AU735549B2 - Stabiliser combinations for chlorine-containing polymers - Google Patents

Description

Our Ref: 750314 P/00/011 Regulation 3:2

AUSTRALIA

Patents Act 1990

ORIGINAL

COMPLETE SPECIFICATION STANDARD PATENT Applicant(s): Witco Vinyl Additives GmbH Chemiestrasse 22 D-68623 Lampertheim

GERMANY

DAVIES COLLISON CAVE Patent Trade Mark Attorneys Level 10, 10 Barrack Street SYDNEY NSW 2000 Address for Service: Invention Title: Stabiliser combinations for chlorine-containing polymers The following statement is a full description of this invention, including the best method of performing it known to me:- 5020 STABILISER COMBINATIONS FOR CHLORINE-CONTAINING

POLYMERS

This application is a divisional of Australian patent application No.

68041/96. The ensuing description is substantially identical to the description of "parent" No. 68041/96. 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 from the following groups: the perchlorate compounds, glycidyl compounds, beta-diketones, beto keto esters, dihydropyridines, polydihydropyridines, polyols, disaccharide alcohols, sterically hindered amines (tetraalkylpiperidine compounds), alkali aluminosilicates, hydrotalcites and alkali aluminocarbonates (dawsonites), alkali- (or alkaline earth-) carboxylates,-(bi)carbonates oder -hydroxides, antioxidants, lubricants or organotin compounds which are suitable for stabilising chlorinei containing polymers, especially PVC.PVC can be stabilised by a number of additives. Compounds of lead, barium and cadmium are especially suitable for the purpose but are controversial today for ecological reasons or owing to their heavy metal content (cf. "Kunstoffadditive" (Plastics additives), R. Gdchter/- H. Miller, Carl Hanser Verlag, 3" Edition, 1989, pages 303-311, and "Kunststoff Handbuch PVC" (Plastics Handbook PVC), Volume 2/1, W.Becker/D.Braun, Carl Hanser Verlag, 2" Edition, 1985, pages 531-538; and Kirk-Othmer: "Encyclopedia of Chemical Technology", 4" Ed., 1994, Vol 12, Heat Stabilizers p.

1071-1091). Other effective stabilisers and stabiliser combinations that are free of lead, barium and cadmium are therefore sought.Compounds of formula I have already been described in DE-PS 1 694 873, EP 65 934 and EP 41 479 and can be prepared in one or several process step(s) by known methods.It has now been found that A) compounds of formula I wherein R*l and R*2 are each independently of the other C1-Cl2alkyl, C3- C6alkenyl. C5-C8cycloalkyl that is unsubstituted or substituted by from I to 3 CI-C4alkyl, C1-C4alkoxy, C5-Cacycloalkyl or hydroxy groups or chlorine atoms, or C7-Cgphenylalkyl that is unsubstituted or substituted ait the phenyl ring by from I to 3 Ci-Coalkyl, C1-C4alkoxy, C5-C8cycloalkyI or hydroxy groups or chlorine atoms, and R*1 and R*2 may additionally be hydrogen and Cl-C1201kyl, and YV is 5 orG0.

can be combined with 8) at least one compound from the following group: perchlorate compounds and/or glycidyl compounds and/or beta-di keto nes, beta-keto esters and/or dihydropyridi nes, polydlihydra pyridines and/or **,pol'yols, disaccharide alcohols and/or sterically hindered amines (tetralkylpiperidine compounds) and/or alkali aluminosilicates (zeolites) and/or hydrotalcites and/or alkali aluminocarbonates (dawsonites) and/or, alkali- (or alkaline earth-) carboxylates,-bi)carboate 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 comprising A) at least one compound of formula I 0

NH

wherein P.zl and R.*2_are each independently. of the other cl-cl~alkyI. C3- C6alkeWyl C-5-Cacycloalkyl -that is unsubsltituted or substiltated by from I to 3 CI-C4,alkyl. C1-C4ulktxy. C5-Cacycloolkyl or by laydroxy- groups or chlorihe atoms. or C7-Cgphenyalkyl that is -unsubstituted or substituted -at the phenyl ringj by from I to 3 CI-C4calkyl. CI-C4aulkoxy. C5-Cacycloalkyl or by hydroxy groups or chlorine atoms and R*j and l*2 may additionally be hydrogen and Cj-C12cdkyl. and V is S- or 0. aid B) at least one perchlorate compound.

For compounds of formula I, CI-C4Alkyl is, for example: methyl, ethyl, n-propyl, isopropyl, iso-, sec- or tert-butyl.

C1-CI2Alkyl is. for example. in addition to the radicals just mentioned.

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

CI-CqAlkoxy is, for example, methoxy, ethoxy. propoxy. isopropoxy. butoxy or isobutoxy.

is, for example, cyclopeniyl, cyclohexyl, cycloheptyl or :cyclooclyl.

C7-C9Phenylalkyl is. for example, benzyl. I- or 2-phenylethyl, 3-phenylpropyl, a.a-dimethylbenzyl or 2 -phenylisopropyl, preferably benzyl.

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

C3-C6Alkenyl is, for example, vinyl, allyl. niethallyl, 1-butenyl or 1-hexenyl, _RA 4,preferably allyl.

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

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

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

The compounds of the groups mentioned under B) are illustrated as follows: Perchlorate compounds Examples are those of formula M(C104)n, wherein M is Li, Na, K; Mg, Ca, Sr, Zn, 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 S 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 reacton. 6lycerol 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 These contain the glycidyl group CH2 which is bonded I

R

2 R 3 directly to carbon, oxygen, nitrogen or sulfur atoms and wherein either R1 and R3 are both hydrogen, R2 is hydrogen or methyl and n=0, or R1 and R3 together are -CH2-CH2- or -CH2-CH2-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, sebdcic 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, oo* phthalic acid, isophthalic acid, trimellitic acid or pyromellitic acid.

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

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

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

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

They are, however, also derived, for example, from cycloaliphatic alcohols, such as 1,3- or 1,4-dihydroxycyclohexaine, bis(4-hydroxycycloihexyl)meithane, 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)diphenylmethane.

The epoxide compounds can also be derived from mononuclear phenols, such as phenol, resorcinol or hydroquinone, or they are based on polynuclear phenols, such as bis(4-hydroxyphenyl)meihane, 2,2-bis(4- :.:hydroxyphenyl)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-bi phenylglycidyl ether, N-(2 ,3epoxypropyl) phthalimide and 2 3 -epoxypropyl-4-methoxyphenyl ether.

If) (N-Glycidyl) compounds obtainable by dehydrochlorinating the reaction products of epichlorohydrin with amnines containing at least one aminohydrogen atom. Those amines are, for example, aniline, N-methylaniline, to luidi ne, n-butylami ne, bis(4-ami nophenyl)methane, m-xylylenediami ne or bis(4-methylami nophenyl)methane, but also N,N,O-triglycidyl-m-ami nopheno I or N,N,O-triglycidyl-p-aniinophenol.

The (N-glycidyl) compounds also include, however, NN",tr-triand N,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 isocyanurate.

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

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

Suitable terminal epoxides are, for example TM denotes 0): a) liquid diglycidyl ethers of bisphenol A, such as AralditeTmGY 240, AralditeTmGY 250, AralditeTmGY 260, AralditeTmGY 266, AralditeTmGY 2600, AralditeTMY 790; b) solid dliglycidyl ethers of bisphenol A, such as AralditermGT 6071, AralditeTmGT 7071, AralditeTmGT 7072, AraldliteTmGT 6063, AralditeTmGT 7203, AralditeTMGT 6064, AraldliteTmGT .7304, AralditeTMGT 7004, AraIditeTMGT 6084, AratditeTmGT 1999, AraldliteTmGT 7077, AralcliteTmGT 6097, AralditeTmGT 7097, AraldliteTmGT 7008, AralditeTMGT 6099, AralditeTmGT 6608, AralditeTmGT 6609, AralditeTmGT 6610; c) liquid diglycidyl ethers of bisphenol F, such as AralciteTmGY 281, AralcliteTmPY 302, AralditeTmPY 306; d) solid polyglycidyl ethers of tetraphenylethane, such as CG Epoxy ResinTmO163; e) 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-cresolformaldlehyde novolak, such as ECN 1235, ECN 1273, ECN 1280, ECN 1299: liquid glycidyl ethers of alcohols, such as ShellTm glycidyl ether 162, AralditeTmDY 0390, AralditeTmOY 0391; h) liquid glycidyl ethers of carboxylic acids, such as ShellTMCardlura E terephthalic acid. ester, trimellitic acid ester, AralditeTAPY 284; i) solid heterocyclic epoxy resins (triglycidyl isocyanurate), such as AraldliteTM PT 810; j) liquid cycloaliphatic epoxy resins, such as AralditeMCY 179; k) liquid N,N,O-triglycidyl ethers of p-aminophenol, such as AralditeTMY 0510; 1) tetraglycidyl-4,4'-methylenebenzamine or N,N,N',N-tetraglycidyldiaminophenylmethane, such as AraldliteTMY 720, AralditeTmMY 721.

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

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

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

Especially preferred as terminal epoxide compounds are diglycidyl ethers based on bisphenols, such as 2 2 -bis(4-hydroxyphenyl)propane (bisphenol

A),

bis(4-hydroxyphenyl)-methane or mixtures of bis(ortho/parahydroxyphenyl)mnethane (bisphenol F).

The terminal epoxide compounds can be used in an amount of, pr eferably, 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 PVIC.

Beta-iketowes, beta-keto esters l,3-icarbonyl compounds that can be used may be linear or cyclic dicarbonyl compounds. Preference is given to the use of dicarbonyl compounds of the following formula: R1ICO CHR2'-COR'3 wherein R' is C1-C22alkyl, C5-Clohydroxyalkyl, C2-Cl8alkenyl, phenyl, phenyl substituted by OH, CJ-C4alkyl, CI-C4alkoxy or by halogen, C7-Clophenylalkyl, CS-Cl 2cycloalkyl, C§-Cl2cycloalkyl substituted by Ci-C4alkyl, or is a group -R m -R'6 or -RS-O-R6, R'2 is hydrogen, C1-C8alkyl, C2-Cl2alkenyl, phenyl, C7-Cl2alkylphenyl, C7- Clophenylalkyl or a group -CO-R'4, R'3 has one of the meanings given for R'l or is Cl-Cl8alkoxy, R'4 is CjC4alkyl or phenyl, is C1-Cloalkylene and R'6 is Cl-Cl2alkyl, phenyl, C7-Cl8alkylphenyl 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, C1-Cl8alkyl, such as methyl, ethyl, iipropyl, isopropyl, n-butyl, tert-bulyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl or octadlecyl.

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

R'l 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, tolyl, xylyl, tert-butylphenyl, methoxyphenyl, ethoxyphenyl, hydroxyphenyl, ch lorophenyl or dicklorophenyl.

Ril and R'3 as phenylalkyl are especially benzyl. R'2 and R'3 as cycloalkyl or .:alkylcycloalkyl are especially cyclohexyl or methylcyclohexyl.

