AU4393001A - Stabiliser combinations for chlorine-containing polymers - Google Patents

Description

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AUSTRALIA

Patents Act 1990

ORIGINAL

COMPLETE SPECIFICATION STANDARD PATENT Applicant(s): Address for Service: Crompton Vinyl Additives GmbH Emst-Schering-Str. 14 D-59192 Bergkamen Germany 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

I-

STABILISER COMBINATIONS FOR CHLORINE-CONTAINING

POLYMERS

This application is a divisional of Australian patent application No.

58328/99. The ensuing description is substantially identical to the description of "parent" No. 58328/99. The parent description has been fully readopted to facilitate identification of the parent/divisional relationship. It is submitted that the invention 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 f rom the following groups: the perchloraft compounds. glycidyl comnpounds. beta-dihetones. beta.

keto esters. dihydropyridines. polydihydropyridlnes. polyols, disaccharide alcohols, sterically hindered amnines (tetralkyllpiperidine. compounds), alkali alumninosilcates. hydrotalkites and alkali aluminocarbonates (dawsonites). alkalifor alkaine eath-) carboxylates,-(bi)curbonates Oder. -hydroxides. antioxidcants.

lubricants or organotin compounds which ame suitble for stabilising chlorine- *::containing polymers. especially PV C.PVC can be stabillised by a nuimber- of .additives. Compounds of lead, barium and codmiun arm especially suitable for the purpose but ame controversial today f or colog9ical resonms or owing to their :"heavy mettall content. (cf. "Kunstaffaddillvew (Plastics -additives). R. Gdchtea-/- H. Miler. C=4 Hanser Verlag. 3 -d Edition. 1959. pages 303-311, and "Kunststoff **IHandbuch PVC* (lastics Handbook PVC). Vokams 2/1. W.Becker/D.Braun. Carl j-ianse Verlag. 2 !d Edition. 1985, pages 531-538; ad Kirk-Othmner.

Encyclopkdin of Chemical Technolog" 4h Ed.. 1994. Vol 12. Heat Stabi li zers p.

.1071-1091). Other effective stabilisers and stabiliser combinations that are free of leod-, barium and cadmium are therefore sought.compounds of formulaI have already-been described in DE-PS 1 6 9 4 873. EP65 934 and EP 41479 and can bi prepared in one or several process step(s) by known methodslt has now been found that A) compounds of formula I 2 wherein R*l and R*2 are each independently of the other CI-Ci2 .alkyl. C3- C6alkenyl. C5-Cacycloalkyl that is unsubstituted or substituted by from I to 3 C1-C4alkyl. CI-C4alkoxy, C5-C8cYcloalkyl or hydroxy groups or chlorine*atoms 1 or C7-Cgphenylalkyl that is unsubstituted or substituted at the phenyl ring by from I to 3 CI-C4alkyl. C1-C4alkoxY. C5-C~cycloalkyl or hydroxy groups or chlorine atoms, and R*1 and R*2 may additionally be hydrogen and Cl-Cl 2alkyI. and 'V is S or 0, con be combined with B) at least one com~pound from the following group: perchiorate compounds and/or glycidyl compounds and/or beta-diketones. beta-keto esters and/or Sdihydropyridines, polydlihydropyridines and/or poiyols. disaccharide alcohols and/or sterically hindered amines (tetralkylpiperidine compounds) and/or I:::::alkali aluminosi licates (zeolites) and/or hycfrotalcites and/or alkali aluminocarbonates (dawsonites) and./or, :alkali- (or alkaline earth-) carboxylates,-bi)carbonates oder -hydropxides, and/or aritioxidants and lubricants and/or organotin compounds for the purpose of stabilising chlorine-containing polymters. especially PVC.

The present invention as claimed provides a stabiliser combination comprising A) at least one compound of formula I wherein Rol wid R-2.ori each indepeuidentlyof the other Ci-Cl~alkyI. Ca- C5-CacytOOkyll that is uhsubsriMud or substituted by from I to 3 c1-c4ako.V CI-C4aftbxy. CS- Cacyc~cmilkyIl or by hydroxy yioups or chlori'is atoms. or C7-CgphehYlolIyi that is -uausubstituted or subtitatedoat the phanyl rnq from I to 3 Ci-Co~a". Cz -Colaflkoy. C5,Cacyclolkyv oi- by hydro~xy groups or Chldri atomi.

a nd R'li and R02 maoy additionalty bmm hydrogwm and Cj-;C2dlkYl. and V is S.or C. aid B) at least -one alkali- (or alkaline earth-) carboxylate, -(bi)carbonate or -hydroxide compound.

For compounds of formula I' cj-c4AikyI is. for example: methyl, ethyl. n-propyl. isopropyl. iso-, sec- or tert-butyL .::CI-C12Alkyll is. for exampIle, in addi tion to the radicals just mentionied.

pentyl. hexyl. heplyl. octyl. 2-ethylhexyl. isooetyl. decyl. nonyl. undecyl or dodecyl.

cjC4Ajkaxy is. for example. rnethoxy. ethoxy, propoxy. isoPropoxy. butoxy or isobutoxy.

is, for example. cyclopentyl. cyrlohexyl. cycloheptyl or, cyclooctyl.

C7-_C9PhenyIlky is. for example. benzyl. I- or 2-pheinylethyl. 3-phenyipropyll.

a,a-dimethyllbenZyll or 2-phenylisopropyl. preferablyf benzyl.

When the cycloalkyl groups or the phenyl group of the phenylalkyl radicals are substitued, then they are substituted preferably by two or one substituent and. of the substituents. especially by C1. hydroxyrnethyl or methoxy.

C3_C6Alkenyl is. for example. vinyl, ollyll. methallyl. I-butenyll or 1-hexenyl.

preferably oillyl.

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

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

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

The compounds of the groups mentioned under B) are illustrated as follows: o 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 compleexed with alcohols (polyols, cyclodextrins) or ether alcohols or ester alcohols. The ester alcohols include also the polyol partial esters. Also suitable in the case of polyhydric alcohols or polyols are their dimers, trimers, oligomers and polymers, such as di-, tri-, tetra- and polyglycols, and di-, tri- and tetra-pentaerythritol or polyvinyl alcohol in various degrees of polymerisation. The perchlorate salts can be introduced in various known forms, for example in the form of a salt or an aqueous solution applied to a substrate, such as PVC, calcium silicate, zeolites or hydrotalcites, or bound in a hydrotalcite by chemical reaction. Glycerol monoethers and glycerol monothioethers are preferred as polyol partial ethers. Other forms are described in EP 394 547, EP 457 471 and WO 94/24 200.

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

Glycidyl compounds 0 These contain the glycidyl group which is bonded R,

R

2

R

3 directly to carbon, oxygen, nitrogen or sulfur atoms and wherein either R1 and R3 are both hydrogen, R2 is hydrogen or methyl and n=0, or R1 and R3 together are -CH2-CH2- or -CH2-CH2-CH2CH-, 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 cycloaliphatic carboxylic acids, such as cyclohexanecarboxylic acid, tetrahydrophthalic acid, 4methyltetrahydrophthalic acid, hexahydrophthalic acid or 4methylhexahydrophthalic acid.

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

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

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

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

Ethers of that type are derived, for example, from acyclic alcohols, such as ethylene glycol, diethylene glycol and higher poly(oxyethylene) glycols, propane-1.2-diol, or poly(oxypropylene) glycols, propane-1,3-diol, butane-1,4diol, poly(oxytetramethylene) glycols, pentane-1,5-diol, hexane-1,6-diol, hexane-2.4,6-triol, glycerol, 1,1,1-trimethylolpropane, bistrimethylolpropane, pentaerythritol, sorbitol, and from polyepichlorohydrins, butanol, amyl alcohol, pentanol, and from monofunctional alcohols, such as isooctanol, 2ethyihexanol, isodlecanol and C7-Cgalkanol and C9-Cllalkanol mixtures.

They are, however, also derived, for exanple, from cycloaliphatic alcohols, such as 1,3 or I ,4-di hydroxycyclohexane, bis( 4 -hydroxycyclohexKyl)methane, 2 .2-bis(4-hydroxycyclohexyl)propane or 1 ,1.bis(hydroxymethyl)cyclohex-3.

ene, or they have aromatic nuclei, such as N,N-bis(2-hydroxyethyl)ani line or p,p'-bis(2- hydroxyethylami no)diphenylmethoine.

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)rnethane, 2,2 -bis(4hydroxyphenyl)propane, 2 ,2-bis(3 .5-di bromo-4-hydroxyphenyl)propane, 4.4'dihydroxydiphenylsulfone, or on condensation products of phenols with :formaldehyde obtained under acid conditions, such as phenol novolaks.

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

MI) (N-Glycidyl) compounds obtainable by dehydrochiorinating the reaction products of epichiorohydrin with amiines containing at least one :aminohydrogen atom. Those amines are, for example, aniline, N-methyla niline, toluidine, n-butylamine, bis(4-aminophenyl)methane, m-xylylenediamine or bis(4-methylami nophenyl)methane, but also NN,O-triglycidyi-m-aminophenol or NN,O-triglycidyl-p-aminophenol.

The (N-glycidyl) compounds also include, however, N,N',N"-triand N,N4,N", N"'-tetra-glycidyl derivatives of cycloalkyleneureas, such as ethyleneurea or 1,3-propyleneurea, and N.N'-diglycidlyl derivatives of hydantoins, such as 5,5-dimethylhydaintoin or glycoluril and triglycidyl isocyanurate.

IV) S-6lycidyl compounds, such cis di-S-glycidyl derivatives, that are derived from dithiols, such as ethane-1,2-dithiol or bis(4mercaptomethylphenyl) ether.

V) Epoxide compounds containing a radical of formula I wherein RI and R3 together are -CH2-CH2- and n is 0 are bis(2,3-epoxycyclopentyl) ether, 2,3-epoxycyclopentyglycidyl 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-methylcyclohexanecarboxyli c 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 AralditeTMIGY 240, AraldliteMGY 250, AralditeTMAGY 260, AralditeTMGY 266, AralditeTmGY 2600, AralditeTMY 790; b) solid diglycidyl ethers of bisphenol A, such as AralditeTmGr 6071, AralditeTMGT 7071, AralditeTmG7T 7072, AraiditeTMGT 6063, AralditeTMGT 7203, AralditeTMGT 6064, AralditeTmGT 7304, AralditeTMGT 7004, :::*AralditeTtAGT 6084, AralditeTMGT 1999, AraldliteTMGT 7077, AralditeTMGT 6097, AralditeTMGT 7097, AraldliteTMGT 7008, AralditeTMGT 6099, AralditeTmGT 6608, AralditeTmGT 6609, ArcilditeTmGT 6610; c) liquid diglycidyl ethers of bisphenol F, such as AralcliteTMGY 281, AralditeTmPY 302, AralditeTAPY 306; d) solid polyglycidyl ethers of tetraphenylethane, such as CG7 Epoxy ResinTmOl63; solid and liquid polyglycidyl ethers of phenolformaldehyde novolak, such as EPN 1138, EPN 1139, GY 1180, PY 307; f) solid and liquid polyglycidyl ethers of a-cresolformaidehyde novolak, such as ECN 1235, ECN 1273, ECN 1280, ECN 1299; g) liquid glycidyl ethers of alcohols, such as ShellTM glycidyl ether 162, AralditeTmtDY 0390, AraldileTmOY 0391; h) liquid glycidyl ethers of carboxylic acids, such as SheliTmCardura E terephthalic: acid ester, trimellitic acid ester, AralditeT'APY 284; i) solid heterocyclic epoxy resins (triglycidyl isocyanurate), such as AraldliteTMA PT 810; j) liquid cycloaliphatic epoxy resins, such as AralditeTMCY 179; k) liquid N,NO-triglycidyl ethers of p-aniinophenol, such as AraldliteTMMY 0510; 1) tetraglycidyl-4,4'-methylenebenzamine or N,N,N.,N'-tetraglycidyldiaminophenylmethane, such as AralditeTMY 720, AralditeTMY 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.

eta-diketones, beta-keto esters 1,3-Dicarbonyl compounds that can be used may be linear or cyclic dicarbonyl compounds. Preference is given to the use of dicarbonyl compounds of the following formula: R'1CO CHR2'-COR'3 wherein :RI is C1-C22alkyl. C5-Ciohydroxyalkyl, C2-ClBalkenyl. phenyl, phenyl subsitued y O. C-C4alkyl. C1-C4alkoxy or by halogen, C-Clophenylalkyl, C5-Cl2cycloalkyl, C5-Cl2cycloalkyl substituted by CI-C4alkyI. or is a group S-R*6 or R50R6 R'2 is hydrogen, C1-C8alkyl, C2-Cl2alkenyl, phenyl, C7'-Cl2alkylphenyl, C7- Clophenylalkyl or a group -CO-R'4, R'3 has one of the meanings given for Ril or is Ci-Clecilkoxy.

