AU2003203275B2 - Stabiliser combinations for chlorine-containing polymers - Google Patents

Description

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Patents Act 1990

ORIGINAL

COMPLETE SPECIFICATION STANDARD PATENT Applicant(s): Address for Service: Invention Title: Crompton Vinyl Additives GmbH Chemiestrasse 22 D-68623 Lampertheim Germany DAVIES COLLISON CAVE Patent Trade Mark Attorneys Level 10, 10 Barrack Street SYDNEY NSW 2000 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 rAWPDOCSiWM. 2CROMPTON D7 ,tc27/03/ -1- STABILISER COMBINATIONS FOR CHLORINE-CONTAINING POLYMERS This application is a divisional of Australian patent application No. 72572/00.

The ensuing description is substantially identical to the description of the earliest "parent" application, No. 68041/96. The parent description has been fully readopted to facilitate identification of the parent/divisional relationship. The invention subject of this divisional application is as defined in the claims which follow.

The broad invention as described and exemplified herein relates to stabiliser combinations consisting of a compound of formula I shown below and at least one further substance from the following groups: the perchlorate compounds, glycidyl compounds, beta-diketones, beta-keto esters, dihydropyridines, polydihydropyridines, polyols, disaccharide alcohols, sterically hindered amines (tetraalkylpiperidine compounds), alkali aluminosilicates, hydrotalcites and alkali aluminocarbonates (dawsonites), alkali-(or alkaline earth-) carboxylates,- (bi)carbonates oder -hydroxides, antioxidants, lubricants or organotin compounds which are suitable for stabilising chlorine-containing polymers, especially PVC. PVC can be stabilised by a number of additives. Compounds of lead, barium and cadmium are especially suitable for the purpose but are controversial today for ecological reasons or owing to their heavy metal content (cf. "Kunstoffadditive" (Plastics additives), R. Gachter/-H. Miiller, Carl Hanser Verlag, 3 rd Edition, 1989, pages 303- 311, and "Kunststoff Handbuch PVC" (Plastics Handbook PVC), Volume 2/1, W.

Becker/D. Braun, Carl Hanser Verlag, 2 n d Edition, 1985, pages 531-538; and Kirk- Othmer: Encyclopedia of Chemical Technology", 4 th Ed., 1994, Vol 12, Heat Stabilisers p. 1071-1091). Other effective stabilisers and stabiliser combinations that are free of lead, barium and cadmium are therefore sought. Compounds of formula I have already been described in DE-PS 1 694 873, EP 65 934 and EP 41 479 and can be prepared in one or several process step(s) by known methods.

FAWPDOCSpWwccs 2ICROMFTUN D7.d27m/3 -2- It has now been found that A) compounds of formula I 0 R*N i N NH 2 R*2 wherein R* 1 and R* 2 are each independently of the other C 1 -Czzalkyl, C 3

C

6 alkenyl, Cs-Cecycloalkyl that is unsubstituted or substituted by from 1 to 3 Ci-

C

4 alkyl, Ci-C 4 alkoxy, Cs-Cscycloalkyl or hydroxy groups or chlorine atoms, or C 7

C

9 phenylalkyl that is unsubstituted or substituted at the phenyl ring by from 1 to 3

C

1

-C

4 alkyl, C 1

-C

4 alkoxy, C 5

-C

8 cycloalkyl or hydroxy groups or chlorine atoms, and R* 1 and R* 2 may additionally be hydrogen and C 1

-C

1 2 alkyl, and Y is S or O, can be combined with B) at least one compound from the following group: perchorlate compounds and/or glycidyl compounds and/or beta-diketones, beta-keto esters and/or dihydropyridines, polydihydropyridines and/or polyols, disaccharide alcohols and/or sterically hindered amines (tetraalkylpiperidine compounds) and/or alkali aluminosilicates (zeolites) and/or hydrotalcites and/or alkali aluminocarbonates (dawsonites) and/or, alkali- (or alkaline earth-) carboxylates,-(bi)carbonates oder -hydroxides, and/or antioxidants and lubricants and/or organotin compounds for the purposes of stabilising chlorine-containing polymers, especially PVC.

P:\WPDOCS\HJW\specs 2\CROMPTON D7doc-290/04 -3- The present invention as claimed provides a stabiliser combination comprising A) at least one compound of formula I 0 R* 1,N In N I (I) Y N NH 2 N~ R*2 wherein R* 1 and R* 2 are each independently of the other C 1

-C

1 2 alkyl, C 3

-C

6 alkenyl, C 5

C

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

C

4 alkoxy, C 5

-C

8 cycloalkyl or by hydroxy groups or chlorine atoms, or Ci7-Cgphenylalkyl that is unsubstituted or substituted at the phenyl ring by from 1 to 3 CI-C 4 alkyl, C 1

C

4 alkoxy, Cs-C 8 cycloalkyl or by hydroxy groups or chlorine atoms, and R*I and R* 2 may additionally be hydrogen and C 1 -Cz 2 alkyl, and Y is 0, and B) an alkali aluminocarbonate (dawsonite) compound.

For compounds of formula I:

C

1

-C

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

C

1

-CI

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

CI-C

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

C

5

-C

8 Cycloalkyl is, for example, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

C

7

-C

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

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

C

3

-C

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

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

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

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

The compounds of the groups mentioned under B) are illustrated as follows: Perch/orate compounds Examples are those of formula M(CIO4)n, wherein M is Li, Na, K. Mg, Ca, Sr, Zn, AI,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-pentaerythritoI or polyvinyl alcohol in various degrees of polymerisation. The perchlorate salts can be introduced in various known forms, for example in the form of a salt or an aqueous solution applied to a substrate, such as PVC, calcium silicate, zeolites or hydrotalcites, or bound in a hydrotalcite by chemical reaction. Glycerol monoethers and glycerol monothioethers are preferred as polyol partial ethers. Other forms are described in EP 394 547. EP 457 471 and WO 94/24 200.

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

Glycidyl compounds 0 These contain the glycidyl group H--CH2 ,which is bonded R, Ra R, directly to carbon, oxygen, nitrogen or sulfur atoms and wherein either R1 and R3 are both hydrogen, R2 is hydrogen or methyl and n=O, or RI and R3 together are -CH2-CH2- or -CH2-CH2-CH2-, in which case R2 is hydrogen and n=O or 1.

I) Glycidyl and b-methylglycidyl esters obtainable by reacting a compound having at least one carboxy group in the molecule with epichlorohydrin or glycerol dichlorohydrin or b-methyl-epichlorohydrin. The reaction is advantageously carried out in the presence of bases.

Aliphatic carboxylic acids may be used as compounds having at least one carboxy group in the molecule. Examples of those carboxylic acids are glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid or dimerised or trimerised linoleic acid, acrylic acid and methacrylic acid, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid and pelargonic acid, and the acids mentioned in connection with the organic zinc compounds.

It is, however, also possible to use cyclooliphatic carboxylic acids, such as cyclohexanecarboxylic acid, tetrahydrophthalic acid, 4methyltetrahydrophthalic acid, hexahydrophthalic acid or 4methylhexahydrophthalic acid.

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

Carboxy-terminated adducts, for example of trimellitic acid and polyols.

such as glycerol or 2 ,2-bis( 4 -hydroxycyclohexyl)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- ,6-diol, hexane-2,4,6-triol, glycerol, 1.1,1-trimethylolpropane, bistrimethylolpropane, pentaerythritol, sorbitol, and from polyepichlorohydrins, butanol, amyl alcohol, pentonol, and from monofunctional alcohols, such as isooctanol, 2ethylkexanol, isodecnol and C7-C9alkanol and C9-C1aIolkanol mixtures.

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

The epoxide compounds can also be derived from mononuclear phenols, such as phenol, resorcinol or hydroquinone, or they are based on polynuclear phenols, such as bis(4-hydroxyphenyl)methane, 2,2-bis(4hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 4.4'dihydroxydiphenylisulfone, or on condensation products of phenols with formaldehyde obtained under acid conditions, such as phenol novolaks.

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

3 -epoxypropyl-4-methoxyphenyl ether.

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

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

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

V) Epoxide compounds containing a radical of formula I wherein RI and R3 together are -CH2-CH2- and n is 0 are bis(2, 3 -epoxycyclopentyl) ether, 2.3-epoxycyclopentylglycidyl ether or 1,2-bis(2,3epoxycyclopentyloxy)ethane An epoxy resin containing a radical of formula I wherein R1 and R3 together are -CH2-CH2- and n is 1 is, for example, 3,4epoxy-6-methylcyclohexnecarboxylic acid (3',4'-epoxy-6'met hylcyclohexyl)-methyl I ester.

Suitable terminal epoxides are, for example TM denotes a) liquid diglycidyl ethers of bisphenol A, such as Araldite'TMGY 240, AralditeTMGY 250, AralditeTMGY 260, AralditeTMGY 266, AralditeTMGY 2600, Araldite"MY 790; b) solid diglycidyl ethers of bisphenol A, such as AralditeTMGT 6071, AralditeTMGT 7071, AralditeTMGT 7072, AralditeTMGT 6063, AralditeTMGT 7203, AralditeTM&T 6064, AralditeTMGT 7304, AralditeTMGT 7004, AralditeTMGT 6084. AralditeTMGT 1999, AralditeTMGT 7077, AralditeTMGT 6097, AralditeTMGT 7097, AralditeTMGT 7008, AralditeTMGT 6099, AralditeTMGT 6608, AralditeTMGT 6609, AmralditeTMGT 6610; c) liquid diglycidyl ethers of bisphenol F, such as AralditeTMGY 281, AralditeTMPY 302, AralditeTMPY 306; d) solid polyglycidyl ethers of tetraphenylethane, such as CG Epoxy ResinTMO"163; e) solid and liquid polyglycidyl ethers of phenolformoldehyde novolak, such as EPN 1138, EPN 1139, GY 1180, PY 307; f) solid and liquid polyglycidyl ethers of o-cresolformaldehyde novolak, such as ECN 1235, ECN 1273, ECN 1280, ECN 1299: g) liquid glycidyl ethers of alcohols, such as ShellTM glycidyl ether 162, ArolditeTMODY 0390, AralditeTMDY 0391; h) liquid glycidyl ethers of carboxylic acids, such as ShellTMCardura E terephthalic acid ester, trimellitic acid ester, AralditeTDPY 284; i) solid heterocyclic epoxy resins (triglycidyl isocyanurate), such as AralditeTM' PT 810; j) liquid cycloaliphatic epoxy resins, such as AralditeMCY 179; k) liquid N,N,O-triglycidyl ethers of p-aminophenol, such as Araldite"MY 0510; I) tetraglycidyl-4,4'-methylenebenzamine or N,N,N',N'-tetraglycidyldiaminophenylmethane, such as AralditeTMMV 720, AralditeTMMY 721.

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

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

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

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

A),

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

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

Beta-diketones, beta-keto esters 1,3-Dicarbonyl compounds that can be used may be linear or cyclic dicarbonyl compounds. Preference is given to the use of dicarbonyl compounds of the following formula: R'1CO CHR2'-COR'3 wherein R'I is CI-C22alkyl, C5-Clohydroxyalkyl, C2-C18alkenyl, phenyl, phenyl substituted by OH, Cl-C4alkyl, C1-C4alkoxy or by halogen, C7-Clophenylalkyl, C5-C12cycloalkyl. C5-C12cycloalkyl substituted by C1-C4alkyl, or is a group S-R'6 or -R'5-0-R'6.

R'2 is hydrogen. CI-C8alkyl, C2-Cl2alkenyl. phenyl, C7-Cl2alkylphenyl, C7- Clophenylalkyl or a group -CO-R'4, R'3 has one of the meanings given for R'i or is Ci-Ci8alkoxy, R'4 is CI-C4alkyl or phenyl, is C1-Cloalkylene and R'6 is CI-C12alkyl, phenyl, C7-C18alkylphenyl 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 U5 4 339 383.

