AU759954B2 - Stabiliser combinations for chlorine-containing polymers - Google Patents

Description

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ORIGINAL

COMPLETE SPECIFICATION STANDARD PATENT Applicant(s): Crompton Vinyl Additives GmbH Chemiestrasse 22 D-68623 Lampertheim Germany DAVIES COLLISON CAVE Patent Trade Mark Attorneys Level 10, 10 Barrack Street SYDNEY NSW 2000 0 0: 00*..

Address for Service: Invention Title: Stabiliser combinations for chlorine-containing polymers The following statement is a full description of this invention, including the best method of performing it known to me:- I-RA 5020 -1I- STABILISER COMBINATIONS FOR CHLORINE-CONTAINING POLYMElRS 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 f ollowing groups: ~tothe perchlorate compounds. gqlycidyl compounds. beta-dihetones, betn.ket esters. dihydropyridines. polydihydropyridlines. polyols, disaccharide :.alcohols. sterically hindered amines (tetraikylpiperidite. compounds). alkali :.~:aluminosilicofes. hydrotalcites ard alkali olumninocarbonatres (dowsonites). alkali- (or alkaline earth-) carboxylates,-(bi)carbonates oder -hdroxdsaniid t, lubricants or organotin compounds which ame suble for stabilising chlorinecontaining polymers, especially PVCPVC can be stabilised by a number of *:.:additives. Compounds of Ilead, barium and cadmium ame especially suitable for the purpose but are controversial today for ecological reasons or owing to their heavy metal content- (cf. "Kunstoffadditlvew (Pilastics additives). R. Gdchter/- R M0ler. Carl Hainser Verlag. Yd~ Edition. 1989. pages 303-311, and 01(unststoff IHowndbch PVC MPastics Handbook PVC). Volkime 2/1. W.Beckcer/.B3roun. Carl Hsanser Verlag. 2 "d Edition, 1985, pages 531-5313; and lKirk-Othmer-.

nEncyclopidia of Chemical TechnoloW. 4"h Ed.. 1994, Vol 12. Heat Stabilizers p.

1071-1091). Other effective stabilisers and stabilliser combinations that are free of lead-0 barium and cadmium ame therefore sought.compounds of formula -I have already been described in DE-PS 1694 873. EP 65 934 and EP 41479 and can We prepared in one or several process step(s) by known met hodslt has now been found that A) compounds of formula I: 0 YAN H2 T2 wherein R*l and R*2 are each independently of the other CI-Cizalkyl. C3- C6al1kenyI, C5-C8cycloalkyl that is unsubstituted or substituted by from I to 3 CI-C4alkyl. CI-C4alkoxy, C5-Cacycloalkyl or hydroxy groups or chlorine atoms, or C7-Cgpheflylalkyl that is unsubstituted or substituted at the phenyl ring by from I to 3 Cl-C4olkyl. C1-C4alkoxy, C5-C8cycloalkyl or hydroxy groups or chlorine atoms.

and R*1 and R*2 may additionally be hydrogen and C1-Cl2alkyl, and V is 5 or 0.

can be combined with 8) at least one conmpound from the following group: perchiorale, compounds and/or glycidyl compounds and/or beta-diketones. beta-kelo, esters and/or dihydropyridines, polydlihydropyridines and/or polyols. disaccharide alcohols and/or sterically hindered amines (tetraalkylpiperidine compounds) and/or alkali aluminosiIi cates (zeolites) and/or hydrotalcites and/or alkali aluminocarbonates (dawsonites) and/or, alkali- (or alkaline earth-) carboxylates.-(bi)carbonates oder -hydroxides, and/or antioxidants and lubricants and/or organotin compounds for the purpose of stabilising chlorine-containing polymers. especially PVC.

The present invention as claimed provides a stabiliser combination comnprising A) at least one compound of formula

I

0

N~

wherein and R1are each independently of the other C1-Cl2alkyl C3_ Coalkenyl. C-5-Cacycloolkyl .that is uhisubsti~gted or subsi1tated -by from I to 3 C-C40lkyll. CI-C4fl11kvy. CS-Cacycholkyl or by hyro.g~ or chlorihg.

atn g.o C7-Chen)4Okyl that is -Ufsubsti~uted or susiwe'tthe pheny ring I* frm It 3 CC 4 CZ-C4alkoxy CS.Cacyc~loalkyl- or by hydroxy -groups or chdrne atom.and 'R*I and R*2 may additionall~y be hydrogen and CI-Ci2dlkyI. and V is S or' 0. aiid 8) at least one alkali aluminosilicate (zeolite) compound.

For compounds of formula 1.

CI-CaIAlkyl is. for example; methyl, ethyl. fi-propyl. isopropyl. iso-, sec- or .00: tart-butyl.

CI-C12Alkyl is. for example. in addition to the radicals just mentioned.

pentyl. hexyl. heptyl, octyl.'2-ethylhexyt. isooctyl. decyl, nonyl. undecyl or dodecyl.

C1-Cq~lkoxy is, for example. methoxy, ethoxy, propoxy. isopropoxy. butoxy or isabutoxy.is, for example. cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

C7-C9Phenylalkyl is. for example. berizyl. 1- or 2-phenylethyl. 3-phenyipropyt, a.a-dimethylbenzyi or 2 -phenytisopropyl, preferably benzyl.

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

C3-C6AlkenyI is. for example. vinyl. ollyl. methallyl. 1-butenyl or 1-hexenyl.

preferably allyl.

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

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

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

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

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

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

R

2

R

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

S*.

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

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

Ethers of that type are derived, for example, from acyclic alcohols, such as ethylene glycol, diethylene glycol and higher poly(oxyethylene) glycols, propane-1,2-diol, or poly(oxypropylene) glycols, propane-1,3-diol, butane-1,4diol, poly(oxytetramethylene) glycols, pentane-1,5-diol, hexane-1,6-diol, hexane-2,4,6-triol, glycerol, 1,1,1-trimethylolpropane, bistrimethylolpropane, pentaerythritol, sorbitol, and from polyepichlorohydrins, butanol, amyl 6 alcohol, pentanol, and from monofunctional alcohols, such as isoocl-anol, 2ethyihexanol, isodlecanol and C7-C9alkanol and C9-Cllalkanol mixtures.

They are, however, also derived, for example, f rom cycloaliphal'ic alcohols, such as 1,3- or 1 ,4-dihydroxycyclohexane, bis(4-hydroxycyclohexyl)methane, 2 ,2-bis(4-hydroxycyclohexyl)propane or 1 ,1-bis(hydroxymethyl)cyclohex-3ene, or they have aromatic nuclei, such as N,N-bis(2-hydroxyethyl)ani line or p,p'-bis(2- hydroxyethylami no)di phenylmethane.

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

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

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

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

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

V) Epoxide compounds containing a radical of formula I wherein R1 and R-3 together are -CH2-CH2- and n is 0 are bis(2,3-epoxycyclopentyl) ether, 2,3-epoxycyclopentylglycidyl ether or 1,2-bis(2,3epoxycyclopentyloxy)ethane. An epoxy resin containing a radical of formula I .7 wherein R1 and R3 together are -CH2-CH2- and n is I is, for example, 3,4epoxy-6-methylcyclohexanecarboxyl ic acid (3 ,4'-epoxy-6'methylcyclohexyl)-methyl ester.

Suitable terminal epoxides are, for example TM denotes 8): a) liquid diglycidyl ethers of bisphenol A, such as AralditeMGY 240, AralditeMGY 250, AralditeTmGY 260, AralditeTmGY 266, AralditeTmGY 2600, AraldliteTMAMY 790; b) solid diglycidyl ethers of bisphenol A, such as AralditeTMGT 6071, AralditeTmGT 7071, AralditeTmGT 7072, AralditeTmGT 6063, AralditeTMGT 7203, AralditeTMGT 6064, AralditeTmGT 7304, AralditeTMG6T 7004, AralditeTMGT 6084, AralditeTmGT 1999, AralditeTMGT 7077, AralditeTM1GT 6097, AralditeTmGT 7097, AralditeTMGT 7008, AralditeMGT 6099, AralditeTmGT 6608, AralditeTMGT 6609, ArclditeTMGT 6610; c) liquid diglycidyl ethers of bisphenol F, such as AraldliteTMAGY 281, AralditeTmPY 302, AralditeTAPY 306; d) solid polyglycidyl ethers of tetraphenylethane, such as C& Epoxy ResinTmOl63; solid and liquid polyglycidyl ethers of phenolformaldlehyde novolak, such as EPN 1138, EPN 1139, GY 1180, PY 307; f) solid and liquid polyglycidyl ethers of o-cresolformaldehyde novolak, such as ECN 1235, ECN 1273, ECN 1280, ECN 1299; g) liquid glycidyl ethers of alcohols, such as ShelTM glycidyl ether 162, AraldliteTmDY 0390, AraldliteT"DY 0391; h) liquid glycidyl ethers of carboxylic acids, such as ShellTCarclura E terephthalic acid, ester, trimellitic acid ester, ArolditeTMPY 284; i) solid heterocyclic epoxy resins (triglycidyl isocyanurate), such as AralditeTM PT 810; j) liquid cycloaliphatic epoxy resins, such as AralditeTMCY 179; k) liquid N,N,O-triglycidyl ethers of p-ciminophenol, such as AralditeTmMY 0510; 1) tetraglycidyl-4,4'-methylenebenzamine or N,N,N,N'-tetraglycidyldiam inophenyl methane, such as AralditeTmMY 720, AralditeTmMY 721.

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

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

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

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

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

Beta-diketanes, beta-keto esters 1,3-Dicarbonyl compounds that can be used may be linear or cyclic dlicarbonyl compounds. Preference is given to the use of dicarbonyl compounds of the following formula: R'iCO CHR2'-COR'3 wherein R-'I is C1-C22alkyl, C5-Clohydroxyalkyl, C2-Cl8alkenyI, phenyl, phenyl substituted by OH, CI-C4al kyl, CI-C4alkoxy or by halogen, C7-Clophenylalkyl, C5-Cl2cycloalkyl, C5-Cl2cycloalkyl substituted by C1-C~alkyI, or is a group S-R'6 or -R.5-O-R'6, R'2 is hydrogen, Ci-C8alkyl, C2-CI201kenyl, phenyl, C7-Cl2alkylphenyl, C7- Clophenylalkyl or a group -CO-R'4, R'3 has one of the meanings given for Ril or is CI-Cl8alkoxy, :R'4 is CI-C4alkyl or phenyl, is CI-Cloalkylene and R'6 is C1-Cl2alkyl, 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.

Ril and R'3 as alkyl may be, especially, Cl-Cl 8alkyl, such as methyl, ethyl, npropyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl. decyl, dodecyl or octadecyl.

Ril 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, allyl, 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, chlorophenyl or dichlorophenyl.

.Ri and R'3 as phenylalkyl are especially befizyl. R'2 and R'3 as cycloalkyl or alkylcycloalkyl are especially cyclohexyl or meihylcyclohexyl.

R'2 as alkyl may be, especially, Cl-C4alkyl. Re 2 as C2-Cl2alkenyl may be, especially, allyl. R'2 as alkyiphenyl may be, especially, tolyL R'2 as phenylalkyl may be, especially, benzyl. R'2 is preferably hydrogen. R'3 as alkoxy may be, for example, methoxy, ethoxy. butoxy, hexyloxy, octyloxy, dodecyloxy, tridecyloxy, :9 tetradecyloxy or octadecyloxy. R'5 as CI-Cioalkylene is especially C2- C4alkylene. R'6 as alkyl is especially C4-Cl2lkyI, such as butyl, hexyl, oclyl, decyl or dodecyl. R'6 as alkylphenyl is especially tolyl. R'6 as phenylalkyl is **.*especially benzyl.