R'4 is C1-C4alkyl or phenyl, is Ci-Cloalkylene and R'6 is CI-CI2alkyl. phenyl, C7-Claalkylphenyl or C7-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, C1-Ct8alkyl, such as methyl, ethyl, npropyl, isopropyl. n-butyl, tert-butyl, penlyl, hexyl, heptyl, octyl, decyl, dodecyl or octadlecyl.

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

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

R'i and R'3 as phenyl substituted by OH, alkyl, alkoxy or halogen may be, for example, to lyl, xylyl. tert-butyphenyl, methoxyphenyl, ethoxyphenyl, hydroxyphenyl, chiorophenyl or dichlorophenyl.

R'i and R'3 as phentylalkyl are especially bem,7yl. R'2 and R'3 as cycloalkyl or alkylcycloalkyl are especially cyclohexyl or metluylcyclohexyl.

*R'2 aS alkyl may be, especially, C1-C4,allkyl. PR2 as C2-Cl2alkenyl- may be, especially, allyll. R'2 as alkylphenyl may be, especially, tolyl. P.'2 as phenylalkyl may be, especially, benzyl. R'2 is preferably hydrogen. R'3as alkoxy may be, for example, methoxy, ethoxy, butoxy, hexyloxy, oclyloxy, dodecyloxy, tridlecyloxy, tetradecyloxy or octadecyloxy. R'5 as Ci..Cioalkylene is especially C2- C4alkylene. R'6 as alkyl is especially C4-Cl2alkyll, such as butyl, hexyl, octyl, decyl or dodecyl. PR'6 as alkylphenyl is especially tolyl. P.6 as phenylalkyl is especially benzyl.

::Examples of 1,3-dicarbonyl compounds of the above formula and their alkali metal, alkaline earth metal and zinc chelates are acetylacetone, butanoylacetone, heptanoylacetone, stearoylacetone, palmitoylacetone, lauroylacetone, 7-tert-nonylthio-heptane- 2,4-dione, benzoylacetone-, di benzoylmethane, lauroylbenzoylmethane, palniitoyl-benzoylmethane, stearoylbenzoylmethane, isooctylbenzoylmel-hane, tribenzoylmethane, bis(4-methylbenzoyl )methcne, benzoyl-pchlorobenzoylmethane, bis(2-hydroxybenzoyl)niethane, 4-methoxybenzoylbenzoylmethane, bis(4-methoxybenzoyl)mnethane, 1-benzoyl-1-acetyinonane, benzoyl-acetyl phenylmethane, stearoyl-4-methoxybenzoylmethane, bis(4-tertbutyl benzoyl)methane, benzoyl-formnylmethane, benzoyl -phenylacetylmethane, biscyclohexanoyl-methane, di-pivaloyl -methane, 2 -acetylcyclopentanone, 2-benzoylcyclopentanone, diacetoacetic acid methyl, ethyl and allyl ester, benzoyl-, propionyl- and butyryl-acetoacetic acid methyl and ethyl ester,

S

S

SSSS*

triacetylmethane. acetoacetic acid methyl, ethyl, hexyl, octyl, dodecyl or.

octadecyl ester, benzoylacetic acid methyl, ethyl. butyl, 2-ethyihexyl, dodecyl or octadecyl ester, and propionyl- and bulyr-yl-cicetic acid CI-Cl 8alkyl ester.

Stearoylacetic acid ethyl, propyl. butyl, hexyl or octyl ester and polynuclear keto esters as described in EP 433 230 and dlehydroacetic acid and the zinc, magnesium or alkali metal salts thereof.

Preference is given to 1,3-diketo compounds of the above formula wherein Wi is C1-C18alkyl, phenyl, phenyl substituted by OH, methyl or by methoxy, C7- Clophenylalkyl or cyclohexyl, R'2 is hydrogen aid 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, f romn 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.

bihydropyridines. polydihydropyridines Suitable monomeric, dihydropyridines are described, for example, in FR 20 39 496, EP 2007. EP 0 362 012, EP 0 286 887 and EP 0 024-754.

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

H

3 CNHI

CH

3

CO

2

CH

3 C0 2

CZH

5

CO

2 "Ci 2

H

25 or CO 2

C

2 RHSn C 12

H

25 Suitable potydihydropyridines are especially compounds of the following formula wherein T is C1-C22alkyl that is unsubstituted or substituted by Ci- Cl 1koxy, C1.C1 Balkylthio, hydroxy, acryloyloxy, methacr-yloyloxy, halogen.

phenyl or by naphthyl; that is unsubstituted or substituted by C1-Cl8alkyl. Cl-Cl8alkoxy or by halogen and that may also be heterocyclic; C3-Cloalkenyl. CH3-CO-CH2-CQ-OR-, CH3-CO-CH2-COO-R', CH3- C(NR' U2)-CH-COOR- or CH3-C(NR "2)=CHCO-G L has the same meanings as T or is a tri- or poly-valent radical from an unsubstituted or Cl-Cl 2alkoxy-. Cl-Cl 2thioal koxy-, C6-ClOaryI-. 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 jis anumber fromlIto 6and the conditions j(k+ m Iand m +n >0are satisfied, R and R' are each independently of the other methylene or phenylene or an alkylene group of the type -(-CpH2p-X-)t CpH2p- that is unsubstituted or carries substituents from the series CI-Cl2alkoxy, CI-Cl2thioalkoxy, C6- Cioaryl, Ctl-Cl2carboxy and hydroxy, p is from 2 to 18, t is from 0 to X is oxygen or sulfur, or, when k is 0 and j 1. R and R' together with L form a direct bond, R" is hydrogen, or Cl-Cl8alkyl, C2-Cl8alkoxycarbonyl or C6-CIOarYl each of which is unsubstituted or substituted by one or more C1-Cl2alkyl, CI-Caalkoxy, halogen or N02 substituents, and the two radicals are identical or different and are hydrogen, Cj- Ci~alkyl. Ci-Cia-hydroxyalkyl or Cl-Cl~alkoxyalky or together are uninterrupted or 0-interrupted or are straight- chained or branched C2-C22alkenyl.

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

Thiodiethylene-bis[5-methoxycarbonyl-2 .6-dimethyl- 1 4-di hydro pyridi ne- 3-.

ccrboxylateJ is especially preferred.

Die (Poly-)Dihydropyridine konnen im chiorhaltigen Polymer zweckrna~ig zu 0,001 bis 5 und insbesondere 0,005 bis 1 Gew.-Teilen, bezogen auf das Polymer, angewandt werden.

Polyols, disaccharide akcohols Examples of suitable compounds of that type are: pentaerythrito I, dipentaerythritl tri pentaerythrito I, bistri methylo Ipropane, bistrimethylolethane, trismethyloipropane, inosite, polyvinylalcohol, sorbitol, maltite, isomaltite, lactite, lycasin, mannitol, lactose, leucrose, tris(hydroxyethyl) isocyanurate, palatinite, tetramethylolcyclohexanol, 6.00 tetramethylocyclopentanolI, tetramethylo lcyclopyranol, glycerol, dig lycero I.

polyglycerol. thiodiglycerol or l-O-a-D-glycopyranosyl-D-mannitol dihydrate. Of those compounds, preference is given to the disaccharide alcohols.

The polyols can be used in an amount of, for example, from 0.01 to 00S000 advantageously from 0.1 to 20, and especially from 0.1 to 10, parts by weight, based on 100 parts by weight PVC.

Stericallyv hindered amines (tetralAyi'piperidine compounds) 0.00.0The sterically hindered amines, especially piperidine compounds, that can be used according to the invention are known especially as light stabilisers. Those .:..*compounds contain one or more groups of the formula

H

3 C

C

H

3

C

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

Especially important as stabilisers are the following classes of tetramethylpiperidline 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 "R1" in formula (II) corresponds to "R 1 in the descriptions.

a) Compounds of formula II HC

CH,

RT-N 0--R2

H

3 C CH 3 wherein n is a number from 1 to 4, preferably 1 or 2, R is hydrogen, oxy. C1-C12alkyl, C3-C8alkenyl, C3-C8alkynyl, C7-C12aralkyl, C-C8alkanoyl, C3-C5alkenoyl, glycidyl or a group -CH2CH(OH)-Z, wherein Z is or acryloyl, and, when n is1, R2 is hydrogen, C1-Cl8alkyl that is uninterrupted or interrupted by one or more oxygen atoms, cyanoethyl, benzyl, glycidyl, a monovalent radical of an aliphatic, cycloaliphatic, araliphatic, unsaturated or aromatic carboxylic acid, carbamic acid or phosphorus-containing acid or a monovalent silyl radical, preferably a radical of an aliphatic carboxylic acid having from 2 to 18 carbon atoms, a cycloaliphatic carboxylic acid having from 7 to 15 carbon atoms, an a,13unsaturated 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-C12alkenylene, xylylene, a divalent radical of an aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid, dicarbamic acid or phosphorus-containing acid or a divalent silyl radical, preferably a radical of an aliphatic dlicarboxylic acid having from 2 to 36 carbon atoms, a cycloaliphatic or aromatic dicarboxylic acid having from 8 to 14 carbon atoms or an aliphatic, cycloaliphatic or aromatic dicarbamic acid having from 8 to 14 carbon atoms, and, when n is 3, R 2 is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, an aromatic tricarbamic acid or a phosphoruscontaining acid or a trivalent silyl radical and, when n is 4, R 2 is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.

When any of the substituents are Cl-C1201lkyl, they are, for example, methyl, ethyl. n-propyl, n-butyl, sec-butyl, tert-bulyl, n-hexyl, n-octyl, 2-ethyl-hexcyl, nnonyl, n-decyl, n-undecyl or n-dodecyl.

In the meaning of C1-Cl8alkyl, R 2 may be, for example, the groups listed above and, in addition, for example, n-tridecyl, n--tetradecyl, n-hexadecyl or noctadecyl.

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

Ras C3-C8alkynyl is preferably propargyl.

As C7-Clzaralkyl, R 1 is especially phenethyl c~nd 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 R 2 is a monovalent radical of a carboxylic acid, it is, for example, an acetic acid. caproic acid, stearic acid, acrylic acid, methacrylic acid, benzoic: acid ::or 0-(3 ,5-di-tert-buyl-4-hyfroxyphenyl)-pr-opio nic acid radical.

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

When R2is a trivalent radical of a tricarboxylic acid, it is, for example, a trimellitic acid or nitrilotriacetic acid radical.

When R 2 is a tetravalent radical of a tetracarboxylic acid, it is. for example, the tetravalent radical of butane-l1.2,3,4-tetracarboxylic acid or of pyromellitic' acid.

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

The following compounds are examples of polyalkylpiperidine compounds of that class: 1) 4-hydroxy-2,2,6,6-tetramethylpiperidine 2) 1 -allyl-4-hydroxy-2 ,2 .6 6-tetramethylpiperidi ne.

3) 1 -benzyl-4-hydroxy-2,2 6 ,6-tetramethylpiperidine 4) 1 -(4-tert-buyl-2-butenyl)-4- hydroxy-2.2,6 .6-tetramethylpiperidi ne 4-stearoyloxy-2.2 .6.6-tetramethylpi peridi ne 6) I-ethyl-4-sailicyloyloxy-2,2.