R'i and R'3 as alkyl may be, especially, CI-Catkyl, such as methyl, ethyl, Apropyl, isoprapyl, n-butyl, tert-butyl, pentyl, hexyl, heplyl, octyl, decyl, dodecyl or octadecyl.

R'j and W3 as hydroxyalkyl are, especially, a group -(CH2)n-O)H, wherein n i-s 6 or 7.

R'i arnd R'3 as alkenyl may be, for example, vinyl, allyl, methollyl. I1-bufenyl, I1hexenyl or oleyl, preferably ollyl.

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

R'i and R'3 as phenylolkyl are especially bezyll. R'2 and R'3 as cycloalkyl or olkylcycloolkyl are especially cyclohexcyl or met~ylcyclohexyl.

RP2 as alkyl may be. especially, C1-C4alkyl. A2as C2-Cl2alkenyl may be, especially, allyl. R'2 as alkyiphenryl may be, especially, tolyl.. R2 as phenylalkyl may be, especially, benzyl. PR'2 is preferably hyrogen. R'3'as alkoxy may be, for example, methoxcy, ethoxy, butoxy. hexyloxy, octyloxy, dodecyloxy. tridecyloxy, tetradecyloxy or octadecyloxy. R'5 as CI-Cloalkylene is especially Cz- C4alkylene. R'6 as alkyl is especially C4-Cl2alkyll. such as butyl, hexyl, octyl, dec)] or dodlecyl. R'6 as alkylphenyl is especially tolyl. R'6 as phenylalkyi is especially benzyl.

Examples of 1,3-dicorbonyl compounds of the above formula and their alkali metal, alkaline earth metal and zinc chelates are acetylacetone, butanoylucetorie, heptanoylaceto ne, steoroylacetone, paini toylaceto ne, lauroylaceto ne, 7-tert-no ny lthio -heptane-2 ,4-dio ne, benzoylaceto ne, di benzoylmetha ne, lauroylbenzoylmethone, pa Iritoyl- benzoylniethane, stearoylbenzoylmethane, isoo ctyl benzoylmer hone, 5-hydroxycapro nyl- berizoy Imethane, tribenroylmethane, bis(4-mefhylbenzoyl)methoie, benzoyl-pch loro ben zoylmethane, bis(2- hydroxybenzoyl)niethane, 4-methoxybenzoylbenzoylmethane, bis(4-methoxybenzoyl)methone, 1-benzoyl- i-acetylno none, benzoyl-acetyl phenylmethane, stearoyl-4-methoxybenzoylmethane, bis(4-tertbul-ylbenzoyl)methane, berizoyl-formylmethane, benzoyl- phenylacetylmethane, bi scyc lo hexanoyl- methane, di-pivaloyl-methane, 2 -acetyicyclopentanone, 2-benzoylcyclopentanone, diacetoacetic acid methyl, ethyl and allyl ester, benzoyl-, propionyl- and butyryl-acetoocetic; 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-Ci8alkyl 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'I is Cl-C18alkyl, phenyl, phenyl substituted by OH, methyl or by methoxy, C7or cyclohexyl, R'2 is hydrogen and R'3 has one of the meanings given for R'l.

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

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

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

CO

2

CH

3

CO

z CzHI COz"C 1 2

H

2 or Suitable polydihydropyridines are especially compounds of the following formula wherein T is C1-C22alkyl that is unsubstituted or substituted by C1- Cigalkoxy, C1-IBalkylthio, hydroxy, acryloyloxy, methacryloyloxy, halogen, phenyl or by naphthyl; that is unsubstituted or substituted by C1-C18alkyl, C1-C18alkoxy or by halogen and that may also be heterocyclic; C3-C10alkenyl, CH3-CO-CH2-CO-OR-, CH3-CO-CH2-COO-R', CH3- C(NR'"2)-CH-COOR- or CH3-C(NR"2)=CHCO- L has the same meanings as T or is a tri- or poly-valent radical from an unsubstituted or C1-C12alkoxy-, C1-C12thioalkoxy-, C6-Claryl-, C1- C12carboxy- or hydroxy-substituted straight-chained or branched alkyl group, m and n ore numbers from O to k is 0 or 1, j is a number from 1 to 6 and the conditions j m n) and m n 0 are satisfied, R and R' ore 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-C12thioalkoxy, C6- Ctl-C12carboxy and hydroxy, p is from 2 to 18, t is from 0 to X is oxygen or sulfur, or, when k is 0 and j 1, R and R' together with L form a direct bond, R" is hydrogen, or Ci-C8olkyl, C2-C1zalkoxycarbonyl or C6-C10aryl each of which is unsubstituted or substituted by one or more C1-C12alkyl, C1-CBalkoxy, halogen or N02 substituents, and the two radicals are identical or different and are hydrogen, Cj1- C18salkyl, Cl-Cia-hydroxyalkyl or Cl-Cisalkoxyalkyl or together are uninterrupted or O-interrupted or are straight-chained or branched C2-C22alkenyl.

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

12 ZTh Iodilethylene- bis met hoxycar bo 6-dimet hyl 1 4 dihydro pyridine3 carboxylate] is especially preferred.

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

ci Pofyols, disaccharide alcohols Examples of suitable compounds of that type are: pentaerythritol, dipentaerythrii'oI. tripentaerythritol, bistrimethylolpropone.

bistrimethylolethane, trismethylolIpropaine, inosite, polyvmnylalcohol, sorbitol, maltite, isomaltite, lactite, lycasin, mannitol. lactose, leucrose, tr,is(hydroxye-thyl) isocyanurote, palati nite, tetramethylo lcyclohexano

I,

tetramethylolcyclopentanol, tetramethylolcyclopyran, glycerol, diglycero 1, polygqlycerol, thiodiglycerol or I.-O0-a-C -glycopyroasyl-t)-mannitog dlil'ydrate. Of .those, compounds, preference is gi-.'en ,t 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.

Sterc1lljhindered amines (te traalkyfpiperine compounds)i 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 G N CH 3 H 3 C

CH,

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 tetromethylpiperidine compounds having a molecular weight of more than 700 that contain no ester _groups.

Especially important as stabilisers are the following classes of tetramethylpiperimne 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 (1I) corresponds to "R 1 in the descriptions.

a) Compounds of formula II H3C CH 3 n wherein n is a number from 1 to 4, preferably 1 or 2,

R

1 is hydrogen, oxy. C1-Cl2alkyl, C3-C8alkenyl, C3-C8alkynyl, C7-C12aralkyl, CI-CBalkanoyl, C3-C5alkenoyl, glycidyl or a group -CH2CH(OH)-Z, wherein Z is hydrogen, methyl or phenyl, R 1 being preferably C1-C4alkyl, allyl, benzyl, acetyl or acryloyl, and, when n isl. R 2 is hydrogen. C1-Cz8alkyl 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 aliphotic carboxylic acid having from 2 to 18 carbon atoms, a cycloaliphatic carboxylic acid having from 7 to 15 carbon atoms, an a,punsaturated carboxylic acid having from 3 to 5 carbon atoms or an aromatic carboxylic acid having from 7 to 15 carbon atoms, and, when n is 2, R 2 is Ci-Ci2alkylene, C4-C12alkenylene, xylylene, a divalent radical of an aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid, dicarbamic acid or phosphorus-containing acid or a divalent silyl radical, preferably a radical of an aliphatic dicarboxylic acid having from 2 to 36 carbon atoms, a cycloaliphatic or aromatic dicarboxylic acid having from 8 to 14 carbon atoms or an aliphatic, cycloaliphatic or aromatic dicarbamic acid having from 8 to 14 carbon atoms, and, when n is 3, R2 is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, an aromatic tricarbamic acid or a phosphoruscontaining acid or a trivalent silyA radical and, when n is 4, R 2 is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.

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

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

When R1 is C3-C8alkenyl, it may be, for example, l-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl or 4 -tert-butyl-2-butenyl.

R

1 as C3-Cealkynyl is preferably proporgyl.

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

R

1 as Cl-C8alkanoyl is, for example, formyl, propionyl, butyryl, octanoyl, but preferably acetyl, and as C3-C5lkenoyl is especially acryloyl.

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

When R is a divalent radical of a dicarboxylic acid, it is, for example, a maolonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, maleic acid, phthalic acid, dibutylmalonic acid, dibenrylmalonic acid, di-tert-butyl-4-hydroxybenzyl)-malonic acid or bicycloheptenedicarboxylic acid radical.

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

When R2 is a tetravalent radical of a tetracarboxylic acid, it is, for example, the tetravalent radical of butane-1,2,3,4-tetracarboxylic acid or of pyromellitic acid.

When P 2 is a divalent radical of a dicarbomic acid, it is. for example, a hexomethylenedicorbamic acid or a 2 4 -toluylene-dicarbamic acid radical.

The following compounds are examples of polyolkylpiperidine compounds of that class: 1) 4-hydroxy- 2 1 2 1 6.6-tetromethylpiperidine 2) 1 -alIlyl 4 -hydroxy- 2,2,6.6 -tetramet hyIp iper idi ne.

3) 2 -benzyl-4-hydroxy-2 .2 .6.6-tetramethylpiperidi ne 4) 1 -(4-tert-bulyl-2-butenyl)-4- hydroxy-2 .2,6 6 -tetramethylpiperidi ne 4-stearoyloxy-2 2 6 .6-tetramethylpiperidine 6) l-ethvl- 4 -salicyloyloxy-2,2,6,6-retramerhylpiperidine 7) 4-methacryloyloxy- 1,2,2,6,6- pentamethylpi peridinve 8) 1,2,2 ,6.6-pentamethylpiperidin-4-yI-8-(3 .S-di-ter-t-butyl-4-hydroxypheny;) propio nate 9) di(1-benzyl-2 .2,6 .6-tetramethylpiperidin- 4-y1) malei note tO) di(2 ,2 ,6.6-tetramethylpiperidin-4-yl) succinate 11) di(2,2.6.6-tetroimethylpiperidin-4-yl) glutcarate 12) di(2,2,6 .6-tetromethylpiperidi n-4-yI) adipai-e 13) di(2,2 .6.6-telramethylpiperidin-4-yI) sebocate 14) di(1 6.6-pentatmethylpiperidi n-4-yI) sebocate di(1.2.3.6-tetramethyl-26-diethylpiperidin-4.yl) sebacate 16) di(l-aIlyI-22.6.6-tetramethylpiperidin4yl) phthalate 17) 1 -pro pargyl-46- cyanoethyloxy- 2.2,6 6 -tetramet hylpi peridi vie 18) 1 -acetyl-2 ,2 .6 6-tetrarnethylpiperidi n-4-yl acetate 19) trimellitic acid tri( 2 2 9 6 6 -tetramethylpiperidin-4ya) ester 1l-acryloyf-4- ben zyloxy-2, 2,6, 6-tetramethylpi perid ine 21) diethylmalonic acid di (2,2 .6.6-tetramethylpi peridi n-4-yl) ester 22) dibutylmalonic acid di(I.

2 2 6 9 6-pentamethylpiperidin-4-yI) ester 23) bulyl-(3 ,§-di-tert-butl-4-hydroxybenzyl)-molonic acid di(1 ,2,2,6,6pentamethylpiperidin-4-yl) ester 24) dibevizyl-malIonic acid di(1 2 2 9 6 6 -pentamethylpiperidin-4-yi) ester d ibenzyl-molonic acid di 3 6 -tetramet hyl-26-diet hyl piper idi n4-yg) ester 26) hexane-1',6'-bis(4-carbamoyloxy-1-n-butyl-2,2 6 6 -tetramethyl-piperidine) 27) toluene- 2%,4'-bis(4-carbamoyloxy-l n-propyl-2 .2.6 6-tetraniethylpiperidine) 28) dimethyl- bis(2,.2,6,6 -tet ramet hy lp iper id iii-oxI)si lane 29) phenyl-tris(2 6 -tetramethylpiperidin4--oxy)sijlane tris(1 propyl- 2,2 .6.6-tetromethylpi pe ridi n-4-yl) phosphite 31) tris(l -propyl- 2,2,6 .6-tetramethylpiperidi n-4-yi) phosphate 32) Phenyl-(bis(1.,226,6-pentamethylpiperidi-4-y,)I phosphonate 33) 4 -hydroxy-l.