Examples of 1,3-dicarbonyl compounds of the above formula and their alkali metal, alkaline earth metal and zinc chelates are acetylacetone, :butanoylacetone, heptanoylacetone, stearoylacetone, palmitoylacetone, lauroylcicetone, 7-tert-nonylthio-heptane-2 .4-dione, benzoylacetone, di benzoylmethane, lauroylbenzoylmethane, palmil-oyl-benzoylmethane, stearoylbenzoylmethane, isooctylbenzoylmethane, tribenzoylmethane, bis(4-methylbenzoyi)methcine, benzoyl-pchlorobenzoylmethane, bis(2- hydroxybenzoyl)methane, 4-methoxybenzoylbenzoylmethane, bis(4-methoxybenzoyl)methane, 1 -benzoyl-l1-acetylno none, benzoyl-acetylphenylmethane, stearoyl-4-methoxybenzoylmethane, bis(4-tertbutyl benzoyl)methane, benzoyl-formylmethane, 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, triacetylmethane, acetoacetic acid methyl, ethyl, hexyl, octyl, dodecyl or octadecyl ester, benzoylacetic acid methyl, ethyl, butyl, 2-ethyihexyl, dodecyl or octcidecyl ester, and propionyl- and butyryl-cicetic acid CI-Cl8alkyl ester.

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

Preference is given to 1,3-diketo compounds of the above formula wherein R'i is C1-Cl8alkyI. phenyl, phenyl substituted by OH, methyl or by methoxy, C7- Clophenylalkyl or cyclohexyl, R'2 is hydrogen and R'3 has one of the meanings given for Ri.

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

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

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

*H

3 CNHI CH 3

CO

2

CH

3 C0 2

C

2

H

5

CO

2 Cu 12 5 or CO 2

C

2

H

4

SC

2

H

25 Suitable polydihydropyridines are especially compounds of the following formula 0 0 0 11 wherein T is C1-C22alkyl that is unsubstituted or substituted by Ci- C18alkoxY, CI-Cl8alkylthio, hydroxy, acryloyloxy. methacryloyloxy, halogen, phenyl or by naphthyl; that is unsubstituted or substituted by Ci-Ciakyl, Cl-Cl8alkoxy or by halogen and that may also be heterocyclic; C3-ClOalkenyl, CH3-CO-CH2-CO-OR-, CH3-CO-CH2-COO-R', CH3- C(NR"'2)--CH-COOR- or CH3-C(NR'2)=CHCO-0 L has the same meanings as T or is a tri- or poly-valent radical from an unsubstituted or Cl-Cl 2a1 koxy-, Cl-Cl 2thioalkoxy-, C6-ClOarYl-. Cl- Cl2carboxy- or hydroxy-substituted straight-chained or branched alkyl group, m and n are numbers from 0 to k is 0ori1, jis anumber fromlIto 6and the conditions j(k+ m >lIandm +n >O0are satisfied, R and R are each independently of the other methylene or phenylene or an 00 0~ alkylene group of the type -(-CpH2p-X-)t CpH2p- that is unsubstituted or *.:carries substituents from the series C1-Cl2alkoxy, CI-Cl2thioalkoxy, C6es.. Cioaryl, C1-Cl2carboxy and hydroxy, p is from 2 to 18, set* ea* t isfrom 0to X is oxygen or sulfur, or, when k isO0 and j R and R' together with L form a direct bond, R" is hydrogen, or Cl-Cl8alkyl, C2-Cl8alkoxycarbonyl or C6-Cloaryl each of which is unsubstituted or substituted by one or more C1-Cl2alkyl, C1-C8alkoxy, 0 halogen or N02 substituents, and the two radicals are identical or different and are hydrogen, Cl- C18alkyl, CI-C18-hydroxyalkyl or Cl-Cl~alkoxyalkyl or together are uninterrupted or 0-interrupted C3 -C5al kylene, 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-dihydropyridine-3carboxylate] is especially preferred.

Die (Poly-)Dihydropyridine kiinnen im chlorhaltigen Polymer zweckmiBig zu 0,001 bis 5 und insbesondere 0,005 bis 1 Gew.-Teilen, bezogen auf dos Polymer, angewandt werden.

Polyols, disaoccharide alcohols Examples of suitable compounds of that type are: pentaerythritol, dipentaerythritol, tripentaerythritol, bistrimethylolpropane, bistrimethylolethane, trismethylolpropane, inosite, polyvinylalcohol, sorbitol, maltite, isomaltite, lactite, lycasin, mannitol, lactose, leucrose, tris(hydroxyethyl) isocyanurate, palatinite, tetramethylolcyclohexanoI, tetramethylocyclopentanol, tetramethylocyclopyranol, glycerol, diglycerol, polyglycerol, thiodiglycerol or 1-0-a-D-glycopyranosyl-b-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 advantageously from 0.1 to 20, and especially from 0.1 to 10, parts by weight, based on 100 parts by weight PVC.

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

H

3 C N

CH

H

3C They may be compounds of relatively low molecular weight (<700) or of S relatively high molecular weight. In the latter case they may be oligomeric or polymeric products. Preference is given to tetramethylpiperidine compounds having a molecular weight of more than 700 that contain no ester groups.

Especially important as stabilisers are the following classes of tetramethylpiperidine compounds.

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

a) Compounds of formula II HC

CH

3 n

(II),

wherein n is a number from 1 to 4, preferably 1 or 2, R is hydrogen, oxy, Cl-C12alkyl, C3-C8alkenyl, C3-C8alkynyl, C7-C12aralkyl, C1-C8alkanoyl, C3-C5alkenoyl, glycidyl or a group -CH2CH(OH)-Z, wherein Z is S hydrogen, methyl or phenyl, R 1 being preferably C1-C4alkyl, allyl, benzyl, acetyl S or acryloyl, and, when n isl, R 2 is hydrogen, C1-Cl8alkyl that is uninterrupted or interrupted by one or more oxygen atoms, cyanoethyl, benzyl, glycidyl, a monovalent radical 00* 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 o I atoms, a cycloaliphatic carboxylic acid having from 7 to 15 carbon atoms, an aPunsaturated carboxylic acid having from 3 to 5 carbon atoms or an aromatic carboxylic acid having from 7 to 15 carbon atoms, and, when n is 2, R 2 is CI-C12alkylene, C4-Cl2alkenylene, xylylene, a divalent radical of an aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid, dicarbamic acid or phosphorus-containing acid or a divalent silyl radical, preferably a radical of an aliphatic dicarboxylic acid having from 2 to 36 carbon atoms, a cycloaliphatic or aromatic dicarboxylic acid having from 8 to 14 carbon atoms or an aliphatic, cycloaliphatic or aromatic dicarbamic acid having from 8 to 14 carbon atoms, and, when n is 3, R2is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, an aromatic tricarbamic acid or a phosphoruscontaining acid or a trivalent sily radical and, when n is 4, PR 2 is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.

When any of the substituents are C1-Cl2alkyl, they are, for example, methyl, ethyl, n-propyl, n-butyl, sec-bulyl, tert-bulyl, n-hexyl, n-octyl, 2-ethyl-hexyl, 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 R1is C3-C8alkenyl, it may be, for example, 1-propenyl, ally, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl or 4-tert-butyl-2-butenyl.

Ras C3-C8alkynyl is preferably propargyl.

As C7-Cl2aralkyl. R 1 is especially phenethyl and more especially benzyl.

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

When R 2 is a monovalent radical of a carboxylic acid, it is, for example, an acetic acid, caproic acid, stearic acid, acrylic acid, methacrylic acid, benzoic: acid or 8-(3 ,5-di-tert-butyl-4-hydroxyphenyl)-propio nic acid radical.

When R2is a divalent radical of a dicarboxylic acid, it is, for example, a malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic: acid, maleic acid, phthalic: acid, dibutylmalonic acid, dibenzylmalonic acid, di -tert-butyl-4-hydroxybenzyl)-maloni c acid or bicycloheptenedicarboxylic acid radical.

*.When Ris 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 tetracirboxylic acid, it is, for example, the tetravalent radical of butane- 1,2,3,4-tetracarboxyli c 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-tetramethylpiperidi ne 2) 1-allyl-4-hydroxy-2 ,2 ,6 6-tetramethylpi peridine 3) 1-benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine 4) 1 -(4-tert-butyl-2-butenyl)-4-hydroxy-2 .2,6 .6-tetramethylpiperidi ne 4-stearoyloxy-2 ,2 ,6,6-tetramethylpi peridine 6) 1-ethyl-4-salicyloyloxy-2,2 .6,6-tetramethylpiperidine 7) 4-methacryloyloxy- 1,2,2,6 .6-pentamethylpi peridi ne 8) 1,2,2 .6,6-pentamethylpiperid; n-4-yl-B-(3 .5-di -tert-buyl-4-hydroxyphenyl) propionate 9) di(1-benzyl-2,2 ,6 .6-tetramethylpi peridi n-4-yl) malei nate di(2,2,6,6-tetramethylpiperidin-4-yI) succinate 11) di(2,2,6,6-tetramethylpiperidin-4-yl) gllutarate 12) di2266t.rmtypieii--l dp 12) di(2,2,6,6-tetramethylpiperidin-4-yl) adipate 13) di(12 ,26,6-etamethylpiperidin-4-y) sebcate 15) di(l,2,3,6-tetramethyl-2,6-diethylpiperidin-4-yl) sebacate 16) di(1-allyl-2,2 .6.6-tetramethylpiperidi n-4-yl) phthalate 17) 1-propargyl-40-cyanoethyloxy-2.2 ,6,6-tetramethylpiperidi ne 18) 1 -acelyl-2 .2,6 .6-tetramnethylpiperidi n-4-yI acetate 19) trimellitic acid tri(2,2,6,6-tetrimethylpiperidin-4-yl) ester 1 -acryloyl-4-benzyloxy-2 ,2,6 .6-tetramethylpiperidi ne *21) diethylmalonic acid di(2,2,6,6-tetramethylpiperidin-4-yl) ester 22) dibulylmalonic acid di(1 ,2,2.6,6-pentamethylpiperidin-4-yl) ester 23) butyl-(3 .5-di-tert-butyl-4-hydroxybenzyl)-malonic acid di(1 ,2 2,6,6pentarnethylpiperidin-4-yl) ester 24) dibenzyl-malonic acid di(l.