6 6 -tetramethylpiperidine 7) 4-methacryloyloxy-1.2.2 6 .6-pentamethylpiperidi ne 8) 1,2,2 .6,6-pentamethylpiperidi n- 4 -yl-B-(3.5-di-tert-butyl-4-hydroxyphenyI) propionate 9) di(l-benzyl-2.2,6.6-tetramethylpiperidin-A..yl) maleinate 10) di(2 .2.6 6-tetramethylpiperidi n-4--yl) succinate 11) di(2 .2.6,6.tetramethylpiperidi n-4-yl) glutarate 12) di(2,2,6,6-tetramethylpiperidin-4-yl) adipate 13) di(2 .2.6 6-tetramethylpiperidi n-4-yl) sebacate 14) di(1.2,2.6.6-pentamethylpiperidin-4-.yl) sebacate di(1.2 .3,6-tetramethyl-2,6-diethylpi peridin-4-yl) sebacate 16) di(l-allyi-2,2,6,6-tetramethylpiperidin-4-yl) phthalate 17) l-pr-opargyl-48-cyanoethyloxy-2 .2 6 .6-tetramethylpi peridi ne 18) 1 -ocelyl-2 .2.6 6-tetramethylpi peridi n-4-yI acetate 19) trimellitic acid tri( 2 2 ,6,6-tetramethylpiperidin-4-yl) ester l-acryloyl-4-benzyloxy-2,2 6 6 -tetramethylpi peridine 21) diethylmalonic acid di(2.2 .6,6-tetramethylpi peridi n-4-yl) ester 22) dibutylmalonic acid di(1 .2,2,6 6 -pentamethylpiperidin-4-yl) ester 23) butyl-(3 .5-di-tert-buyl-4-hydroxybenzyl)-maloni c acid di(1 .2,2,6,6pentaniethylpi peridin-4-yl) ester 24) dibenzyl-malonic acid di(1 .2.2,6 6 -pentamethylpiperidin-4-yl) ester dibenzyl-malonic acid di(1,2 .3 6 -tetramnethyl-2,6-diethyl-piperidtn4yl) ester 26) hexane-1' ,6'-bis(4-carbamoyloxy- 1-n.-bulyl- 2,2 6 ,6-tetramethyl-piperidi ne) 27) to luene- 2' bis carbamoyloxy-1I n -pro pylI- 2 2,6 .6-tetramethylpiperidine) 28) dimethyl-bis(2 2 ,6,6-tetrmethylpiperidin-4-oxy)si lane 29) phenyl-tris(2 ,2.

6 ,6 -tetramethylpi per idi n-4--oxy)si lane tris(1-propyl-2 ,2 .6,6-tetramethylpiperidi n-4-yl) phosphite 31) tris(1-propyl-2 ,2 ,6,6-tetramethylpiperidi n-4-yi) phosphate 32) phenyl-[bis(1 ,2 2 .6,6-pentamethylpiperidi n-4-yl)] phosphonate 33) 4-hydroxy-1 ,2,2 ,6 .6-pentamethylpiperidimn 34) 4-hydroxy-N-hydroxyethyl-2 ,2 .6 6-tetranethylpiperidi ne 4-hydroxy-N-(2-hydroxypropyl).2 ,2 6 ,6-tetramethylpiperidi ne 36) 1-glycidyl-4-hydroxy-2 ,2 6 6 -tetramethylpiperidine b) Compounds of formula (MI)

.C

.3 *3 wherein **is the number Ior 2,

R

1 is as defined for a),

R

3 is hydrogen, CI-Cl2alkyl C2-Cshydroxyailkyll, C5-C7cYcloalkyl, C7- Caaralkyl. C2-C18alkanoyl, C3-Csalkenoyl or benzoyl. and, when n is 1, R 4 is hydrogen, CI-Ciaalkyl, C3-C~alkenyl, C5-C7cycloalkyl, Cl- C~alkyll substituted by a hydroxy, cyano, alkoxcycarbonyl or carbamide group, glycidyl, a group of the formula -CH2-CH(OH)-Z or of the formula -CONH-Z, wherein Z is hydrogen, methyl or phenyl: and, when n is 2, R 4 is C2-Cl2alkylene, C6-Cl2arylene, xylylene, a -CH2-CH(OH).-CH2- group or a group -CH2-CH(OH)- CH2-O-O-O-. wherein t is C2-Cloalkyleme, C6-Cl5arylene or C6- Cl2cYcloalkylene, or, with the proviso that R 3 is not alkanoyl, alkenoyl or benzoyl, R4may also be a divalent radical of an aliphartic, cycloaliphatic or aromatic dicarboxylic acid or dlicarbamic acid or also the group -CO- or, when n is 1, R 3 and R 4 together may be the divailent radical of an aliphatic, cycloaliphatic or aromatic 1,2- or 1,3-dicarboxylic acid.

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

When any of the substituents are C5-C7cYcloalkyl, they are especially cyclohexyl.

As C7'-C8aralkyl. R3 is especially phenylethyl or more especially benzyl. As

R

3 is especially 2-hydroxytthyl or 2-hydroxypropyl.

R3as C2-CI8alkanoyl is, for example, propiomyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl, octadecanoyl, but preferably acetyl, and as C3is especially acryloyl.

4 When R 4 is C2-C~alkenyl. then it is, for example, allyl, methallyl, 2-butenyl, 2-penlenyl, 2-hexenyl or 2-octenyl.

*R

4 as CI-C4alkyl substituted by a hydroxy, cyano, alkoxycarbonyl or ccrbamide group may be, for example, 2-hydroxcyethyl, 2-hydroxypropyl, 2cyanoethyl, methoxycarbonylmethyl, 2-ethoxycerbonylethyl, 2aminocarbonylpropyl or 2-(dimethylaminocarboftyl)-ethyl.

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

When any of the substituents are C6-Cl5orylene. they are, for example, o-.

m- or p-phenylene, 1,4-naphthylene or 4.4'-diphenylene.

As C6-Cl2cycloolkylene, D 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 )hexcimethylene-1 .6-diami ne 38) N.N'-bis(2,2,6 ,6-tetramethylpiperidi n-4-yl )hexamethylere-1 .6-diacetamide and 1,6-diformamide 39) 1-acetyl-4-(N-cyclohexylacetamido)-2,2 6 ,6-tetramethylpiperidine 4- benzoylamino-2,2,6 6 -tetramethylpiperidi ne 41) N,N'-bis(2 ,2,6 6 -tetrmethylpiperidin-4-yl )-N,N'-dibutyl-adipamide 42) N,N'-bis(2 ,2 .6 6-tetramethylpiperid in-4-yl)-N.N'-dicyclohexyl-2 hydroxypropytene-1 .3-diamine 43) N,N'-bis(2 .2 6 ,6-tetrcimethylpiperidi n-4-yl)-p-xylylene-diami ne 44) NN'- bis(2 .2,6 .6-tetramethyl pi peridi n-4-yI)succine-diamide N-(2 ,2 6 6 -tetramethylpiperidin-4-yi)..amindipropioni c acid di(2 .2,6,6tetramethylpiperidin-4-yl) ester 46) the compound of the formula

CH

3 OH 3

C

CHIj-N N-CH 2

-CH(OH)-CH-Q-

OH

3

OH

3 CHi--C-CH 3

H

3

O

3 CHS-N

N-CH

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

OH

3 47) 4-(bis-2-hydroxyehyl-amino)-1,2.2 6 6 -pentamethylpiperidine :48) 4-(3-methyl-4-hydroxy-5-tert- butyl-benzoiccacid amido)-2 .2,6.6tetramethylpiperidine 49) 4-methacrylamido-! .2,2,6,6 -pentamethylpiperidi ne c) Compounds of formula (IV) [R-N Z <4

(IV).

wherein n is the number 1 or 2,

R

1 is as defined under a) and, when n is 1. R5is C2-C8alkylene or C2-C8hydroxycilkylene or C4- C22acyloxyalkylene, and, when n is 2, R 5 is the group (-CH2)2C(CH2-) 2 When R 5 is C2-C8alkylene or C2-C8hydroxyalkylene, it is, for example, ethylene, 1-methyl-ethylene, propylene. 2-ethyl-propylene or 2-ethyl-2hydroxymethyipropylene.

As C4-C22acyloxyalkylene,

R

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

The following compounds are examples of polyalkylpiperidine comhpounds of that class: 9-aza-8 .8 10,1-tetrmethyl-1 .5-dioxaspiro 51) 9-aza-8,8 ,lO,lO-etramethyl-3-ethyl-1I,5-d ioxaspiro 52) 8-z-,,,.,-e~ehl-.-ixsio45dcn 53) 9 -aza-3-hydroxy'methyI-3-ethyl-8.8.9,1o,1o..pentarnthyl.1,5 54) 9 -aza-3-ethyl-3-cetoxymethyl-9-acetyl..8,8 .lO,1-tetramelhyl-1 2,2 .6.6-tetramethylpiperidinie-4-spiro-.2' -(1,3'-dioxane)-5' .3"-dioxane)-2u-spiro-4' ".60 "-tetramethylpiperidi ne).

d) Compounds of formulae VA, VB and VC NJ

(VA)

'H 1 R-N

(VB)

H

3 C 'CH 3

H

H

3

T

1

(VC)

*H

3 C OH 3 0 wherein n is the number 1 or 2, RI is as defined under a), Ris hydrogen, CI-Cl2alkyI, allyl, benzyl, glycidyl or C2-C6calkoxyalkyI and, when n is 1, R 7 is hydrogen, CI-Cl2alkyl. C3-C5alkenyl, C7-C9aralkyl, C7cYcloalkyl, C2-C4hydroxyalkyl, C2-C4alkoxyalkyl, C6-ClOaryl. glycidyl or a group of the formula -(CH2)P-COO-Q or of the formula -(CH2)P--O-Q, wherein p is 1 or 2 and Q is Ci-C4alkyl or phenyl, and, when n is 2, R 7 is C2- C12alkylene, C4-Cl2alkenylene, C6-Cl2"ryene. a group -CH2-CH-(OH)-CH2-0-D- O-CH2-CH(OH)-CH2-. wherein D is C2-Clolkylene. C6-Cl5ar'ylene. C6- Cl2cycloalkylene, or a group -CH2CH(OZ')CH2-(OCH2-CH(OZ')CH 2 2 wherein Z' is hydrogen, Cl-Cl8alkyl, allyl. benzyl, C2-Cl~alkanoyl or benzoyl, Ti and T2 are each independently of the other hydrogen, C1-Claalkyl, or unsubstituted or halo- or CI-C4alkyl-substituted C6-ClOaryl or C7-Cgaralkyl, or Ti and T2 together with the carbon atom that binds themr form a C5-Cl2cycloolkane ring.

When any of the substituents are C1-Cl2alkyl, they are, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-bulyl, n-hexyl, n-octyl, 2-ethyl-hexyl, nnonyl, n-decyl, n-undecyl or n-dodecyl.

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

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

When any of the substituents are C2-C6alkoxyalkyl, they are, for example, methoxymethyl, ethoxymethyl, pro poxymethyl, tert- butoxymethyl, ethoxyethyl.

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

When R7is C3-C5alkenyl, it is, for example, 1-propenyl, allyl. me1thallyl, 2butenyl or 2-pentenyl.

As C7-Cgaralkyl, R Ti and T2 are especially phenethyl or more especially benzyl. When Ti and T2 together with the carbon atom form a cycloalkane ring.

that ring may be, for example, a cyclopentane, cyclohexane, cyclooctane or cyclodlodecane ring.

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

As C6-Cioaryl, R7, Ti and T2 are especially phenyl, a- or B-naphthyl, which are urisubstituted or substituted by halogen or by CI-C4alkyl.

When R~7 is C2-Cl2alkylene, it is, for example, ethylene, propylene, 2.2di met-hylpropylene, tetraniethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.

AsC4-Cl201kenylene, R is especially 2-butenylene, 2-pentenylene or 3hexenylene.

When R 7 is C6-Ci2arylene. it is. for example, mi- or p-phenylene, 1,4naphthylene or 4,4'-diphenylene.

When Z7 is C2-Ci2alkanoyl, it is, for example, propionyl, butyryl, octanoyl, dodecoanoy I, but preferably acetyl.