2 1 2,6.6-pentomethylpiperidin 8 34) 4-hydroxy-N-hydroxyethyl-.Z,2 ,6 6 -tetranethylpiperidinve 4-hydroxy-N-(2-hydroxypropyl)-2,2 6 .6-tetramethylpi peridi ne 36) l-glycidyl-4-hydroxy-2 ,2 6 6 -tetramethylpi peridine b) Compounds of formula (Mn) wherein n is the number I or 2,

P

1 is as defined for a),

P

3 is hydrogen, Cl-Cl2alkyl, C2-C5hydroxyolkyl. C-~ylakl 7 C8oralkyl, C2-Czatkanoyl, C3-C5alkenoyl or benicyl, and, when n is 1, is hydrogen, CI-Ca~alkyl, Ca-Caalkenyl, C5-C7cycloalkyl. Cj- C4alkyl substituted by a hydroxy, cyano, alkoxycarborryl or carbumide group, glycidyl, a group of the formula -CI-J-CH(OH)-r or of the formula -CONI-z, wherein Z is hydrogen, methyl or phenyl: and, when n is 2, R4 is CZ-Cl2alkylene, C6-Cz2arylene, xylylene, a -CH2-CH(O-lcH 2 group or a group -CH2-CH(oHy- CH2-O-D)-O-, wherein D is C2-Cloalkylene, C6-Cl5arylene or C6- Cl2cYcloalkylene, or, with the proviso that P 3 is not alkanoyl, olkenoyl or benzoyl,

P

4 may also be a divalent radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbarnic acid or also the group -CO- or, when ni is 1, Rand P 4 together may be theclivalent radical of an aliphatic, cycloaliphatic or aromatic 1,2- or 1,3-dicarboxylic acid- When any of the substituents are C1.-C12- or CL-C18-alkyl, they are as already defined above under a).

When any of the substituents are C5-C7cycloalkyi, they are especially cyc lo hexyl.

As C7-Csaralkyl. R3 is especially phenylethyl or more especially benryl. As R3 is especially 2-hydroxyethyl or 2-hydraxypropyl.

R

3 as C2-Cl~olkanoyl is, for example, propionyl, butyryl, actanoyl, dodecanoyl, hexadecanoyl, octodecanoyl, but preferably acetyl, and as C3jis especially ocryloyl.

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

R

4 as Ci-C4alkyl substituted by a hydroxy, cyano, alkoxycarbonyl or carbamide group may be, for example. 2-hydroxyethyl, 2-hydroxypropyl, 2ayanoethyl, methoxycarbonylmethyl, 2 -ethoxyccarbonylethyl, 2ominocarbonyipropyl or 2-(dimethylaninocarbonyl)-ethyl.

When any of the substituents are C2-Cx2olkylene, they are, for example, ethylene, propylene, 2,2 -dimethylpro pylene, tetraniethylene, hexomethylene, octane-thylene, decamethylene or dodecamethylene.

When any of the substituenis are C6-Cl5orylene. they are, for example, o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.

As C6-Cl2cycloalkylene, D) is especially cyclohexylene.

The following compounds are examples of polyalkylpiperidine compounds of that class; 37) N,N'-bis(2 ,2 .b, 6 -tetramethypiperdin-4-yl)hexamethygene-.6.diamjne 38) N,N'-bis(2 ,2 .b.

6 -tetraiethylpiperidin-4-yl)hexamethyenet 6 -diacetamide and 1,6-diformamide 39) 1-acelyl-4-(N-cyclohexylocetamido-2 ,2 6 6 -tetramethylpiperidine 4- ben zoylami no- 2,2 6 1 6 -tetramethylpi periciine 41) N.N'-bis( 2 2 6 6 -tetramethyipiperidin4yu-NN'-dibuty.odipamid 8 42) bis( 2 ,266 -tetram ethyp iper id n yl>-NN'-d i cohexyI -2 hydroxypropylene-1I 3-diomine 43) N,N'-bis(2,6,6-tetramethylpiperidi n- 4 -yI)-p-xyiylene-diamine 44) N,N'-bis(2 .2,6 .6-tetramethylpiperidirn-4-yi)succine-diom ide N-(2 2 6 u 6 -tetramethylpiperidin-4-y;)4Banidipropionic acid di (2,2,6,6tetromethylpiperidin-4-yl) ester 46) the compound of the formula

CH

3

CH-I

3

C

4

H

OH-N -N-CH 2 -OH(Ol--CH---o

CH

3

OH

3

OK

3

CH

3 G~r--N -CH 2 -CH(OH)-CH----o

CH

3

OH

3 47) 4-(bis-2-hydroxyethyl-amirio)-1,2,2 6 6 -pentamethylpiperidine 48) 4-(3-methyl-4-Ihydroxy-5-tert- bly- benzoi c acid amido)-2,2 .6.6tetrumethylpiperidi ne 49) 4-methacrylomido-1 ,2 .2.6.6 -pentamethylpiperidine c) Compounds of formula (IV) wherein n is the number I or r2, Pis as defined under a) and, when n is 1, R5is C2-8alkylene or C2-C~hydroxyaikylene or C4- C22acyloxyalkylene, and, when n is 2, R5is the group (-CH2)2CcH2-) 2 When R5 is C2-C8alkylene or C2-C~hydroxyalkylene, it is, for example, ethylene, 1-methyl-ethylene, propylene, 2 -ethyl-propylene or 2-ethyl-2hydroxymethyipro pylene.

As C4-C22acyloxyalkylene,

R

5 is, for example, 2-ethyl-2aocetoxym ethyl propylene.

The following compounds are examples of polyalkylpiperidine compounds of that class: 9-aza-B,8.1O,1O-.tetrmethyl-1 .5-dioxaspiro 51) 9 -nza- 8,8.1O,1-etramethyl-3 -ethyl- ,5 -d ioxaspi ro 52) 8-azo-2 .l.

7 1 8 9 0 9-hexamethyl-l.4-dioxaspirof45]gec 0 n 53) 9 -aza- 3 -hydroxmethyl-3 -ethy[-889,10,10 54) 9-aza-3-ethyl-3-ocetoxymerhyl-9-ocetI..8,8,lOlO-tetr'amethyl..a,5- 2,2 .6.6-tetramethylpiperidine-4-spiro-2 '-dioxane)-5' (1,"dooe-"sio4"(1,1,","-ermtypprdn) d) Compounds of formulae VA, VB and VC NJ\ H3I

(VA)

H 3 C CH 3 R-N 0-C- V9

II

H 3 C *CHS3H H T 1_

(VC)

wherein n is the number I or 2, Ris as def ined under a), P 6 is hydrogen, C1-Cl2uikyl. allyl. benryl. glycidyl or C2-C6alkoxcyalkyl and, when n is 1. R7 is hydrogen, Cl-Cl2al1kyl, C3-C5alkenyl, CY-Cgarolkyl, Cicycloalkyl, C2-C4hydroxyalkyl, C2-C6alkoxyaIkyI, C6-Cloaryl. glycidyl or g group of the formula -(CH2)p-COO-Q or of the formula -(CH2)p-O-cO-Q.

wherein p is 1 or 2 and Q is CI-C4alkyl or phenyl, and, when n is 2 P 7 is C2- Cl 2alkylene, C4-CI 2alkenylene, C6-CI 2aryiene, a group -CHz-CH(OH)-Cjq 2 o-j O-CH2-CI-(Oi-Q-CH2-. wherein 0 is C2-Cloalkylene, C6..Clclrylene, C6- Cl 2cycloalkylene, or a group -CH2CH(OZ')CH2-(ocH2-cH(or)cH 2 wherein Ztis hydrogen, Cl-Cl8alkyl. allyl, benzyi, C2-Clzaikonoyl or benzoyl, Ti and T2 are each independently of the other hydrogen, Cl-Ciaalkyl, or unsubstituted or halo- or Cl-C4alkyl-substituted C6-Cloaryl or C7-Cgaralkyl, or Tj and T2 together with the carbon atom that binds them form a C5-Cl2cycloaikane ring.

When any of the substituents are C1-Cl2alkyI, they are, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl. n-hexyl, n-octyl, 2-ethyl-hexyl, nnonyl, n-decyl, n-undecyl or n-dodecyl.

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

When any of the substituents are C2-C6alkoxyalkyl, they are, for example, rethoxymethyl,'ethoxymethyl, propoxymethy, tert-butoxymethyl, ethoxcyethyl.

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

When R7 is C3-Calkenyl, it is, for example, I-propenyl, allyl, methallyl, 2butenyl or 2-pentenyl As C7-Cgaralkyl,

R

7 Ti and T2 are especially phenethyl or more especially benzyL. When Ti and T2 together with the carbon atom form a cycloalkane ring, that ring may be, for example, a cyclopentane, cyclohexone, cyclooctane or cyclododecone ring.

When R7 is C2-C4hydroxyalkyl, it is, for example, 2 -hydroxyethyl, 2hydrocypropyl, 2-hydroxybutyl or 4-hydroxybu-yl.

As C6-Cl~aryI.

R

7 Tj and T2 are especially phenyl, a- or 8-naphthyl, which are unsubstituted or substituted by halogen or by Ci-C4alkyl.

When P. is C2-Cl2alkylene, it is, for example, ethylene, propylene, 2,2dimethylpropylene. tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene- As C4-Cl2olkenylene, R7 is especially 2 -butenyiene, 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 Z' is C2-Ci2alkanoyl, it is, for example. propionyl, butyryl, octonoyl, dodecnoyl, but preferably acetyl.

D Cs C2-Cloolkylene, C6-ClSorylene 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-7,7,9,9-tetramethylspiror45]decane24dione 57) 3-n-oclyl-i,3 triaza-, 7 9 9 tetramethylspiro [4.5]decane-2 4-dione 58) 3 -allyl-I,3 ,6-triciza-1 .ll, 9 9 9- pentamethylspiro 4 .5]decane-2.4-dione 59) 3 -glycidyl-l 1,3, 8-triazo-7,7,8,99 -pentamethylspiro(4.Sdecone2,4dio ne 1 .3,7,7,8,9.9-hepramethyl-1.3 8 -triazaspiro(4.5]decune-2 ,4-dione 61) 2 -isopropy-l799-tetramethyl z-oxass8 diaza-4oxo.spiro 4 62) 2,2-dibutyl-7,7,9.9-tetramethyl- 1 -oxa- 3 uB-diaza-4-oxo-spiro[(4.5decone 63) 2,2,4,4-tetramethyl -7-oxa- 3, 2O-d ia zo-2 1-oxo-dispi ror5.I1.11.

2 l]hen icosane 64) 2- butl-I77,9,9-tetramerhyl-1 0xa- 4 8-acetyl-3-dodecyl-l,3 .B-triaza-Y,7,9,9-tetramethyspiro(4.5rJec 0 1 e., 4 diorie or the compounds of the following formulae: CH I3 OH 3

OH

3

OH,

3 NH-C =0 0=0 CHr--N C--HO I

N-CH

3 3 C-N-CH2C(OH)CHzroCH 2

CH(OH)HN-C

CHR

3 CR0 11 66) H 0 H 3 67) OH 3 01-3 OCI O H 3 C-ij--N NHC IO-N N-OH 3 -N (CH 2

)-N

OH

3

OH

3 0 OH 3 OH 3 68) OH.