000R'2 as alkyl may be, especially, C1-Cakl as 2Caleymyb, especially, aly.R'2 as alkyiphenyl may be, especially, tolyl. R a2 as phenylalkyl may be, especially, benzyl. R'2 is preferably hydrogen, R' 3'as alkoxy may be, for oo* example, methoxy, ethoxy, butoxy, hexyloxy, oclyloxy, dodecyloxy, tridecyloxy, tetradecyloxy or octadecyloxy. R'5 as CI-Cloalkylene. is especially C2- C4alkylene. R'6 as alkyl is especially C4-Cl2alkyl, such as butyl, hexyl, octyl, 0 0 decyl or dodecyl. R'6 as alkylphenyl is especially tolyl. R'6 as phenylalkyl is 0:.0 especially benzyl.

Examples of 1,3-dicarbonyl compounds of the above formula and their alkali metal, alkaline earth metal and zinc chelates are acetylacetone, butanoylacetone, heptanoylacetone, stearoylacetone, palmitoylacetone, lauroylacetone, 7-tert-nonylthio-heptane-2 ,4-dione, benzoylacetone, di benzoylmethane, lauroylbenzoylmethane, palmitoyl-benzoylmethane, stearoylbenzoylmethane, isooctylbenzoylmethane, tribenzoylmethane, bis(4-methylbenzoyl)methahe, benzoyl-pch lorobenzoylmethane, bis(2-hydroxybenzoyl)methane, 4-methoxybenzoylbenzoylmethane, bis(4-methoxybenzoyl)methane, 1 -benzoyil-acetylnonane, benzoyl-aicetylphenylmethane, 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-ethylhexyl, dodecyl or octadecyl ester, and propionyl- and butyryl-acetic acid Cl-C18alkyl ester.

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

Preference is given to 1,3-diketo compounds of the above formula wherein R'1 is Cl-C18alkyl, phenyl. phenyl substituted by OH, methyl or by methoxy, C7- Cl0phenylalkyl or cyclohexyl, R'2 is hydrogen and R'3 has one of the meanings given for R'1.

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

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

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

H

3 C NH CH 3 COzCH 3 COzC 2 H CO2"C 1 2

H

2 5 or COzC 2

H

4

S"CIH

25 Suitable polydihydropyridines are especially compounds of the following formula *t wherein T is C1-C22alkyl that is unsubstituted or substituted by Ci- Ci 8a1 koxy, Cl-Cl 8al kylthio, hydroxy, acryloyloxy, methacryloyloxy, halogen, phenyl or by naphthyl; that is unsubstituted or substituted by C1-Cl8alkyl, C1-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' CH-COOR.- or CH3-C(NR"' 2)=CHCO-G L has the same meanings as T or is a tri- or poly-valent radical from an unsubstituted or C1-Cl2alkoxy-, C1-Cl2thioalkoxy-. C6-CloarYl-, Cj- C12carboxy- or hydroxy-substituted straight-chained or branched alkyl group, m and n are numbers from 0 to k is 0ori1, :j is a number from I to 6 and the conditions j m n) >'land m n 0 are satisfied, R and are each independently of the other methylene or phenylene or an alkylene group of the type -(-CpH2p-X-)t CpH2p- that is unsubstituted or carries substituents from the series C1-Cl2alkoxy, CI-Cl2thioalkoxy, C6- Cloaryl, Cl-Cl2carboxy and. hydroxy, p is from 2 to 18, :t is from 0 to X is oxygen or sulfur, or, when k isO0 and j Rand PR together with L form a direct bond, R' is hydrogen, or CI-Cl8alkyl, C2-Cl8alkoxycarbonyl or C6-Cloaryl each of which is unsubstituted or substituted by one or more Cl-Cl2alkyl, C1-C8alkoxy, halogen or N02 substituents, and the two R' radicals are identical or different and are hydrogen, Cj- Ci8alkyl, Cl-Ci8-hydroxyalkyl or C1-Cl8alkoxyalkyl or together are uninterrupted or 0-interrupted or are straight-chained or branched C2-C22oalkenyl.

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

12 Thiodiethylene-bis[5-methoxycarbonyl-2,6-dimethyl-1,4-dihydropyridine-3carboxylate] is especially preferred.

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

Polyols, disaccharide 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, tetramethylolcyclohexanol, tetramethylocyclopentanol, tetramethylocyclopyranol, glycerol, diglycerol, polyglycerol, thiodiglycerol or 1-0-a-I-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 (tetraalky/piperidine 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

3 C> CH3 They may be compounds of relatively low molecular weight (<700) or of relatively high molecular weight. In the latter case they may be oligomeric or polymeric products. Preference is given to tetramethylpiperidine compounds having a molecular weight of more than 700 that contain no ester groups.

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

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

a) Compounds of formula II

H

3 C

CH

3 IR N 0--R2 L H 3 C CH 3 wherein i n is a number from 1 to 4, preferably 1 or 2,

R

1 is hydrogen, oxy, C1-C12alkyl, C3-C8alkenyl, C3-C8alkynyl, C7-C12aralkyl, C1-C8alkanoyl, C3-C5alkenoyl, glycidyl or a group -CH2CH(OH)-Z, wherein Z is hydrogen, methyl or phenyl, R being preferably C1-C4alkyl, allyl, benzyl, acetyl or acryloyl, and, when n is1, R 2 is hydrogen, C1-C18alkyl that is uninterrupted or interrupted by one or more oxygen atoms, cyanoethyl, benzyl, glycidyl, a monovalent radical of an aliphatic, cycloaliphatic, araliphatic, unsaturated or aromatic carboxylic acid, carbamic acid or phosphorus-containing acid or a monovalent silyl radical, preferably a radical of an aliphatic carboxylic acid having from 2 to 18 carbon atoms, a cycloaliphatic carboxylic acid having from 7 to 15 carbon atoms, an 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 C1-C12alkylene, C4-C12alkenylene, xylylene, a divalent radical of an aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid, dicarbamic acid or phosphorus-containing acid or a divalent silyl radical, preferably a radical of an 14 aliphatic dlicarboxyli-c 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 phosphoruscontai ni ng acid or a trivalent si lyl. radical and, when n is 4, P.

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-butyl, tert-butyl, n-hexyl, n-oclyl, 2-ethyl-hexyl, nnonyl, n-decyl, n-undecyl or n-dodecyl.

In the meaning of C1-Cl8alkyl, R~ may be, for example, the groups listed above and, in addition, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or noctadecyl. C3C a eylitm yb.fre m le -rpnlalym ha yl When R 1 is 3Caknlitmybfreape -rpn, lym hly, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl or 4-tert-butyl-.2-butenyl.

R1as C3-C8alkynyl is preferably propargyl.

As C7-Cl2aralkyl, 11 1 is especially phenethyl and more especially benzyl.

R 1 ais C1-C8alkanoyl is, for example, formyl, propionyl, butyryl, octanoyl, but preferably acetyl, and as C3-C~alkenoyl is especially acryloyl.

When R 2 is a monovalent radical of a carboxylic acid, it is, for example, an acetic acid, caproic acid, ste~ric: acid, acrylic acid, methacrylic acid, benzoic acid or B-(3 5 -di-tert-butyl-4-hydroxyphenyl)-propionic acid radical.

When R 2 is a divalent ra dical 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, dibenzymalonic acid, di-tert-buyl-4-hydroxybenzyl)-malonic acid or bicycloheptenedicarboxylic acid radical.

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

When R2is a tetravalent radical of a tetracarboxylic acid, it is, for example, the tetravalent radical of butane- 1,2,3,4-tetracarboxylic acid or of pyromellitic acid.

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

The following compounds are examples of polyalkylpiperidine compounds of that class: 1) 4 -hydroxy-2,2,6,6-tetramethylpiperidine 2) 1-al lyl-4.-hydroxy-2 ,2,6 .6-tetramethyl p1peridi ne 3) 1 -benzyl-4-hydroxy-2 ,2 .6 6-tetramethylpiperidine 4) 1 -(4-tert-bu-yl-2-butenyl)-4-hydroxy- 2,2,6 .6-tetramethylpi peridi ne 4-stearoyloxy-2 .2,6 .6-tetramethylpi peridi ne 6) 1 -ethyl-4-sali cyloyloxy-2 .2.6,6-tetramethylpi peridi ne 7) 4-methacryloyloxy-1 .2,2,6 .6-pentamethylpi peridine 8) 1,2,2 .6,6-pentamethylpi peridi n- 4 -yl-1-(3,5-di-tert-butylA...hydroxyphenyl) propionate 9) di(1-benzyl-2 ,2 .6 6-.tetramethylpi peridi n-4-yl) malel nate di(2,2,.,6-tetramethylpiperidin-4.yl) succinate 11) di(2 ,2.6,6-tetramethylpiperidi n-4-yl) glutarate 12) di(2,2,6,6-tetramethylpiperidin-4-yl) adipal-e 13) di(2 ,2.6 ,6-tetramethylpiperidi n-4-yl) sebacate 14) di(1,2,2,6,6-pentamethylpiperidin-4-yi) sebacate di(i .2,3 ,6-tetramethyl-2 .6-diethylpi peridin-4-y) sebacate 16) di(1-allyl-2,2.6,6-tetramethylpi peridi n-4-yi) phthalate 17) 1-propargyl-40-cyanoethyloxy- 2,2,6 .6-tetramethylpiperidine 18) l-acetyl-2,2,6,6-tetramethylpiperidin-4yI acetate 19) trimellitic acid tri(2 2 6 ,6-tetrcimethylpiperidin-4-yl) ester 1 -acryloyl-4-benzyloxy-2 .2,6 .6-tetramethylpi peridine 21) diethylmalonic'acid di(2 .2.

6 6 -tetrmethylpi peridin-4-yl) ester 22) dibutylmalonic acid di(1 .2,2,6 .6-pentamethylpperidi n-4-yl) ester 23) butyl-(3 .S-di-tert-butyl-4-hydroxybenzyl)-malonic acid di(1 .2,2,6,6pentaniethylpi peridi n-4-yl) ester 24) dibenzyl-malonic acid di(1 ,2 .2.

6 6 -pentamethylpiperidi n-4-yl) ester dibenzyl-malonic acid di(1,2,3 .6-tetramethyl-2 .6-diethyl-piperidi n-4-yl) ester 26) hexane-1l.6'-bis(4-carbamoyloxy- 1-n-butyl- 2,2 .6,6-tetramethyl-piperidi ne) 27) toluene-2',4'-bis(4-carbamoyloxy-i -n-propyl-2 .2,6 .6-tetramethylpiperidine) 28) dimethyl-bis(2 ,2 ,6,6-tetramethylpiperidin-4-oxy)si lane 29) phenyl-tris(2 ,2 ,6 6-tetramethyl pi peridi 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-pentamethyl pi peridin-4-yl)J phosphonate 33) 4-hydroxy-1 .2,2 .6,6-pentamethylpiperidine 34) 4-hydroxy-N-hydroxyethyI-2 ,2 ,6 6-tetramethylpiperidi ne 4-hydroxy-N-(2-hydroxypropyl)- 2,2,6 .6-tetramethylpi peridi ne 36) 1-glycidyl-4-h'ydroxy-2 ,2.6,6-tetramethylpi peridine b) Compounds of formula (MI)

H

3 C CH 3 RTN

N-'R

IH3C CH 3 wherein n is the number I or 2, Iis as defined for a),

R

3 is hydrogen, C1-Cl2alkyl, C2-C~hydroxyalkyl, C5-C7cycloalkyl, C7- C8aralkyl, C2-Cl8alkanoyl, C3-Csalkenoyl or benzoyl, and, when n is 1, R 4 is hydrogen, CI-Cl8alkyl, C3-C8alkenyl, C5-C7cycloalkyl, Cl- C4alkyl substituted by a hydroxy, cyano, alkoxycarbonyl or carbamide group, glycidyl, a group of the formula -CH2-CH(OH)-Z or of the formula -CONH-Z, wherein Z is hydrogen, methyl or phenyl; and, when n is 2, R 4 is C2-Cl2alkylene, C6-Cl2ar-ylene, xylylene, a -CH2-CH(OH)-CH2- group or a group -CH2-CH(OH)- CH2-O-D-O-, wherein rt is C2-Cloalkyleme, C6-Cl~arylene or C6- C12cycloalkylene, or, with the proviso that R3is not alkanoyl, alkenoyl or benzoyl, R4may also be a divalent radical of an aliphatic, cycloaliphotic or aromatic dicarboxylic acid or dicarbamic acid or also the group -CO- or, 17 when n is 1, R 3 and R. 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-C7cycloalkyl, they are especially cyclohexyl.