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

The following compounds are examples of polyalkylpiperidine compounds of that class: 56) 3-benzyl-i ,3,8-triaza-7,7,9 9 -tetrmethylspiro[4.5]decane-2,4dione 57) 3-n-octyl-i,3 8 -triaza-7,7,9,9-tetramethylspiro[4.5]decane-2 .4-dione 58) 3 -allyI-l, 3 8 -triaza-I, 7 7 9 9 -pentamethylspiro(45]decane.24-dione 59) 3-glycidyl-1 .3 8-triaza-7,7,8 .9,9 -pentamethylspiro[4.5]decane-2 .4-dione 1.3,7,7,8,9 ,9-heptcimethyl-1.3 8 -triazaspiro[4.5]decane-2 ,4-dione 61) 2- isopropyl-7.7,9,9-tetramethyl- l-oxa-3,8-diaza-4-oxo-spiro 62) 2 .2-dibutyl-7,7,9.9-tetramethyl- l-oxa-3,8-diaza-4-oxo-spiro 63) 2,2 ,4,4-tetrimethyl-7-oxci-3 .20-diaza-21-oxo-dispiro[5.l.1 l.2]henicosane 64) 2 -butylk 7 7 9 9 -tetramethyl-oxa48diz..3-oxo..spiro[4.5]decane 8-acetyl-3-dodecyl-1 .3 ,8-triaza-7,7,9,9-tetramethylspiro[4.5]decone-2 4dione or the compounds of the following formulae:

OH

3

CH

3

CH

3

OH

3 NH-C=O0=0 CHi-N

IN-CH

3 N- CH 2 CH(0H)CH1 2

-[OCH

2

-CH(OH)CFJ

2

N-CI

CH* CH 3 O O0CH CH 3 66)3 67)

CH

3

OH

3 CH CH 3 ::NH-00 O C-NH *CHi-N 1-C 3

C-N-(CH

2

)-N-C~KI

3

OH

3 0O 3

OH

68) OH 3

OH

3 CH 3 OH 3 HNNH-C0 i-NH

N

C_ .10

-H

2

OH

3

OH

3 0 0 OH H 3 HO3

CH

3 69) HN -C

(CH

2 11 C- -C 2 C2 OOC 2 H 2

OH

3 CH 3 0 e) Compounds of formula VI

R

e N" N

(VI),

RJ- R n.

wherein n is the number 1 or 2 and R 8 is a group of the formula

CH

3 CH.

N-R

x *CH CH, wherein

R

1 is as defined under a), E is or -NR 11 A is C2-C6alkylene or -(CH2)3-0- and x is the number 0 or 1, 9 is identical to R 8 or is one of the groups -NR 1

R

12

-OR

13 -NHCH2OR 13 or -N(CH2OR )2, o when n 1, R 0 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,

CHR

N-R

I 1

CH

2

R

R

12 is C1-Cl2alkyl, cyclohexyl, benzyl, CI-C4hydroxyalkyl and

R

13 is hydrogen, C1-Cl2alkyl or phenyl, or

R

11 and R12 together are C4-C5alkylene or C4-C5oxaalkylene, for example -C H fl C H w r

-CH

2

CH

2 -y 22

N-R

,or -CH CH--/ 2 2 are a group of the formula -C2H2- 0

-CH

2

CH

2 -CH2CH2----\ -CH

N-F

2 2 or alternatively

R

11 and R 12 are each a group of the formula When any of the substituents are Cl-Cl2alkyl they are, for example, methyl, ethyl, n-propyl, n-buty sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethyihexyl, nnonwyl, n-decyl, n-undecyl or n-dodecyl.

When any of the substituents ame C1-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, 2,2d imethylpropylene, tetramethylene or hexamethylene.

WhenR11andR12together are C4-C5calkylene or C4-C5oxaalkylene, they are, for example, tetramethylene, pentamethylene or 3 -oxapenlfamethylene.

The compounds of the following formulae are examples of polyalkylpiperidinie compounds of that class:

CH

3 H C I OH 3

N

7)H 3 C

H

3 N-O H

(CH

3

CH

2 2 N(HCA

N(C

4

H

9 2 C H 3

OH

3 NJ NOH CH 3 7) 2

H

5 -N N-t l N N-0 2

H

0 2

H

5

CAH

CH *.O 3

OH

3 C.M OH 3 R H 3 C OH 3 72) Nj.'N weinR -NH-H 2 CH 2 C"2-0 N-OH3 R RH 3 0 OH 3

OH

3 CH 3 CH2-CH 2 NH 73) CH 3

OH

3 NH

H

3

H

3 C3C HN CH 2

-CH

2 -NHI -N HC2C2

NH

CH

3

OH

3 C

C

CH,

C*H

ICAH

*N NH H H M HNfNN oe N- A9 H. N-NM N NNCH CH Cm M Vt Cm74)NC CH,-N

HN

H H.* R

R*

R-NH(H)N J-(CH I -N(CH NH..R wherein R is CO H 3 CH 3 9*CA 9 -I CH/

OH

3

OH

3 CH 3 76)

R-NH-H

2 3 (CH 2 'CH1 2 1 3

H..R

wherein R

C

4

H

9

CH

3

ICH

3

@OOS

*0O C S

S

*SS*

S

S.

S S

**SS

S

S

CH

3 7) CH 3 R

CH

3 (CH2I)j-- N C2)'

CH

3 CH 3 N

C

4

H

9 "T-N

N-CH

3 wherin N<NCH 3

CH

3

CH

3 ICH 3 COH s7

CH

3 78) 0000 0 0000 00 OS @0 S

S

5.55

SS

0* S @5

S

S

S

555.

@000

S

6.5.5.

0 *000 0* 0S S 506 S

S

*55@ 5* 0 C 5685 0

CH

3 CH

CH

2

CH

2

OH

CH3 C H 3 79)

CH

3

CH

3

OH

3

H

3

C

H

3 C CH 3 N~YN

CH

3

CH

3 2

C=HC-H

2 0-N -N N N-H- C2

C

4

H

9 CH 9

H

3 C OH 3

CH

3

OH

3 f) Oligomeric or polymeric compounds. the structural repeating unit of which contains one or more 2 6 6 -tetracilkylpiperidine radicals of formula especially polyesters, polyethers, polyamides, polycuiines, polyurethanes, polyureas, polyciminotriazines, poly(meth)crcylates, polysiloxones, poly(meth)acrylamides and the copolymers thereof that contain such radicals.

Examples of 2 2 ,6,6-polyalkylpiperidirwe light stabilisers of that class'are the compounds of the following formulae wherein m is a number from 2 to approximately 200.

CH

3 CH 3 0 0 11 11 81) C-CH 2

-CH

2 C-O-CH 2 -CHi---N 0-- 4bm CH CH, 0

CH$

3

CH,

82) 0-C(H) C 0 N--C 1 CH-O C(CH) 4 83) C CH, 2 H H CM 3

NH-(CH

2 b-N NH-C C N

N-(CH

2 )3-NH-c CH3 CH 3 H-CH -it 1KC 3 Cl-ta N~ N 84) -4PJZ'Z JLN

P)

CH

3 CH 3 -Cl- 3

CH

3

CH-

86)

CH

3 CH 3 0 CAH 0 0-C C

C

4

H

9 m CH/' CH 3 87) 88) C C

C

C

*CCC..

C

89) CH CH 3

CH

3 -Pg -CHi I CH 3

CH

3 m 0

N-CH

3

CH

3

CH

3 CH 3 91) O H 3

OH

3 m CSH 13 -N N;-CH 3

OH

3 H 3 0

N

J- N-(CH z--

NN

:CHA

3 1OH 3

OH

3 OH 3

OH

3 N H 3 C H H

H

N- C 0 C 2

H

2 93) OH1 3 0113

OH

3 CH 3 C H 3 C~ H 3 OH 3 to CH 3 H H 3 0 0 11 1I 94)m

CH-

CH3 Si 403 (CH 2 1 3 wherein R =H or CH3 CHi-

CH

3 CH 3 96) 19 NH

H

9

C

4 N(R)C 4

H.

H

3 0-

CH

3 wherein P.= HAC(R)N JZ'Nk N(R)C 4 H 9 and R'= or H (obtainable by reacting the reaction product of trichiorotriazine and NH-2- (CH2)3-NH-(CH2)2-(CH2)3-NH 2 with 4-N-butyl-2 .2,6 .6-tetramethylpiperid, neI Of those classes, classes e) and f) are especially suitable, especially those tetrolkylpiperidine 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-triazines is known from the literature for example, Houben-Weyl *Methoden der organischen Cheuniew, Vol. VII, p. 233-237, Yd~Ed., Thieme Verlag Stuttgart 1971). There may be used as starting material for the reaction with various 1-piperidylamines cyanuric chloride, diami no-chloro-! .3 .5-triazine or variously substituted bisdialkylami noch loro- 1,3 .5-triazines or dialkyloMio- or alkylam ino-dichloro-! .3 5-triazi vies.

rTechnically important exampiss of tetra* and pentoalkylpiperidine compounds are: bis(2,2.6.6-tetr eO~thl-piperidyl) sebacate, bis(2.2,6,6- ***tetramethyl-piperidyl) supCclngte. bis(1 2 2 6 6 -pentamethylpiperidyl) sebacate.

n- bulyl-3 .5-di-tert-b y 14 0bxy*Imaoric; acid bis(1 pentamethylpiperi dyl) ester, the. condeatilon product of 1-hydroxyethyl- 2,266-tetramethylA-hyopiperdine and succinic acid, the. condensation product of N.-i(.,.-ermhl4pieiy)hxmtyeeimn and 4-tert-octylami no-2 .6-dichloro- 1,3, -s-triazine. -tris(2 .2 6,6-tetramethyI-4.

piperidyl)nitrilotriacetate, tet-rakis(2.2,6-tetrame thyl-4-p, peridyl}-1 .2,3,4butanetetraoate, 1 .1'-(1,2-cthaewciOI)-..is(s 3 1 5.-tetramethyl-piperazinre), 4benzoyl-2.2,6,6-tetramt4yp 10cift 4 -Stearylox;y-2,2,6,6tetramethylpiperidine, bis~.* penamnethylpiperidyl)- 2-n-butyl-2-(2hydroxy-3 ,5-di-tert-butyb.11zt)-Malonizte, 3 -n-octyl-7,7,9.9-tetrmethyl.

1,3 ,8-triazaspiro(4.5detag-..2,4-dlone bis(1-octyloxy-2 .2,6,6tetraimethylpiperidtyl) sebaccate, bis(1-octyloxy-2.2 .66-tetranmethylpiperidyl) succi nate. the condensation product of NN'-bis(2,2 .6 ,6-tetramethyl-4pi peridyl)hexamethylendianmine and 4-morpholino-2 ,6-dichloro-1.3 the condensation product of 2 -chlor-4,6-di(4-n.bylamino22,6,6 tetramethylpiperidyl)-1 .3,5-triaztine and.1 2 -bis(3-aminopropylami no)ethane, the condensation product of 2-chkoro-4.6-di(4-n-butylamino-1,2 .2,6,6- .t4Ioip-;i anqd .1 2 -bis(3-aminopropylamino)ethane 8acetyl-3-dodecyl-7.7.9,-.ttrzMethyl 1,3,8 -triazaspi ro[4.5]decane-2,.4-diane, 3-dodecyl- 1-(2,2 6 6 -tetr-amethyl-4-piperidyl)pyrro lidi ne-2 .5-dione, 3 -dodecyl- 1-(1 6 -pentamethyl-4-piperidyl)-pyrro 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- 1-lyro takcites and alkali (alkaline eai-th) aluminosilicates (zeolites) The chemical composition of these compounds is known to a person skilled in the art. for example from patent specifications DE 38 43 581, US 40 00 100, EP 062 813, WO 93/20135.

Compounds from the hydrotalcite series can be described by general formula M 1-x M 3 x(OH)2 (Ab-)x/b .d H20 (Vri) wherein 2.

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

M

3 Al, or 8, An is an anion having the valency n.

b is anumber fromlIto 2, o (X C 0.5, and m is a number from 0 to Preferably, An O C104-, HC03-, CH3COO-, C6HScOO- C03 2 (CHOHCOO)2 (CH2COO)2 2 CH3CHOHCOO HP03 or HP04 2 Examples of hydrotalcites are Al2O3.6MgO.CO2.12H2O Mg4S5A2(OH-)13.Ccj 3 .3.5H 2 c, (ii).