3

OH

3

OH

3 OH13 NH-00= 0=0-NH HN

NH

II

OH

2 -aC

OH

3 1H 0OH 3 CH 30

OCH,

H0 O H 3 o 0 (OH 2 1 69) HN Ij\- O -N-CH 2 CH 2 0000 2 H 2 OH H, 0 e) Compounds of formula VI N N

(VI),

wherein n is the number 1 or 2 and R 8 is a group of the formula CH, CH, N-R 1 C H 3 CH wherein

R

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

R

9 is identical to R 8 or is one of the groups -NRIIR 12

-OR

1 3 -NHCH2OR 1 3 or -N(CH20R 13 )2, when n 1, R 10 is identical to R 8 or R 9 and, when n 2, R 1 0 is a group -E-Bwherein 8 is C2-C6alkylene that is uninterrupted or interrupted by -N(R 11

R

1 1 is Ci-C12alkyl, cyclohexyl, benzyl or C1-C4hydroxyalkyl or a group of the formula

RCH

3

,CHR

l12 i CI-Cl2aikyl, cyclahexyl, benryl, CL-C4hydroxyalkyl and 13is hydrogen, C1-Cl2alkyl or phenyl, or R11 and P 12 together are C4-C5ailkylene or C4-C5oxaolkylene, for example -OH OHR 22> -CH CH-_/ 2 2\ are a group of the formula

-CH

2

CH

2 N F -C 2 O-CHI CN- j or alternatively

R

11 and R 12 are each a group of the formula CH 3 CH 3

N

N IN CH 3

CH

3

C,

4

H,-N

CH,3 CH 3 OH, N CH 3

H

When any of the substituents are Cl-Cl2alkyl, they are, for example, methyl.

ethyl, n-propyl, n-butyl, sec-butyf, tert-butyl, n-hexyl, n-octyl, 2-ethyihexyl, nnonyl, n-decyl, n-undecyl or n-dodecyl.

When any of the substituents are Cl-C4hydroxyalkyl, they are, for example, 2 -hydroxyethyl, 2 -hydroxypropyl, 3- hydroxypro pyl, ?-hydroxybutyl or 4hydroxybutyl- When A is C2-C6oikylene, it is, for example, ethylene, propylene, 2,2- 6 irethylpropylene, fe -traneihylene or hexamethylene.

When P 11 and R 12 together are C4-C5alkylene or C4-C5oxaalkylene, they are, for example, tetrame-hylene, pentamethylene or 3 -oxapen-romethylene.

The compounds of the following formulae are examples of polyalkylpiperidine compounds of that class: C H 3

H

3 C I CH3 3

N

7)

H

3 C qH 3 N-C H

(CH

3

CH

2 2 N)"NS

N(CH

2

CH

3 2 01-3 OH 3 NC

H

3

OH

3 7)C 2 Hc-N N N 2 52C Cf- 3

CH

3

CHCH

5 C~ CH 3 R

H

3 0 CH 3 7) N)I"N weinR=-NH-CH 2

CH

2 O- N-CH 3 Rt<N<R whri R C C 3

OH

3 73) CH 3 CH 3 Cl-f 3 CH 3 74) 04, cx 1 CHH

CH,

I

.CJLCH,

H

R

R

A-NH IH) (CH 2 S C 2

)NH..R

CH O H 3 wherein R is

CH

3 ICH 3 CH 3 R NHH 2 3 (CH 2 )r N(HV 3

I-R

wherein R

OH

3 77) CH3R CH 3 R-N -(CHN~i--(CH 2

N-(CH

2

)-N

GH

3 CM3 O4H 9 N

NIH

N N wherein R r w OHNH ,0H 3 11

H

3 c HO cHO' t

HO

(62L

,HO

1 C( O)HN

EHO

UHO'

CH,-CH=CH,

H

3

C,

HC

H3C

SCH

CH

CH,

f) Oligomeric or polymeric compounds, the structural repeating unit of which contains one or more 2 2 6 6 -tetraalkylpiperidine radicals of formula especially polyesters, polyethers, polyamides, polyamines, polyurethanes, polyureas, polyaminotriazines, poly(meth)acrylates, polysiloxanes, poly(meth)acrylamides and the copolymers thereof that contain such radicals.

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

CH

3 l CH- 0 0 II II 81) C-CH,-CH,--C--CH,-CH,-N m

CH

3 82) 83) 84) CH fi 0 0 C3 C 0 C]ICHJ C-a N-CH,.CH,-O IICH.

CH, CH CH.

CH-

3 CR 3 86) CH3

CH

3 CH 3 CH8 3 1 2 -N 0-C C

C;

4

H

9 in CH 3 CRHA 3

CH

3 87) 88)

OH

3 89) CH"

OH

3 CH 3 91) 92) 93)

CH

3 I

CH

2

C

CH

3

G

3 m

C

6 H 13 -N N-CH 3 CH( CH 3

ICH

3 CH3 94) s-I 0 wherein R H or CH3

-CH

3 CHi 3 HC,,R)Ny

N(R)C

4 Hg N N~ 96)

H,JR)N-

H

3 C,

CH

3 wherein P:=

HC

4 (R)N Nj N(R)C 4 H13 and R'= or H (obtainable by reacting the reaction product of trichlorotriazine and NH2- (CH2)3-NI--(Cf-2)2-(CH)3-NH2 with 4 -N-butyl-2,2,6,6tetramethylpiperidinej Of those classes, classes e) and f) are especially suitable, especially those tetroalkylpiperidine compounds that contain 5-triazine- groups. Also especially suitable are compounds 74, 76, 84, 87, 92, 95 anid 96.

The preparation of the N-piperidinyl-triazires is known from the literature for example, H-ouben-Wey

T

Methoden der organischen Chemie;, Vol, yVn, p. 233-2 37, 3' Ed., Thiemne Verlag Stuttgart Therec may be used as startin~g material for the reaction with vario .us N-piperidylomines cyanuric chloride, diaminto-chloro-l .3.5-triazine or variously substituted bisdialkylomino-.

chlaro-1,3 ,5-triazines or dlalkyldminto- or alkymiino-dichloro-1!, 3 5 -triazine-s.

Technically important examples of tetra- and penta-alkylpiperidine compounds are: bis(2.

2 6 1 6 -tetramethy-pipridyg) sebacate, bis(2,2,6 ,6fetramethyl-pi peridyl) succlrntc, bii(1 ,2,2,6.

6 -pentamethylpiperidyl) sebacate.

n- butyl-3 .§-di-tert-bntyl. hydrOxybetay-m loinic acid bis(1,2 .2.6.6pentamethylpipericiyl) ester,, the condensation product of 1-hydroxyethyl-.

2.2.66-etramethyl-4hyoxy-piprldin 2 and succinic acid, the, condensation product of NN-bis(2 .2,6,6tta hl4pprdy)hxmtyeeimn and.

4-ter--oc-ylani no- 2,6-dick bra- 1.3 .S-s-triazine, -tris(2 .2 6 6 -tetramthy..4p1 peridyl )nitrilotriacetate, tetrakis(2,2 6 5 6 -tetrmmethyl-4-pi peridyl)-1,2.3.4butonetetruoute. l.l'-(1.2-thanediyl}.bis(3.3, tetramethyl-pipea-azi none,), 4benzoyl-2.2.6.6-tctrwct-hlppqrldfn. 4 -steorylcxy-2.26,6-.

tetramethylpiperidine, bif ,26.pntwnethydpi peridyl)- 2-n- butyl-2-(2hydroxcy-3 .5-di-tcrt-butylbienzyl) inalonate. 3 f-octy-7.7,9.9-tetramethy..

1,3 .8-triazaspi ro(4.5jdecane-2,4-dlone, bis(i-octloxy- 2,2,6,6 te-tramethylpi peridyl) sebacate, bis(1-ectyloxy-z 2,6 .6-tetramethyl pi peridyl) sued note, the condensation product of N,N'-bis(2, 2.6 ,6-tetramtethyl-4-.

piperidyl)hexamethylenedbomine and 4-morpholino-z,6-dich loro-! 3,S-triazine, the condensation product of 2-chloro-46-di(.-n.butylami no-2 .2,6,6and I., 2 -bis( 3 -aminopropylamrino)ethon,~ the condensation product of a-chloro-.6.-cc4-nA-buwlamninol .2,2.6,6pentaniethylpiperidyl)-1,3, 5-triazi.'i and I ,2-bis(3 -amninopropylamino)ethane, 8acety-3-dodecyl-7 .l.

9 1 9-tetramrethyl- 1,3,8 -triazas p1ro 4 .5)decane-2.4-diane, 3 -dodecyl-l-( 2 2 1 6 6 -tetramnethy[-4piperidyl)pyrrlidi ne-2 .5-dione, 3-dodecyl- 1-(1 ,2,2 .6 6 -pentamnethyl-4-piperidyl)-pyrrolidi ne- Instead of a single sterically hindered amine, it is possible within the scope of the present invention also to use a mixture of different sterically hindered amines.

The amount of sterically hindered amine added depends on the desired degree of stabilisation. In general, from 0.01 to 0.5 by weight, especially from 0.05 to 0.5 by weight, based on the polymer, is added Hydrotalcites and alkali (alkaline earth) aluminosilicates (zeolites) The chemical composition of these compounds is known to a person skilled in the art. for example from patent specifications DE 38 43 581, US 40 00 100, EP 062 813, WO 93/20135.

Compounds from the hydrotalcite series can be described by general formula

VII

M

2 -x M 3 +x(OH)2 (Ab-)x/b d H20 (VII) wherein

M

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

M

3 4 Al. or B.

A

n is an anion having the valency n, b is a number from I to 2, 0 <x E 0.5. and m is a number from 0 to Preferably.

An OH-, CIO4-, HC03-, CH3COO-, C6H5COO-, C032- (CHOHCOO)22-, (CH2COO) 2 2 CH3CHOHCOO HP03-or HP04 2 Examples of hydrotalcites are A12O3.6M9O.COa.12H20

M

9 4,5A12(OH)1aCO3J5H2o 0ii), 4M90.A1203.C02.9H2o (iii 4MgO.A 1203.COZ.H20, ZFIO.3Mq0.A120 3 -COZ 9H20 and ZnO.3MgO.A23.c2.§-6H 2 0- Special preference is given to types i,i and iii.

2"ecites (alkali and alkaline ear-th alumifosilicates) These can be described by general formula (VIMI) Mxt'n((A02)x(5102)yj.wH2o

(VIII)

wherein ni is the charge of the cation M: M is an element of Group I or Group 11, such as Li, Na. K. Mg. Ca, Sr or Ba;: y:x is a number from 0.8 to 15, preferaby from 0.8 to 1.2: and w is a number from 0 to 300, preferably from 0.5 to Examples of zeolites are sodium aluminosilicotes of the formulae aU11l2Si12O48. 27 R20 Czeolite Nc6A65i 6

O

2 4 2 NaX 7.5 X= OH, halogen, Cl04 [sodaliteJ; NG6AI6I 3 oQ7 2 24 H20; NaeAlaSi 4 oog 6 24 H20: Na1i6Al165v240 8 0 16 H20; NG16Al65i 3 2 O6. 16 NG56Als65il3603 8 4 250 H20 (ColiteY]. NOB6A86S1 1 6

O

3 8 4 264 HzO (zeohite X}: or -the zeolites that con be formed by partial or complete replacement of the Na atoms by Li. K. Mg, Ca. Sr or Zn atoms, such as (Nai,K)1oAllo~i2206 4 20 H20: C04.5NQ3[(A02)12(i0 2 )lzJ 30 K9N3(A02)12(5i02)zzJ. 27 Preferred zeolites correspond to the formulae Nax12Alz5ii 2 27 H-20 [zeolite A], Na6Al6Si6O2 4 2NoX.- 7.5 H120, X =OH, Cl, C104, 1/2C03 [sodal1ite] Na6Al6SiaO0z2. 24 H120, NaBAla5i4009 6 241H20, Nal6Alz6Si2 4 O0o. 16 H120.