2 ,2,6,6-pentamethylpiperidin-4-yl) ester dibenzyl-malonic acid di(1,2,3 ,6-tetramethyl-2 .6-diethyl-piperidi n-4-yl) ester 26) hexaine-1'6-bis(4-carbamoyloxy- i-n- butyl- 2,2,6,6-tetramethyl-piperidi ne) 27) toluene-2',4'-bis(4-carbamoyloxy-1 -n-propyl-2 ,2,6 .6-tetramethylpiperidine) 28) dimethyl-bis(2.2 .6.6-tetraimethylpiperidi n-4-oxy)si lane 29) phenyl-tris(2 .2 6,6-tetramethylpiperidi n-4-oxy)si lane tris(1-propyl-2 .2 6,6-tetramethylpiperidin-4-yl) phosphite 31) tris(1-propyl-2 ,2 .6 6-tetramethylpiperidin-4-yl) phosphate 32) phenyl-[bis(1 .2.2.6,6-pentamethylpi peridin-4-yl)] phosphonate 33) 4-hydroxy-1,2,2.6 .6-pentamethylpiperidine 34) 4-hydroxy-N-hydroxyethyl-2 .2,6 6-tetranethylpiperidi ne 4-hydroxy-N-(2-hydroxypropyl)-2.2 .6.6-tetramethylpiperidi ne 36) 1-glycidyl-4-hydroxy-2 ,2 .6,6-tetramethylpi peridine b) Compounds of formula (II) EKE §:H3I) wherei ishaerefinefoa) R3~ is hydrogen, C1-Cl2alkyl, C2-C5hydroxyalkyl, C5-C7cYcloal kyl C7- C8aralkyl, C2-Cl8alkanoyl. C3-C5alkenoyl or benzoyl. and, when n is 1, R4is hydrogen, C1-Cl8alkyl, C3-C8alkenyl, C5-C7cycloalkyl, Cj- C4alkyI substituted by a hydroxy, cyano, alkoxyccirbonyl 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)-C-f2- group or a group -CH2-CH(OH)- CH2-O-b)-O-, wherein D) is C2-Cloalkylene, C6-Clsarylene or C6- C12cycloalkylene, or, with the proviso that R3is not alkanoyl. alkeiioyl or benzoyl, R4may also be a divalent radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid or also the group -CO- or, when n is 1, R 3 and R 4 together may be the divalent radical of an aliphatic, cycloaliphatic or aromatic 1,2- or 1,3-dicarboxylic acid.

When any of the substituents are C1-C12- or CI-CIB-alkyl they are as already defined above under a).

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

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

R

3 is especially 2-hydroxyethyl or 2-hydroxypropyl.

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

When R 4 is C2-C80lkenyl, then it is, for example, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl or 2-octenyl.

R4as C1-C4alkyll substituted by a hydroxy, cyano, alkoxycarbonyl or carbamide group may be, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2cyanoethyl, methoxycarbonylmethyl, 2-ethoxyccirbonylethyl, 2aminocarbonylpropyl or 2-(dimethylami nocarboriyl)-ethyl.

:When any of the substituents are C2-Cl2alkylene, they are, for example, octamthylee, deamethlenherxamethyetenee When any of the substituents are C6-Cl5arylene, they are, for example, o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.

As C6-Cl2cycloalkylene, b is especially cyclohexylene.

0. The following compounds are examples of polyalkylpiperidine compounds of that class: 37) N,N-bis(2 ,2 ,6,6-tetrimethylpiperidin-4-yI)hexamethylene-1 ,6-diami ne 38) N,N-bis(2 ,2 ,6,6-tetramethylpiperidi n-4-yl )hexamethylene-1 ,6-diacetamide and 1,6-diformamide 39) I-acetyl-4-(N-cyclohexylacetamido)-2 ,2 ,6,6-tetramethy Ipiperidi ne 4- benzoylamino-2 ,2 ,6,6-tetramethylpi peridi ne 41) N,N-bis(2 ,2 ,6,6-tetramethylpiperidin-4-yl butyl -adi pamide 42) N,N'-bis(2,2 .6 6-tetramethylpiperidi n-4-yI)- N,N'-dicyclohexyl-2 hydroxypropylene-1 .3-diami ne 43) NN-bis(2,2 .6,6-teiramethylpi peridi n-4-yl)- p-xylylene-diami ne 44) N,N'-bis(2 .2,6 .6-tetramethyl pi peridi n-4-yI)succi ne-diamide N-(2 ,2 ,6,6-tetramethylpiperidin-4-y)-B-ami nodi propionic acid di(2 ,2 ,6,6tetramethylpiperidin-4-yl) ester 46) the compound of the formula

O.H

3 OH 3

CH

C

4

H

9 CH--N N-CH 2 -OH(QH)-CHi---

OH

3

OH

3

OHT-C-CH

3

OH

3

OH

3 CHS- N N-CH 2 -CH(OH)-CHF--0

OH

3

OH

3 9* 47) 4-(bis- 2-hydroxyethyl-ami no)- 1,2,2,6,6- pentamethylpiperidi ne 48) 4-(3-methyl-4-hydroxy-5-tert-butyl-benzo ic acid amido)-2 .2,6,6tetramethylpiperidline 49) 4-methacrylamido-1 ,2 .2.6,6-pentamethylpiperidi ne c) Compounds of formula (IV) [Ri-N 4

(IV),

n wherein n is the number 1 or 2, Pis as defined under a) and, when n is 1, R 5 is C2-C8alkylene or C2-C8hydroxyllkylene 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-e-thyl-propylene or 2-ethyl-2hydroxymethyipropylene.

As C4-C22acyloxyalkylene, R 5 is. for example, 2-ethyl-2acetoxymethyipropylene.

The following compounds are examples of polyalkylpiperidine compounds of that class: 9-aza-8 ,8,10,1O-tetramethyl-1 .5-dioxaspiro 51) 9-aza-8,8 ,10,1-tetramethyl-3-elhyl-1 .5-d 52) 8-aza-2 ,7,7,8,9,9-hexamethyl-1 .4-dioxaspiro 53) 9-aza-3-hydro ynethyl-3-ethyl-8 .8,9 .10,10-pentamethyl- dioxaspiro 54) 9-aza-3-ethyl-3-acetoxymethyl-9-acetyl-8.8 ,1,1-tetramethyl-1 2,2,6 .6-tetramethylpiperidinie-4-spi ro-2' -(',3'-dioxane)-5' "-dioxane)-2"-spiro-4' '".6',6"'-tetramethylpiperidi ne).

d) Compounds of formulae VA, VO and VC *HA RH 1

(VA)

K R7

H

3 C C 3 0 n H 3 C T H3 1 3 C H 3 H

(C

R

1 isaNefnduneO) C R groupn if the fombra or of2,frua-(H)--OQ wherin pas 1efore2 ande QasC), lylo hnl ad hnnis2 7 i 2 C6li haydrgen, -Ci2lenyl, C6-Cl, 2arylen,gyl o ro C2-CH(lOH)-CH2-O ad- -H-H)C2,wherei ns1,R ishyrgn C2-Cl~alkyl-ken 6-lar kl,C- Z is haydrge, C-Cl~aydroxallyl, benzyl C-Clalkayl, or benoyl, iandrT2 Sa~reoahu nepenl of the foml (H -ohe r dog te formulal -Co unubsitutd o whri halo- I or andlQsusu C6-Cl~rlo 7Caalkyl, or Tieyl andwenis2 7s T2togethye wthth C4clarbonylnC-aye ao thtbidrte om a CH-CH(OcyCloalane ing W-hen anyof he-H- whbeients aeC-Clalkyle ae, f~rlexae, metyl etihyd-ropyn, nl-butayl, ecbuyl, tertbyl, -hexlanyl nortl -ehyhyl, n-an T nonyl, n-decyl, n-undecyl or n-dodecyl.

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

When any of the substituents are C2-C6alkoxyalkyl, they are, for example, methoxymethyl, ethoxymethyl, propoxymethyl, tert-butoxymethyl, ethoxyethyl, ethoxypropyl, n- butoxyethyI, tert- butoxyethyl, isopropoxyethyl or pro poxypropyl.

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

As C7-Cgaralkyl, R 7, 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 R7is C2-C4hydroxyalkyl, it is, for example, 2-hydroxyethyl, 2hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

C6-CIOaryl, R 7 Ti and T2 are especially phenyl, a- or B-naphthyl, which are unsubstituted or substituted by halogen or by Ci-C4alkyl.

~:When R7 is C2-Ci2alkylene, it is, for example, ethylene, propylene, 2,2dimethyipropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.

As C4-Ci2alkenylene, R 7 is especially 2-butenylene-, 2-pentenylerie or 3hexenylene.

When R7 is C6-Ci2arylene, it is, for example, m- or p-phenylene, 1,4- :naphthylene or 4,4'-diphenylene.

When Z~ is C2-Ci2alkanoyl, it is, for example, propionyl, bulyryl, octanoyl, dlodecanoyl, but preferably acetyl.

b as C2-ClOalkylene, C6-Ci5arylene 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-tetramethylspiro[4.5]decane-2,4-dione 57) 3-n-octyl-i,3 ,8-triaza-7,7,9,9-tetramehylspiro4.5]decane-2 ,4-dione 58) 3-allyl-1,3,8-tricza-1 ,7,7,9,9-pentamethylspiro[4.5]deccine-2,4-dione 59) 3-glycidyl-l ,3 ,8-triazo-7,7,8,9,9-pentamethylspiro[4.5]decane-2 ,4-dione 1,3,7,7,8,9 ,9-heptamethyl-193 ,8-triazaspiro [4.5]decane-2 ,4-dione 61) 2-isopropyl-7,7,9,9-tetramethyl--oxci-3,8-diaza-4-oxo-spiro[4.5]decane 62) 2 ,2-dibulyl-7,7,9,9-tetramethyl-1-oxa-3,8-diazci-4-oxo-spiro[4.5]decane 63) 2,2 ,4,4-tetramethyI-7-oxa-3 ,20-diazcx-21-oxo-dispiro[5.1.1 l.2]henicosxne 64) 2- bulyl-7,7,9 .9-tetramethyl- 1-oxa-4,8-diaza-3 8-acetyl-3-dodecyl-1.3 ,8-triaza-7,7,9 ,9-tetramethylspiro(4.5]decane-2 .4dione or the compounds of the following formulae:

CH

3

OH

3 CH 3

OH

3 NH-C=O0=0 CHi-N -C N-OH 3 -PZ~ CN -CH 2

CH(OH)CH

2

-OCH

2

-OH(OH)CH

2 2 -N -CH

OH

66)3 67) OH 3

OH

3

OH

3

OH

3 NH-= 0C N S**S I I N-OH 3 S- -(CH 2 OH 3

OH

3 0

OH

3

OH

3 68) OH 3

OH

3

OH

3

OH

3 HN 1//I

NH

OH

2

H

3 OH3 I

'CH

*HO O H 3 69) HNO-C

(OH

2 1 1 OH 3

OH

3 00 12 2 e) Compounds of formula VI1 N N (VI), wherein n is the number I or 2 and R 8 is a group of the form ula

CH

3 CH3 -E-(A)N-R1

CH

3

CH

3 wherein R1 1 is as defined under a) E is -0-or -NR A is C2-C6alkylene or -(CH2)3-O- and x is the number 0 or 1, R922 is identical to R8or is one of the groups -NR 11

R.

12

-OR

13 -NHCH2OR 13 or -N(CH20R 13 )2, e*when n Rio is identical to R 8 or R 9 and, whenn Rio is a group -E-Bwherein B is C2-C6alkylene that is uninterrupted or interrupted by -N(R 11

)Y,

P.1is C1-Cl2alkyl. cyclohexyl. benzyl or C1-C4hydroxyalkyl or a group of the formula R CH 3 CH 2

R

N-R

CH

2

R

R

12 is CI-Cl2Qlkyl, cyclohexyl, benzyl, CI-C4hydroxyalkyl and

R

13 is hydrogen, C1-Cl2alkyl or phenyl, or

R-

11 and R 12 together are C4-C5alkylene or C4-C5oxaalkylene, for example -C H 2 C H 2 o 4 .H C H r Ro

-CH

2

CH

2 2 -CFI CHare a group of the formula -CH CH 2 0o C 2 H N

F

-CH

2 CH 2

-CF-CR-

or alternatively R 11 and R 1 are each a group of the formula

CH

3

OH

3 4 H9 N HN N-f *-NH-A- N {N

CH

3

OH

3 4

H

9

-N

C H39 C H

CH

3 N OH 3 When any of the substituents are Cl-C1201kyl, they are, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl. n-octyl, 2-ethylhexyl, nnonyl, n-decyl, n-undecyl or n-dodecyl.