4MgO.A203.C02.9H20 (iii), 4MgQ..A 1203.C02.6H20, ZnO.3MgC.A l2O3.CO2-8- 9H-20 and ZnO.3MgO.A203.CC25-6H 2 0- Special preference is given to types i, ii and iii, Zeoites (alkali and alkaline earth aluminosiicates) These can be described by general formula (VII) Mx/n((AI02)x(5i02}y].wH2o

(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. Sr or 8a; 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 sodiumn aluminosilicates of the formulae Na 12A12Si12O48. 27 H20 (zeolite Na6Al6Si6O24. 2 NaX. 7.5 X= OH, halogen, C104 [sodalite]; Na6Al6Si3Ocil2. 24 H20; Na8Al8Si 4 0 0 96 24 H20; Na16Al16Si24O 8 O. 16-H20; Na16AI16Si32Og 6 16 ~:Na56AI565i136O 3 8 4 250 H20 (zeolite Y1, N"086A186S14O 6

O

384 264 (zeolite X]; or the zeolites that can be formed by partial or complete replacement of the Naatoms by Li, K, Mg, Co. Sr or Zn atoms, such as (Na,K)1OA1OSi220 64 20 H20; Ca4.5NO3((Al02)l2(5 1 0 2 12 J. 30 K9NO3[(AI02)12(5i0 2 12 27 Preferred zeolites correspond to the formulae NaC1 12 S2i 12 c 4 8 27 H 2 0 [zeolite A], Nc'6Al65i6O 24 2N'aX.- 7.5 H20, X =OH, Cl, C104, 1/2C03 [sodaIi te] Na6Al6Si300 72 24 Na8A18Si 4 0 0 96 24 Na16AlI6Si24080. 16 N016A116i 32 O%6. 16 Na'56Al56Si136O384. 250 H20 [zeolite Y] Na86Al865i1060384. 264 H20 (zeolite X] and zeoliles 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 conplete replacement of the Na atoms by Li, KC, Mg, Ca, Sr, Ba or Zn atoms, such as (Na,K)1oAlcjSi22064. 20 Ca4,5Na3[(AI02)12(5i02)1 2] 30 KgNO-J3(A02)12(i02)12]. 27 The zeolites listed may also have a lower water content or may be anhydrous.

Other suitable zeolites are: Na2O-AI 2 0 3 to 5) SiO 2 to 10) H 2 0 [zeolite P] Na2O-AI203-2 Si02-(3.5-I0)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,Na,K,H) 0 Al 10 Si 2 2

O

6 4 20 H 2 0 lC9 N 3 [(A0 2 12 (i0 2 12 27 H 2 0 K4Al 4 Si4O1 6 -6 H20. [zeolite K-F] Na8A18Si 40 0 96 .24 H 2 0 zeolite as described in Barrer eta/f., J. Chemn.

Soc. 1952. 1561-1571, and in US 2 950 952; The following zeolites are also suitable.

potassium offretite, as described in EP-A-400 961; zeolite R. as described in GB 841 812; zeolite LZ-217, as described in US 4 503 023; Ca-free zeolite LZ-218, ais described in US 4 333 859; zeolite T, zeolite L.Z-2 20, as described in US 4 503 023; Na3K6A 1 9 5i 27 0 7 2 .21 H 2 0 [zeo lite L]; zeolite LZ-211, as described in US 4 503 023: zeolite LZ-212, as described in US 4 503 023; zeolite 0, zeolite LZ-217, as described in US 4 503 023; zeolite LZ-219, as described in US 4 503 023; zeolite Rho, zeolite LZ-2 14, as described in US 4 503 023; zeolite ZK-19, ais described in Am. Mineral. 54 1607 (1969): zeolite W as described in Barrer etal, J. Chem. Soc. 1956, 2882; Na 30 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 S practical interest. The structure of zeolite P-1 corresponds to the gismondite structure known from the above-mentioned Atlas of Zeolite Structures. In more recent literature (EP-A 384 070) a distinction is made between cubic (zeolite B or-Pc) and tetragonal (zeolite P 1 zeolites of the P type. That publication also mentions relatively new zeolites of the P type having Si:AI ratios of less than 1.07:1. Those are zeolites designated MAP or MA-P for "Maximum Aluminium P".

Depending upon the preparation process, zeolite P may contain small quantities 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 orghnic dispersants.

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

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

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

Alkali aluminocarbonates (dawsonites) These are compounds of the formula ((M20)m.(A1203)n.Zo.pH20) wherein M is H, Li, Na, K, Mgl/2, Cal/2, Srif2 or Znl/2; Z is CO2, 502, (C1207)1/2, B406, 5202 (thiosulfate) or C20 2 (oxalate); m is a number from 1 to 2 when M is M91/2 or Cal/2, and in all other cases is a number from I 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 alumina salt compounds of formula that can be used according to the invention may be naturally occurring minerals or synthetically prepared compounds. The metals may parIdW-P eplace, 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 opoun s ore indigiie #uiie aluminohydrocalcite, para-alu~olnohN~orocalcite. strontiodresserite and hydrostrontiodresseait. Other'exdmnples of alumino salt compounds are potassium aluminocarbo~ote ((K20)(A1203).(C02)2.2H2). sodium aumi~thosufat .1)($202)2.2490), potassium aluminosulfite; ((K20)(Al2O3).(5O2)2.-2H2O). COIChAMi Gluminooxalate ((Ca0).(Al2O3).(C202)2.5H26). magnewsiu au notetraborate f(Mg.(A 1203).(B406)2.5H-20). (MgO.2NaO.6J20)(A 1203 ).(C02)2.4.1 (([MgO.2Nczo.6J20).(A 1203).(CO2)2.4.3H20O) and (((Mg.3Nao.4]20).(AI203).(C02)2.2.4.9H 2 0).

The mixed alumina salt compounc$, can be obtained in accordance with processes known per se b aon 0dW~se preferably from the alkali alumina salt compounds or by oomn'! dp; Ition (see, for example, US 5 055 284).

Preference is given-to Olumino, salt compounds of the above formula wherein M is Na or K.,Z is C02, 502 or (4 1 207)1/2; In is 1-3; n isl1-4; ois 2-4 and pis 0-20. Z is especially C02.' Preference is given also to compounds that can be represented by the following formulae: M20.A1203.(C02)2 .pH2O (IQ) (M20)2.(Al203)2.(C02)2 pH2O (11) M20.(AI203)2.(C02)2 -pH2Q (Ic) wherein M is a metal, such as Na, K, Mg1/2, Cal/2, Srl/2 or Znh/2 and p is. at number from 0 to 12.

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

Dawsonites may also be substituted by lithiumclumohydroxycarbonates or lithium-magnesiuni-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 dihydropyridmnes and polydihydropyridine-s.

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, compo *unds 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-C1601kyl-substituted, phenyl-Cl-Cl6alkylcarboxylates, or phenolates that are unsubstituted or C1-Cl2alkyl-substituted, or abietic acid.

There may be mentioned specifically, as examples, the zinc salts of monovalent carboxylic acids, such as acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, oenanthic acid, octanoic acid, neodecanoic acid, 2ethylhexanoic acid, pelargonic acid, dlecanoic acid. undecanoic acid, dodecanoic acid, tridecanoic acid, myristic acid, palmitic acid, lauric acid, isostearic acid, stearic acid, 12-hydroxystearic acid, 9,lQ-dihydroxystearic acid, oleic acid, 3.6dioxaheptanoic acid, 3,6,9-trioxadecanoic acid, behenic acid, benzoic acid, ptert-buiylbenzoi c acid, dimethyl hydroxybenzoic acid, 3 ,5-di -tert-butyl-4hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, npropylbenzoic acid, salicylic acid, p-tert-octylslicyhic 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, lheptane-1,7-dicarboxylic acid, octane-I .8-dicarboxyli c acid, 3,6 .9-trioxadecarte- l,1O-dicairboxylic acid, lactic acid, malonic acid, maleic acid, tartaric acid. -cinnamic acid. mandelic acid, malic acid, glycolic acid, oxalic acid, salicylic acid, polyglycol-dlicarboxylic acid (n=l0- 12), phthalic acid, isophthalic acid, terephthalic acid and hydroxyphthalic acid: and the di-- or tni-esters of tri- or fetra-valent carboxylic acids, such as hemimellitic acid, tnimellitic acid, pyromellitic acid, citric acid and also so-called overbased zinc car boxylates.

The zinc enolates are preferably enolates of acetylacetone, benzoylacetone.

or dibenzoylmethane and enolates of acetoaiceta-es and benzoyl acetates and of dehydroacetic acid. In addition,* inorganic zinc compounds, such as zinc oxide, zinc hydroxide, zinc sulfide or zinc carbonate, cam also be used.

Preference is given to zinc carboxylates of a carboxylic acid having from 7 to carbon atoms (zinc soaps), such as benzoates or alkanoates, preferably *C~alkanoates, stearate, oleate, laurate, palmitate, behe nate, versatate.

hydroxystearates, dihydroxystearates, p-tert-buylbenzoate, or (iso)octanoate.

Preference is given especially to stearate, oleate. versatate, benzoat-e, p-tentbutylbenzoate and 2-ethyihexanoate.

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

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

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

and tliophosphates, 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 propellanrts, and antifogging agents (cf. "Handbook of PVC Formulating" by E. J. Wickson, John Wiley A Sons. New York 1993).

Tn a non-limiting manner, some of the known additives and processing auxiliaries'are mentioned here: Alkali metal arnd alkaline earth metal compounds.

These are to be understood to include especially the carboxylates of the acids described above. but also corresponding oxides or hydroxides or (bi)cairltnates. Mixtures thereof with organic acids are also suitable. Examples are NoOH. N-stearate, N~aHCO 3 KOH, K-steorate, KHCO3, LiOl-I Li 2

CO

3 Listearate, COO. Ca(0H2). Mg0. Mg(OH)2. Mg-stearate, CGCO3, *gCO3 as well -cs dolomite, huntit. chalk, basic Mg-carbonate and other Na- and K-salts of fatty acids.

NaOH, KOH-, CoO. Ca(0H2). MgO., Mg(OH)2. CaCO3 and MqCO3 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) 2 (M Ca, Mg, Sr or Zn), so-called moverbased* compounds, to be used.

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

Other Af etal Stabilisers S pecial 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.

Glidants(LURIRICANITS) Suitable glidants are, for example: Montan wax, fatty acid esters, 'PE waxes, amnide waxes, chloroparaffins.

glycerol esters or alkaline earth metal soaps. Suitable glidants are also described in "Kunststoffadditive" (Plastics additives), R. Gichter/H. MUller, Carl )4anser Verlag, 3V 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, ais 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-2ethyihexyl, di-n-ociyl, diisooctyl, diisononyl, diisodecyl, diisotridecyl, dicyclohexyl, dimethylcyclohexyl, dimethylglycol, dibutlglycol, benzylbutyl and diphenwyl phthalate and mixtures of phthalates, such as C7-Cg- and C9- CII-alkyl phthalates from predominantly linear alcohols. C6-Clo-h..alkyl Phthalates and Ca-Clo-n-alkyl phthalates. Of those compounds, preference is given to dibutyl, dihexyl, di-2-ethylhexyl, di-n-octyl, diisooctyl, diisononyl.

diisodecyl, diisotridecyl and benzylbu-tyl phthalate and to the mentioned mixtures of alkyl phthalates. Special preference is given to di-2-ethylhexyl, diisononyl and diisodecyl phtha 'late, which are also known by the customvary abbreviations r)OP (dioctyl phthalate, di-2-ethylhexyl phthalate), bINP (diisononyl phthalcate), D)IbP (diisodecyl phthalate).

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

C) Trimellitic acid-esters, for example tri-2-ethylhexyl trimellitate, triisodecyl trimel litate (mixture), tri isotridecyl trimellitate, tri isooclyl trimel litate (mixture) and tri -C6-C8alkyl, tri-C6-ClOalkyl, tri-C7..C90lkyl and tri-C9-C1 lalkyl trirnellitate. The last-mentioned trimellitates are formed by eslerifying triunellitic acid with the appropriate alktinol mixtures. Preferred trimellitates are tri-2-ethylhexyl trimellitate and the mentioned trimellitates from alkanol mixtures. Customary abbreviations are TOTM (trioctyl trimellitate, lri-2-ethylhexyl trimellitats). TIOTM (triisodecyl trimellitate),and

TITM

(tri isotridecyl trimellitate).

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

Polymer plasticisers A definition of taepkwtflsers and examples thereof are given in "KunststoffadditiviO (plastics additives), k. Sdchter/H. MUller, Carl H-anser Verlag. V~ Ed., .1989. Chapter 59 6. pages 412-415, and in "PVC Technology", Titow, 4 Ed.. ELsIpfaL 194,pages'165-170. the most commonly used starting materials for the preparation of polyester, plasticisers are: dicarboxylic acids, such qa dipc hhlc zl and sebacic acid; diols, such as 1.2-propanedil 1.3bUltanediol, 1,4-butanediol, 1.6-hexanediol, neopentyl glycol and diethylene -glycol.

F) Phosphoric acid esters.