N016A165i320 9 6 26 Na56Al56Sil360384. 250 H20 [zeolite Y] Na86Al86Si1060384 264 H20 [zeolite X] and zeolites of the X od Y type possessing on AI/Si ratio of about 1:1.

or the zeolites that can be formed by partial or complete replacement of the Na atoms by Li, K, Mg, Ca, Sr, Ba or Zn atoms, such as (Na,K)1OAllOSi22064.20 Ca4,5Na3[(Ai02)12(Si02)12] 30 K9Na3[(A0O2)12(Si02)12-] 27 The zeolites listed may also have a lower water content or may be anhydrous.

Other suitable zeolites are: Na 2 0-AI203-(2 to 5) SiO2-(3.5 to 10) H20 [zeolite P] Na20-A1 2 0 3 -2 5i02-(3.5-10)H 2 0 (zeolite MAP) or the zeolites that con be formed by partial or complete replacement of the Na atoms by Li, K or H atoms, such as (Li,Na,K,H)1oAl1oi 2 2064. 20

K

9 Na3[(AlO2)12(Si02)12] 27 H 2 0 K4A1 4 Si4016- 6 H20 [zeolite K-F] Na 8 A185 4 0 096.24 H20 zeolite D, as described in Barrer et J. Chem.

Soc. 1952, 1561-1571, and in US 2 950 952; The following zeolites are also suitable: potassium offretite, as described in EP-A-400 961; zeolite R, as described in GB 841 812; zeolite LZ-217, as described in US 4 503 023; Ca-free zeolite LZ-218, as described in US 4 333 859; zeolite T, zeolite LZ-220, as described in US 4 503 023; Na 3

K

6 Al 9 5i27072.21 H 2 0 [zeolite L]; zeolite LZ-211, as described in US 4 503 023; zeolite LZ-212. as described in US 4 503 023; zeolite 0, zeolite LZ-217, as described in US 4 503 023; zeolite LZ-219, as described in US 4 503 023; zeolite Rho, zeolite LZ-214, as described in US 4 503 023; zeolite ZK-19, as described in Am. Mineral. 54 1607 (1969); zeolite W as described in Barrer et J. Chem. Soc. 1956, 2882; Na3 0 A1 3 0 Si 6 6 01 9 2 98 H 2 0 [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-I and P-2.

According to that publication, zeolite P-3 is very rare and is therefore of little practical interest. The structure of zeolite P-1 corresponds to the gismondite structure known from the above-mentioned Atlas of Zeolite Structures. In more recent literature (EP-A 384 070) a distinction is made between cubic (zeolite B or Pc) and tetragonal (zeolite PI) zeolites of the P type. That publication also mentions relatively new zeolites of the P type having Si:AI ratios of less than 1.07.1. Those are zeolites designated MAP or MA-P for "Maximum Aluminium P".

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

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

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

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

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 (dowsonites) These are compounds of the formula 203)n.Zo.pH20), wherein M is H, Li, Na, K, Mgl/2, Cal/2, Srl 2 or Znl/2: Z is CO2, S02, (C1207)1/2. B406. 5202 (thiosulfate) or C20 2 (oxalate); m is a number from 1 to 2 when M is M91/2 or Cal/2, and in all other cases is a number from I to 3: n is a number from 1 to 4; a is a number from 2 to 4: and p is a number from 0 to The alumino salt compounds of formula that can be used according to the invention may be naturally occurring minerals or synthetically prepared compounds. The metals may partiall replace one another. The mentioned alumino salt compounds are crystalline, partially crystalline or amorphous or may be present in the form of a dried gel. The alumino salt compounds may also be present in relatively rare crystalline modifications. A process for the preparation of such compounds is described in EP 394 670. Examples of naturally occurring alumina salt oompounds are indigirite, tunisite, aluminohydrocalcite, parn-aluininhydrocalcite, strontiodresserite and hydrostrontiodresserite. Other exadmples of alumino salt compounds are potassium aluminocarbonate (K20).(AI203).(C02).2H 2 sodium aluminthiosulfate ((NgO).(A1O)($2z02)2.21120), potassium aluminosulfite I203)(S02)2 H20) cknt aluminooxalate 1203)(C202)2.5-120). magnesium alurn inotetraborate 12 03).(B406)2.5H20), (([M90.2 a O.620).(A 1203).(C2)2.41 H2 0), ((lMg.2Nao.6 120}(A 1203).(CO2)2.4.3 H20) and ((Mgo.3Nao.4120).(A 1203).(C2)2.2.4.9H20).

The mixed alumina salt compound can be obtained in accordance with processes known per se by catloi td"ne preferably from the alkali alumino salt compounds or by combin tion (see, for example, US 5 055 284).

Preference is given to alumina salt compounds of the above formula wherein M is No or K: Z is C02, 502 or (C1207)l/2; mn is 1-3; n is 1-4; o is 2-4 and p is 0-20. Z is especially CO2.

Preference is given also to compounds that can be represented by the following formulae: M20.A1203.(C2)2 pH20 (19) (M20)2.(A1203)2.(CO2)2 pH20 (Ib) M20.(A203)2.(CO2)2 pH2O (Ic) wherein M is a metal, such as No, K, Mgl/2, Cal/2, Srl/2 or Zni/2 and p is a number from 0 to 12.

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

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

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

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

The stabiliser combination according to the invention can be used together with further additives that are customary for the processing and stabilisation of chlorine-containing polymers, such as: Zinc compounds The organic zinc compounds having a Zn-O bond are zinc enolates and/or zinc carboxylates. The latter are, for example, compounds from the series of aliphatic saturated C2-C22carboxylates, aliphatic unsaturated C3- C22carboxylates, aliphatic C2-C22carboxylates that are substituted by at least one OH group or the chain of which is interrupted at least by one oxygen atom (oxa acids), cyclic and bicyclic carboxylates having from 5 to 22 carbon atoms, phenylcarboxylates that are unsubstituted, substituted by at least one OH group and/or Cl-Cl6alkyl-substituted, phenyl-CI-Cl6alkylcarboxylates, or phenolates that are unsubstituted or C1-C12alkyl-substituted. or abietic acid.

There may be mentioned specifically, as examples, the zinc salts of monovalent carboxylic acids, such as acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, oenanthic acid, octanoic acid. neodecanoic acid, 2ethylhexanoic acid, pelorgonic acid, decanoic acid, undecanoic acid, dodeconoic acid. tridecanoic acid, myristic acid, palmitic acid, lauric acid, isostearic acid, stearic acid. 12-hydroxystearic acid, 9 ,10-dihydroxystearic acid, oleic acid, 3,6dioxaheptanoic acid. 3,6,9-trioxadecanoic acid, behenic acid, benzoic acid, ptert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3.5-di-tert-butyl-4hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, npropylbenzoic acid, salicylic acid, p-tert-octylsalicylic acid, and sorbic acid; zinc salts of divalent carboxylic acids or the monoesters thereof, such as oxalic acid, malonic acid, succinic acid. glutaric acid, adipic acid, fumaric acid, dicarboxylic acid, hexane-1,6-dicarboxylic acid, heptane-1, 7 -dicarboxylic acid, octone-1,8-dicarboxylic acid, 3 6 9 -trioxadecane-1,O-dicarboxylic acid. lactic acid, malonic acid, maleic acid, tartaric acid,.cinnamic acid, mandelic acid, malic acid, glycolic acid, oxalic acid, salicylic acid. polyglycol-dicarboxylic acid 12), phtholic acid, isophthalic acid, terephthalic acid and hydroxyphthalic acid; and the di- or tri-esters of tri- or tetra-valent carboxylic acids, such as hemimellitic acid, trimellitic acid, pyromellitic acid. citric acid and also so-called overbased zinc carboxylates.

The zinc enolates are preferably enolates of acetylacetone, benzoylacetone or dibenzoylmethane and enolates of acetoacetates and benzoyl acetates and of dehydroacetic acid. In addition, inorganic zinc compounds, such as zinc oxide, zinc hydroxide, zinc sulfide or zinc carbonate, 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, laurate, palmitate, behenate, versatate.

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

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

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

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

The stabiliser combination can be provided with further stabilisers auxiliaries and processing agents, such as alkali metal and alkaline earth metal compounds, glidants, plasticisers. pigments, fillers, phosphites, thiophosphites and thiophosphates, mercaptocarboxylic acid esters, epoxidised fatty acid esters, antioxidants, UV absorbers and light stabilisers, optical brighteners, impact strength modifiers and processing aids, gelling agents, antistatic agents, biocides, metal deactivators, fireproofing agents and propellants, and antifogging agents (cf. "Handbook of PVC Formulating" by E. J. Wickson, John Wiley 5ons. New York 1993).

In a non-limiting manner, some of the known additives and processing auxiliaries are mentioned here; AIkwli metal and alkaline earth metal compounds.

These are to be understood to include especially the carboxylates of the acids described above, but also corresponding oxides or hydroxides or (bi)carlonates. Mixtures thereof with organic acids are also suitable. Examples are NaOH. Na-steorate, NaHCOs, KOH, K-steorate. KHCO 3 UOH, Li 2

CO

3 Listeoratc, CaO, Ca(OH2). MgO. Mg(OH)z. Mg-stearate, CaC03, MgCO3 as well as dolomite, huntit, chalk, basic Mg-carbonate and other Na- and K-salts of fatty acids.

NaOH. KOH. CaO. Co(OH2). MgO, Mg(OH)2, CoCO3 and MgCO3 and also fatty acid sodium and potassium salts.

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

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

6/idants(LUBRICANTS) Suitable glidants are, for example: Monton wax, fatty acid esters, PE waxes, amide waxes, chloroparaffins.

glycerol esters or alkaline earth metal soaps. Suitable glidants are also described in "Kunststoffadditive" (Plastics additives), R. Gidchter/H. Mfiller, Carl Hanser Verlag, 3" Ed., 1989. pages 478-488. Mention may also be made of fatty ketones (as described in DE 42 04 887) and of silicone-based glidants (as described in EP 225 261) or combinations thereof, as listed in EP 259 783.

Plasticisers Suitable organic plasticisers are, for example, those of the following groups: A) Phthclic acid esters: Examples of such plasticisers are dimethyl, diethyl, dibutyl, dihexyl, di-2ethyihexyl, di-n-octyl, diisooctyl, diisononyl, diisodecyl, diisotridecyl.

dicyclohexyl, dimethycyclohexyl, dimethylglycol, dibutylglycol, benzylbutyl and diphenyl phthalate and mixtures of phthalates, such as C7-C9- and Cg Cli-alkyl phthalates from predominantly linear alcohols, C6-CIO-n-alkyl phthalates and CS-Cao-n-alkyl phthalates. Of those compounds, preference is given to dibutyl, dihexyl, di-2-ethylhexyl, di-n-octyl diisooctyl, diisononyl.

diisodecyl, diisotridecyl and benrylbutyl phthalate and to the mentioned mixtures of alkyl phthalates. Special preference is given to di-2-ethylhexyl, diisononyl and diisodecyl phtholate, which are also known by the customary abbreviations DOP (dioctyl phthalate, di-2-ethylhexyl phthalate). tINP (diisononyl phthalate), DIDP (diisodecyl phthalate).

B) Esters of aliphotic dicarboxylic acids, especially esters of adipic.

ozelaic and sebacic acid: Examples of such plorasticisers are di-2-ethylhexyl adipate, diisooctyi adipate (mixture), diisononyl adipate (mixture), diisodecyl adipate (mixture), benzylbutyl adipate, benzyloctyl adipate, di-2-ethylhexyl azelate, di-2ethylhexyl sebacate and diisodecyl sebacate (mixture). Di-2-ethylhexyl adipate and diisooctyl adipate are preferred.