When any of the substituents are C1-C4hydroxyalkyl, they are, for example, 2 -hydroxyethyl, 2 -hydroxypropyl, 3-hydroxypropyl, 2-hydroxybulyl or 4hydroxybutyl.

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

When R1and R 12 together are C4-C5Qlkylene or C4-C5oxaalkylene, they are, for example, tetramethylene, pe ntamethylene or 3 -oxapentamethylene.

The compounds of the following formulae aire examples of polyalkylpiperidine compounds of that class:

CH

3 H C I CH3 3

N

7)

H

3 C q

H

3 N-C H (CH3CH N -N N(CH 2

CH

3 2

N(C

4

H

9 2

OH

3

OH

3 NJ 'N OH 3 CH 3 71) C 2

H

5 -N

N-

1 1 N

N-C

2

H

OH

3

OH

3 2H 0 2

H

R H 3CCHH 00 00 00

CH

3 OH 3

CH

2 -0H 2

NH

73) CH 3

CH

3

NHCH

3

H

3 HN 0H 2

-CH

2 -NH NHC2-H

CH

3

OH

3 CH, m HN NNHCHp4H-OCH,H CH, CH,

N.

74) 14.-ILIl 2 -(CH 2 3

-NH-R

OH

3 CH 3 N NH N N

OH

3

CH

3 C4H9-N CH 3-1OH 3 ,wherein R is

CH-"

76) R R R-NH(0 2 3

(CH

2

-C

2 3

N

OH

3 wherein R=

CH-'

CH

3

CH

3 CHR ROH

(CH)-NI-(CH

2 N- (H 2

)-N-R

OH

3 OH 3

N

N N-OH 3 N N wherein R CH 3 W H 3

OH

3 78) CH 3 79) 9*

CH

3

C

4

H

9 CH/ OH 3 GH-I

OH

3

CH

2 -CH=0H 2

H

3 C N C 3 H C OH 3

N-C

4

H

9

H

3 C OH 3 N'0YkN

CH

3

OH

3

H

2

C=HC-H

2 C-NI N1 N

N-CH

2

-CH=CH

2

U

4

H

9 4

H

9

H

3 C C 3 OH 3

OH

3 f) Oligomeric or polymeric compounds, the structural repeating unit of which contains one or more 2,2,6,6-tetraalkylpi peridine radicals of formula especially polyesters, polyethers, polyamides, polyamines, polyurethaines, polyureas, po lycmi notriazi nes, poly(meth)acrylates, pa lysi loxanes, poly(meth)acrylamides and the copolymers thereof that contain such radicals.

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

CH

3 OH 3 *0 0 81) [-oH-H 2 H2-OH-N *S

H

3

OH

3

CH

3 CH, CH, CH, 0 00 82) CI4-CH,-N 0 C 0 -HCHO- C CH, CH, CHmH

CH

3

C

2 HS CHI CA,~ 0 0 83) Ei NH-(CH 2 3 HC(, N N -CI-NH-Cc

CH

3 C H 3

CH

3

C

2

H

5 CH 3 CH

OH

3 OH 3 I I 37H~-L;CH-I2-LO-LH3 I~ N 84) rN IL (CH 2 6

N

m OH 3 OH 3 CH O H 3 OH H 3 CH N H H 3

O

3 C H 3 N 0CH 2

-CH(OH)-OH

2 OHmH

OH

3 N OH3

H

86)

OH

3 OH 3 OH 3

OH

3 0 CAH 0 N-CHCH=C-H -N II I 3 3H 87) NC4H9 H 31- OH3

CCH

3

N

CH

3 MI CH3

H

3

O

3 O 3

CH

3 0 0 88) N-H 2o-C- (0H 2 4

-C

OH

3

OH

3 OH 3 OH 3 0 CAH 0 OH -O 3

H

2 -N _0 IJ

OH

3

OH

3

H

3 OHc 3

O

3 m 0

N-OH

3

*H

OH

3 I 91) I~ O 3

O

3 m 0 H13-N

N-OH

3

OH

3

O

3 92) N (H) m

OH

3

OH

3

OH

3

O

3

OH

3 N H 3

OH

3 N H 3 H H L- (OH 2 6 N -C2C2 :9 3 O HmH H H

H

3 NNN. OH 3

OH

3 N~ OH 3

HH

0 0 94)m C H 3

OH

3

OH

3

OCH

3

OH

3 Is'J OH 3

OH

3 N~ OH 3

HH

96) wherein R H or CH3 **ac S S

H

3

C-

,CH 3 CH 3 wherein R=

HC

4 N N N(R) C 4 H 9 and R'= or H (obtainable by reacting the reaction product of trichiorotriazine and NH2- (CH2)3-NH-(CH2)2 -(CH2)3-NH2 with 4-N-butyl- 2,2,6 .6-tetramethylpiperidi neI Of those classes, classes e) and f) are especially suitable, especially those tetraalkylpiperidine compounds that contain s-triazine groups. Also especially suitable aire 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 Chemie", Vol. VII, p. 233-237, 3 rd Ed., Thieme Verlag Stuttgart 1971). There may be used as starting material for the reaction with various N-piperidylamines cyanuric chloride, diamino-chloro-l.3 ,5-triazine or variously substituted bisdialkylami nochloro- 1,3 .5-triazines or dialkyklsuino- or alkylamino-dichloro-1.3 ,5-triazi nes.

Technically important examples of tetra' and penta-alkylpiperidine compounds are: bis(2 .2.6A-tetramethyl-pi peridyl) sebacate, bis(2 .2,6,6tetramethyl-piperidyl) succipate, bis(1,2,6 .6-pentamethylpiperidyl) sebacate, n-butyl-3 .5-di-tert-butylA -hyd oxybtizyl-alonic acid bis(1,.2,,6-.

pentamethylpiperidyl) ester, the condlensation product of 1-hydroxyethyl- 2,2,6,6-tetramethyl-4-hydroxy-piperldine and succinic acid, the. condensation product of N.N4-bis( 2 2 6 6 -tetramethyl-4-piperidyl)-hexamethylenediamine and 4-tert-octylamino-2 ,6-dichloro-1 .3 ,5-s-triazi ne, tris(2.2 ,6,6-tetrameth'yl-4benzoyl-2 ,2,.66-tetrmeth ylp'pp*dins 4-stearyloxy-2, 6,6tetramethylpiperidine, bis(t,246 .6-pntmethylpiperdyl)-2-n-butyl-2-(2hydroxy-3,5-di-tert-butylbeazyl) .malonate. 3-n-octl-7,7,9,9-tetramethyl- 1,3 ,8-triazaspiro[4.5deane-2,4!-dlone, bis(l-octyloxy-2 ,2 .6,6tetramethylpiperidyl) sebacate, bis(1-oclyoxy-2 ,2 .6,6-tetramethylpiperidyl) succinale, the condensation product of NN'bis(2.2,6,6-tetramethyl-4pi peridyl)hexamethylenedlamine and 4-morpholino-2,6-dichloro-1 .3 the condensation product of 2 -chloro-4,6-di(4-n-butylamino-2 ,2 .6,6- *::teiramethylpiperidyl)-1,3,5-triazine, and l1, 2 -bis(3-aiminopropylamino)ethane, the condensation product of 2-chloro-4,6-di(4-n.-butylami no- ,2 ,2 .6,6pentamethylpiperidyl)-1,3,5-ti'zn Jf.-nd 1 2 -bis(3-aminopropylami no)ethane, 8acetyl-3 -dodecyl-7,7,9,9-*ttram .ethyl 1,3 .8-triazaspiro [4.5]decane-2 ,4-dio ne, 3 -dodecyl-1I-(2 2 6 6 -tetramethyl-4-piperidyl)pyrro lid i ne-2 ,5-dione, 3-dodecyli-cl ,2,2 ,6,6-pentamethyl-4-piperidyl)-pyrrolidine-25dione..

Instead of a single sterically hindered amine, it is possible within the scope of the present invention also to use a mixture of different sterically hindered amines.

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

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

Compounds from the hydrotalcite series can be described by general formula

VII

M

2 1 I-x M3+x(OH)2 (Ab-x/b d H20 (VII) wherein

M

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

:M

3 AI, or B, An is an anion having the valency n, e" b is a number from 1 to 2, 0 <x E 0.5, and m is a number from 0 to Preferably, An OH-, C104-, HC03-, CH3COO-, C6H5COO-, C03 2 (CHOHCOO)22-, (CH2COO)22-, CH3CHOHCOO-, HPO3-or HP04 2 Examples of hydrotakcites are A120O.MgO.C02.12H-20 Mg4,5AI2(OH)13.C03.3.5H20 00i, 4MgO.A 1203.C02.9H20 (iii), 4MgO.A 1203.C02.6H20, ZnO.3MgO.A 1203.C02.B- 9H-20 and ZnO.3MgO.Al2O3.CO2.5-6H20. Special preference is given to types i, ii and iii, Zeoltes (alkali and alkaline earth aluminosilica tes) These can be described by general formula (VII) Mx/n((A 102)x(SiO2h,].wH2o

(VII)

wherein n is the charge of the cation M: M is an element of Group I or Group 17, such as Li, Na. K, Mg, Ca, Sr or Ba; y:x is a number from 0.8 to 15, preferably from 0.8 to 1.2; and w is a number from 0 to 300, preferably from 0.5 to Examples of zeolites are sodium aluminosilicates of the formulae Na12Al12Si12O48. 27 H20 (zeolite. Na06Al6Si6O24 2 NaX. 7. 5 X= OH, halogen, C104 [sodalite]; Na6AI6Si300 7 24 H20; Na.8AI8Si400g 6 24 H20; NaQ16Al16Si24O8O. 16 H20; Nal6AI16Si32Og 6 16 Na56A150Si36O384. 250 H20 (zeolite Y1, Nc'86AI86Si1603B 4 264 00 zeolite X]; or the zeolites that can be formed by partial or complete replacement of the Na atoms by Li, K, Mg, Ca, Sr or Zn atoms, such as (Na,K)10Al1OSi22O64. 20 H20; Ca4.5Na3[(Al02)12(SiO2)1 2 J. 30 KgNa3((AI02)12(5i02)12]. 27 46SPreferred zeolites correspond to the formulae Nal 2

AI

2 Sil 2

O

4 8 27 H 2 0 [zeolite A], Na6Al6Si6024. 2NaX. 7.5 H20, X OH, Cl, C104, l/2C03 Na6Al6i30072. 24 Na8Al8Si40096. 24 Na16A116Si24O80. 16 NMlAI16532O96. 16 Na56AI56S1136O384. 250 H20 [zeolite Y] Na86AI86Si1O6O384. 264 H20 [zeolite X] and zeolites of the X od Y type possessing an Al/Si ratio of about 1:1, or the zeolites that can be formed by partial or complete replacement of the Na atoms by Li, K, Mg, Ca, Sr, Ba or Zn atoms, such as (Na,K)10Al0Si22O64. 20 Ca4,5Na3[(Al02)12(SiO2)12]. 30 K9Na3((AlO2)12(SiO2)12]. 27 The zeolites listed may also have a lower water content or may be anhydrous.