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

R

3 is especially 2-hydroxyethyl or 2-hydroxypropyl.

R3as C2-Cl8alkanoyl is, for example, propionyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl, octadecanoyl, but preferably acetyl, and as C3- CWaen Py4 is epcially acryloythe it is, for example, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl or 2.-octenyl.

as C1-C4alkyl substituted by a hydroxy, cyano, alkoxycarbonyl or carbamide group may be, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2cyanoethyl, methoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2-* aminocarbonyipropyl or 2-(dimethylaminocarbonyl)-ethyl.

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

: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.

The following compounds are examples of polyalkylpiperidine compounds of that class: 37) bis(2 ,2 ,6,6-tetramethylpiperidi n-4-yl)hexcimethylene- 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) 1-acetyl-4-(N-cyclohexylacetamido)-2 ,2 ,6,6-tetramethylpiperidi ne 4-benzoylamino-2,2,6,6-tetramethylpiperidine 41) N,N-bis(2 ,2,6 ,6-tetramethylpiperidi n-4-yl butyl-adi pamide 42) NN-bis(2,2,6,6-tetramethylpiperidin4-y)-NN'dicIclohey.2hydroxypropylene-1 ,3-diami ne 43) N,N'-bis(2.

2 6 6 -tetramethylpiperidin-4-y)-p-xylyene-diamine 44) N,N-bis(2 ,2 .6 6-teiramethylpi peridi n-4-yl)succine-diamide N-(2 ,2,6 .6-tetramethylpiperidi n-4-y)-B-ni nodipropioni c acid di(2 ,2.6,6tetramethylpiperidin-4-yl) ester 46) the compound of the formula

OH

3 OH 3

C

CHi- N -N-CH 2 -CH(OH)-H---0

CH

3

OH

3 *0 0 .4 3CH3 OA

H

3

OH

Ci-N N0 2 -C(SH- SH 3

H

3 0 4

H

4n Cwherei n is the number I or 2, Ris as defined under a) and, when n is 1, R 5 is C2-C8alkylene or C2-C8hydroxyalkylene or C4- C22acyloxyalkylene, and, when n is 2, R 5 is the group (-CH2)2C(CH2-)2.

When R5.is C2-C8alkylene or C2-C8hydroxyalkylene, it is, for example, ethylene, 1-methyl-ethylene, propylene, 2-ethyl-propylene or 2-ethyl-2hydroxymethylpropylene.

As C4-C22acyloxyalkylene.

R

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

The following compounds are examples of polyalkylpiperidine compounds of that class: 50) 9-aza-8 ,8,10.10O-ttromethyl-1 .5-dioxaspiro 51) 9-aza-8.8,l0,10-tetramethyl-3-ethyl-1 ,5-d ioxaspiro 0 .0 52) 8-aza-2,7,7,8,9 9 -hexamethyl-1,4-dioxaspiro[4.5]decarne 53) 9-aza-3-hydroxyethyl-3ethy-88,9 ,1O,1-pentamethyl-1 54) 9-aza-3-ethyl-3-acet oxymethyl-9-aceyl.8 ,8 ,1O.10-tetramethyl-1 2,2 .6,6-tetramethylpiperidine-4-spiro-2' ,3'-dioxane)-5 -spiro-5" ,3"-dioxane)-2"-spiro-4' .6'"-tetramethylpiperidine).

d) Compounds of formulae VA, VB and VC F$2Y >Z!yj 1\ (VA) H 3 C

CH

3 R-N 0 L 12B N I H1 3 C CH 3

H

H

3 CH OH3 R- NJ

O-

(VC)

H1 3 C OH 3 0 n is th nubrIr2 P. isa.eie ne wen pis nubr 2 ord 2,sC-~ly rpeyanwe s2 7i 2 ishlydrgen CI-Cl2alkyl, a6-lly, enyle, gridorp -C2-CHalkoxyalkyI ad, *~~OC2C(H-H- whenei nDs1 ishdren C2-Cloalki. C-Clken, C7-~arlkl, C6- Z' scyrogeny, C-Cl~hyoxalkyl, C2-yC2lkoxalkly or Clnryl, lciylo andT grouph nepenl of the formul hyd)pCO- r ofgte formulakl -C)por -CO-Qtt o hel- r p i 1 r and Q ubsit C-Clorl 7Caalkyl, or pheyl and, whnniT2 i 2togaete wih4heclarboyne CCm thantem fogrou aC-C2yCH(oH)-CH-ring.

W-hen-Cnyof he-H- whereiun ts aeC-Cl~alkyley e,C forlexape, metyl Zeithydn-rogen, C-Ctlal, allbuyl, bezuyl, C2-elanyl nortl bexy, TIan T nonyl, n-decyl, n-undecyl or n-dodecyl.

Any substituents having the definition of C1-Cl8alkyl may be, for example, the groups listed above and in addition, for example, n-tridecyl, n-tetradecyl, nhexadecyl or n-octadecyl.

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

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

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

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

As C6-CiOaryl, R 7 Ti and T2 are especially phenyl, a- or B-naphthyl, whic h :are unsubstituted or substituted by halogen or by Ci-C4alkyl.

When R 7 is C2-Cl2alkylene, it is, for example, ethylene, propylene, 2,2dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.

:As C4-Cl2alkenylene, R7 is especially 2-butenylene, 2-pentenylene or 3hexenylene.

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

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

0) as C2-CiOalkylene, C6-Ci5arylene or C6-Cl2cycloalkylene is as defined under b).

The following compounds are examples of polyalkylpiperidine compounds of that class: 56) 3-benzyl- 1,3 ,8-triaza-7,7,9 1 9 -tetramethylspiro [4.5]decane-2 ,4-dione 57) 3-n-octyl-i ,3 8 -triaza-7,7, 9 9 -tetrcmethylspiro [4.5]decane-2 ,4-dione 58) 3-al lyl-1.3 ,8-triaza-1 .7,7,9 ,9-pentamethylspiro[4.5]decane-2 .4-dione 59) 3-glycidyl-1.3 ,8-triaza-7,7,8,9 ,9-pentamethylspiro[4.5]decane-2 .4-dione 1,3 .7,7,8,9,9-heptameihyl-1.3 ,8-triazaspiro[4.5]decane-2 4-diane 61) 2-isopropyl-7,7,9 .9-tetramethyl- 1-oxa-3.8 -dioza-4-oxo-spiro 62) 2 ,2-dibulyl-7,7,9 .9-tetramethyl- 1-oxa-3.8 -diaza-4-oxo-spiro 63) 2,2 .4,4-tetramethyl-7-oxa-3 ,20-diazo-2 1-oxo-dispiro (5.1.11.2 Iheni cosane 64) 2 -butyl-7,7,9 .9-tetramethyl- 1-oxa-4,8-diaza-3-oxo-spiro 8-acelyl-3-dodecyl-1.3 ,8-triaza-7,7,9 .9-tetramethyispi ro (4.5]decane-2 .4dione or the compounds of the following formulae:

OCH

3 66) 67) -CH 3 68) 69) PCH 3 ON OH 3 0

H

3 0 O H 3 0-C (OH) 1 1 N -H 2

CH

2 COO 12

H

2 OH 3

OH

3 0 OH 3 e) Compounds of formula VI N ~N (VI), n wherein n is the number I or 2 and R 8 is a group of the formula 3

CH

3 N-R1 x

CH

3

CH

3 wherein ft 1 is as defined under a), E is -0-or -NRt- A is C2-C6alkylene or -(CH2)3-O- and x is the number 0 or 1, Ris identical to Rt 8 or is one of the groups -NP.

11

R

12 _011 13 -NHCH2OR 13 or -N(CH20R 13 )2.

when n 1, Rio 0 is identical to R 8 or R 9 and, when n Rio is a group -E-Bwherein 8 is C2-C6alkylene that is uninterrupted or interrupted by -N(P 11 ft 1 is C1-Cl2alkyl, cyclohexyl, benzyl or C1-C4hydroxyalkyl or a group of the formula R CH 3

CH

2

R

N-R

CH 3 CH 2

R

R

12 is Cl-Cl2alkyI, cyclohexyl. benzyl, CI-C4hydroxyalkyl and

R.

13 is hydrogen, C1-Cl2alkyl or phenyl, or RIand R 12 together are C4-C5alkylene or C4-C5oxaalkylene, for example O H 2 C H 2 H C H 2 0or N-Ror are a group of the formula -O H 2 H o Ir -CH 2 CH 2 2

CH

2

N-R

1 -/CH 2 or alternatively Ril and R12 are each a group of the formula CH CH HNN

HA

NyN

H

3

CH

3

C

4

H,-N

OH

3 OH 3

HNH

When any of the substituents are C1-Cl2al kyl they are, for example, methyl, ethyl, n-propyl, n-butyl' sec-bulyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, nnonyl, n-decyl, n-undecyl or n-dodecyl.

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

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

When R 11 and R12 together are C4-C5alkylene. or C4-C!5oxaalkylene, they are, for example, tetramethylene, pentamethylene or 3-oxapentamethylene.

The compounds of the following formulae are examples of polyalkylpiperidline compounds of that class;

CH

3 H 0 I OH3 3

N

7)H 3 C H 3 N-C H9 (CH3H2)N IN N(CH 2

CH

3 2

(CH

3

OH

2 2

N

N(

4

H

9 2 C H. C H 3. C H C 2

H

5 -N 12 N N-CH 5

OHS

OH

3

OH

3 OH OH 3 R

H

3 C OH 3 *72) N whriR -NH-CH 2

CH

2 CH2-O N-OH 3 ii 'N R H H eCH 3 4H

CH

3 73)

CH

3

CH

3

CH

3 4 74)

OHH

HN N -Z-ZNHCH c CH, y

N

H{CH H

I

CHf H CH.~ 1 H

CH>NI

H

R-H-CH)--(CH

2

(IC..

2 3

-H-R

OH

3 CH 3 ,wherein R is 76) 2

N-

2 3

-N-R

wherein R=

C

C

C C

C

OCH

3

-CH

3 77) CH 3 R R CH3

CH

3 wherein R=

OH

3

OH

3 ICH 3 78) NH(CH213--+- O

H

3

S.

S

S. S

SS

SS

5* S S .9 S S 55

S

S

5**S

SS

S. 9 5.5.

S S

S

S

S

S.