C) Trimellitic acid esters, for example tri-2-ethylhexyl trimellitate, triisodecyl trimellitate (mixture), triisotridecyl trimellitate, triisooctyl trimellitate (mixture) and tri-C6-C8alkyl, tri-C6-Cloalkyl, tri-C7-C9alkyl and tri-C9-CI1alkyl 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 ore TOTM (trioctyl trimellitate, tri-2-ethylhexyl trimellitate), TIOTM (triisodecyl trimellitate) and TrTDTM (triisotridecyl trimellitate).

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

E) Polymer plasticisers A definition of these plasticisers and examples thereof are given in "Kunststoffadditive (Plastics additives), it tichter/H. Miller, Carl Hanser Verlag, 3 "d Ed., 1989, Chapter 5,9,6, pages 412-415, and in "PVC Technology" W.V. Titow, 4' Ed., ElsevirdtbI. 984, pages 165-170. The most commonly used starting materials for the preparation of polyester plasticisers are: dicarboxylic acids, such as adipic, phthalic, azelcic and sebacic acid dials, such as 1.2-propnediol., 1,3-bijtonediol, 1.4-butanediol, 1,6-hexanediol neopentyl glycol and diethylene glycol.

F) Phosphoric acid esters A definition of those tt is to be found in the above-mentioned "Taschenbuch der Ku"tofWitive (Handbook of Plastics Additives), Chapter 5.9.5, p.p. 408-41a. nples of such phosphoric acid esters are tributyl phosphate, tri-2-ethylbutyl phosphate, tri-2-ethylhexyl phosphate trichloroethyl phosphate, 2-ethyl-hexyl-diphenyl phosphate, cresyl diphenyl phosphate, triphenyl phosphate, tricresyl phosphote and trixylenyl phosphate. Tri-2-ethylhexyl phosphate and WmReofos 50 and 95 (Ciba-Geigy) are preferred.

6) Chlorinated hydrocarbons (paraffins) H) Hydrocarbons I) Monoesters, eg. butyloleate, phenoxyethyl oleate, tetrahydrofurfuryl oleate and alkylsulfoic acid'eiters; J) Glycol esters, e.g. diglycol benzoates.

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

'PVC Technology', W.V. Titow, 4 t Ed., Elsevier Publishers, 1984, Chapter 6.10.2. pages 171-173, (group Chapter 6.10.5, page 174 (group Chapter 6.10.3, page 173, (group I) and Chapter 6.10.4, pages 173-174 (group J).

It is also possible to use mixtures of different plasticisers.

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

Pigments Suitable substances are known to the person skilled in the art. Examples of inorganic pigments are TiOz, carbon black, Fe 2 0 3 SbzO3, (Ti,Ba,Sb)O 2 .CrzO3, spinels, such as cobalt blue and cobalt green, Cd(5,Se), ultramarine blue. Organic pigments are, for example, azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, diketo-pyrrolopyrrole pigments and anthroquinone pigments. Preference is also given to TiOz in micronised form.

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

Filers Fillers (HANDBOOK OF PVC FORMULATING, E.J.Wickson John Wiley Sons, Inc., 1993 pp. 393-449) and reinforcing agents (TASCHENBUCH der KA'e (HANDBOOK of Plastics Additives), R.Gichter H.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 triphienyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosph ites, trs-(nonylphenyl) phosphite, trilauryl phosphite, Irioctadecyl phosphite. distearyl-perlaerythritow diphosphite, tris(2.4-di-tert-buwylpheny,) phosphit'e. diisodecylpentqerythritol diphosphite, bis(2 ,4-di-er-- ,buylphenyl)penoerythrito I dipho sph ite, bis(2 6 -di-tert-butyl-4-.methylp heny}..

pentaerythritol diphosphite, bi s- isodlecy foxy- pe ntaeryth rpto diphosphire, bis(2 4 -di-tefl-buyl-6-merhylphenyI)pentoeeythrito I diphosphite. bis(2.46-ri..

tert- butylphenyl)pentaerythrijo I di phosph ic, tristearyl-sorb ito I triphosph ite, bis(2.4-di-ter-bul-..6-methyl phenyl~rethyl phosphite, bis(2,4-di -tert- butyl-6.

methylphenyl)eihyl phosphite.

Especially suitable are trioctl, tridecyl. tridodecyl tritetradecyl, tristeuryl.

trioleyl, triphenyl-, tricresyl, tris-p-nonylphenyl or tricyclohey1 phosphite and special preference is given to the aryf-dialkyl anud alkyl-diaryl phosphites, such as phenyldidecyl phosphite, 2 4 -di-tert-butylpienyl)-gi.doJcqI phosphite, (2.6di-tefl-butylpheyl)di.&)decyl phosphite and to the dialkylI- aind diay penlaerythrito I di phosp hites, such as distearylpenterythrito I diphosph ite, and non--roaichiometric triaryl phosphites, for examrple those having the composition (HI 9C9-C6H4)O1 !5P(OCj 2.13 H25.2fl1.5 Preferred organic phosphites are disteuuryI-pentaeryrhritoI diphosphi-e.

trisnonyiphenwyl phosphi-te and phenyldidecyl phosphite-.

The organic phosphiles can be used in an amount of, for example, from 0.01 to 10, advantageously from 0.05 to 5, and especially from 0.1 to 3.prsb weight, based oh 100 parts by weight PVC.atsb T-hiophosphites and thiophosp hates There are to be understood by thiophosphites and thiophosphates compounds of the general type: (RShP, (PS)P-O or (R5) 3 P5, which are described in patent specifications DE 28 09 492.

EP 090 770 and EP 573 394.

Examples of those compounds are: frithiohexyl phosphite, trithiooc-yl phosphite, trithialouryl phosph ite, tnithiobenzyl phosphite, trithiophosphorous acid tris(corboisooctyloxy~nethyl ester, trithiophosphorous acid tris(carbotrirnet hylcyclo hexyloxy)rnethyl ester, trithiophosphoric acid 5,5,5tris(corboisooctyloxy)methyl ester, trithlophosphoric acid 5,5,5-tris(corbo- 2ethyl hexyloxy)methyl ester, trit hio phosphoric acid (carbohexyloxy)-ethyl ester, trithiophosphoric acid 5SS-tris-1-(carbo-2ethylhexyloxy)-ethyl ester, trithiophosphoric acid 5.5.5-f ris-2-(carbo-2 ethylhexyloxy)-ethyl ester.

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

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

Epboxidised 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 f rom, natural sources (f atty acid glyceridles), such as soya oil or rape oil. It is, however, also possible to use synthetic products, such ais epoxidised butyl oleate.

A ntioxidan ts Suitable antioxidanits are, for example: 1. A Ikylated monophenols. for example 2 6 -di-tert-butyl-4-methylphenol, 2-tert-butyl-46-dimethylphenol, 2 6 -di-tert-butyl-4-ethylphenol, 2,6-ditert-butyl-4-n-butylphenal, 2,6-di-tert-butyl-4-isobu-ylpheol, 2.6dicyclopentyl-4-methylphenol, 2 -(cz-methylcyclohexyl)-4.6-dimethylphenolj 2,6-dioctadecyl-4-methylphenol, 2 ,4,6-tricyclo hexylphenol, 2 ,6-di-tertbutyl-4-methoxymethylpheial, 2 .6-di-nonyl-4-methylphenol, 2.4-dimethyk-6.

(1'-nethyl-undec-1'-yl)phenol, 2, 4 -dimethyi-6-(1'-methyl-heptadec. yl)phenol, 2.4-dimethyl-6-(t'-methyl-tridec-'-yl)phenol, octylphenol, nonyiphenol, dodecyiphenol and mixtures thereof.

2. Alkylthiomethylphenols. for example 2 4 -di-octylthiomethyl6teppbutylphenol, 2 4 -di-octylthomethyl-6-methylphenol, 2 9 4-di-octylthiomethyk.

6-ethylphenol, 2 6 -di-dodecylthiomethyl-4-nonylphenol.

3. Alykted hydroguinones. for example 2 9 6-di-tert-butyl-4methoxyphenol, 2 .§-di-te-rt-butyl-hydroquinone, 2 hydroquinone, 2 6 -diphenyl-4-octadecyloxypheno I, 2 .6-di-tert-bu-.

hydroqui none, 2 ,5-di-tert- butyl-4-hydroxyamiiso Ic, 3 .5-di -tert-buyl-4hydroxycanisole, 3 ,5-di -ter-t- butyl-4-hydroxyphenylsteorute, bis(3 ,5-di -tertbutyl-4-hydroxyphenyl) adipote.

4. -lyroxylated thiodiphenyl ethers. for example 2.2'-thio-bisC6-twl...

butyl-4-methylpheno 2 ,2'-thio- bis(4-octypheno 4.4'-th io-bis(6 -tertbutyl 3 -methylpheno 4 4 '-thio-bis(6-tert-buyl2-methy phenol). 4.4'-th io.

bis(3 .6-di-sec-omyipheno 4,4-bis(2 .6-dimethyl 4 -hydroxypityl) disulfide.

Alkylidene bisphenols. for exml 2 Z-methylene-bis(6-tert-butyl4-.

methyipheno 2 .Z'-methvlew-big(6-ten-butyl.4.etyhyeo, 2,2'mcthylen-bis[4-methyl-6 -(a-mcthylcyclohexyl)phesoi], 2 .2'-rnethylenebis(4-methyl-6-cyclohexylphcnol). 2 .Z-niethylene-bi -s(6-'nonyl-4methylphenol), 2 ,2'-methylene-bis(4.6di -ter-t- butylpheno 2,2'-ethylidene..

bis(4.6-di-tert-butylphenol), 2 ,2'-ethylidene-bis(6 -tert-butyl-4isobutylphenol), 2, 2 '-methylene--bis6-(a.methyltsenzI nonyipheno 2,2'methylene-bis(6-(a .a-dimethylbenryl)-4.nornyipheno methylemvebis(2.6-di-tert-butylphenol), 4 e4'-methyene-bis(6-merttburyI-2-.

methylphenoQl, l.I-bis(5-tert-butyl-4-hydroxy-.2-methylphenylbutoine 2.6bisp -tert-bulyl-5-methyl- hydroxybenzyi)-4-methylpIhenoI. 1.1,3 tert-butyl-4-hydroxy- Z-mcthylphenyl)butane, l.1-bis(5-terv. butyl-4hydroxy- 2-methylphenyl)- 3 n-dodecylmercapto butane. ethylene g lycolbis[3 .3 -bis(3'-tert-butyl-4'- hydroxyphervyl) but-yrate]. bis(3 -tert- butyl-4.

d' cyclopenlodiene, bis(2 -(3'-tert- butyl- 2'-hydroxy..

5'-methyl-benryl)-6-tert-buyl.4-methyIphenyl] terephthalate, I 1-bis(3 dimethyl-2-hydroxyphenyl)burane, 2,2-bis(3 ,5-di -tert-buIyl-4hydroxyphenyl)proparie, 2,2- b is(4- hydroxyphenyl)pro pane, 2,2- buy--yrxy2mtypeyl---o1ymecpoucn,155 butyl-4- hydroxy-2 rmethvlphenyl)pentone.

6. Benzyt compo2unds, for example 3 .5,3'5-tetra-tert-butyl..44t dihydroxydi benzyl ether, o ctade cyl-4- hydraxya 3,5-d imet hylbenzylI mercaptoacetote, tris( 3 .S-di-tert-but-y.4-hydroxybe-nzy>amije, bis(4-tertbutyl-3-hydroxy- 2,6 -dimethylbenryl) dithiotereph1thalate, bis(3 butyl-4-hydroxybenryl) sulfide, isooclyl-3 5 -di-tert-buty-4-hydroxybenzyI mercaptoocetate.

7. I-tydroxybenzylate-d molonotes. for example dioctadecyl-2.2-bis(s di-tert- butyl-2-hydroxybcnzyl) malonate, di-octodecyl- 2-(3 -teflt- bttyl-4nttlsnai'te, dldodecylmercaptoethys -29 2-bis(3 ,5-di tert-butyl-4-hydroxybenzy) moloncte, di-(4-(1,1,3,3tetramethylbutyl)phenyl]-2 ,2-bis(3 ,5-di -tert-butyl-4-hydrocybenzys) malonate.