A definition of thos rtrsis to be found in the above-mentioned "Taschenbuch der KuA0tffoddtive" (Handbook of Plastics. Additives), Chapter 5.9.5, p.p. 4O316 xanpe of such phosphoric acid esters are *tributyl phosphate.- tri-2-iethylbut yl phosphate, tri-2-ethylhexyl phosphate, trichioroethyl phosphate. 2 -6thyl-hexyl-diphenl phosphate, cresyl diphenyl phosphate, triphenyl phosphate, tricresyl phosphate and trixylenyl phosphate. Tri-2-ethylhexyl phosphate and mReofos 50 and 95 (Ciba-Geigy) are preferred.

G) Chlorinated hydrocarbons (paraffi ns) H) Hydrocarbons I) Monoesters, eig. butyl oleate, phenoxyethyl oleate, tetrahydrofurfuryl oleate and -alkylsuftfO1 acid e"tri.

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: "lKunststoffadditive"' (Plastics Additives), R. Gydchter/H. Muller. Carl Hanser Verlag, 3' Ed., 1989, Chapter 5.9.14.2, p.p. 422-425 (group and Chapter 5.9.14.1, p. 422 (group H).

"PVC Technology", W.V. Titow. 4 th 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 1) and Chapter 6.10.4, pages 173-174 (group 3).

it is also possible to use mixtures of differerit 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 inorganc pigments are TiO 2 carbon black, Fe 2 0 3 Sb 2 0 3 (Ti,Ba,Sb)O 2 .CrZO 3 spinels. such as cobalt blue and cobalt green, Cd(S,Se), ultramarine blue. Organic pigments are, for example, azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, diketo-pyrrolopyrrole pigments and anthroquinone pigments. Preference is also given to T0iO 2 in micronised form.

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

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

Chalk is preferred.

Phosphites Examples are triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris-(nonylphenyl) phosphite, trilauryl phosphite, irioctadecyl phosphit-e, distewryl-pentaerythritol diphosphite, tris( 2 ,4-di--tert-butylphenyl) phosphite, diisodlecylpentqerythritol diphosphite, bis(2,4-di-tertbutylplhenyl)pentaerythrito I diphosph ite, bis(2 .6-di-tert- butyl-4-methylphenyly..

pentaerythritol diphosphite, bis-isodecyloxy-pentaery1.hritol diphosphite.

bis(2 4 -di-tert-butyI-6-methylphenye)pentaerythrito I diphosphite, bis(2 .4.6-tn.tert-butylphenyl)pentaerythrit 0 I diphosphite, tristearyl-sorbitl triphosph ite, bis(2.4-di -tert-butyl-6-methylphenyl)methyI phosphite, bis(2 .4-di-tert-btyl.6.

methylphenyl)ethyl phosphite.

Especially suitable are trioclyl, -tridecyl, tnidodecyl, tnitetridecyl. tnistearyl.

trioleyl, triphenyl-, tricresyl, tnis-p-nonylphenyl or t ricyclohexyl phosphite and special preference is given to the aryl-dialkyl anfd alkyl-diaryl phosphites, such as .phenyldidecyl phosphite, 2 4 -di-tert-butylpluenyl)..di-.dodecyI phosphite. (2,6di-.tert-buylpenyl)-djrorjecI Oopht and to the dialkyl- and diarylpentaerythritol dliphosphites, such as distearylpentaerythito I diphosphite, and non-stoichiometric triaryl phosphites, for example those having the composition (H19C9C6H4)015P(0C1 2 13

H

2 5 2 7 1 Preferred organic phosphites are distearyl-pentaerythrito I diphosphite, trisnonyiphenyl phosphite and phenyldidecyl phosphite.

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

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

(RS)

3 P, (RS) 3 P:-O or (RS) 3 PS, which are described in patent specifications D)E 28 09 492.

EP 090 770 and EP 573 394.

Examples of those compounds are: trithiohexyl phosphite, trithiooctyl phosphite, trithiolauryl phosphite, trithiobenzyl phosphite, trithiophosphorous acid tris(carboisooctyloxy)nethyl ester, trith io phosphorous acid tris(carbotrimethylcyclohexyloxy)methyl ester, trithiophosphori c acid S,S,S-' tris(carboisooclyloxy)methyl ester, trithiophosphoric acid S,S,5-tris(carb,..2.

ethylhexyloxy)methyl ester, trithiophosphoric acid SASS-tris-1- (carbohexyloxy)-ethyl ester, trithiophosphoric acid SS,S-tris-I-(carbo-2-.

ethylhexyloxy)-ethyl ester, trithiophosphoric acid SASS-tris-2-(carbo-2ethylhexyloxy)-ethyl ester.

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

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

wee* poxidised fatty acid esters so *0 The stabiliser combination according to the invention may additionally comprise 066 preferably at least one epoxidised fatty 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 @666 epoxidised butyl oleate.

Antioxidants Suitable antioxidants are, for example: 1. Alkylated mOno~henots. for example 2, 6 -di-tert-butyl-4-methylpheol, 2-tert-buyl-46-dimethylphenol, 2 .6-di-tert-butyl-4-ethylphenol, 2 ,6-ditert- butyl-4-n-butylpheno I, 2 ,6-di -tert-buyl-4-isobutylphenol, 2.6dicyclopentyl-4-methylphenol, 2 -(a-methylcyclohexyl).4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2 .4,6-tricyclohexylphenol, 2 .6-di-tertbutyl-4-methoxymethylphenol, 2,6 -di-nonyl-4-methylpheno I, 2,4-dimethy-6 (1'-methyl-undec-IV-yl)phenoI, 2 .4-dimethyl-6-(1'-methyl-heptadec 1'yl~phenol, 2,4-dimethyl-6-(-methyl-tridec-lV-yl)phenol, oclpheno I, nonylphenol, dlodecylphenol and mixtures thereof.

2. Alythiomethylphenols. for example 2 4 -di-octylthiomethyl-6-tert.

butylphenol. 2 .4-di-oclylthiomethyl-6-methylphenol, 2 .4-di-oclylthiomethyl- 6-ethylphenol, 2,6-di-dodecylthiomethyl-4nonylphenol.

3. Alkylated hydroguiriones. for example 2,6-di-tert-butyl-4methoxypheno I. 2 .5-di-tert-bulyl- hydroquinone, 2 hydroqui none, 2 .6-di phenyl-4-ocladecyloxypheno I. 2 ,6-di -tert-butylhydroquinone, 2 .5-di-tert-buiyl-4- hydroxyarinisole, 3 ,5-di -tert-butyl -4hydroxyanisole. 3 .5-di-tert-butyl-4- hydroxyphenylstearate, bis(3 .5-di -tertbutyl-4-hydroxyphenyl) adipate.

4. Hycloxlatod thiodiphenyl ethers- for example 2,2-thio-bis(6-tertbutyl-4-methylpheno 2 2 '-thio-bis(4-octlpheno 4.4'-thio-bis(6-tertbutyl-3-methylphenol), 4 4 '-thio-bis(6-tertbutyl-2-methylphenoI). 4,4'-thiobis(3 .6-di-sec-amyiphenol), 4.4'-bis(2 .6-dimethyl-4-hydroxyphenvyl) disulfide.

Alkylidene bisphenols. for example 2 ,2-methylene-bis(6-tetbutyl..- :methyiphenol), 2 e 2 '-methylene-bis(6-ert-butyi-4-ethylphenol), 2,2'methylene-bis4-methyl 6-(amethylyclohxyIphenol], 2 ,2-methylenebis(4-methyl-6-cyclohexylphenol). 2 2 '-methylene-bis(6-*nonyl-4.

methylphenol), 2 2 -methylene-bis(4,6-di-tert-butylphenol), 2 ,2-ethylidenebis(4,6-di-tert-butylpheno 2 2 -ethylidene.-bis(6-tert-buyl-4-..

isobutyipheno 2.

2 '-methylenebis6-(a.methylbenyl}.4-nnylpheno 2,2'methylene-bis(6-(oaa-dimethylbenzy)4noryphen, 4,4%-rethylene- *bis(2.6-di-tert-buiylphenol), 4 4 -mcthylene.-bis(6-tert-butyl-2.

9:meihylphenol)i ,1 i(-etbtl4hdox--ehlhnlbtr- 2.6bis(3-tert-butyl-5-methyl-2 -hydroxybenzyl)-4-methylphenol. 1.1 tert-butyl-4-hydroxy- Z-methylphenyl)butane, 1 .1-bis(5-tert-butyl-4hydroy- 2 -methylpheny)-3-n-dodecylmercaptobutane. ethylenie glycolbis[3 .3-bis(3'-tert-butyl-4-hydroxyphenwyl) butyrate], bis(3-tert-butyl-4.

dicyclopentadiene, bis(2-(3-tert-butyl-2-hydroxy- 5'-methyl-benzyl-6-tert- butyl-4-methylphenyl] terephthalate, 1,1- bis(3 dimethyl-2-hydroxyphenyl)butane. 2 ,2-bis(3.5-di-tert-butyl-4hydroxyphenyl)propane, 2 ,2-bis(4- hydroxyphenyl)propane, 2 ,2-bis(5-1ertbuy--yrx--ehlhnl)4nddclecpouoe 1,1,5.5tetra(5-tert-butyl-4-hydroxy-2:methylphenyl)pentane.

6. Benjyl compou nds. for example 3 ,5,3'5-tetra-tert-buty[.4,4'di hydroxydi benzyl ether, octadec'yl-4-hydroxy-3 mercaptoaceta-e, tris(3 .5-di-tert- butyl-4- hydroxybenzyl )anine, bis(4-tertbulyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis(3 bulyl-4-hydroxybenzyl) sulfide, isooctyl- 3 5-di -tert-butyl-4- hydroxybenzyl mercaptoacetate.

7. Hydroxybengylatied ualonciles. for example dioctadecyl-2.2-bis(3,.di-tert-butyl-2-hydroxybenzyl) malonate, di-octadecyl-2-(3 -tert-butyl-4arsloreite, dldodecylmercaptchyl -2 .2-bis(3.5-ditert-butyl-4-hydroxybenzyl) molonate, di-[4-(1,1,3,3tetramethylbutyl)phenyl]-2.2'-bis(3 5 -di-tet-butyl-4-hydrybenzyl) malonate.

8. k m~j~Mr~ goLn~j IlL- for example 1,3,5-tris(3,5-ditet-butl- 4 -hybcn zyl)2, 6trimthybenzene, 1.4-bils(3 butyl-4-hydroxyboy)-2.,6-tetamethybezen 2 .4.6-tris(3 bulyl-4-hydroxybenyphemioi Tri-azine -06mwwwg for example 2 .4-bis-ocymrcapto-6{3..43itert-butyI-4-hyde oqniieno)=a.3a,.-.trk'Ilge 2-oct lflpto-4,6-bs(354.

tea t-butyl-4-hydroxyhf* *y).1,3*,.5-triazfn.a 2 4 6tris(3,5-di-tert-butyIA...

hydroxyphenoxy)-l.2,3-n'Ir lne, 1,3,5-tris(3.5S-di-tcrt-butyI-4 hydroxybenzyl) isocyanurate, tris(4-tert-brtyl-3-hydroxy-.2 .6dimiethylbenzyl) isocyanurate, 2.

4 ,6-tris(35-di-tert-buty-4.

hydroxyphenylethyl).1,3,54triazi.e. l.3,5-trs(35-di-tert-butyl-4.

hydroxypheuyiproplonyl~hpwAhdro-.3,5triazlne, 1.3.5-1rls(3 dicyclohexy-4-hydroyb ij) isocyqwos PhoSphonates 91W~ toiI* for compig buty-4-hydroxybenzyl phootplioncte, Oisthyk,,15-di-tert-bull-4hydroxybenzyl phosphonate, dic*"-.itr-uy--yrxbny phosphonate, dicoey-Str.btl4hdoy3mtybny phosphonate. calcium silt of 3 e 5 -di-.tert-buy-4-hydroxybenzylphosphonic acid monoethyl ester, tetrakis(2u 4 -di-tti ylpheyl)4,'biphenylere diphosphonite, 6-isooctyloxy-2 .4,8 .1O-tetra-tert-butyl-1 2H-di benzo ~d~gJ- 153,2-dioxaphosphocine, 64fluoo- 2,4.8 .lO-telra-tert-butyl-12 -methyldibenzo~dgJ-1 .3.2-dioxophosphocine.

