.9 3.5 4.4 5.4 8.9 18.0 yr y 3.9 2.3 4.1 2.3 5.3 3.5 7.5 5.4 13.9 9.3 27.2 17.5

YI

2.9 3.7 4.5 6.3 11.3 23.8

VI

4.4 4.9 6.7 8.2 11.9 21.3 33.7 65.8 45.1 31.8 64.2 32.3 62.6 38.4 "Thiodiethylene-bis(5-methoxy-corbonyl-2.6-dimethyl-1,4-dihydro-pyridine)-3carboxylate supplied by LAGOR '93-bisdodecyloxycrbonyl-2 6-dimethyl-.4dihydropyridine supplied by ATOCHEM The test shows that stabiliser combinations comprising dihydropyridines (VII4 to VII8) have improved initial colour and colour maintenance (mean colour).

PAWPDOCS'Niwspec 2C ROMTTON D5loc-27/m03/ 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 (13)

1. A stabiliser combination for chlorine-containing polymers comprising A) at least one compound of formula I 0 R*l, Y N NH2 R*2 wherein R*i and R* 2 are each independently of the other Ci-C12alkyl, C 3 -Cs 6 alkenyl, C 5 Cecycloalkyl that is unsubstituted or substituted by from 1 to 3 Cl-C 4 alkyl, C1- C 4 alkoxy, Cs-C 8 cycloalkyl or by 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-C8cycloalkyl or by hydroxy groups or chlorine atoms, and R* and R* 2 may additionally be hydrogen and Ci-C1 2 alkyl, and Y is 0, and B) a glycidyl compound.

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

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-uracilI, 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.

PWPOCS\IwVA- 2CROMPIVN 05.d-27OMI3 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. P:\WPDO~\j4,s 2\CROMPTON DS~do-3O01/O5 68

13. A stabiliser combination of claim 1, or a polymer containing the same substantially as hereinbefore described with reference to the Examples (excluding the Comparative Examples). DATE[) this 31st day of January 2005 CROMPTON VINYL AbbITIVES GMBH By its Patent Attorneys DAVIES COLLISON CAVE