8. 8hd xOgly ntrmstic woi~nds for example l.3,5-tris(35-gi.

tefl-butyl-4-hydroxybeizyl)-2 .4.

6 -trimethylbenxene. 1,4- bis(3 butyl-4-hydroxbtnpl)-23A56-ewnethylbetzep.. 2,4.6-tris(3.5-dk-tert 9. 'Tri.4zine Cofd~s. for example 2.4-his-or tert-buy-4iydoxanIIno}4i3t.-trkczine, Z-ortylimercapio-4,6-bis(a tert-buryl-4-hydroxya npn) I35tlzre 'Symrato"46-ls3.~j.

tert-buyl-4-hydroxypheo)xy)-4,3'.5-triozine,, 4,6-tri's(3',5-dI-ten-buwIA...

hydroxyphenoxy}-1 .2,3-triazlne, 1,3 .5-tris(3. '5-di tert-butyt -4hydroxybenzyl) isocyanurte. l.

3 ,§etris(4-.tert-.butyl-3dlydiroxr-2 6dime-thylbenzyl) isocyanurote, Z.

4 6 -tris(3.5-di-tert-butyl4hydroxyphemyethyO)-1,3.Sdtriazine, 1 3 hydroxypheuiylproplonyl~uhqnohydro-1.3,5-triazlns, l,3.5-tris(3 dicyc~ohwwyI-4-hydronybeny.X Gyanurats.

Phosphonats an' 66ovfn0"s for example butylA4-hydroxybenzylA phospbonate, disethyl-3.5di-tert-butl-4 hydroxybenzyl phosphonhatc diocftodecyl-3 5 1d-ter-buwyl-.4-hydoybenryl phosphonate, dioctodcyl5-ert-butyl-4-hycy-3-mthylenzy phosphonore, calcium salt of acid monoethyl ester, tetrakis(2 .4-dil-tert-butylphenyl).4,4'-bi phenylenediphosphonite, 6-isooctyloxy-2 4 1 8 lO-tetra-ltert-butyl-1 2H-dibenzo~d,g]- 1,3,2 -dioxaphosphocine, 6-fluoro-2.4,8 .IO-tetra-tert-buyl-12-me-hyl.

dibenzo(d,gJ-1.2-dioxophosphoci ne.

11. A IpM o example 4-hydroxy-lauric acid anilide, 4hydroxysteari c acid'dail ide.. N- (3 ,5-d i-tert-butl hydroxyphenyl )-corbaeni c acid octyl ester.

12. Esters of b-(3 .S-di-tert-buvi.4-hydroyphenyypr 0 i 0 nic acid with mono- or poly-hydric alcohols, such as methanol, ethanol, octanol, octodecanol, l,6-hexanediol, l 9 -nonianediolethylen~e glycol, l, 2 -propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, trierhylene glycol, pentoerythriro I, di pentaerythrito I, tris(hydroxyethy I) isocyonurate,

NWN'-

bis( hydroxyethyl)oxali c acid diaunide, 3 -thiaundecano I 3-thi opentadeciano

I,

trimethylhexonediol, trimethyloipropone, di-trimethylolpropane. 4hydroxymethyl-1 -phospha-2 .6,7-trioxobi cyc lo[ 2 2 .2]octane.

13. Esters of b-(5-fert-bu 1l-4-h droa-3-mett I he I itionic a~cid with mono- or poly-hydric alcohols, such as methanol, ethanol, octanol.

octcadecanol, 1,6-hexane-diol, 1.9-nonanediol. ethylene glycol, I, 2 -propanedJiof, neopentyl glcl hodehln glycol, diethylene glcol, triethylene glycol, pentaeryrhritof, tris(hydroxy)erhyl isocyanrrte,

N,N'-

bis(hydroxyethyl)oxali c acid dicunide, S -thiwindecano1, 3 -thiopen-radecono

I,

trimethylhexanedio I, trimethylo Ipropane, 4- hydroxynethyl.. -phospha- 2,6,.

trioxabicyclo(?2.2]octane.

14.Esters of b-( 3 5 -dicvclohevl-4-hdroxynhenvl.)-Mpionic acid with mono- or poly-hydric alcohols, such as methaonol, ethanol, octonol,.

octadeconol, 1,6-hexanediol, l.9-nonanediol, ethylene glycol, l.

2 -propanediol; neopentyl glycol, thiodiethylene glycol, dieflrylene glycol, triethylene glfycol, pentaerythriro I, tris(hydroxy)ethyl isocycinurate, bis- (hydroxyerhyl)oxal ic acid diamnide, 3-thiaundecamol 3 -th iapentodecanol, trimethylhexanediol, trimethylo Ipropane, 4-hydroxymethyl. l-phospha-2 .6,7triaxabicyclo [2.2.2 )octane.

Esters of 3.5di-tert-bul-4hydrovhicetic acid with mono- or poly-hydric alcohols, such as methanol, ethanol, octanol, ocladecanol, 1,6hexonediol, 1,9-nonanediol, ethylene glycol. 1,2-propanediol, neopentyl glycol.

thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythrilol, tris(hydroxy)ethyl iso cyonurate, NN-bis(hydroxyethyl)oxolic acid diamide, 3-thioundeconol, 3-thiaipentadecanot, trimethyihexanediol, trimethylolpropane, 4- hydroxymerhyl-! -phospha-2 ,6 ,7-trioxobicyc lo[2.2.2J..

octane.

.16. Amides of b- 3 S-di-tert-uy4hydroqphenyl)prp 0 njc acid, such as NN'-bis(3,5-di-tert-buty1.4.

hydroxyphenyl pro pio nylI)hexamet hy le nedj 0 ajin N,N'-bis(3 ,§-di-tert-bu-y1-4.

hydroxyphenylpropionyt)trimethylenediami ne, NN-bis(3 1 hydroxyphenylpropionyl) hydrazine.

Preference is given to antioxidants of groups I to 5, 10 and 125 especially 2,2bis(4- hydroxyphenyl)propane, esters of 3,5-di-tert- butyl-4hydroxyphenylpropioriic acid with ocranol, octadecanol or pentaerythrital or tris(2 ,4-di -tert-buliphenyl) phosphkite.

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

The antioxidants can be used in an amount of, for example, from 0-01 to jo, advantageously from 0.1 to 10, and especially from 0.1 to 5, parts by weight, based on 100 pars by weight PVC.

UVabsarbers and light stabilisrs Examples are: 1. 2-.(2'-Hydroxhenyll-benzorriazo les, Such as 2-(2'-hydroxy-ss..

niethylphenyl)-benzotriozo Ic, 2- (3,5-di -tertr-butyl-2 2-hydroxyphenyl)-.

benratriazo le, 2-(5'-tert- butyl-2'-hydroxyphenyly. benrotriazole, hydro6xy-5Y-(1, 1,3--tetranethylbutyl)phenyl)- benrotriazo Ic, Z-( 3 2-(3'-tert-butyl-.2..

benzotriazole, 2 3 butyl-2 -hydroxyphenvyl)-benzotriazo Ic, 2 -(2!-hydroy-4-octoxyphnyiy benzotriazo Ic, -tert-amy!- 2 Thydroxyphenyl)- benzotriazo le, 2methylbenzyl}-2'- hydroxyphenyl)- benzotrioizo It, a mixture of 2-(3--tert- butyl -2'-hydroxy-5'-(2 -octy loxycorbo benzotriaro be, 2 -(3'-tert-butyl-5'- [2 -(2-ethyl hexyloxy)- car bonylerhyl]- 2'loro-benrotriazo Ic, 2- (3'-tert- butyl- methoxycarbo nylethyl)phenyl)- 5- it loro -ben zotr iazo le, 2 '-tert- butyl-2'hydroxy-5'-(2-methoxycarbonylethyl)phenyl) benzotriazole, 2 3 -tert-bu-.

2 '-hydroxy-5'-(2-octyloxycarbonylethyI)phenyl)ytenzotriayole, 2 3 *-tertbutyl [2 -ethyl hexyloxy)cor bony let hylj].-2- hydroxyphenylI)benrotriazole, 2 3 '-dodecyI- 2 -hydroxy-5'-methylphenyl)-benz 0 tri 0 a 0 be, and 2-(3'-tert-buyl-2'-hydroxy-5'-(2 -isoo ctyloxycorbonybethyl)phenyr.

beniotriazole, 2,2'-met hylene- bis[(4- (1,1,3 ,3 -tetram ethyl buty1)- 6benzotriazol-2-ylphenolj; the transesterificatian product of 2 .(3'-tert--Z butyl- 5 2 -methoxycarbonylethyl)-2T-hydroxy-phenylji,~enzotrj 0 a 0 I with polyethylene glycol 300; wherein R 3 '-tert-buril-4'-hydro§...5'2H-.

benzotriazol-2-ylphenyl.

2. 2-Hydroxybenzophenones such as the 4-hydroxy-, 4-methoxy-, 4octy loxy-. 4-decyloxy-, 4-dodecyloxy-, 4-ben zylaxy-, 4, 2',4'-tri hydroxy- or 2'-hydroxy-4.4'-di methoxy derivative.

3. Esters of unsubstituted or substituted benzoic acids, such as 4-teri'butyl-phenyl salicylate, phenyl salicylate, octyiphenyl salicylate, di benzoylresorcinol, bis( 4 -tert-butylbenzoyl )resorcino I, benzoyiresorcino

I,

3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di-tert-butyphenyl ester, di-tert-butyl-4-hydroxybenzoic acid hvcade-cyl ester, 3.5-di-tert-buyl.4 hydroxybenzoic acid octudecyl ester, 3 .5-di-tert-butyI.4..hyiroxybenzoic acid 2-methyl-4,6-di-terr-butylphenyl ester.

4. A cryes such as a-cyano-bb-diphenylac-yiic acid ethyl ester or isooctyl ester, a-carbomethoxy-cinnamec acid methyl ester, c-cyuno-bmethyl-p-methoxy-cinnamnic acid methyl ester or butyll ester, acarbornethoxy-p-methoxy-cinnam ic acid methyl ester, l'-(b-'carbomethoxry b-cyanoviriyl)-2-methyl-indoli ne.

Nickel compounds, such as nickel complexes of 2.2'-thio-bis[4..(11a 3tetromethylbutyl)phenol], such as the 1;1 or the 1:Z complex, where appropriate with additio 'nal ligands, such as ri-butylamine, triethanolarnine or N-cyclohexyl diethanokunine, nickel dibutyl dithiocarbaniure, nickel salts of 4-hydroxy--3.5-di-tert-butylenzylphosph 0 pic acid monoolkyl esters, such as methyl or ethyl ester, nickel complexes of ketoximines, such as 2 hydroxy.eb methylphenyl-undecylketoximne, hickel cornplexes of 1-phenyl hydroxy-pyrazole, where appropriate with additional ligonds.

6. trcaffhinderedmines, such as bis(2 .2.6 .6-tetramethyl-pi peridyl) sebacate, bis(2,2 6 6 -tetramethyl-piperidyl) succinate, bis(l ,2 ,2,6 ,6pentamethylpiperidyl) sebocate, fl-butyl-S.5-di-tert-butyl.4-hydroxyezylmalonic acid bisO., 2 .Z,6,6-pentame'hylpiperidyl) ester; the condensation product of l-hydroxyethyl-2,2 6 6 -tetromethyl-4-hydroypiperijihe and succinic acid, the condensation product of NN'-bis(2.66tetramethyl-4 piperidyl)hexaenethyleiediaimine and 4 -tert-oclylamino-2,6-dichioro-j triazine, tris(2, 2 6 6 -tetromethyl-4-piperidyl)nitri lotriacetate, tetra k is(2,2,.