11. Agylaniinoh 'WI~ for example 4-hydroxy-lauric acid anilide, 4hydroxyslearic* acid'danilide, N-(3 5 -di-tert-butyl-4-hydroxyphenyI)-carbomi c acid octyl ester.

12. Esters of b-(3 .5-di -tert-butyl-4- hydroxyvhenfl)-propionic acid with mono- or poly-hydric alcohols, such as methainol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, l.

2 -propainediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythrito I, di pentaerythritol, tris(hydroxyethyl) isocyanurate,

N,N'-

bis( hydroxyethyl)oxalic acid diamide, 3-thioundecanol, 3 -thiapentcidecanol, tri methyihexanediol, trimethyloipropane, di-itrimethylo Ipropane, 4hydroxymethyl-l -phospha-2 .6,7-trioxabi cyc lo[ 2 2 .2]oclaone.

13. Esters of b-(5-tert-buvl-4-hydrox 3 -methylphenyl)-pRropionic acid with mono- or poly-hydric alcohols, such as methanol, ethanol, octanol,' octadecano I. 1 ,6-hexanedio I, 1,9-no nanedio I, ethylene glycol, 1, 2 -proponedio

I.

neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylerie glycol, pentaerythritol. tris(hydroxy)eihyl isocycintrate,

N,N'-

:.bis(hydroxyethyl)oxalic acid diamide, 31-thicurmlecanol, 3 -thiapentade cano I, *trimethyihexanediol, trimethylolpropane, 4-;hydrogxymethyl-1-phospha... 6,7!trioxabicyclo[2.2.2 ]octane.

*14. Esters of b-35dccoev--ym hnl-poi acid with mono- or poly-hydric alcohols, such as methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, I1.9-nononediol, ethylene glycol, l, 2 -propanediol; neopentyl glycol, thiodiethylene glycol, dietiylene glycol, triethylene glycol, pentaerythritol, tris(hydroxy)ethyl isocycinurate, NN-bis- (hydroxyethyl)oxalic acid dianiide. 3-thiaunciecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxyinethyl- 1-phospha-2 .6,7trioxabicyclo[2.2.2 joctane.

Estrs of 3 di-tert-buly-4-hydrovphenyacetic acid with mono- or poly-hydric alcohols, such as methanol, ethanol, octanol, octadecanol, 1.6hexanediol, 1,9-nonane-diol, ethylene glycol. 1,2-propanediol, neopenlyl glycol, thiodiethylene glycol, diethylene glycol. triethylene glycol. pentaerythritol, tris(hydroxy)ethyl isocyanurate, N,N-bis(hydroxyethyl)oxalac acid d jamide, 3-thiaundecanol, 3-thiapentakdecanot, trimethyihexanediol, trimethylotpropane, 4-hydroxymethyl-l-phosph..2 ,6 ,7-trioxabicyclo octane.

16..Amides of b-( 3 di-tert-butl4hydroyphenyl)-propionic acid, such as NN-bis(3,5-dli-tert-butyl-4hydroxyphenylpropionyl)hexamethylenediamine, N,N'bis(3 .5-d-tert- butyl-4hydroxyphenylpropionyl)trimethylenediami ne, N,N-bis(3,5-di-tert-butyl-4.

hydroxyphenylpropionyl) hydrazine.

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

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

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

V: :absorbers and light StabiliSers .Examplesar' 1. 2 -;(2-Hvdoxyhenyl)-benzotriazo les such as 2-(2'-hydroxy-5'methy lphenyl)-benzotriazo le, 2 3 .S'-di-tert-butyl-2-hydroxyphenyl)-.

*benzotriazole, 2-(5'-tert-butyl- 2 -hydroxyphenyl)-benzotriiazole. hydroxy-5 .3 3 -tetramethylbutyl)phenyl)-benzotriazole. 2 3 2-(3'-tert-butyl-2'hydroxy-5"-methylphenyl)-5-chloro-benzo1.riazole, 2-(3'-sec4butyl-5-te.&.

buty-2'-hydroxyphenyl)-benzotriozole, 2-(2-hydroy4octoxypheyl}..

benzotriazole, 2-(3'.5'-di-tgrt-amyl- 2'-hydroxyphenyl)-benzotriazo le, 2- 3 .S5'-bis(aa-dimethylbenzyl)-2'-hydroxyphenyl)-benzotiazole. a mixture of 2-(3-tert-butyl-2-hydroxy-5'-(2 benzotriazole, 2 -(3'-tert-butyl-5'-[2 -(2-ethyl hexyloxy)-carbonylethyl]- 2'loro-berizotriazo le. 2-(3'-tert-buyl-2-hydroxy-5..(2meihoxycarbo nylethyl)phenyl)-5- ch loro- berizotriazo le, 2 '-tert- butyl- 2'hydroxy-5'-(2-methoxycarbonylethyl )phenyl)- berizotriozole, 2 -(3'-tert-butyl.

2 '-hydroxy-S'-(2-octyloxycarbonylethyl)phenyl).benzotriazole, 2- (3'-tert- (2-(2-ethyl hexyloxy)carbonylethyl hydroxyphenyl)benzotriazole, 2 -(3'-dodecyl- 2 -hydroxy-5'-methylphenyl)-benzotriazo le, and 2-(3'-tert-butyl- 2 -hydroxy-5'-(2-isoocyloxycarbonylethyl)phenyl.

berizotriazole, 2 ,2'-methylene-bis[4- (1,1,3,3 -1etramethylbutyl)-6benzotriazol-2-ylphenol]; the transesterif iction product of 2 -[3'-iertbutyl-5'-(2-methoxycarbonylethyl)-2'-hydro xy-phenyl]-benzotriazo le with polyethylene glycol 300; wherein R 3'-tert-butyl-4'-hydroxy-'-2H-.

benzotricizol- 2-ylphenyl.

2. 2-Hvdroxybenzophenones, such as the 4-hydroxy-, 4-methoxy-, 4octyloxy-, 4-decyloxy-, 4-dodecyloxy-, 4-beinzyloxy-, 4,2',4'-tri hydroxy- or 2'-hydroxy-4,4'-dimethoxy derivative.

3. Esters of unsubstituted or substituted benzoic acids, such as 4-tertbutyl-phenyl sal icylate, phenyl sali cylate, octyiphenyl talicylate, di benzoylresorcinol, bis(4-tert-butylbenzoyl )resorci not, benzoylresorcin,I 3,5-di.-tert-butyl-4-hydroxybenzoic acid 2.4-di-tert-butylphenyl ester, di-tert-butyl-4-hydroxybenzoic acid hexadeacyl ester, 305-di-ter-butyl.4.

hydroxybenzoic acid octadecyl ester, 3 5 -di-tert-butyl-4-hydroxybenzoic acid 2-methyl-4,6-di- tert-butylphenyl ester.

4. Acryles such as a-cyano-b,b-diphenylacrylic acid ethyl ester or *..isooctyl ester, a-carbomethoxy-cinnamic acid* methyl ester, a-cyano-bmiethyl-p-mnethoxy-cinnamnic acid methyl ester or butyl ester, acarbornethoxy-p-methoxy-cinnami c acid methyl ester, N-(b-'carbomethoxcy 0 b-cyanovinyl)-2-methyl-indo line.

Nickel compounds, such as nickel complexes of 2.2'-thio-biS[4-(1,1,3,3tetramethylbutyl)phenol], such as the 1--I or the 1:2 complex, where appropriate with additional ligands, such as ri-butylamnine, triethanojamine or N-cyclohexyl diethanolamine, nickel dibutyl dithiocarbamnate. nickel salts of 4-hydroxy-3.5-di-tert-butylbenzylphosphonic acid monoalkyl esters, such as methyl or ethyl ester, nickel complexes of ketoximines, such as 2-hydroxy-4..

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

6. Sterically hindered amines, such as bis( 2 2 6 ,6-tetranmethyl-piperidyl) sebacate, bis(2 ,2 .6 6-tetramethyl-piperidyl) succinate, bis(l ,2 ,2,6 ,6pentamnethylpiperidyl) sebacate, n- butyl-3 ,5-di-tert-butyl-4-hydroxybenzl malonic acid bis(l.

2 2 6 6 -pentmethylpiperidlyl) ester, the condensation product of 1-hydroxyethyl- 2,2,6,6 -tetraimethyl-4-hydroxypiperidine and succinic acid, the condensation product of N.N'-bis(2,2,6,6-tetramethyl-4.

piperidyl)hexamethylenediamine and 4 -tert-octylami no- 2,6-dich loro-1,3 triazi ne, tris(2 ,2,6 .6-tetramethyl-4-pj peridyl)nitri totriacetczte, tetraki s(2,2,6,6 -tetramethyl -4-p i peridyl)- 1,2,3,4- butane tetraoate, ethanediyl)-bis(3 ,3 .5.5-tetramethyl-piperazi none), 4-benzoyl-2 .2,6,6tetramethylpiperidine, 4-stear-yloxy- 2,2,6,6 -telr-anethylpiperidi ne, bis(1 ,2,2 .6 .6-pentamethylpiperidyl)-2-n-butyl-2-(2 -hydroxy-3.5-di -lertbulylbenzyl) malonate, 3 -n-octyI-7,7.9,9-tetrmethyl-1 .3.8triazaspiro(4.5Jdeamne2 .4-dione, bis(I-octloxy-2 .2,6,6es s i-ocyloxy-2,2,66-tetranethylpipe.,dyl) succinate, the condensothln product of N,M-bis(2266-tetrwnethyl..4.

piperidyl)-hexarnethyiknedlamine and 4-morpholino-2,6-dichloro-1,3,5triazine, the condensation product of 2-chlor-o-4,6-di(4-n-buylwnino-.

2,2 .6.6-teltamthylplp.erly)l).3.5-triazine and I .2-bis(3aminapropykamino*thans, the condensation product of 2-chloro-4,6-di-(4--nbU~yino1.*~6As~t -A !ypiperldyl)-1,35trizine and 1.2-bis(3aminopoylit~)gse S-oft 1=3-dodecyI-7,7,9.9-tetramethI.13pieridI~yrrolldin.,m~~~ 3-dodecyl-l-(l .2,2 ,6,6-pentamthyl-4piperidy)-p fdZ5", td IChl.0masm .966.

7. OxalIc acid glai, such as 4,4-di-octloxy-oxanilide, 2,2'-dioctyy-.d-to't+butyl oc" ide, 2,2'-didodeyloxy-5,5'di-tert.butyI oxani lide, 2-ethoy24.etky oxdni lids, N.'-Ibis(3-dimethylaminopropyl) oxakamide, 2-ethoxy-5-tert-butyl-2'-ethyl aonilide and a mixture thereof with 2-toy2-ehl5W.d-t -uy oxanilide, mixtures of o- and pmethoxy- and Q-wan thx~ .b,9ntuted oxanllides.

8& 2 (*7y,44~raIissc as 2A46-ti4s(2hydroxy-4octyoxypheyl-1.3.0 t ihe, (hy-dr !4-ac ykoxyphe o)-46- bit(2 4-.

dimnethylphenyl)-1 ,3.5-:triazine,, 2.-(2.4-dihydroxyphenyl)-4.6-bis(2 .4dimethylphenyl)-1,3,0.tiainc, 2.

4 -bis(2-hyroxy-4-propykxyphenyl).6-.

(2 .4-dimethylphenyt)-1,3.-ti.Iln, 2 -(2-hydroxy-4-oc tyloxyphenyg)-4,6.

bis(4-methylphenyl)4.5-trkW!*n. 2 2 -hydrxy-4-dodecyopen)-s6 bis(2 ,4-dimethylI'pke.'rl)-1 ,3,5'fr"i'azi ne, 2-(2-hydroxy-4-(2-hydroxy.3.

buiyloxy-propyloxy)phenylj-4.6-bis(2 .4-dimethylphenyl}-l .3,5-triazi ne, 2-(2hydroxy-4-(2-hydroxy,-3..otyoxypropyloxy)phenyl]J4,6.bi(2 ,4dimethylphenyl)-1 .3 Propellants Propellants are organic azo and hydrazo compounds, tetrazoles, oxazines, isatoic ainhydride, and sodium carbonate and sodium hydrogen carbonate.