Other suitable zeolites are: Na2O-Al 2 03-(2 to 5) SiO 2 to 10) H 2 0 [zeolite P] Na2O-AI203-2 SiO2-(3'.5-10)H 2 0 (zeolite MAP) or the zeolites that can be formed by partial or complete. replacement of the Na atoms by Li, K or H atoms, such as (Li,Noa,K,H) 0 A1 0 Si 22

O

64 20

K

9 Na3[(AI02)12(SiO2) 12 27 H 2 0 K4Al4Si4O16*6 H20 [zeolite K-F] N ,a8AI8Si40096.24 H 2 0 zeolite as described in Barrer et al., 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 6B 841 812; zeolite LZ-217, as described in US 4 503 023: Ca-free zeolite 12-218, ais described in US 4 333 859; zeolite T, zeolite LZ-220, as described in US 4 503 023; Na3K6A l 9 5i 2 7 0 7 2 .21 H20 (zeolite L]; zeolite LZ-211, as described in US 4 503 023; zeolite LZ-2 12, as described in US 4 503 023; zeolite 0, zeolite LZ-217, as described in US 4 503 023; zeolite LZ-219, as described in US 4 503 023; zeolite Rho, zeolite LZ-214, as described in US 4 503 023; zeolite ZK-19, as described in Am. Mineral. 54 1607 (1969); zeolite W as described in Barrer eta/., J. Chem. Soc. 1956, 2882; Na30A130Si 66 0 19 2 98 H20 [zeolite ZK-5, zeolite Q].

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

According to that publication, zeolite P-3 is very rare and is therefore of little practical interest. The structure of zeolite P-1 corresponds to the gismondite structure known from the above-mentioned Atlas of Zeolite Structures. In more recent literature (EP-A 384 070) a distinction is made between cubic (zeolite B or Pc) and tetragonal (zeolite 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 organic dispersants.

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

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

S: 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, Srl/2 or Znl/2; Z is C02, 502, (C1207)1/2, B406, 5202 (thiosulfate) or C202 (oxalate); m is a number from 1 to 2 when M is M9l/2 or Cal/2, and in all other cases is a number from 1 to 3:.n is a number from 1 to 4; o is a number from 2 to 4; and p is a number from 0 to The 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 parIAly 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 alumina salt compounds may also be present in relatively rare crystalline modifications. A process for the preparation of such compounds Is discribed in EP 394 670. Examples of naturally occurring alumino salt componds are indigirite, tunisite, cluminchydrocalcite, para-alumin0hyrocallclte, strontiodresserite and hydrostrontiodresserit. Othe -exdmples of altuino salt compounds are potassiumn aluminocarbohate (C0(A 03.0)2 H} sodium alumi nothiosulfate aO).(AljO3)$042.21119O) potassium aluminosulfite ((K20X.Al2O3).(SO2)2.2H2O0)V c*16t~ alumninooxalate 1203).(C202)2.5H20), magnesium alum inotetraborate (M9O).0A1203).(8400)2.51-20), (Mgo.2NaO.6J20).(A 1203).(C02)2.4.1 (([Mgo.2NaO.6 J20).(A 1203).(C02)2.4.3 H20) ard (([Mgo.3Nao.4120).(A 1203).(C02)2.2.4.9H20) The mixed alumino salt. compounds can be obtained in accordance with processes known per se by catOn #dWC#, preferably from the alkali alumino salt compounds or by comblined #"c~tOn (see, for example, US 5 055 284).

Preference is given- to alumitio salt compounds of the above formula wherein M is Na or K. Z is C02, 502 or (41207)1/2; nn is 1-3; n is 1-4; o is 2-4 and p is 0-20. Z is especially C02.

Preference is given also to compounds that can be represented by the following formulae.

M20.A1203.(C02)2. pH2O (19) (M20)2.(AI203)2.(C02)2. pH-20 (Ib) M20.(AI203)2.(C02)2 .pH2O (Ic) wherein M is a metal, such as Na, K, Mgl/2, Cal/2, Sr1/2 or Znl/2 and p is a number from 0 to 12.

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

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

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

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

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

There may be mentioned specifically, as examples, the zinc salts of monovalent carboxylic acids, such as acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, oenanthic acid, octanoic acid, neodecanoic acid, 2ethylhexanoic acid, pelargonic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, myristic acid, palmitic acid, lauric acid, isostearic acid, stearic acid, 12-hydroxystearic acid, 9 ,10-dihydroxystearic acid, oleic acid, 3,6dioxaheptanoic acid, 3,6,9-trioxadecnoic acid, behenic acid, benzoic acid, ptert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-di-tert-butyl-4hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, npropylbenzoic acid, salicylic acid, p-tert-octylsalicylic acid, and sorbic acid; zinc salts of divalent carboxylic acids or the monoesters thereof, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, dicarboxylic acid, hexane-1,6-dicarboxylic acid, heptane-1,7-di'carboxylic acid, octane-1,8-dicarboxylic acid, 3,6,9-trioxadecne-1,10-dicarboxylic acid, lactic acid, malonic acid, maleic acid, tartaric acid, cinnamic acid, mandelic acid, malic acid, glycolic acid, oxalic acid, salicylic acid, polyglycol-dicarboxylic acid 12), phthalic acid, isophthalic acid, terephthalic acid and hydroxyphthalic acid; and the di- or tri-esters of tri- or fetra-valent carboxylic acids, such as hemimellitic acid, trimellitic acid, pyromellitic acid, citric acid and also so-called overbased zinc carboxylates.

The zinc enolates are preferably enolates of acetylacetone, benzoylacetone or dibenzoylmethane and enolates of acetoacetates and benzoyl acetates and of Sdehydroacetic acid. In addition, inorganic zinc compounds, such as zinc oxide, zinc hydroxide, zinc sulfide or zinc carbonate, can also be used.

:Preference is given to zinc carboxylates of a carboxylic acid having from 7 to 25 carbon atoms (zinc soaps), such as benzoates or alkanoates, preferably C8alkanoates, stearate, oleate, laurate, palmitate, behenate, versatate, hydroxystearates, dihydroxystearates, p-tert-butylbenzoate, or (iso)octanoate.

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

Also suitable in addition to the mentioned zinc compounds are organic aluminium, cerium or lanthanum compounds having a metal-O bond. The aluminium compounds that can be used and that are preferred include carboxylates and 0 enolates.

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

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

and thiophosphates, mercaptocarboxcylic acid esters, epoxidised fatty acid esters, antioxidaints, UV absorbers and light stabilisers, optical brighteners.

impact strength modifiers and processing aids, gelling agents, antistatic agents, biocides, metal deactivators, fireproof ing agents and propellants, and antifogging* agents (cf. "Hakndbook of PVC Formulating" by E. J. Wickson, John Wiley A Sons. New York 1993).

In a non-limiting manner, so me of the known additives and processing auxiliaries are mentioned here: Alkeili metal and alkaline ear'th metal compoundrs These ame to be understood to include especially the carboxylates of the acids described above, but also corresponding oxides or hydroxides or (bi)carbonates. Mixtures thereof with organic acids are also suitable. Examples are NaOH, Ni-stearate, WaHCO 3 KOH, K-stearate. KHCO 3 UOH, Li 2

CO

3 Listeorate, COO. Ca(0H12). Mg0, Mg(OH)2. Mg-stearate, CaCO3, *9CO3 as well -as dolomite, huntit. chalk. basic Mg-carbonate and other Nla- and K-salts of fatty acids.

NciOH. KOH, CaO, Ca(0H2). Mg0, Mg9(OH)2. CaCO3 and MgCO3 and also fatty acid sodium and potassium salts.

In the case of alkalioe, earth metal and zinc carboxylates, it is also possible for their adducts with MO or M(OH) 2 (M =Co. Mg, Sr or Zn), so-called a. "overbased* compounds, to be used.

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

6lidants(L UBRICANTS) Suitable glidants are, for example: Montan wax, fatly acid esters, PE waxes, amide waxes, chioroparaffins, glycerol esters or alkaline earth metal soaps. Suitable. glidants are also described in "Kunststoffadditive" (Plastics additives), R. Gichter/H. Muller, Carl Hanser Verlag. 3 "d Ed., 1989, pages 478-488. Mention may also be made of fatty ketones (as described in D)E 42 04 887) and of silicone-based glidants (as described in EP 225 261) or combinations thereof, as listed in EP 259 783.

Plasticisers Suitable organic plasticisers are, for example, those of the following groups: A) Phthalic acid esters: Examples of such plasticisers are dimethyl, diethyl, dibulyl, dihexyl, di-2ethylhexyl, di-n-octyl, diisooctyl, diisononyl, diiisodecyl, diisotridecyl1, dicyclohexyl, dimethylcyclohexyl, dimeth ylglycol, di butyiglycol, benzylbutyl :1,:and diphenyl phthalate and mixtures of phthalates, such as C7-C9- and C9- CII-alkyl phthalates from predominantly linear alcohols, C6-Clo-n-alkyl phthalates and C8-Clo-n-alkyl phthalates. Of those compounds, preference is :given to dibutyl, dihexyl, di-2-ethylhexyl, di-n-octyl, diisoociyl, diisononyl, diisodecyl, diisotridecyl and benzylbutyl phthulcrti and to the mentioned mixtures of alkyl phthalates. Special preference is given to di-2-ethylhexyl, dilsononyl and diisodecyl phthalate, which are also known by the customary abbreviations [)OP (dioctyl phthalate, di-2-ethylhexyl phthalate), DINIP (diisononyl phthalate), [)IOP (diisodecyl phthalate).

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

C) Trimellitic acid esters, for example tri-2-ethylhexyl trimellitate, triisodecyl trimel litate (mixture), triisotridecyl trimel litate, tri isooctyl trimellitate (mixture) and tri-C6-C8alkyI. triC-lakl tri-C7-.C901kyl and tri-C9-Cllalkyl trimellitate. The last-mentioned trimellitates are formed by eserifying trimellitic acid with the appropriate alkanol mixtures. Preferred trimellitates are tri-2-ethylhexyl trimellitate and the mentioned trimellitates from alkanol mixtures. Customary abbreviations are TOWM (trioctyl trimellitate, tri-2-ethylhexyl trimellitate)i TIMTM (triisadecyl trimellitate) and IT[)ITM (tri isotridecyl trimellitate).

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

Polyme plasticisers A -definition of these ptclsers and examples thereof are given in "lKunststoffadditive (Plastics additives), R. GSichter/H. Miller, Carl Hainser qVerlag. rd Ed., 1989, Chapter 5,6 page 412-415, and in "PVC Technology", W.V. TI tow, Ed.. ElsevirPbL #I84 pages 165-170. Te mos commonly used starting materials for the preparation of polyester plasticisers are: :dicarboxylic acids, suchasa dipic, phthalic, azelaic: and sebacic acid; diols, such as 1,2-propahediol, 1,3bu.tanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and diethylerie -glycol.