5

S

2

CHCH

2

OH

CH

CH 3 N C3

OH

3

OH

3 79)

OH

3

CH;'

29

CH

2

-CH=CH

2

CH

H

3 N 3

H

3 CV CH 3

N-C

4 H9

H

3 C CH C~ H 3

CH

3

H

2

C=HC-H

2 C- NX)

N-CH

2

-CH=CH

2

H

3 C CH 3 01-3 OH 3 Oligomeric or polymeric compounds, the structural repeating unit of which contains one or more 2 .26,6-tetraalkylpiperidine radicals of formula especially polyesters, polyethers, polyamides, polyamines, polyurethanes, ~po lyureas, polyami notriazi nes, po Iy(meth)acrylates, polysi loxanes, poly(meth)acrylamides and the copolymers thereof that contain such radicals.

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

CH

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

C

2

-COCH

2

C

2 a-I

CH

3 CH, CH, 0 0 CH, Cm, 0 0 82) -CCCN0 C-C24- C 0 -FCN0 m CH, CH, CH, CF 3 83) CAll 84) A OH 3 N

CH

2 -CH(OH)i-CH 2 m

CH

3 OH 3

OH

3 N CH3

H

86)

OH

3

OH

3 OH CH 3 0 49 0 N CH=CH-0H 2 -N 0-0 0

C;

4

H

9

OH

3

CH

3

OH

3

OH

87) a a a.

a 88)

OH

3 89)

OH

3

ICH

3 m

I-CH

3

OH

3

CH

3 91 OH 3

OH

3 m CH -N

N-OH

3 6 13

OH

3

OH

3 0)

N

H H m OH CH 3

OH

3 OH3 H 3 CH N. OiC H H 3 C~ H 3

H

H HH 0 0

-N-(OH

2 6 N-C Cr C 94)

J,

ICH

3

OH

3

CH-

CH

3

(CH

2 3 0 wherein R H or CR3

OH

3

OH

3 CH3-

NR

OH

3

OH

3

H

9 0 4 (R)N ~N N(R)CAH

NN..

NNH

CH 2)3H

H

9

C

4 (R)N "NN-(EN~i--N R1

NHN

N:k

H

9

C

4 (R)N NN N(R)C4H.

H3 CH3-' whena orHCH CtnQ K or H (obtainable by reacting the reaction product of trichiorotriazine and NH-2- (CH2)3 -NH-(CH2)2-(CH2)3-NH2 with 4-N-butyl-2 ,2 .6 6 -tetramethylpiperidi ne) Of those classes, classes e) and f) are especially suitable, especially those tetraalkylpiperidine compounds that contain s-triazine groups. Also especially suitable are compounds 74, 76, 84, 87,.92, 95 and 96.

The preparation of the N-piperidinyl-triazines is known from the literature for example, Houben-Weyl 'Methoden d&r organischen Chemie', Vol. VII, p. 233-237, 3 rd Ed., Thiem e Verlag Stuttgart 1971). There may be used as starting material for the reaction with various N-piperidylamines cyanuric chloride, diamino-chloro-1.3,5-triazine or variously substituted bisdialkylaminochloro- 1,3 ,5-triazines or dialkylaMino- or alkylamino-dichlor-o-1 .3,5-triazi nes.

Technically important examples of tetra' and pentoalkylpiperidine compounds are: bis( 2 2 ,6,6-tetrdmethyl'piperidyl) sebacate, bis(2,2,6,6tetramethyl-piperidyl) sop-clNate, bis -l,2.

2 .6,6-pentamethylpipericiyl) sebacate, n-butyl-3 ,5-di-tert-buty!lA-h d-yeey.malonic acid bis(1 .2,2 6,6pentamethylpiperidyl) ester., the condensation product of 1-hydroxyethyl- 2 2 6 6 -tetramethyl-4 hydroxy-piperldine and succinic acid, the. condensation product of N,N'-bis(2 ,2,66tta ty-4pprdl-eamtyeeim and 4-tert-ocylamino-2 .6-dichloro-1 3 ,S5-s-triazine, tris(2 .2,6 .6-tetramethyl-4pi peridyl)nitrilotriacetate, tetakis(2,2,6,6-tetramethyl4-pi peridyl)-1 .2,3,4butanetetraioate, Il'(,-tc.dy)-:bgs(3 3 ,5.-tetramethyl-piperazi none), 4benzoyl-2 ,2 .6.6-tetran64 .t4 yppedn,-stearyloxy-2,2,6,6tetramethylpiperidine, bis(t,, 6 kp nitamethylpiperdyl)- 2-n-butyl-2-(2hydroxy-3 ,5-di-ter-t-butylbenzl) maolona te, 3-n-oclyl-7,7,9 .9-tetramethyl- 1,3 ,8-triazaspiro[4.5Jde ae2,4-4lne, bis(1-octyoxy-2 .2,6,6tetramethylpiperidyl)-sebacarte, bil'4Ocyloxy-2,2,66*tetraethylpiperidyl) succi note, the condensation product of N,N -bis(2 .2 6,6-tetramethyl-4pi peridyl)hexamethylenedlomin'e and 4-morpholi no-2 ,6-dichloro-l .3 the condensation produ ct of 2 -chloro-4,6-di(4-n-butylamino.2 ,2 ,6,6tetramethylpiperidyl)-1 ,3,5-!triai ne and ,1,2-bis(3-ami nopropylami no)ethane, the condensation product of.

2 -chloro-4,6-.di(4-n-butylami no-i ,2 ,2 6,6pentamethylpiperidyl)- I3 .5fiziead 1 2 -bis(3-aminopropylami no)ethane, 8acetyl-3-dodecyl-7.7.9-,9-1t. 00methyl..l 3 .8-triazaspiro [4.5]decane-2 .4-dione, 3 -dodecyl-1-(2.2 6 6 -tetramethyl-4 piperidyl)pyrrolidine-2 ,5-dione, 3-dodecyl- 1 6 -pentamethyl-4-piperidyl)-pyrrolidi ne-2 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.

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

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

M

3 Al, orB, n.

An is an anion having the valency n, b is anumber fromlIto 2, 0 -x E 0.5, and m is a number from 0 to Preferably, An 0H-, C104-, HC03-, CH3COO-, C6HS1COO-, C03 2 (CHOHCOO)2 (CH2COO)2 2 CH3CHOHCOO HP03 or HP04 2 Examples of hydrotalcites are Al 203.6MgO.C02.1 2H20 Mg4,5A 12(OH)1 3.C03.3.5H20 (ii), 4MgO.Al2O3.CQ2.9H2o (iii), 4MgO.A1203.C02.6H20, ZflO.3M90.A20 3 .C0 2 -8 9H-20 and ZnO.3MgO.Al2O3.CO2.5-6H 2 0. Special preference is given to types i, ii and iii.

Zeolites (alkali and alkaline earth alum inosilicates) These can be described by general formula (VIII) Mxn*I0)*i2)]W2

(V

.2 wherein n is the charge of the cation M: Mis an element of Group I or Group 171, such as Li, Na, KC, Mg, Ca, Sr or 8a;~ y:x is a number from 0.8 to 15, preferably from 0.8 to 1.2; and w is a number from 0 to 300, preferably from 0.5 to Examples of zeolites are sodium aluminosilicates of the formulae Na 12AI12Si12O48. 27 H20 (zeolite N 0A16Si6O2 4 2 NaX. 7.5 X: OH, halogen, C104 (sodalite]: Na6AI6Si300l 2 24 H20; Na8Al8Si4009 6 24 H20; Na1A116Si24O 8 O. 16-1H20; Na16A1165i32C) 96 16 Na56A150Si36O 384 250 H20 [zeolite YJ, NcI86Al86Si1O0 384 264 (zeolite X] or the zeolites that can be formed by partial or complete replacement of the lNa atoms by Li, KC, Mg, Ca, Sr or Zn atoms, such as (NaK)1OAl1OSi2206 4 20 H20; Ca4.5Na3[(Al02)12(Si0 2 121 30 K9NaS[(A02)12(i0 2 12 27 Preferred zeolites correspond to the formulae Na12All 2 5il 2

O

48 27 H 2 0 (zeolite A], Na6Al65i6O24. 2NaX.- 7.5 H20, X OH, Cl, C104, 1/2C03 [sodalite] Nk6AI6Si3O72. 24 N08AI8S4009 6 24 Na16AlI6Si240 8 0. 16 Na16Al16532O 96 16 Na56Al565i1360384. 250 H20 (zeoliteY] Na86Al86Si106O384. 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 No atoms by Li, K, Mg, Ca, Sr, Ba or Zn atoms, such as (Nc,K)Al1Si22O64. 20 Ca4,5a3[(A102)12(SiO2)12]. 30 K9NaG3((AlO2)12(SiO2)12]. 27 :The zeolites listed may also have a lower water content or may be anhydrous.

Other suitable zeolites are: Na2O*AI20 3 to 5) SiO 2 to 10) H 2 0 [zeolite P] :N020-AI20 3 -2 Si02-(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,Na,K,H) 0 Al 10 Si 22

O

64 20 H 2 0 K9NO4 3 (A0 2 12 (SiO 2 12 J. 27 K4AI 4 Si 4

O

16 '6 H20. [zeolite K-F] Na8Al8Si4J0g6.24 H20 zeolite 0, as described in Barrer et al, J. Chem.

Soc. 1952, 1561-1571, and in US 2 950 952: The following zeolites are also suitable: potassium offretite, as described in EP-A-400 961; zeolite kas described in 6B 841 812; zeolite LZ-217, as described in US 4 503 023; Ca-free zeolite LZ-2 18, as described in US 4 333 859; zeolite T, zeolite LZ-220, as described in US 4 503 023; Na3K 6 A1 9 Si 27

O

72 .21 H20 [zeolite L]; zeolite LZ-211, as described in US 4 503 023; zeolite LZ-212, as described in US 4 503 023; zeolite 0, zeolite LZ-2 17, 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 etal, J. Chem. Soc. 1956, 2882; Na 30 A1 30 Si 6 6 0 1 92. 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 orPc) and tetragonal (zeolite Pi) zeolites of the P type. That publication also mentions relatively new zeolites of the P type having Si:Al ratios of less than 1.07:1. Those are zeolites designated MAP or MA-P for "Maximum Aluminium P".

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

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

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

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

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

Alkali aluminocarbonates (dawsonites) These are compounds of the formula ((M20)m.(A1203)n.Zo.pH20), wherein M is H, Li, Na, K, Mgl/2, Cal/2, Srl/2 or Znl/2; Z is C02, S02, (C1207)1/2, B406, 5202 (thiosulfate) or C202 (oxalate); m is a number from 1 to 2 when M is Mgl/2 or Cal/a, and in all other cases is a number from 1 to 3; n is a number from 1 to 4; o is a number from 2 to 4; and p is a number from 0 to The alumino salt compounds of formula that can be used according to the irnvention may be naturally occurring Minerals or synthetically prepared componds. he meals my patilyrplc one another. The mentioned alumino salt compounds are crystalie partially crystalline or amorphous or may be present in the form of a dried gel. The alumino salt compounds may also be present in relatively rare crystalline -modifications. A process for the preparation of such compounds Is described in EP 394 *670. Examples of :00 naturally occurring alumino salt copounds are indigirite, tunisite, :0 aluminohydrocalcite, para-alumninohyrclie m.otoresrt an hydrostrontiodresserit& Other eximples of alumni no salt compounds are potassium aluminocdarbonate ((K20).A120).C022.2H-20). sodium -lmntislae(N~)(lO)(2222 O. potassium aluminosul fite (OC2OMA1203).(502)2.2IH20}, cdlciw .Maluminooxalate ((CaO)(A203).(C202)2.5H20), magnesium, aluminotetraborate ((MgO).A 1203).(E1406)2.5H20O). (([MgO.2NaO.6]20).(A 1203 ).(C02)2.4.l (([Mgo.2NaO.6]20).(A 1203).(C02)2.4.3H20) and (Q[MgO.3Nac.4]20).(A 1203).(C02)2.2.4.9H20).