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

Definitions and examples of impact strength modifiers and processing aids, gelling agents, antistatic agents, biocides, metal deactivators, optical brighteners, fire-proofing agents and antifogging agents are described in "Kunststoffadditive" (Plastics Additives), R.Gdchter/H.Muller, 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 theadditional 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 polynerisable compounds such as acrylonitrile, vinyl acetate or ABS, which may be suspension, bulk or emulsion polymers. Preference is given to PVC homopolymers also in combination with polyacrylates.

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

SThe 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 S PVC, which comprises mixing components and described hereinbefore and, where appropriate, any further additives with the PVC using apparatus, such as calenders, mixers, kneaders, extruders and the like.

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

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

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

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

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

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

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

Example 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 190 0

C)

Mixture 11 12 13 Solvic 268 RC KC value 68) 100 100 100 Omyalite 30 Ca stearate 0.6 0.6 0.6 Hostalub H4 2 1.0 1.0 Hostalub, H12 2 a) 0.2 0.2 0.2 CH 30W)~ 0.4 0.4 0.4 Mark 6045 ACM 4 0.3 0.3 0.3 Stabiliser 5 0.2 0.2 0.2 NaCIO4 0.05 VI Y3I Y1 eMinutes 10 20.7- 29.9 22.2 28.4 66.6.' 29.1 40.2 108.4 39.2 ')Chalk 2 )Ghidant supplied by Hobechst (paraffin wax) '461idant supplied by H-oechst (polar ethylene wa) Phenylisodecyl phosphite 4) Mixftre of 9%.

NczClO 4 .457. CaCOq, 40. CaSiO3. 6% H20a 0)6-Amino-1.3-dimethy-urcmg it is found that the use. of inmall amounts of perchiorate compound as component B in mixtures II and 13 accorcllng to the invention results in considerably better stabilisation than without component B.

Table I1I: Static heat test at 190 0

C

Mixture 111 112 113 Evipol SH 6030 (PVC K value 60) 100 100 100 CH 3003) 0.8 0.8 0.8 Wax E'6) 0.4 0.4 0.4 Epox. soya oil 5.0 5.0 Araldite GY 2507)/ Araldite PT 810") Stabiliser 15) 1.0 Stabiliser 29) 1.0/ Stabiliser 3' 0 1.0 V1 I VI (rolled for 5 min at 170*C) 12 41-15 116 117 118 119 100 0.8 0.4 5.0.

1.0 100 0.B 0.4 5.0 1.0 100 0.8 0.4 1.0 100 0.8 0.4 5.0 100 0.8 0.4 5.0 100 0.8 0.4 a a.

a a a VYI Y1 I YVIVI YI Minutes 30 17.4 17.3 15.6 23.2 33.7 29.5 33.6 54.9 46.3 13.4 17.8 11.8 18.5 12.5 17.7 14.8 16.2 17.1 21.2 24.4 24.0 27.2 33.6 30.8 23.5 29.9 27.8 3Phenylisodecyl phosphite 6)Ester wax (based on: montanic acid)7)biglycidyl ether of bisphenol A (liquid epoxide) 8) Solid heterocyclic epoxy resin (triglycidyl isocyanurate) 9 )6-Amino-1 .3-di-n-butyluracil I 0 6-Amnino-l .3-di-ethyl-thiouraci

I

The stabiliser combination (114 to 119). of glycidyl and aminouracil compound according to the invention is found to be superior.

Table III: Static heat test at 190 0 C (rolled for 5 min at 170*C) Mixture Evipol SH 6030 (PVC K value 60) CH 3003) Wax E) Epox. soya oil Rhodiastab 50 Ca stearate Zn steorate DASC'2 Alkamizer I') Stabiliser 1l Stabiliser 29) Stabiliser 30) III I2III3 11141TI5III6 III7III8III9 100 0.8 0.4 5.0 0.2 0.3 0.5 1.0

YI

100 0.8 0.4 5.0 0.2 0.3 0.5 1.0

YI

100 0.8 0.4 5.0 0.2 0.3 0.5 1.0

YI

100 0.8 0.4 5.0 0.2 0.3 0.5 1.0 1.0

YI

100 0.8 0.4 5.0 0.2 0.3 0.5 1.0 1.0

YI

100 0.8 0.4 5.0 0.2 0.3 0.5 1.0 1.0

VI

100 100 0.8 0.8 0.4 0.4 5.0 5.0 0.2 0.2 0.3 0.3 0.5 0.5 1.0 1.0 1.0 1.0 Vyi y 100 0.8 0.4 0.2 0.3

YI

C

C

C

C

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-POULENC 10.0 16.3 24.1 10.2 12.4 17.0 18.8 29.7 26.5 ")Stearoyl-benzoyl-methane supplied 1 )Dihydroxyaluminium sodium carbonate (DASC) 13 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°C (rolled for 5 min at 170C) Mixture Evipol SH 6030 (PVC K value 60) CH 3003) Wax E 6 Epox. soya oil Rhodiastab 501 Chimassorb 94414) Malbit CR (maltite) Dipentaerythritol Stabiliser 1 s Stabiliser 29) Stabiliser 319) Minutes 25 IV1 IV2 IV3 IV4 IV5 IV6 IV7 IV8 IV9 IVIOIV11 IV12 100 0.8 0.4 2.0 0.2 1.0 100 0.8 0.4 2.0 0.2 1.0 100 0.8 0.4 2.0 0.2 1.0 100 0.8 0.4 2.0 0.2 0.15 1.0 100 0.8 0.4 2.0 0.2 0.15 1.0 100 100 0.8 0.8 0.4 0.4 2.0 2.0 0.2 0.2 0.15 0.5 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 2.0 0.2 0.5 1.0 100 0.8 0.4 0.2 YV YI VI YI YI yI yI yI I yI yI yr 6.0 10.1 6.6 12.7 10.3 6.6 5.8 18.7 7.8 7.7 9.0 5.8 6.2 11.1 7.3 7.2 15.4 8.9 9.4 24.8 11.1 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 47.9 13.8 59.9 >70 >60 29.1 10.6 32.1 .b.

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

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

C)

Mixture Evipol SH 6030 (PVC K value 60) CH 3003) Wax E 6 Epox. soya oil Rhodiastab 5011) Ca steorate Zn stearate Wessalite P' 5 Zeolite P'6) Stabiliser 1 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

VI

100 100 0.8 0.8 0.4 0.4 2.0 2.0 0.2 0.2 0.3 0.3 0.5 0.5 1.0 1.0 YI YI 100 100 0.8 0.8 0.4 0.4 2.0 2.0 0.2 0.2 0.3 0.3 0.5 0.5 1.0 1.0 1.0 1.0 YI YI 100 0.8 0.4 2.0 0.2 0.3 0.5 1.0 1.0

VI

100 0.8 0.4 2.0 0.2 0.3 0.5 1.0 1.0

VI

100 0.8 0.4 2.0.

0.2 0.3 0.5 1.0 1.0

VI

100 0.8 0.4 0.2 0.3

YI

9 a. S. *9a.

a

S

.5 0

S

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 ")Na zeolite A supplied by DEGUSSA 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 stearote Rhodiastab 50") D-26-155'7) Stabiliser PD Stabiliser 29) VII V12 100 100 0.4 0.4 0.8 0.8 5.0 5.0 0.55 0.55 0.250.25 1.0 YI VI 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 Y1 Minutes 20 18.5 9.7 36.518,8 30 103 33.3 7 NBketo ester of the formula 11.4 15.6 21.9 28.3 46.0 59.2 0 QANJ

NY

Y (CH 2 2 -0.CO-CH- 2

-CO-CH

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

Table VII: Static heat test at 190°C (rolled for 5 min at 170"C) Mixture VIII VII2 VII3 VII4 VII5 VII6 VII7 VII8 Evipol SH 6030 (PVC K value 60) CH 3003) Wax E 6 Epox. soya oil Ca stearate Zn stearate Synesal M e Stavinor 0 507 9) Stabiliser 15) Stabiliser 29) Stabiliser 3 0) 100 100 100 0.8 0.8 0.8 0.4 0.4 0.4 5.0 5.0 5.0 0.55 0.55 0.55 0.25 0.25 0.25 100 100 100 0.8 0.8 0,8 0.4 0.4 0.4 5.0 5.0 5.0 0.55 0.55 0.55 0.25 0.25 0.25 0.2 0.2 0.2 1.0 1.0 1.0 100 100 0.8 0.8 0.4 0.4 5.0 0.55 0.55 0.25 0.25 0.2 0.2 1.0

S

S

S

S

*5t* 1.0 1.0 1.0 5.55

S.

*5*5 MinuTes YI YI YI YI YI YI YI YI 0 5.4 4.8 6.3 2.9 3.9 2.3 2.9 4.4 6.4 4.7 6.7 3.5 4.1 2.3 3.7 4.9 10 6.7 5.5 7.0 4.4 5.3 3.5 4.5 6.7 7.3 7.6 8.3 5.4 7.5 5.4 6.3 8.2 20 10.8 12.3 12.5 8.9 13.9 9.3 11.3 11.9 25 19.9 28.5 22.9 18.0 27.217.5 23.8 21.3 33.7 65.8 45.1 31.8 64.2 32.3 62.6 38.4 l 8 Thiodiethylene-bis(5-methoxy-carbonyl-2,6-dimethyl-1,4-dihydro-pyridine)-3carboxylate supplied by LAGOR 9)3-bisdodecyloxycarbonyl-2,6-dimethyl-1,4dihydropyridine supplied by ATOCHEM The test shows that stabiliser combinations comprising dihydropyridines (VII4 to VII8) have improved initial colour and colour maintenance (mean colour).

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.

Amendments have been made to the claims which follow and new claims have been proposed to more closely define the invention. The claim amendments are based on various preferred embodiments as described and exemplified in the description. However, for the purpose of maintaining integrity of the text of the disclosure, substantial amendments have not been made to the description in light of the claim amendments. It is submitted that there is no disconformity in the specification as a consequence of amendment of the i' claims given the limitation of claim scope of various preferments of the invention described.

oo** 6 o o

Claims (10)

1. A stabiliser combination comprising A) at least one compound of formula I Y N NH 2 R- 2 wherein RVI and R*2.are each independently. of the other Cl-Clzalkyl. C3- C6alkenyI. C5-Cacycloalkyl that is unsubstituted or substituted by from 1 to 3 .*Owe. Cj-Cqalkyl. C1-C4alk~Ixy, C5-Cacycloalkyl or by kydroxy groups or chlorine atos. r C-C~hehlalylI that'is unsubstituted or substituted'at the phenyl ring by from I to 3 C1-C4alkyl. CI-C4alkoxy. C5.Cacycloolkyl. or by hydroxy groups or chlorine atoms.- and R*i and R1*2 may additionally be hydragen and CI-Cl~alkyl. and V is S or and B) at least one alkali- (or alkaline earth-) carboxylate, -(bi)carbonlate or *~.-hydroxide compound. A stabiliser combination according to claim 1, wherein R*1 and R*2 are each independently of the other H and C1-C4alkyl or C1-C4,alkyl.

3. A siabiliser combination according to claim 1, wherein the compound of comporleat A) is 6-arriiro-1.3-dimethyl-uracil.

6-cinino-13-di-n-propyl-uracii., 6- amino- 1.3-di-n-butyl-uracil. 6-amino-I .3-diethyl-thiouracil or 6-camino-l.3-dli-n- butyl-thiouracil. 4. A stabiliser combination according to any one of claims 1 to 3. which additionally comprises at least one epoxidised faty acid ester. A stabiliser combination according to anyone 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, antioxidclants. beta-dicarbonyl compounds, plasticisers. fillers. glidants and pigments.

7. A stabiliser combination according to claim 6, wherein the filler is chalk a. 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. sees

10. A composition comprising a chlorine-containing polymer and a stabiliser combination according to any one of claims 1 to 9.

11. A composition according to claim 10. wherein PVC is used as the chlorine-containing polymer.

12. A method of stabilising chlorine-containing polymers, which comprises incorporating into the chlorine-containing polymers a stabiliser combination S S according to any one of claims 1 to 9.

13. A stabiliser combination of claim 1, or a polymer containing the same See. e* substantially as hereinbefore described with reference to the Examples.

14. The steps, features, compositions and compounds disclosed herein or referred to or indicated in the specification and/or claims of this application, individually or collectively, and any and all combinations of any two or more of said steps or features. DATED this 16th day of May 2001 Crompton Vinyl Additives GmbH By its Patent Attorneys bAVIES COLLISON CAVE