F) Phosphoric acid esters Adefinition of those Is t efudi h above-mentioned "Taschenbuch der Ku I tf0a*0iive" (Handbook of Plastics Additives) ::::*Chapter 5.9.5, p.p. 408.2 kxamples of such phosphoric acid esters are tributyl phosphate, tri-2-ethylbutyl phosphate, tri-2-ethylhexyl phosphate, trichloroethyl phosphate,' 2-e4thyl-hexyl-diphenyl phosphate, cresyl diphenyl phosphate, triphenyl phosphate, tricresyl phosphate and trixylenyl phosphate. Tri-2-ethylhexyl phosphate and 'Reofos 50 and 95 (Ciba-Geigy) are preferred.

G) Chlorinated hydrocarbons (paraffi ns) H) Hydrocarbons 1) Monoesters, eig. butyl oleate, phenoxyethyl oleate, tetrahydrofurfuryl oleate and -alkylsulfo"Ic acidd eters.

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

Definitions and examples of plasticisers of groups G) to J) are to be found in the following handbooks: "Kunststoffadditive" (Plastics Additives), R. Gichter/H. Muiller, 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, 4k Ed., Elsevier Publishers, 1984, Chapter 6.10.2, pages 171-173, (group Chapter 6.10.5, page 174 (group Chapter 6.10.3, page 173, (group I) and Chapter 6.10.4, pages 173-174 (group J).

It is also possible to use mixtures of different plasticisers.

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

Pigments Suitable substances are known to the person skilled in the art. Examples of inorganic pigments are TiO 2 carbon black, Fez0 3 SbzO 3 (Ti,Ba,Sb)O2.Cr 2 Os, 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 anthraquinone pigments. Preference is also given to TiO 2 in micronised form.

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

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

Chalk is preferred.

Phosphites Examples are triphenyl phosphite, diphenyl alkyl phosphites, phenyl dial kyl phosphites, tris-(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distear'yl-pentaerythrito I diphosphite, tris(2 .4-di-tert-butlyphenyl) phosphite, diisodecylpentqerythritol di phosphile, bis(2 .4-di-tertbutylphenyl)pentaerythritol diphosphite, bis(2 6 -di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis-isodecyloxy-pentaerythritol diphosphite, bis(2 g4bditert-bulyl- 6 -methylphenyl)pentaerythritol diphosphite, bis(2 .4,6-tritert-butylphenyl)pentaerythritol di phosphite, tristearyl-sorbito I triphosph ite, bis(2 4 -di-tert-butyl-6-methylphenyl)methyl phosphite, bis(2 .4-di-tert-buty-6-.

methylphenyl)ethyl phosphite.

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

trioleyl, triphenyl-, tricresyl, tris-p-nonylphenyl or t ricyclohexyl phosphite and special preference is given to the aryl-dialkyl and alkyl-diaryl phosphites, such as phenyldidecyl phosphite, 2 4 -di-tert-butypenyl)..di..dodjecI phosphite, (2,6di-trt-uylpeny~i~jcylphosphite and to the dialkyl- and diarylpentaerythritol diphosphites, such as distearylpentaerythritol diphosphite, and non-stoichiometric triaryl phosphites, for example those having the composition :(H19C9C6H4)015P(0C12 13

H

2 5.

2 7 :Preferred organic phosphites are distearyl-pentaerythritol diphosphite, trisnonyiphenyl phosphit-e and phenyldidecyl phosphite..

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

Thiophosphites and thiophosphates There are to be understood by thiophosphites and thiophosphates compounds of the general type: aP, (RS)P0 or (RS) 3 P=S, which are described in patent specifications DE 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)methyl ester, trithiophosphorous acid tris(carbotrimethylcyclohexyloxy)methyl ester, trithiophosphoric acid tris(carboisooctyloxy)rnethyl ester, trithiophosphoric acid S,S,S-tris(carbo-2elhylhexyloxy)methyl ester, trithiophosphoric acid SS,S-tris-1- (carbohexyloxy)-ethyl ester, trithiophosphoric acid SS,S-tris-1-(carbo-2ethylhexyloxy)-ethyl ester, trithiophosphori c acid SS,S-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.

Epoxidised fatty acid esters The stabiliser combination according to the invention may additionally comprise 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 epoxidlised butyl oleate.

Antioxidants Suitable antioxidlants are, for example: 1. Aftklated monophenols. for example 2 ,6-di -tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylpheno I, 2 ,6-di-tert-butyl-4-ethylphenol, 2 ,6-diterl-butyl-4-n-butylphenol, 2 ,6-di-tert-buyl-4-isobutylphenol, 2,6dicyclopentyl-4-methylphenol, 2-(cz-methylcyclohexyl)-4,6-dimethylphenol, ,6-dioctadecyl-4-methylphenol, 2 ,4,6-tricyclohexylpheno I, 2 ,6-di-tertbutyl-4-methoxymethylphenol, 2 .6-di-nonyl-4-methylphenol, 2 ,4-dimethyl-6- (1'-methyl-undec-1'-yl)phenol, 2 ,4-dimethyl-6-(1'-methyl-heptadec- 1'yl)phenol, 2 ,4-dimethyl-6-(1'-methyl-tridec-V-yl)phenol, octylphenol, nonylphenol, dlodecyiphenol and mixtures thereof.

2. A Ikyithiomethyipheno Is. for example 2 .4-di -octyllhiomethyl-6-tert-, butylphenol, 2 .4-di-octylthiomethyl-6-methylphenol, 2 ,4-di -octyithiomethyl- 6-ethylphenol, 2 ,6-di-dodecylthiomethyl-4-nonylphenol.

3. Alkylaled hydroguinones. for example 2,6-di-tert-butyl-4methoxypheno I. 2 ,5-di -1ert-bulyl-hydroqui none, 2 hydroquinone, 2 ,6-diphenyl-4-octadecyloxypheno I, 2 .6-di-lert-butylhydroquinone, 2 .5-di-tert-butyl-4-hydroxyanisole, 3 .5-di-teri-butyl -4hydroxyanisole. 3 ,5-di-tert-buyl-4-hydroxyphenylsiearate, bis(3 bulyl-4-hydroxyphenyl) adipate.

4. Hycroxlated thiodiphenyl ethers, for example 2,2'-thio-bis(6-tertbulyl-4-methylphenol), 2 ,2'-thio-bis(4-ocllphenol), 4,4'-thio-bis(6-tertbutyl-..3-methylphenol), 4,4'-thio-bis(6-tert-buly-2-methyl phenol), 4,4'-thiobis(3 .6-di-sec-oamyiphenol), 4,4-bis(2,6-dimethyl-4-hydfroxyphenwyl) disulfide.

Alkylidene bisphenols. for example 2,2-methylene-bis(6-tert-butyl-4methylphenol), 2.2'-methylene-bis(6-tert-buyl-4-ethylphenol).* 2,2-.

methylene-bis[4-methyl-6-(a-methylcyclohexyl)phenol], 2 ,2-methylenebis(4-meth'yl-6-cyclohexylphenol), 2,2'-methylene-bis(6-'nonyl-4methylphenol), 2 ,2-methytene-bis(4,6-di-ter-t-butylpheno 2,2'-ethylidenebis(4,6-di-tert-buylphenol), 2,2'-ethylidene-bis(6-tert-butyl-4isobutylphenol), 2.

2 '-methylene-bis[6-(x-methylbenzyl)-4-nonylphenol], 2,2'methylen-bis[6-(oo-dimethylbenzyl)-4-nonylphenol], 4,4'-methylenebis(2.6-di-tert-butylphenol), 4.4'-methylene-bis(6-tert-butyl-2methylphenol), 1 .l-bis(5-tert-butyl-4-hydroxy-2-methylpheylbutane, 2.6bis(3 -tert-bulyl-5-methyl-2 -hydroxybenzyl)-4-mnethylphenol, 1,1,3-tris(5tert-butyl-4-hydroxy- 2-methylphenyl)butane, 1,1 -bis(5-ter-t-bulyl-4hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, ethylene glycolbis[3 .3-bis(3'-tert-butyl-4-hydroxyphenyl) butyrate], bis(3-tert-butyl-4dicyclopentadiene, bis[2-(3-terl- butyl-2'-hydroxy- 5'-methyl-benzyl)-6-tert-buyl-4-methylphenyl] terephthakate, 1,1 -bis(3 dimethyl-2-hydroxyphenyl)butane, 2.2- bis(3 ,5-di -tert- butyl-4hydroxyphen'yl)propane, 2 ,2-bis(4- hydroxyphenyl)propane, 2 butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane, 1.1,5.5butyl-4-hydroxy-2-methylphenyl)pentane.

6. Bengyl compounds. for example 3.5,3',5-tetra-tert-butyl-4.4'di hydroxydibenzyl ether, octadecyl-4-hydroxy-3 mercaptoacetate, tris(3 .5-di-tert-butyl-4-hydroxybenzyl )ani ne, bis(4-tertbulyl-3-hydroxy-2,6-dimetliylbenzyl) dithioterephthalcite, bis(3 butyl-4-hydroxybenzyI) sulfide, isooctyl-3,5-di -tert-butyl-4- hydroxybenzyl mercaptoacetate.

7. E+droxybenZylated Mglonates. for example dioctcdecyl-2.2-bis(3,5di-1ert-bulyl-2-hydroxybenzyl) niolonate, di-octadecyl-2-(3 -tert-bulyl-4mllt, dldodecytmercaptoethyl-2 .2-bis(3 tert-buyl-4-hydroxybenz .yl) malonate. di-[4-(1 .1,3,3tetramethylbutyl)phenyfJ-2,2-bis(3,5-di-ter-buty-4-hydroxybenzyl) malonate.

8. Hvdrxvbuizl armatic gnMponds. for example 1,3,5-tris(3,5-ditert-butyl-4-hydroxybenzyl .4.6-trimethylbenzene, I ,4-bis(3,5-di-teribuyI-4-hydroxybo-y)-,3~.56-tetrmethyIbenzene, 2 .4.6-tris(3 butyl-4-hyroxybenylphehol.

9. rriazane c rnans. for excample 2.4-bis-oclymercapto-6-(3,5-ditert-butyl-4-hyd o ni h)l,0trale. 2-octylmercapto-4,6-bis(3 tert-butyt-4-hydr*oxyaihi~ ,3 t0tloine, 2ocllmercapto-4,6-bis(3, ter-buyl-4-hydroxyhtnoxy)-I,3,-r azine, 2,4,6-tris(3 ,5-d-tert-butyl-4hydr'oxyphenoxy)-1,2,3-riazine, I ,3,5-tris(3 .5-di -tert-buly-4hydr'oxybenzyl) isocyanurate. 1,3 .5-tris(4-tert-buty-3-hydroxy-2 .6dimelhylbenzyl) isocyanurate, 2A,6-tris(3 .5-i-tert-butyl-4hydroxyphenylethyl)-1,3,5-.triazine, 1 .3,5-tris(3,5-di-tert-butyl-4hydroxyphenylpr'opiornylkb cro-l.3 .5-triazlne, 1 .3.5-1ris(3,5dicyclohe4-hydmoy~zl ioyanurat.