*The mixed alumino salt compounds can be obtained in accordan ce with processes known per se by ukt6o~ #C%1,prfral0fo the alkali alumino salt compounds or by oombined w$tin(see, for example, US 5 055 284).

Preference is given- to aluminao salt compounds of the above formula wherein M is Na or K; Z is C02, S02 or (C1207)1/2; Mn 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 pH-2O (TO) (M20)2.(A1203)2.(02)42 PH20 (Ib) M20.(A1203)2.(02)2 pH2O6 (1c) wherein M is a metal, such as Na, K, Mgl/2, Cal/2, Sri/2 or ZnI/2 and p is a number from 0 to 12.

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

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

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

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

The stabiliser combination according to the invention can be used together with further additives that are customary for the processing and stabilisation of chlorine-containing polymers, such as: :Zinc compounds The organic zinc compounds having a Zn-O bond are zinc enolates and/or zinc i carboxylates. The latter are, for example, compounds from the series of aliphatic saturated C2-C22carboxylates, aliphatic unsaturated C3- C22carboxylates, aliphatic C2-C22carboxylates that are substituted by at least one OH group or the chain of which is interrupted at least by one oxygen atom (oxa acids), cyclic and bicyclic carboxylates having from 5 to 22 carbon atoms, phenylcarboxylates that are unsubstituted, substituted by at least one OH group and/or Cl-Cl6alkyl-substituted, phenyl-Cl-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, 3,6dlioxaheptanoic acid, 3,6,9--trioxadecanoic acid, behenic acid, benzoic acid, ptert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3 .5-di-tert-bulyl-4.

hydroxybenzoic acid, toluic acid, dlimethylbenzoic acid, ethylbenzoic acid, npropylbenzoic acid, salicylic acid, p-tert-ocylsalicylic 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-dicarboxyli c acid, heptane-1 .7-dicarboxylic acid, octane-I ,8-dicarboxylic acid, 3,6 ,9-trioxadecane-l .10-dicarboxyli c acid, lactic acid, malonic acid, maleic acid, tartaric acid, cinnamic acid, mandelic. acid, malic acid, glycolic acid, oxalic acid, salicylic acid, polyglycol-dicarboxylkc. acid 12), phthalic acid, isophthafic acid, terephthalic acid and hydrdxy*4rhalic acid; and the di- or tni-esters of tri- or fetra-valent carboxylic acids, so&ch as hemimellitic acid, trimellitic acid,. pyromellitic acid, citric acid and 6ilso so-called overbased zinc carboxylates.

The zinc enolates are preferably enola-tes of acelylacetone, benzoylacetone or dibenzoylmethane and enolates of acetoacetciles and benzoyl acetates and of dehycfroacetic acid. In addition, inorganic zinc compounds, such as 2.inc oxide, 00 zinc hydroxide, zinc sulfide or zinc carbonate, can also be used.

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

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

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

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

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

and thiophosphates, mercaptocarboxylic acid esters, epoxidised fatly acid esters, antioxidlants, UV absorbers and light stabilisers, optical brigqhteners,' impact strength modifiers and processing aids, gelling agents, antistatic agents, biocides, metal deactivators, fireproofing agents and propellants, and antifogging'agents (cf. '1Handbook of PVC Formulating" by E. J. Wickson, John Wiley 4& Sons, New York 1993).

In a non-limiting manner, some of the known additives and processing auxiliaries are mentioned here: Alkali metal and alkaline earth metal compoundr These are to be understood to include especially the carboxylates of the acids describe-d above, but also corresponding oxides or hydroxides or .:(bi)carbonates. Mixtures thereof with organic acids are also suitable. Examples V,0 are Na-OH, No-stearate, NaHCO 3 KOH. I-stearate, KCHCO 3 LiOHI U 2 C0 3 Li- ::stearate, CO. Ca(0H2). Mg0. Mg(OH)2. Mg-stearate, CaCO3. M9C03 as well o 0. -as dolomite, huntit. chalk, basic Mg-carbonate and other Wa- and K-salts of fatty acids.

NaOH, KOH. Coo, Ca(0H2). Mg0, Mg(OH)2, CaC03 and MgCO3 and also 0 fatty acid sodium and potassium salts.

In the case of alkaline earth metal and zinc carboxylates. it is also possible for their adducts with MO or M(OH) 2 (M Ca. Mg, Sr or Zn), so-called *0 "overbased" compounds, to be used.

0:00 Preference is given to alkali metal, alkaline earth metal and/or aluminium, *.:carboxylates in addition to the stabiliser combination according to the invention.

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

i6lidan ts(L UBRICA NTS) suitable glidants are, for example: Montan- wax, fatty acid esters, PE waxes, amiide 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, T4 Ed., 1989, pages 478-488. Mention may also be made of fatty ketones (as described in DE 42 04 887) and of silicone-based glidants (as described in EP 225 261) or combinations thereof, as listed in EP 259 783.

Plasticisers Suitable organic plasticisers are, for example, -those of the following groups: Phthalic acid esters: Examples of such plasticisers are dimethyl., diethyl, dibutyl, dihexyl, di-2ethylhexyl, di-n-ocil diisooctyl, diisononyl, diisodecyl, diisotridecy1, dicyclohexyl, dimethylcyclohexyl, dimethylglycol, dibutyiglycol, benzylbutyl and diphenyl phthalate and mixtures of phthalates, such as C7-C9- and C9- CuI-alkyl phthalates from predominantly linear alcohols, C6-CIo-n-akyl phthalates and C8-Clo-n-alkyl phthalates. Of those compounds, preference is given to dibutyl, dihexyl, di-2-ethylhexyl, di-n-octyl, diisooclyl, diisononyl, diisodecyl, diisotridecyl and benzylbutyl phthalat e and to the mentioned mixtures of alkyl phthalates. Special preference is given to di-2-ethylhexyl, diisononyl and diisodecyl phthalate, which are also known by the custonmry abbreviations DOP (dioctyl phthalate, di-2-ethylhexyl phthalate), IDINP (diisononyl phthalate), DIbP (diisodecyl phthalate).

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

C) Trimellitic acid-esters, for example tri-2-ethylhexyl trimellitate, triisodecyl trimellitate (mixture), triisotridecyl trimellitate, triisooctyl trimellitate (mixture) and tri -C6-C8alkyl, tri-C6-ClOalkyI, tri-C7.Cgalkyl and tri-C9-C1 lalkyl trimellitate. The last-mentioned trimellitates are formed by esterifying trimellitic acid with the appropriate alkanol mixtures. Preferred trimellitates; are tri-2-ethylhexyl trimellitate and the mentioned trimellitates from alkanol mixtures. Customary abbreviations are TOTM (trioctyl trimellitate, tri -2-ethyilhexyl trimellitato)i TIMTM (triisodecyl trimellitate) and TIMbTM (triisotridecyl trimeltitate).

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

**QE Polymer plasticiSers A definition of teeplasticisers: and examples thereof are given in SlKunststoffadditive (Plastics additives), R. GSchter/H. M~ller, Carl Hanser **:Verlag. T'i Ed., 1989,'Chapter 5. 16, pages 412-415, and in "PVC Technology", SW.;V. Titow, 4" d.Esvp*NL 94 pages 165-170. 'The most commonly used starting materials for the preparation of polyester'plasticisers are: dicarboxylic acids, such as adipic, phthalic, azelaic and sebacic acid; diols, such as 1 ,2-pr-opanediol,1I 3Obu'tanediol, I .4-butanediol, 1 .6-hexantediol, neopentyl glycol and diethylene -glycol.

F) Phosphoric acid. esters.

A definition of thoseg 'qsIs to be found in the above-mentioned "Tschebuc derl~unt~fIaddtive(Handbook of Plastics Additives), Chapter 5.9.5, p.p. 46ei E xamples of such phosphoric acid esters are tributyl phosphate., tri-2-ethylbutyl phosphate, tri-2-ethylhexyl phosphate, trichloroethyl phosphate, 9-ethyl-hexyl-diphenyl phosphate.. cresyl diphenyl phosphate, triphenyl phosphate, tricresyl phosphate and trixylenyl phosphate. Tri-2-ethylhexyI phosphate and TMReofos 50 and 95 (Ciba-Geigy) are preferred.

G) Chlorinated hydrocarbons (paraff ins) H) Hydrocarbons I) Monoesters, eig. .butyl oleate, phenoxyethyI oleate, tetrahydrofurfuryl oleate and alkyi4uf~cai estes 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. Giichter/H. Miller, Carl Hanser Verlag, 3" Ed., 1989, Chapter 5.9.14.2, p.p. 422-425 (group and Chapter 5.9.14.1, p. 422 (group H).

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

It is also possible to use mixtures of different plasticisers.

The plasticisers can be used in an amount of, for example, from 5 to 120, S- 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, FezOs, SbzOs, (Ti,Ba,Sb)O 2 CrzO 3 spinels, such as cobalt blue and cobalt green, Cd(S,Se), ultramarine blue. Organic pigments are, for example, azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, diketo-pyrrolopyrrole pigments and anthraquinone pigments. Preference is also given to TiOz in micronised form.

Definitions and further descriptions are to be found in the "Handbook of PVC Formulating", E.J.Wickson, John Wiley Sons, 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.Gdchter H.Miller, 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 dialkyl phosphites, tris-(nonylphenyl) phosphite, tri lauryl phosphite, trioctadecyl phosphite, distearyl-pentaerythriiol di phosphite, tris(2 .4-di-tert-butylphenyl) phosphite.. diisodecylpentgerythritol di phosphite, bis(2 .4-di-tert- .butylphenyl)pentaerythritol di phosphite, bis(2 6 -di-tert-buyl-4-metylphenyl).

pentaerythritol diphosphite, bis-isodecyloxy-pentaerythritol diphosphite.

bis(2 .4-di -tert-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2 ,4,6-tritert-butylphenyl)pentaerythritol diphosphite, tristearyl-sorbitol triphosphite, bis(2,4-di-tert-buyl-6-methylphenyl)methy phosphite, bis(2 .4-di-tert-bulyl-6met hylphenyl)ethyl phosphite.

**.Especially suitable are trioclyl, tridecy-1. tridodecyl,. tritetradecyl, tristear-yl, trioleyl, triphenyl- tricresyl, tris-p-nonylphenyl or tricyclohexyl phosphite and special preference is given to the aryl-dialkyl and alkyl-diaryl phosphites, such as phenyldidecyl phosphite, (2 ,4-di-tert-butylphenyl)-di.dodecyI phosphite, (2,6di-tert-butylphenyl)-di-dodecyl phosphite -and to the dialkyl- and diarylpentaerythritol diphosphites, such as distearylpentaerythritol diphosphite, and non-stoichiometric triaryl phosphites, for example those having the composition (Hi 9C9-C6H4)O1.5P(OCi 2.13 H25.27)l.5.