10. Phosphyonat an tsolt. for example dimethyt-2.8-i-iertbuty-4-hydroxybenzyl-phosphonate, disthyl-3.5-i-tert-butyl-4hydroxybenzyl phosphonate, dioctod4ecyl- -itr-uy--hydroxybenzyl phosphonate, dioctodecIi5itrt.butyA-hydr-oxy-3-methylbenzyl phosphonate, calcium salt of'3.5-di-tert-butyl-4-hydroxybernzylphosphonic acid monoethyl ester, tetrakis(2 .4-di-tert-bullphenwyl)-4.4'-bi phenylenediphosphonite, 6-isooctyloxy- 2,4,8 ,lO-tetra--tert-buyl-1 2H-di benzo (d~gJ- 1,3,2 -dioxaphosphocine-, 6-f luoro-2 .4.8 .10-teira-tert-butyl- 12-methyldi benzo(d,g]-1 .3 2-.dioxaphosphoci ne.

11. Agylominophgjo.s~jfor2 exmple 4-hydroxy-lauric acid anilide, 4hydroxystearic acid' onlide, N-(3 .5-di-tert-buyl-4-hydroxyphenyl)-carbami c acid octyl ester.

12. Esters of b-(3.5-di-tert-buvl-4-hydroyphenyl)-propionic acid with mono- or poly-hydric alcohols, such as methaznol, ethanol, octanol, ocladeccinol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propxnediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythrito I, di pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'bis(hydroxyethyl)oxali c acid diamide, 3-thioundecanol, 3 -thiapentodeciano

I,

trimethyihexanediol, trimethyloipropane, di--rimethylolpropane, 4hydroxymethyl-1 -phospha-2 .6,7-trioxabi cyc Io[2.2.2 ]ocl~ane.

13. Esters of b-(5-tert-buly-4-hydroxy- 3-methylphenyl)-proptio ni c acid with mono- or poly-hydric alcohols, such as methanol, ethanol, octanol' octadeconol, 1,6-hexonediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxy)ethyl isocyonurate, N,N'bis(hydroxyethyl)oxalic acid diamide, 3-thiciundecanol, 3 -thicapentadecanol.

trimethyihexanediol, trimethyloipropane, 4-hydroxyniethyl-1-phospha-2,6 ,7trioxabicyclo [2.2.2 ]octane.

14. Esters of b-(3 .5-di cyclohexy-4-hvdroxyphenyl)-propionic acid with mono- or poly-hydric alcohols, such as methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1.9-nonanediol, ethylene glycol, 1,2-propanediol, neopenlyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxy)ethyl isocyainurate, N,N-bis- (hydroxyethyl)oxalic acid dianiide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol. trimethylolpropane, 4-Iuydroxymethyl-l-phospha-2 ,6 ,7trioxabicyclo[2.2.2]octane.

Esters of 3 .5-di-tert-butyl-4-hydroxphenyacetic acid with mono- or poly-hydric alcohols, such as methanol, ethanol, octanol, octadecanol, 1,6hexanediol, 1,9-nononediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxy)ethyl isocyanurate, NN"-bis(hydroxyethyl)oxalic acid diamide, 3-thiaundecano I, 3 -thiapentodecano I, trimethylhexanedio

I,

trimethylolpropane, 4-hydroxymethyl-1-phospha-2 ,6 ,7-trioxabicyclo[2.2.2]octane.

16. Amides of b-( 3 di-tert-buyl-4-hydroxyphenyl)-propionic acid. such as NN"-bis(3,5-di-tert-butyl-4hydroxyphenylpropionyl)hexamethylenediamine, N.N'bis(3 .5-di -tert-bu-yl-4hydroxyphenylpropionyl)trimethylenediamine, N,N'-bis(3 ,5-di -tert-butyl-4-: hydroxyphenylpropionyl) hydrazine.

Preference is given to antioxidants of groups 1 to 5, 10 and 12, especially 2,2bis(4- hydroxyphenyl)propane, esters of 3 .5-di -tert- butyl-4hydroxyphenyipropionic acid with octanol, octadecanol or pentaerythritol or tris(2 .4-di-tert-butyphenyl) phosphite.

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

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

UV absorbers and light stabilisers Examples are'.

1. .2-;(2-Hdroxyphenyl)-benzotriazo le, such as 2-(2'-hydroxy-5'methylpheriyl)-benzotriazo Ic, 2 -tert- butyl-2-hydroxyphenyl)-.

benzotriazole, 2 -(S-tert-butyl-2-hydroxyphenyl)-benzotriazole, .1,3 ,3-tetramethylbutyl)phenyl)-benzotriazole, 2-(3',5-di-tert- 2-(3'-tert-butyl-2'- 2-(3'-sec-bulyl-5'-tertbuty-2'-hydroxyphenyl)-benzotriazo le, 2 -(2'-hydroxy-4C-octoxyphenyl)benotrazoe, -(3,V-i-trt-myl 29 -hydroxyphenyl)-benzotriazol,2 ***(3',5'-bis(aa-dimethylbenzyl)-2'-hydroxyphenyl)-benzotriazole, a mixture of 2 -(3'-tert-butyl-2'-hydroxy-5'-(2 benzotriazole, 2-(3'-tert-bulyl-5'-[2-(2-ethythexyloxy)-carbonylethyl]-2'hydroxyphenyl)-5-chloro-benzotriazole, 2 -(3'-tert-butyl-2'-hydroxy-5'-(2melhoxycairbonylethyl)phenyl)-5- ch loro- benzotriazole, 2 -(3'-1ert-butyl-2'hydroxy-5'-(2-methoxycarbonylethyl)phenyl)- benzotriazole, 2-(3'-tert-butyl- 2 '-hydroxy-5-(2-octyloxycarbonylethyl)phenyl)-benzotriazole, 2 -(3-tert- 2 -(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl benzotriazole, 2 -(3'-dodecyl-2'-hydroxy-5'-methylphenyl)-benzotriazo le, and 2-(3-tert-butyl- 2'-hydroxy-5'-(2 -isooctyloxycarbo nylethyl)phenyl benzotriazole, 2 ,2'-methylene-bis[4-(1 ,1,3 ,3-tetramethylbutyl)-6benzotriazol-2-ylphenol]; the transesterif iccition product of 2 -[3*-tert- 2 -methoxycairbonylethyl)-2'-hydroxy-.phenyl].Lbenzotriazole with polyethylene glycol 300; wherein R: =3-tert-butyl-4'-hydroxy-5'-2H-1 benzotriazol- 2-ylphenyl.

2. 2-Hydroxvbenzophenones, such as the 4-hydroxy-, 4-methoxy-, 4octyloxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 4,2',4!-trihydroxy- or 2'-hydroxy-4,4'-dimethoxy derivative.

3. Esters of unsubstituted or substituted benzoic acids, such as 4-tertbulyl-phenyl salicylate, phenyl sali cylate, octyiphenyl salicylate, di benzoylresorcinol, bis(4-tert-butylbenzoyl )resorci fbI, benzoylresorcino

I,

3.5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di-tert-bulphenyl ester, di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester, 3.5-di-tert-buy- 4hydroxybenzoic acid octadecyl ester, 3 ,S-di-tert-buyl-4-hydroxybenzoic acid 2-methyl-4,6-di-tert-butylphenyI ester.

4. Acrylates, such as a-cyano-b,b-diphenylacrylic acid ethyl ester or isooctyl ester, a-carbomethoxy-cinnamic acid methyl ester, a-cyano-bmethyl-p-methoxy-cinnaniic acid methyl ester or butyl ester, acarbomethoxy-p-methoxy-cinnamic acid methyl ester, N-(b-carbomethoxyb-cyanovinyl)-2-methyl-i ndo line.

5. Nickel compounds, such as nickel complexes of 2.2'-thio-bis[4-(1,1,3,3tetraunethylbutyl)phenol], such as the 1-.1 or the 1:2 complex, where appropriate with additional ligands, such as n-butylamine, triethanolamine or N-cyclohexyl diethanolamine, nickel dibutyl dithiocarbamate, nickel salts of 4-hydroxy-3.5-di-tert-butylbenzylphosphonic acid monoalkyl esters, such as *...methyl or ethyl ester, nickel complexes of ketoximines, such as 2-hydroxy-4methylphenyl-undecylketoxime, nickel complexes of 1-phenyl hydroxy-pyrazole, where appropriate with additional ligands.

6. Stericalty hindered amins such as bis( 2 2 ,6,6-teramethyl-piperijyl) sebacate, bis(2 ,2,6,6-tetramethyl-piperidyl) succi nate, bis(1 ,2 ,2,6 ,6pentamethylpiperidyl) sebacate, n-butyl-3,5-di -tert-butyl-4-hydroxybenzyl.

:malonic acid bis(l, 2 2 ,6,6-pentamethylpiperidyl) ester, the condensation product of 1-hydroxyethyl-2 ,2 6 6 -tetramethyl-4-hydroxypiperidi ne and succinic acid, the condensation product of N.N'-bis(2 ,2 ,6,6-tetramethyl-4piperidyl)hexamethylenediami ne and 4-tert-octylami no- 2,6-di ch loro-1 ,3 triazi ne, tris(2 ,2,6 ,6-tetramethyl-4- pi peridyl)nitri lotriacetate, tetrakis(2 ,2 ,6 ,6-tetramethyl -4-pi peridyl)- 1,2,3,4- butane tetraoate, ,2ethanediyl)-bis(3 .3 5.5-tetramethyl-pipercaz i none), 4-benzoyl-2,2 .6,6tetrcunethylpiperidine, 4-stearyloxy- 2,2,6,6 -tetramethylpiperidi ne, bis(1 .2,2,6 ,6-pentomethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3 .5-di -tertbulylbenzyl) malonate, 3-n-ocly-7,7,9,9-tetramethyl-1 .3.8triozaspiro[4.5]deon2.4-dione, bis(1-octyoxy-2 .2,6.6tetramethylpiperdyl) esb.#at. bis(1-octyoxy-2 ,2 .6,6-tetramethylpiperidyl) succinate, the condssat .tproduct of NN-bis(2,2,6,6-tetrauethy..4piperidyl)-hexaunethylqonsliarine. and 4-morpholino-2,6-dichloro-1,3,5triazine, the condensation product of 2-chloro-4,6-di(4-n-bulylamino- 2,2,6 ,6-teranithylpiperkdyl)-1.3 .5-triazine and 1 .2-bis(3aminopropylamino)6thgoo, the condensation product of 2-chloro-4,6-di-(4-nbutykamino-1.*o.. idl135tizn and I ,2-bis(3aminopropylamnin0)#$.:..,.. t.e 8ae1y-3dodecyI-7,7,9,9-tetramethyI-l .3,8- 4.dne, 3-dod cyt-1-(2,2,6,6-tetramethyl-4pipeidyI*yrnOtIdWe.R4io4i. 3-dodecyl-1-(l.2 ,2.6,6-pentamethyl-4piperidy)-pyroIdI 4 ad-ChlImassrb 966.

7. Oxallc.odaI~ uha .'d-cyoyoaiie ,-l ociyloxy-5.5'-l-t14*uy 'oxanilide, 2,2'-didociecyloxy-5.5' -di-tert.butyl ~oxani lide, 2-ethoXy.-4tIyt oxoni lide, N.N'bis(3 -dimethylainopropyl) oxolamide, 2-ethoxy-5-tert-butyl-Z-ethyl oxanifide and a mixture thereof with 2-ethoxy-2-ethy4.5,,4-..di.e.rt-butyI oxanilide, mixtures of o- and pmeihoxy- and o-and p"th y'd. subttut0d aonflides.