Preferred organic phosphites are distear-yl-pentaerythritol diphosphite, trisnonylphenyl phosphite and phenyldidecyl phosphite..

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

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

(RS)

3 P, (RS) 3 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, trithio phosphorous acid tris(carboisooctyloxy)methyl ester, trithio phosphorous acid tris(carbotrimethylcyclohexyloxy)methyl ester, trithiophosphori c acid S ,S,Stris(carboisooctyloxy)methyl ester, trithiophosphoric acid S,S,S-tris(carbo-2elhylhexyloxy)methyl ester, trithiophosphoric acid S,SS-tris-1- (ccrbohexyloxy)-ethyl ester, trithiophosphoric acid SS,S-tris-l-(carbo-2ethylhexyloxy)-ethyl ester, trithiophosphori c acid S,S,S-tris-2-(carbo-2e-thylhexyloxy)-ethyl ester.

Mercaptocarboxylic acid esters Examples of these compounds are: esters of the thioglycolic acid, thiomnalic 4* acid, mercaptopropionic acid, mercoptobenzoic 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 (fartty acid glycerides), such as soya oil or rape oil. It is, however, also possible to use synthetic products, such as epoxidised butyl oleate.

Antioxidants Suitable antioxidants are, for example: 1. 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-.ditert-butyl-4-n-butylphenol, 2 ,6-di-tert-butyl-4-isobutylpheno I, 2,6dicyclopentyl-4-methylpheno I, 2 -(a-methylcyclohexyl)-4,6-dimethylphenol, 2 ,6-dioctadecyl-4-methylphenol, 2 ,4,6-tricyclohexylpheno I, 2 ,6-di-tertbutyl-4-methoxymethylphenol, 2 ,6-di-rnonyl-4-methylpheno I, 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-'-yl)phenol, octylphenol, nonylpheno I, dlodecylpheno I and mixtures thereof.

2. Alkylthiomethyiphenols. for example 2 ,4-di-octyl1thiomethyl-6-tert-.

butylpheriol. 2 .4-di-oclylthiomethyl-6-methylphenol, 2 .4-di-octylthiomethyl- 6-ethylphenol, 2 .6-di -dodecyithiomethyl -4-rnonylphenol.

3. Alykted hydroguinones. for example 2.6-di-tert-butyl-4methoxyphenol, 2 .5-di-tert-butyl-hydroquinone, 2,5-di -tert-amylhydroquinone, 2 .6-diphenyl-4-octadecyloxypheno 12 ,6-di -teri-butylhydroquinone-. 2 .5-di-tert-bulyl-4-hydroxyanisole, 3 ,5-di-tert-bulyl-4hydroxyanisole, 3 .5-di-tert-buiyl-4-hydr-oxyphenylstearate, bis(3 butyl-4-hydroxyphenyl) adipate.

4. Hydoxylated thiodiphenyl ethers, for example 2,2-thio-bis(6-tert- *e butyl-4-methylphenol), 2 .2'-thio-bis(4-octyphenol),.4-thio-bis(6-tertbutyl-3-methylphenol), 4.4'-thio-bis(6-tert-buyl-2-methylphenol), 4,4'-thiobis(3 .6-di-sec-amylphenol), 4,4'-bis(2,6-dimethyl-4-hydroxyphenvyl) disulfide.

5. Alkylidene-bi-Sphenols. for example 2,2'-methylene-bis(6-tert-butyl-4.

:methyiphenol), 2, -m-rethylee-bis(6-tet-buyl-4-ethylphenol), 2,2'methylene.-bis[4-methyl-6-(a-mnethylcyclohexyl)phenol], 2,2'-~methylene- *bis(4-mnethyl-6--cyclohexylphenol), 2,2'-methyene-bis(6-'nonyl-4.

~.methylphenol). 2,2'-methylene-bis(4,6-di-tert-buylphenol), 2,2'-ethylidenebis(4,6-di-terl-butylphenol), 2 ,2'-ethylidene-bis(6-1ert-bulyl-4- '**isobulylphenol), 2.

2 '-methylene--bis[6-(a-methylbenzyly.4-nonylphenol], 2,2'methylene.-bis[6-(aa-dimethylbenzyl)-4-onylphenol], 4,4'-methylenebis(2.6-di-tert-butylphenol), 4.4'-methylene-bis(6-tert-buty-2meihyiphenol), I .l-bis(5-tert-butyl-4-hydroxcy-2-methylpheiyl)butane, 2,6bis(3-tert-buyl-5-methyl-2-hydroxybenzyl)-4.methylphenol, 1,1 tert-butyl-4-hydroxy-2-iethylphenyl)butane, 1,1-bis(5-tert-buiyl-4-.

hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, ethylene glycolbis[3 .3-bis(3'-tert-butyl-4-hydroxyphenyl) butyrate], bis(3-1ert-butyl-4dicyclopentadiene, bis[2-(3'-tert-buyl-2'-hydroxy- 5'-methyl-benzyl)-6-tert-butyl-4-methylphenyt J terephthalate, 1 ,1-bis(3 dimethyl-2-hydroxyphenyl)butarne, 2 ,2-bis(3 .5-di -tert-butyl-4hydroxyphenyl)propane, 2 2 -bis(4-hydroxyphenyl)propane., 2 butyl- 4 -hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane, 1,1,5.5tetra(5-tert-butyl-4-hydroxy-2methylphenyl)pentane.

6. Senjyl compounds, for example 3.5,3.,5'-tetra-tert-butyl-4,4'dihydroxydibenzyl ether, octadecyl-4-lrydroxy-3 mercaptoacetate, tris(3 .S-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tertbutyl-3-hydroxy-2 .6-dimethylbenzyl) dithioterephtholate, bis(3 butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert-buyl-4-hydroxybenzyI mercaptoacetate.

7. Hyro25ybenzylated malooq1-e. for example dioctodecyl-2.2-bis(3,5di-tert-buyl-2-hydroxybenzyl) malonate, di-octadecyl-2-(3-tert-butyl.4 dldodecytmercaptoeihyl -2 .2-bis(3,5-di- 1ert-bulyl-4-hydroxybenzl). malonale, di.(4-(1 .1.3,3tetrarnethylbuyl)phenylJ-2,2-bis(3 .5-di-ter-t-buly-4-hydroxybenzyl) maloniate.

8. E~IcLQ jtwW~ic cmgds for example 1,3,5-tris(3,5-ditert-butyl-4-hydxybenzyl)-2.4.6-trmethylbenizene, 1,4-bis(3,5-di-tertbuy-4-hydroxybonMyl-4.6-tete'wuthyll. ene 2.6-tris(3 ~:butyl-4-hydroxyboniyl Vpheurl.

9. rizin Ow&.flor excample 2+4biS-octlmercapto-6-(3,5.di.

~.:~:tert-butyl4hcfr'byunal1n4-z1 4rlazine, 2-octlytmercapto-4,6-bis(3,5-ditert-bulyl-4-h7ydrxawf4 ,3,trezNs 2-"ctlmercipto-4,6-bs(3,5-di-.

tert-butyl-4-hydroxyphernxyt)-1.3*,5-iricizine, 2,4,6-tras(3 .5-dI-tert-buty-4hydroxyphenoxy)-1.2,3-tHlazlne, 1,.3,5-tris(3 .5-di-tert-bull-4hydroxybenzyl) isocyanurafte 1 ,3,5-tris(4-tert-butyl-3-hydroxy-2,6dimethylbenzyl) isocyanrute,' 2 .4,6-tris(3,5-di -tert-butyl-4hydrw'cyphaetelyl)-1 .3,5-triazine, 1.3 .5tris(35-di-tet-butyl-4-.

hydroxyphetylproponyeywhq.% t.dro-z .3.5-tritizine, 1.3.5-1rls(3 dicyclohexy1-4-h drycXY0 9w ocyamw'ot.

Phosphonae n o dmty-2,-di-tertbuy-4-hydroxybenzyl. plwsponalte, dlethyl-3.5-di-tert-butyl-4hydroxybenzyl phosphonate, d~tdcl35d-etbll4yrxbny phosphonate, dioctady4,l.5ttbuty4hydroxy3-rmethylbenzyl phosphonate, calcium saltf. .'itr-uy--yrxbnypopoi acid monoethyl ester, tetraikis(2 4 -dil-tert-butylphenyl)-4,4'-biphenylene.

diphosphonite,. 6-isootyloxy-2 .8,1-tetra-tert-buty-12H-dibenzo~d~g]- 1,3 .2-dioxophosphocine, 6-fluoro-2 .4.

8 ,1O-tetra-tert-butyl-12-methyldiben'zo(d,g]-1 .3 2-cdioxcaph6*ho ci ne.

11. AgylanroIdos f'b x ple 4-hydroxy-lauric acid anilide, 4hydroxysteari ac d te.(3 .5-di-tert-buy 1-4-hydroxyphenyl)-carbamicacid octyl ester.

12. Esters of b-( 3 .5-di-tert-butyl-4-hydroxyhenyl)-ropionic acid with mono- or poly-hydric alcohols, such as methanol, ethanol, oclanol, oclodecanol, 1 ,6-hexainediol, 1 .9-nonanediol, ethylene glycol, 1.2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythrito I, di pentcierythritol, tris(hydroxyethyl) isocyanurate, N,N'Ybis( hydroxyethyl)oxali c acid diamide, 3-thioundecanol, 3-thiapentadecianol, tri methylhexanediol, trimethylolpropane, di -trimethylolpropane, 4hydroxymethyl-1-phospha-2 .6,7-trioxabicyclo 2 2 .2]octaone. 13. Esters of b-(5-tert-buyl-4-hdroy3-methylphenyg)-Mpioni c.acid with mono- or poly-hydric alcohols, such as mnethanol, ethanol, octanol, octadecanol, 1,6-hexanediol, l,9-nonanediol, ethylene glycol, 1.2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, ~:pentaerythritol, tris(hydroxy)ethyl isocyanurate, N,N'- 4. bis(hydroxyethyl)oxalic. acid diamide, 3-thioundecanol, 3-thiapentadecanol.

trimethyihexonediol, trimethylolpropcine, 4-hydroxymethyl-l1-.phospha-2 6,7frioxabicyclo[(2.2.2 ]octane.

14. Esters of 5 -dicyclohexl-4-hdoxyhenyl).pRopI~onic acid with mono- or poly-hydric alcohols, such as methanol, ethanol, octanol, octcxdecanol, 1,6-hexanediol, 1,9-nonaned iol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diel-hylene glycol, triethylene glycol, pentaerytlwitol, tris(hydroxy.)ethyl isocyanurate, N,N-bis- (hycfroxyethyl)oxalic acid dianiide, 3-thiaundecanol, 3-thiaipentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha..z 6,7trioxabicyclo(2.2.2 )octane.

Esters of 3 di-tert-buvl-4-hydroyphnyacetic acid with mono- or poly-hydric alcohols, such as methanol, ethanol, octanol, *octadecanol, 1,6hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, trielhylene glycol, pentaerythritol, tris(hydroxy)ethyl isocyanurate, N,lN-bis(hydroxyethyl)oxalic acid diamide, 3-thioundecanol, 3-thiapentadecanol, trimethyhexanediol, trimethylolpropane, 4-hydroxymethyl- 1-phospha-2 ,6,7-trioxabicyclo octane.

16. Amides of b-( 3 di-et-buvl4hydroyphenyl)-tpropionic acid, such as NN-bis(3,5-di-tert-butyl-4r hydroxyphenylpropionyl)hexamethylenedicrnine, N,N'-bis(3 .5-di -tert- butyl -4hydroxyphenylpropionyl)trimethylenediami ne, N,N'-bi,(3 .5-di -tert-butyl-4hydroxyphenyipropionyl) hydrazi ne.

Preference is. given to antioxidaints of groups 1 to 5, 10 and 12, especially 2,2bis(4-hydroxyphenyl)propane, esters of 3 ,5-di-tert-bulyl-4hydroxyphenyipropionic acid with octanol, octadecanol or pentaerythritol or tris(2,4-di-tert-buylphenyl) 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 advantageousl from 0.1 to 10, and especially from 0.1 to 5, parts by weight, based on 100 parts by weight PVC.

.9.U UVabsorbers and light stabilisers Examples are: L' 1 2-;(2'-Hydroxyheny~l)benzotriazoles, such as 2-(2'-hydroxy-5'methylphenwyl)-benzotriazole, -ter-butyl-2-hydroxyphenyl)-.

benzotriazole, 2-(5'-tert-butyl-2-hydroxyphenyl)-benzotriazole, 2-(21hydroxy-5'-(1,1 .3 3-tetramethylbutyl)phenyl)-benzotriazole, 2-(3',5-di-tert- 2-(3-tert-butyl-'-, 2-(3-sec-butyl-5'-tertbutyl-2'-hydroxyphenyl)-benzotriazole, 2-(2'-hydroxy-4-octoxyphenyl)benzotriazole, 2-(3',5-di-tert-amyl- 2'.-hydroxyphenyl)-benzotriazole, 2- (3Y.5'-bis(a,a-dimethylbenzyI)-2'-hydroxyphenyl)-benzotriazole, a mixture of 2 3 '-tert-bul-2'-hydroxy-5'-(2-octyloxycrbonylethyl)phenyl)-5-chloro.

benzotriazole, 2-(3-tert-butyl-5'-[2-(2 -ethylhexyloxy)-carbonylethyl]-2'- 2-(3'-tert-butyl-2'-hydroxy-5 chlor'o-benzotriazole, 2 -(3'-tert-butyl-2'hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-benzotriazo le, 2-(3'-tert-butyl- 2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyly. benzotriazole, 2-(3-tertbutyl-5'-[2-(2-ethylhexyloxy)carbo6nylethyl hydroxyphenyl)benzotriazole, 2-(3'-dodecyl-2-hydroxy-5'-methylphenyl)-benzotriazole, and 2-(3'-tert-butyl- 2-hydroxy-5'-(2 -isoociyloxycarbonylethyl)phenylbenzotriazole, 2 ,2'-methylene-bi 1,3,3 -tetramethylbutyl)-6benzotriazol-2-yipheno the transesteri fication product of 2 -(3-tertbutl-5'-(2-methoxycarbonylethyl)-.

2 '-hydroxy-phenyl]-benzotriazo le with polyethylene glycol 300; wherein R 3-tert-butyl-'-hydroxy-§'-2Hbenzotriazol-2-ylphenyl.

2-Myroxvbenzophenones, such as the 4-hydroxy-, 4-methoxy-, 4oclyloxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloky-, 4.2',4V-tri hydroxy- or 2'-hydroxy-4,4-dimethoxy derivative.

3. Esters of unsubstituted or substituted benzoic acids, such as 4-tertbulyl-phenyl salicykite, phenyl salicylate, octyiphenyl salicylate, di benzoylresorci nol, bis(!4-tert-butylbenzoyl )resor'cinol, benzoylresorcmnol, 3,-itr-utl4hdoybnocai 2..t-di-tert-Dutylpflenyl ester, di-tert-buyl-4-hydroxybenzoic acid hexadlecyl ester, 3.5-di-tert-lbutyl-4- :hydroxybenzoic acid octadlecyl ester, 3 ,5-di-tert-butl-4-hydroxybenzoic acid 2 -methyl-4.6-di-tert-butylpheny ester.

AMrlts such as a-cya .no-b,b-diphenylacrylic acid ethyl ester orisooctyl ester, a-carbomethoxy-cinnamic acid methyl ester, a-cyano-b- :methyl-p-mnethoxy-cinnamnic acid methyl ester or butyl ester, acarbomethoxy-p-methoxy-cinnamic acid methyl ester, N-(b-carbomethoxyb-cyanovinyl)-2-methyl-i ndolinte.

Nickel compounds, such as nickel complexes of 2,2'-thio-bis[4-(1.1,3,3tetramethylbutyl)phenoll, 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-4-Iauroyl-5hydroxy-pyrazole, where appropriate with additional ligands.

6. Stericaliy hindered amines, such as bis( 2 ,2,6,6-tetramethyl-piperidyl) sebacate, bis(2 ,2 .6 6-tetramethyl-piperidyl) succinate, bis(1 ,2 ,2 ,66pentamethylpiperidyl) sebacate, n-butyl-3 .5-di-tert-butyl-4-hydroxybenzy..

malonic acid bis(1 .2.2 6,6-pentamethylpi peridyl) ester, the condensation product of l-hydroxyethyl -2,2 6 6 -tetramethyl-4-hydroxypiperidi ne and succi nic acid, the condensation product of N,N'-bis(2 ,2 ,6,6-tetramethyl-4piperidyl)hexamethylenediamine and 4 -tert-octylamino-2,6-dichloro-1,3,5-striazi ne, tris(2 .2,6 6 -tetramethyl-4-piperidyl)nitri lotriacetate, tetrakis(2 ,2 6 6 -tetramethyl-4-pi peridyl)- butane tetraoate, 1 ethanediyl )-bis(3 .3.5,5-tetramethyl -piperazi none), 4-benzoyl-2 ,2 ,66tetramettylpiperidine, 4-stearyloxy- 2,2,6,6 -tetramethylpiperidi ne, bis(1 ,2,2.6 ,6-pentamethylpiperidyl)-2-n- butyI-2-(2-hydroxy-3,5-d,..tertbutylbenzyl) malonate, 3-n-octyl-7,7,9,9 -tetramethyl -1,3,8triazaspiro(4.5]decane-2 .4-diane, bis(1-oclyloxy-2 ,2 .6,6tetramethylpiperidy.l) seboae bis(1-ociyloxy-2 ,2 .6,6-tetramethylpiperidyl) succinate, the condensatikri product of N.N'-bis(2,2,6,6-tetramethylA..

pi peridyl)- hexamethylenedlamine and 4-morpholi no-2 ,6-dichloro- 1,3.5triazine, the condensation product of 2-chloro-4,6-di(4-n-butylamino.

2,2,6 ,6-tetraniethylpperidyl)-1 3,5-triazine and 1 ,2-bis(3aminopropylaniino)ethane, the condensation product of 2-chloro-4,6-dj bulyamio-1.2, pen0~ehy. ieridy)-1,3 ,5-triazi ne and I ,2-bis(3aminopropylamin6o hne, B-acet-3-dodecyl-7,7,9,9-tetrmethy.1 ,3,8triazaspiro[4.51decn-.~~n 3-dodecyl ,6,6-tetramethyl-4pi peridyI)pyrroldine-2:5-d one, 3-dodecyl- l-(l ,2 ,2,6,6-pentamethyl-4piperidyI)-pyrroidi'ne-.2,6,..di:onem, and Chimassorb 966.

7. -Oxalic acid iMides, such as 4,4 -dictyloxy-oxanilide, 2,2-dioxanilide, 2 ,2'-didodecyloxy-5,5'-di-tert-.butyI oxani lide, 2-ethoxy-2'-ethy1 oxani lide, N,N'-bi 5(3-dimethylaminopropyl) oxalamide, 2 -ethoxy-5-tert-butyl-2'-ethyl oxanilide and a mixture thereof with 2-ethoxy-2'-ethy- 5,4-d.i-.ert-.butyI oxanilide, mixtures of o- and pmeihoxy- and o- and p-ethoxy-disubstituted oxanilides.

8. 2-(-!MCPMrxybhey)1 3 trazings, such as 2 .4,6-tris(2-hydroxy-4- :::oclyloxyphentyl)-l .3,5 fr.iie, 2..(2-hydroxy-4-octytoxyphenyl)-4,6-.bis(2 .4dimethylphenyl)-1 .3 .5-triazine, 2-(2 ,4-dihydroxyphenyl)-4,6-bis(2 .4dimethylphenyl)-1 .3 5-triazine, 2 ,4-bis(2 -hydroxy-4-propyloxyphenyl)-6..

(2 ,4-dimethylphenyl)-1,3,.triazine, 2-(2 -hydroxy-4-ocyloxyphenyl)-4,6-.

bis(4-meffhylphenyl)-1 .3 5-tricizine, 2-(2 -hydroxy-4-dodecyloxyphenyl)-4,6..

bis(2 ,4-di methytpheny ,5-trazi ne, 2- [2 -hydroxy-4-(2-hydroxy-3 butyloxy- propyloxy)phenyl ]-4,6-bis(2 .4-dimethyphenyl 1,3,5-triazi ne, 2- [2hydroxy-4-(2-hydrox-y- 3 -octyloxypropyloxy)phenyl ]-4,6-bis(2 .4dimethylphenyl)- 1,3 Propel/an ts Propellants are organic azo and hydrazo compounds, tetrazoles, oxazines, isatoic anhydride, and sodium carbonate and sodium hydrogen carbonate.

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

Definitions and examples of impact strength modifiers and processing aids, gelling agents, antistatic agents, biocides, metal deactivators, optical brighteners, fire-proofing agents and antifogging agents are described in "Kunststoffadditive" (Plastics Additives), R.G&chter/H.Miller, Carl Hanser Verlag, 3 d Ed., 1989, and "Handbook of Polyvinyl Chloride Formulating", E.J.Wilson, J.Wiley Sons, 1993. Impact strength modifiers are also extensively described in "Impact Modifiers for PVC", J.T.Lutz/D.LDunkelberger, John Wiley Sons, 1992.

The stabiliser combination can be prepared not only by mixing the components in apparatus suitable for the purpose, but also by preparing some of the additional components in situ in a melt of glidants and/or metal soaps before adding component That method is suitable especially for the in situ preparation of calcium acetyl acetonate (cf. EP 336 289) Examples of chlorine-containing polymers to be stabilised or of the Srecyclates 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, S 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 i propellant residues, traces of lacquer, traces of metal, and initiator radicals.

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

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

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

"i 'The invention thus also relates to a process for the preparation of stabilised 1PVC, 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 d Ed., 1985, Carl Hanser Verlag, pages 1236-1277.

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

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

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

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

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

C)

Mixture 11 12 13 Solvic 268 RC (S-PVC K value 68) 100 100 100 Omyalite 30 Ca stearate 0.6 0.6 0.6 Hostalub H4 2 1.0 1.0 1.01 Hobstalub H12 2 0.2 0.2 0.2 CH 0.4 0.4 0.4 Mark 6045 ACM 4 0.3 0.3 0.3 Stabiiser 5 0.2 0.2 0.2 NaClO 4 //0.05 VI Y3I VI minutes 20.7 2.9 22-.2 15 28".4 66.6- 29.1 40.2 108.4 39.2 *Chalk 2 )Glidant supplied by Hoechst (paraffin wax) '46lidant supplied by Hoechst (polar ethylene wax) '*Phenylisodecyl phosphite 4) Mixture of 9% NI IClO 4 *45% CaCOs. 40. COSAO. H-lO 5 )6-Amino-1,3-dimethyl-uracil it is found that the use of ftwi uuiuuunts of peclrt copon as component B in mixtures II and 13 according to the invention results in considerably better stabilisation than without component B.