8.IM, such as 2,4,6-tr~s(.2+4YdroxY-4octyloxypheuIyl-l,3,'8 jrte 2.yro-4cyoyp )4,6-bis(2,4.

dimethylphenyl)-1 ,3.5-trialine, 2-(2 ,4-dihydroxyphenyl)-4,6-bis(2 .4dimethylphenyI)-1,3,0-..1riozne.2.4--bis(2-hydroxy-4-pr-opyoxyhentyl)-6- *.(2,4-dimethylpheny)-13,5 triozine 2-(2-hydroxy-4-oclyloxyphenyl)-4,6bis(4-methylpheniyl .13 .5-triozie, 2-(2-hydr-oxy-4-dodecyloxyphenyl)-4,6bis(2 I A4-dimethylphe661V)4l3 ,541 rlaiine, 2-[2-hydroxy-4-(2-hydroxy-3butyloxy-propyloxy)phenyl]-4,6-bis(2 .4-dimethylphenyl)-1.3 ,5-triazi ne, 24[2hydroxy-4-(2-hydr oxy-3-octyloxypropyloxy)phenyl]-4,6-.bis(2,4dimethylphenyl)-1 .3 Propellants Propellants are organi c aizo and hydrazo compounds, tetrazoles, oxazines, isatoic anhydride, and sodium carbonate and sodium hydrogen carbonate.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The Examples that follow illustrate the invention further without, however, 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 0 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 Sthermostability of the stabilised polymer can also be determined from the sudden appearance of discolouration throughout the polymer.

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*C) Mixture 11 12 13 Solvic 268 RC (S-PVC KC value 68) 100 100 100 Omyalite 30 Ca stectrate 0.6 0.6 0.6 Hostalub H4 2 1.0 1.0 H-ostalub H12 2 4) 0.2 0.2 0.2 CH 3003) 0.4 0.4 0.4 Mark 6045 ACM 4 0.3 0.3 0.3 Stabiliser 5 0.2 0.2 0.2 NoaCIO4 0.05 YI VI YI Minutes 20.7- 29.9 22-.2 28.4 66.6. 29.1 40.2 108.4 39.2 ego" QChalk 2 )Glidant supplied by Hoechst (paraffin wax) '46lidant supplied by Hoechst (polar ethylene wax) 3 )Phenylisodecyl phiosphite 4 Mixture of 9% *O0S NCIO.4 45% CoCO 3 40% CaSiO,* 6% K~(O 5)6-Amino-1.3-dimthyl-urcil *.ee*It is found that the use of small amounts of perchlorate compound as component B in mixtures It and 13 arccording to the invention results in considerably better stabilisation than without component B.

Table II: Static heat test at 190 0 C (rolled for 5 min at 170*C) Mixture Evipol SH 6030 (PVC K value 60) CH 3W3)~ Wax E 6) Epox. soya oil Araldite GY 2507) Araldite PT 8108) Stabiliser 15) Stabiliser 2") Stabiliser 3'0) 111 112 113 114 115 116 117 128119 100 100 0.8 0.8 0.4 0.4 5.0 5.0 1.0 1.0 100 0.8 0.4 1.0 100 0.8 0.4 5.0.

1.0 100 0.8 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 YIYI YI YI Y1 YI VI YI YI Minutes 17.4 17.3 15.6 23.2 33.7 29.5 33.6 54.9 46.3 13.4 17.8 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 3)Phenylisodecyl phosphite, 6)Ester wax (based on: montanic acid)7~)iglycidyl ether of bisphenol A (liquid epoxide) 8) Solid heterocyclic epoxy resin (triglycidyl isocyanurate) 9 )6-Amino-1 ,3-di-n-butyluracil I 0 6-Amino-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 MI: 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)~ Epox. soya oil Rhodiastab 5011) Ca stearate Zn stearate tDASC' 2 Alkamizer V) Stabiliser 15) Stabiliser 29) Stabiliser 310) 111 1T12113 11141115116 M171118119 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

VI

100 0.8 0.4 5.0 0.2 0.3 0.5

YI

100 0.8 0.4 5.0 0.2 0.3 0.5

YI

100 0.8 0.4.

5.0 0.2 0.3 0.5

YI

100 0.8 0.4 0.2 0.3 1.

YI

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 11 3tearoyl-benzoyl-methane supplied 2 )bihydroxyaluminium sodium carbonate (bASC) 3 )Hydrotalcite supplied by ICYOWA (Japan) The addition of dawsonite and the addition of hydrotalcite both increase the stability.

61 Table IV: Static heat test at 190 0 C (rolled for 5 mmin at 170 0

C)

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 1M Stabiliser 29) Stabiliser 319) IVI IV2 IV3 IV4 IV5 IV6 IV7 IV8 IV9 IV10IV11 IV12 100 0.8 0.4 2.0 0.2 1.0 100 0.8 0.4 2.0 0.2 1.0 100 0.8 0.4 2.0 0.2 1.0 100 0.8 0.4 2.0 0.2 0.15 1.0 100 0.8 0.4 2.0 0.2 0.15 1.0 100 0.8 0.4 2.0 0.2 0.15 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 2.0 0.2 0.5 1.0 100 0.8 0.4 0.2 YI yI VI yI YI yI VI YI YI VI Minutes 10 15 6.0 10.1 6.6 12.7 10.3 18.7 6.6 7.8 5.8 9.0 7.7 11.1 5.8 7.3 8.9 11.1 6.2 7.2 9.4 19.5 8.1 10.4 11.1 16.1 5.4 6.7 11.7 21.9 VI yI 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 15.4 24.8 "'sterically hindered amine supplied by CIBA-GEIGY AG (HALS) The stabiliser combinations according to the invention (IV4 to IV12) are found to give improved stabiliser activity.

Table V: Static heat test at 190 0 C (rolled for 5 min at Mixture Evipol SH 6030 (PVC K value 60) CH 3003) Wax E6) Epox. soya oil Rhodiastab 50l).

Ca stearate Zn stearate Wessalite P" 5 Zeolite P6') Stabiliser 15) Stabiliser 29) Stabiliser 310) VI V2 V/3 V4 V5 170 0

C)

V7 V8 V9 100 0.8 0.4 2.0 0.2 0.3 0.5 1.0

YI

100 0.8 0.4 2.0 0.2 0.3 0.5 1.0

YI

100 0.8 0.4 2.0 0.2 0.3 0.5 1.0

VI

100 0.8 0.4 2.0 0.2 0.3 0.5 1.0 1.0 /1 100 0.8 0.4 2.0 02 0.3 0.5 1.0.

YI

V6 100 0.8 0.4 2.0 0.2 0.3 0.5

YI

100 0.8 0.4 2.0 0.2 0.3 0.5 1.

1 100 0.8 0.4 2.0.

0.2 0.3 0.5 1.

YI

100 0.8 0.4 0.2 0.3 *b

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 13.3 25.0 9.4 15.7 15.3 22.6 29.2 34.8 5 Na zeolite A supplied by DEGUSSA "6)11. zeolile 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 for 5 minutes at 170 0

C)

Mixture VII VI2 VI3 VI4 Evipol EH 6030 (PVC K value 60) 100 100 100 100 Wax E 6 0.4 0.4 0.4 0.4 CH 300 0.8 0.8 0.8 0.8 Epox. soya oil 5.0 5.0 5.0 Ca stearate 0.55 0.55 0.55 0.55 Zn stearate 0.25 0.25 0.25 0.25 Rhodiastab 50' 0.3 0.3 D-26-155'7 0.3 Stabiliser 1 1.0 Stabiliser 29) 1.0 10 1i 4. 4 4* 4.

44 .44* 44 4 .4 4 Minutes 25 YI YI 18.5 9.7 36.518.8 103 33.3 yVI Y 11.4 15.6 21.9 28.3 46.0 59.2 0 o,Y O N O

Y

"B-keto ester of the formula Y (CH 2 2

-O-CO-CH

2

-CO-CH

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

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

C)

Mixture VIII VnI2 V1I3 VI4 VII5 VI6 VII7 VII8 Evipol SH 6030 (PVC K value 60) CH 3003) Wax E6 Epox. soya oil Ca stearate Zn stearate Synesal M' Stavinor D 50719) Stabiliser 15) Stabiliser 29) Stabiliser 3") 100 100 100 0.8 0.8 0.8 0.4 0.4 0.4 5.0 5.0 5.0 0.55 0.55 0.55 0.25 0.25 0.25 100 0.8 100 0.8 100 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 1.0 1.0 100 100 0.8 0.8 0.4 0.4 5.0 0.55 0.55 0.25 0.25 0.2 0.2 1.0 YI YI 2.9 4.4 3.7 4.9 4.5 6.7 6.3 8.2 11.3 11.9 23.8 21.3 62.6 38.4 Minutes 0 15 20 YI YI YI 5.4 4.8 6.3 6.4 4.7 6.7 6.7 5.5 7.0 7.3 7.6 8.3 10.8 12.3 12.5 19.9 28.5 22.9 33.7 65.8 45.1

YI

2.9 3.5 4.4 5.4 8.9 18.0 31.8 YI YI 3.9 2.3 4.1 2.3 5.3 3.5 7.5 5.4 13.9 9.3 27.2 17.5 64.2 32.3 t 1 )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 a.a 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 claims given the limitation of claim scope of various preferments of the invention described.

aoa ooa

Claims (14)

1. A stabiliser combination for chlorine-containing polymers comprising A) at least one compound of formula I 0 Y N NH 2 wherein R*1 and- R*2. are each independently. of the other Cl-C1201 kyl C3- C6ollkenvyl, C5-Cscytcalkyll that is unsubstituted or substituted by from I to 3 Ci-C4a4lkyl., Cj-C4alk~xy, C5-C8cycloalkyl or by hydroxy. groups or chlorine atoms. or C7-Cgphenylalkyl that'is un.substituted or substituted -at the phenyll ring by from I to 3 Cl-C4olkyl, Cl-C4alkoxy, C5-C8cycloalkyi. or by hydroxy groups or chlorine atoms.* and R*1 and R*2 may additionally be hydrognadC-llylad Y is Sor 0.and B) at least one alkali aluminosilicate, (zeolite) compound.

2- A staGbiliser combination according to claim 1. wherein R*1 and R*2 are each independently of the other H and CI-C4alkyll or C1-C4alkyl.

3. A stabiliser combination according to claim 1, wherein the compound of compotient A) is 6-amino-I .3-dimethyl-uracil, 6-amino-i ,3-di-n-propyl-uraci 1. 6- amino-i .3-di-n-butyl-ur-acil, 6-amino-1.3-diethyl-thiouracil or 6-amino-1,3-di-n- butyl--thiouracil.

4. A stabiliser combination according to any one of claims 1 to 3, which additionally comprises at least one epoxidised faztty aicid ester.

A stabiliser combination according to any one of claims 1 to 4, which additionally comprises zinc and/or alkali metal and/or alkaline earth metal carboxylates or aluminium carboxylates.

6. A stabiliser combination according to any one of claims 1 to 5, which additionally comprises at least one further substance from the groups of the phosphites; antioxidants, beta-dicarbonyl compounds, plasticisers, fillers, glidants and pigments.

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

8. A stabiliser combination according to claim 6, wherein the glidant is calcium stearate.

9. A stabiliser combination according to claim 6, wherein titanium dioxide is used as the pigment.

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

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

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

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

14. A method for stabilising chlorine-containing polymers, substantially as hereinbefore described with reference to the Examples. :b DATED this 29th day of December 2000 S" -WTO VINYL ADDITIVES GMBH sTR By their Patent Attorneys sC DAVIES COLSON CAVE DAVIES COLLISON CAVE Y