Table II: Static heal lest at 190*C (rolled for 5 min at 170*C) Mixture I11 112 113 114 115 116 Il17 118 119 Evipol 5H 6030 (PVC K value 60) 100 100 100 100 100 100 100 100 100 CH 3)03) 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 Wax E6) 0.4 .0.4 0.4 0.4 0.4 0.4 0.4 0.4' 0.4 Epox. soya oil 5.0 5.0 5.0/ Araldite GY 2507)/ 5.0-5.0 5.0/ Araldite PT 8108) /5.0 5.0 Stabiliser 1 5 1.0 /1.0 /1.0 Slabiliser 29) 1.0 1.0 Stabiliser 3" 0 1.0 I 1.0 VI VI VI YI VI VI VI VI1 VI Minutes 17.4 17.3 15.6 13.4 11.8 12.5 14.8 16.2 17.1 23.2 33.7 29.5 17.8 18.5 17.7 21.2 24.4 24.0 33.6 54.9 46.3 23.5 29.9 27.8 27.2 33.6 30.8 3 )Phe nylisodecyl phosphite ')Ester wax (based on: monlanic acid) %tiglycidyl ether of bisphenol A (liquid epoxide) 6) Solid heterocyclic epoxy resin (triglycidyl isocyanurate) 9 )6-Amino-1.3--di-n-butyluraci I 10 6-Amino-13-di-eihyl-thiouraci

I

The stabiliser combination (IN4 to 119). of glycidyl and aminouracil compound according to the invention is found to be superior.

Table III: Static heat test at 190*C (rolled for 5 min at 170*C) Mixture Evipol SH 6030 (PVC K value 60) CH 3003) Wax E'6) Epox. soya oilI Rhodicistab 5011) Ca stearate Zn stearate tDASC 2 Alkamizer 113) Stabiliser 15) Stabiliser 29 Stabiliser 310) IrIl M2M3 M14M5M6 11171181119 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

VI

100 0.8 0.4 5.0 0.2 0.3 0.5 1.0 1.0

YI

100 0.8 0.4 5.0 0.2 0.3 0.5 1.0 1.0.

YI

100 0.8 0.4 5.0 0.2 0.3 0.5

YI

100 0.8 0.4 5.0 0.2 0.3 0.5 Y1.

100 0.8 0.4.

5.0 0.2 0.3 0.5 1.

YI

100 0.8 0.4 0.2 0.3 1.

1

S

S

S

S.

S.

Minfutes 15.2 22.7 37.4 31.4 66.9 57.2 "0Stearoyl-benzoyl-methane supplied 12.9 20.6 10.6 16.1 22.5 26.5 10.0 16.3 24.1 10.2 12.4 17.0 18.8 29.7 26.5

S

34.0 49.1 41.8 by RHONE-POULENC ')ihydroxyaluminium sodium carbonate (I)ASC) 13 )Hydrotalcite supplied by KYOWA (Japan) The addition of dawsonite and the addition of hydrotalcite both increase the stability.

Table IV: Static heat test at 190 0 OC (rolled for 5 min at 170 0

C)

Mixture Evipol 5H 6030 (PVC K value 60) CH 3W3)~ Wax I Epox. soya oil Rhodiastab 5011) Chimassorb 9444) Malbit CR (maltite) Oipentaerythritol Stabiliser 15) StabilIiser 29 Stabiliser-319) IVI IV2 IV3 1V4 IV5 IV6 IV7 IV8 1V9 IVIOIVII IV12 100 0.8 0.4 2.0 0.2 1.0 100 0.8 0.4 2.0 0.2 1.0 100 0.8 0.4 2.0 0.2 1.0 100 0.8 0.4 2.0 0.2 0.15 1.0 100 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 t00 0.8 0.4 2.0 0.2 1.0- 100 0.8 0.4 2.0' 0.2 0.5 100 0.8 0.4 2.0 0.2 0.5 100 0.8.

0.4 0.2 a a a a a a a. a YI YI YI YI Y1 YI YI YI YI YI Minutes 15 20 6.0 10.1 24.2 6.6 10.3 12.7 18.7 6.6 7.8 5.8 9.0 5.8 7.7 11.1 7.3 10.6 15.4 8.9 32.1 24.8 11.1 6.2 7.2 9.4 19.5 8.1 10.4 11.1 16.1 5.4 6.7 11.7 21.9 YI YI 5.8 10.0 9.9 11.2 20.1 15.7 48.0 25.2 29.5 47.9 13.8 59.9>'70 >60 29.1 4 )sterically hindered amine supplied by CIBA-GEIGY AG (HALS) The stabiliser combinations according to the invention (1V4 to IV12) are found to give improved stabiliser activity.

a.

a a..

Table V: Static heat test at 190*C (rolled Mixture Evipol SH 6030 (PVC K value 60) CH 3W)~ Wax E'6) Epox.. soya oil Rhodiastab 5011).

C~a stearate Zn stearate Wessalite p 1 5) Zeolite Pi6) Stabiliser 1i) Stabiliser 29) Stabiliser 310) VI V2 V3 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 Y1 V4 100 0.8 0.4 2.0 0.2 0.3 0.5 1.0 /1 for 5 min V5 V6 at 170 0

C)

V7V8 V9 100 0.8 0.4 2.0 0.2 0.3 0.5 1.0.

-1.0

YI

100 0.8 0.4 2.0 0.2 0.3 0.5 1.0

YI

100 0.8 0.4 2.0 0.2 0.3 0.5 1.

100 100 0.8 0.8 0.4 0.4 2.0. 0.2 0.2 0.3 0.3 0.5 1.0 Y1 YI Minutes 10.3 12.3 15.4 19.6 34.7 28.6 41.1 29.5 58.8 8.8 12.4 10.6 16.8 14.2 19.5 9.3 9.4 13.3 15.3 2:5.0 29.2 15.7 22.6 34.8 21.0 32.5 30.5 1 5 )Na zeolite A supplied by C)EGUSSA 16)Na zeolite P supplied by r)EGUSSA The stabiliser combination comprising hydrotalcite and zeolites is found to give better results.

Table VI: Static heal test at Mixture VII V12 Evipol EH 6030 (PVC K value 60) 100 100 Wax E6) 0.4 0.4 CH 3003) 0.8 0.8 Epox. soya oil 5.0 5.0 9* 0* a. a a a.

a.

a a a a 0* a.

a a Ca stearate Zn stearate Rhodiastab 50) D -26-155'7) Stabiliser P Stabiliser 29) 0.55 0.55 0.25 0.25 1.0 Y1IYI 190 0 C (rolled for 5 minutes at 170 0

C)

V13 V14 100 100 0.4 0.4 0.8 0.8 5.0 0.55 0.55 0.250.25 0.3 0.3 /0.3 1.0

YIVIY

Minutes 18.5 9.7 36.518,8 103 3 3.3 'NB-keto ester of the formula 11.4 15.6 21.9 28.3 46.0 59.2 0

O

Y= (CH 2 2

-O-CO-CH

2

-C.CH

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

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

C)

Mixture VIII VII2 VII3 VII4 VI5 VnI6 VII7 VII8 Evipol SH 6030 (PVC K value 60) CH 3003) Wax E 6 Epox. soya oil Ca stearate Zn stearate Synesal M' 8 Stavinor b 507"9) Stabiliser 15 Stabiliser 2 9 Stabiliser 3'0)

S

S.

S

S

S. S

S.

S

S

0 S. 5 100 100 100 0.8 0.8 0.8 0.4 0.4 0.4 5.0 5.0 5.0 0.55 0.55 0.55 0.25 0.25 0.25 1.0 1.0 1.0 YI YI YI 5.4 4.8 6.3 6.4 4.7 6.7 6.7 5.5 7.0 7.3 7.6 8.3 10.8 12.3 12.5 19.9 28.5 22.9 100 100 100 0.8 0.8 0,8 0.4 0.4 0.4 5.0 5.0 5.0 0.55 0.55 0.55 0.250.25 0.25 0.2 0.2 0.2 1.0 1.0 1.0 100 100 0.8 0.8 0.4 0.4 5.0 0.55 0.55 0.25 0.25 0.2 0.2 1.0 YI YI 2.9 4.4 3.7 4.9 4.5 6.7 6.3 8.2 11.3 11.9 23.8 21.3 Minutes 0 20

YI

2.9 3.5 4.4 5.4 8.9 18.0 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 33.7 65.8 45.1 31.8 64.2 32.3 62.6 38.4 1 9 Thiodiethylene-bis(5-methoxy-carbonyl-2,6-dimethyl-l,4-dihydro-pyridine)-3carboxylate supplied by LAGOR 1 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).

P:\WPDOCS\Hjwv\Spccs\750314.doc-15105I I 64A- Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", and variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.

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

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

0.

Claims (7)

1. A stabiliser combination comprising A) at least one compound of formula I 0 RN YANN H R- wherein R*1 and- R*2 are each independently. of the other CI-Cl2alkyl, C3- C6alkenyl, C5-Cacycloalkyl that is unsubstituted or substituted* by from 1 to 3' Cl.-C4alk. Cl-C4alk6xy, C5-Cscycloalkyl- or by hydroxy- groups or chlorine atoms, or C7-Cqphenylalkyl that is unsubstituted or substituted at the phenyl ring9 by from I to 3 CI-C4alkyt. Ci-C4alkoxy. C5.C8cycloalkyi. or by hydroxy :groups or chlorine atoms.- and R*i and R*2 may additionally be hydrogen and CI-Cl2alkyl, and YisSorO~and B) at -least one perchlor'ate compound.

2. A stcabiliser combination according to claim 1. wherein R*l and R*2 are each independently of the other H and Cj-C4alkyl or

3. A stabiliser combination according to claim 1, wherein the compound of compoient A) is 6-amino-i .3-dimethyl-uracil., 6-amino-i .3-di-n-propyl-uracii. 6- amino-i .3-di-n-butyl-uracil, 6-amiro-i,3-diethyl-thiouracil or 6-oamino-i.3-di-n- butyl-Ithiouracil.

4. A stabiliser combination according to any one of claims 1 to which ~~-...additionally comprises at least one epoxidised fatty acid ester. 66 .A stabiliser combination according to any one of claims 1Ito 4. which additionally comprises zinc and/or alkali metal and/or alkaline earth metal carboxylites or aluminium carboxylateS.

6. A'stabiliser combination according, to any one of claims I 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. 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. I*11. A composition according to claim 10, wherein PVC is used as the chlorine-containing polymer. *12. A method of stabilising chlorine-containing polymers, which comprises incorporating into the chlorine-containing polymers a stabiliser combination according to any one of claims I to 9. A stabiliser combination of claim 1, or a polymer containing the same substantially ais hereinbef ore described with reference to the Examples. 0 UATED this 14th day of May 2001 Crompton Vinyl Additives GmbH By its Patent Attorneys ,7 b A AVIES COLLISON CAVE