6 6 -tetra methyl pi perlyl12,3,4- butane tetraoate, 1 ethcxnediyO)-bis(3,3.5,5-tetramethyl-piperazi none), 4-benzoyl-2,2 ,6 tetramethylpiperidine, 4-stearyloxy- 2.

2 6 1 6-tetranieihylpiperidine, bis(1 .2,2.6,6 -pentwnethylpiperidyl)-2 bueyl-2 -(2-hydroxy- 3 5-di -tertbutylbenzyl) malonate, 3 -h-ocl- 7 9 7.9.9-ietrarethyl13,8rriazospiro[4.5]deoan-.2.4-dione, bis(l-octyoxy-2,2,6,6tetramevhyipiperldy) seatatef. bis(1-octyloxy-2 ,2.6,6-tetromethylp iperidy1) succinoate, the condenttion .product of Njt4-bis(2.2,6.6-tetrwthyl.4 piperidyl)4texamthylndlqmine and 4-morpholino-z.6-d~ichbm..-.3.

triazine. the condensaion product of 2-choro-4.6-(4-n-tlimino.

22,6 .6-tetramthypsrdyl)-1.3,,5-iria zine and 1,2 -bis(3 wrnimopropylnin)etwfa, the condensation product of 2-chloro-4,6-di-(4-n.

butykmilno-4-.1,*,Ax.enoeehypperidyl)4,3§..trijgnp. and l,2-bis(3 aminopmwlamnfltane 8 G1VI 3 -odecvI-7,7,9.9-tstramethy..1 .3.8triazospiro E4.5J*"S4 2 ,4one. 3 -dodety-l-(2,2,66tetmetye.4-.

piperiyl~pyrolidivns2,.dlpnp, 3odecy-1- (1,2,2,6 .6-pentamettyl-4piperiylrrhdb.&dwt and hlmasrb 966.

7. Oxatl id owu= 'Such as, 4 9 4'-di-octyloxy-oxanifide, 2,2'"di octyloxy-545'-lttibty oxonilide, Z 2 od~decoxy-,'-ui-tenrtutyj oxoni tide. 2-ethoxy-24ethl oxoni lids, NN-bis(3-dimethyanjinopropyl) oxalamide, 2-et-hoxy-5-tert-butyl-Z'-ethyI oxanilide and a mixture thereof with 2-toy2-ehl!5,-Oktr-uy oranilide, mixtures of a- and pmethoxy- and d p bjtittdoxn~d 8. 2(Z4ldq mu442ramns.sc .4t6-trif(24tydroxqvA.

ocitykxypheny-,S,3 wk.e Z4 2 hdxy4ctyoxyphaaWyg.q6..bj.(.4dimerhylphernyI)-1 ,3,5-triazineJ 2-(2.4-dihydroxyphenylH-46bis(z .4dinmthyiphenyl)- 1,35-triazinp Z-bis(2-hrx4-propykheprry6...- (2 .4-dimethylpheryl-13,5-triaii.ne, 2 2 -hydroxy-4-octyloryphenyI)-46bis(4-unethylpheyl).-1 1 3,5-tiroxin, 2 2 -hydroxy-4-dodecyloxyphenyl)-4 6bis(2 .4-dimethylphvlrl) 3 .5'-friuizine, 2- (2-hydroxy-4-(2- hydroxy-3 butyloxy-propyloxy)phenylj-4,6-bis(2 ,4-di methylpheny)-l, 3,5-tricz inc. 2- [2hydroxy-4-(2-hydrox y-3 -octyloxypropyloxy)phenyl 1-4,6 -biscz .4- Propellants Propellants are organic ozo and hydrazo compounds, tetrazoles, oxozines.

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 ore described in "Kunststoffadditive" (Plastics Additives), R.Gachter/H.MiUller, Carl Hanser Verlag, 3 r 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/b.LDunkelberger, John Wiley Sons, 1992.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Table I: Static heat test at 190*C (rolled for 5 min at 190*C) Mixture I1 I2 13 Solvic 268 RC (S-PVC K value 68) 100 100 100 Omyalite 30 T 3.0 Ca stearate 0.6 0.6 0.6 Hostalub H42) 10 1.0 Hostalub H122 a 0.2 0.2 0.2 CH 3003 0.4 0.4 0.4 Mark 6045 ACM 4 0.3 0.3 0.3 Stabiliser* 0.2 0.2 0.2 NaCI04 0.05 YI VY YI Minutes 20.7 29.9 22.2 28.4 66.6 29.1 40.2 108.4 39.2 1 )Chalk 2 Glidant supplied by Hoechst (paraffin wax) GIlidant supplied by Hoechst (polar ethylene wax) ')Phenylisodecyl phosphite 4) Mixture of 9% NoCIO4, 45% CaCO,, 40% CoSiOa, 6% HdO )6-Amino-1,3-dimethyl-uracil It is found that the use of small amounts of perchlorate compound as component B in mixtures II and 13 according to the invention results in considerably better stabilisation than without component B.

Table II: Static heat test at 190 0 C (railed for 5 min at 1700C) Mixture Evipol 5R 6030 (PVC KC value 60) CR 3003) Wax E6) Epox. soya oil Aruldite GY 25&7 Aroldite PT 8108) Stabiliser 15) Stabiliser 29) Stobiliser 310) 111 112 r13 114 115 116 117 I1[19 100 0.8 0.4 5.0 1.0 100 100 0.8 0.8 0.4 0.4 5.0 1.0/ 1.0 100 0.8 0.4 5.0 1.0 100 0.B 0.4 100 0.8 0.4 100 0.8 0.4 5.0 200 0.8 0.4 5.0 1.0 100 0.8

L/

YI Y Minutes 17.4 23.2 33.6 17.3 15.6 33.7 29.5 54.9 46.3 YI YIYE 13.4 11.8 12.5 17.8 18.5 17.7 23.5 29.9 27.8 YV-VI YE 14-8 26.2 17.1 21.2 24.4 24.0 27.2 33.6 30.8 ')Phe nylisodecyI phosphite ')Ester wax (based on: inontanvic acid) 7biglycidyl ether of bisphenol A (liquid epoxide) 8) Solid heterocyclic epoxy resin (triglycdy isocyanurate) 9 )6-Amino-1 ,3-di-n-butyluraci 0 )6-Amino-.3-di-ethyl-thiouraci

I

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

Table III: Static heat test at 190°C (rolled for 5 min at 170°C) Mixture Evipol SH 6030 (PVC K value 60) CH 3003) Wax E6 Epox. soya oil Rhodiastab 50 Ca stearate Zn stecrate bASC" Alkamizer I' 3 Stabiliser 1 5 Stabiliser 29) Stabiliser 3 0) III III2III3 III4II5III6 rnI7III8 II9 100 0.8 0.4 5.0 0.2 0.3 0.5 100 0.8 0.4 5.0 0.2 0.3 0.5 100 0.8 0.4 5.0 0.2 0.3 0.5 100 100 0.8 0.8 0.4 0.4 5.0 5.0 0.2 0.2 0.3 0.3 0.5 0.5 1.0 1.0 100 0.8 0.4 5.0 0.2 0.3 0.5 1.0 100 0.8 0.4 5.0 0.2 0.3 0.5 1.0 1.0

VI

100 0.8 0.4 5.0 0.2 0.3 0.5 1.0 1.0

I

S100 0.8 0.4 0.2 0.3

YI

1.0 yI 1.0

VI

1.0 1.0 1.C YI YI YI Minutes 15.2 22.7 37.4 31.4 66.9 57.2 "'Stearoyl-benzoyl-methane supplied 12.9 10.6 16.1 20.6 22.5 26.5 34.0 49.1 41.8 by RHONE-POULENC 10.0 16.3 24.1 10.2 12.4 17.0 18.8 29.7 26.5 "'Dihydroxyaluminium sodium carbonate (DASC) 1)Hydrotalcite supplied by KYOWA (Japan) The addition of dawsonite and the addition of hydrotalcite both increase the stability.

Table IV: Static heat test at 190°C (rolled for 5 min at 170"C) Mixture Evipol SH 6030 (PVC K value 60) CH 300' Wax E' Epox. soya oil Rhodiastab 50

L

Chimassorb 94414) Malbit CR (moltite) Dipentaerythritol Stabiliser 1I Stabiliser 29) Stabiliser 319) IVI IV2 IV3 IV4 IV5 IV6 IV7 IV8 IV9 IVIOIV1l IV12 100 0.8 0.4 2.0 0.2 1.0 100 0.8 0.4 2.0 0.2 1.0 100 100 0.8 0.8 0.4 0.4 2.0 2.0 0.2 0.2 0.15 1.0 1.0 100 100 0.8 0.8 0.4 0.4 2.0 2.0 0.2 0.2 0.15 0.15 1.0 1.0 100 0.8 0.4 2.0 0.2 0.5 1.0 100 0.8 0.4 2.0 0.2 0.5 1.0 100 0.8 0.4 2.0 0.2 0.5 1.0 100 0.8 0.4 2.0 0.2 0.5 1.0 100 100 0.8 0.8 0.4 0.4 2.0 0.2 0.2 1 0.5 1.0 YI YI I VI YI YI yI YI YI yI YI y Minutes 6.0 10.1 24.2 6.6 10.3 6.6 5.8 9.0 5.8 12.7 18.7 7.8 29.5 47.9 13.8 7.7 10.6 11.1 7.3 15.4 8.9 6.2 7.2 9.4 19.5 8.1 10.4 11.1 16.1 5.4 6.7 11.7 21.9 5.8 10.0 9.9 11.2 20.1 15.7 48.0 25.2 59.9 >70 >60 29.1 32.1 24.8 11.1 ")sterically hindered amine supplied by CIBA-GEIGY AG (HALS) The stabiliser combinations according to the invention (IV4 to IV12) are found to give improved stabiliser activity.

r 4drl Table V: Static heat test at 190°C Mixture Evipol SH 6030 (PVC K value 60) CH 3003) Wax E' Epox. soya oil Rhodiastab 50") Co steorate Zn stearate Wessalite p15) Zeolite P"6) Stabiliser 10) Stabiliser 2 9 Stabiliser 3 10) 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

VI

100 0.8 0.4 2.0 0.2 0.3 0.5 1.0 yI (rolled V4 100 0.8 0.4 2.0 0.2 0.3 0.5 1.0 for 5 min V5 V6 at 170 0

C)

V7 V8 V9 100 0.8 0.4 2.0 0.2 0.3 0.5 1.0 100 0.8 0.4 2.0 0.2 0.3 0.5 1.0 100 0.8 0.4 2.0 0.2 0.3 0.5 1.0 1.0 Yr 100 0.8 0.4 2.0 0.2 0.3 0.5 1.0 1.0

YI

100 0.8 0.4 0.2 0.3 yr 1.0 1.0

I.C

YI YI YI Minutes 10.3 12.3 15.4 19.6 34.7 28.6 41.1 29.5 58.8 8.8 12.4 21.0 10.6 14.2 16.8 19.5 32.5 30.5 9.3 9.4 13.3 15.3 25.0 29.2 15.7 22.6 34.8 5 No zeolite A supplied by DEGUSSA "'4a zeolite P supplied by DEGUSSA The stabiliser combination comprising hydrotalcite and zeolites is found to give better results.

Table VI: Static heat test at 190 0 C (rolled for 5 minutes at 170"C) Mixture Evipol EH 6030 (PVC K value 60) Wax E') CH 3003) Epox. soya oil Ca stearte Zn stearate Rhodiastab 50") D-26-155'" Stabiliser 1') Stabiliser 2 9 VII VIZ VI3 VI4 100 100 0.4 0.4 0.8 0.8 5.0 5.0 0.55 0.55 0.25 0.25 1.0 1.0 YI YI 100 100 0.4 0.4 0.8 0.8 5.0 0.55 0.55 0.25 0.25 0.3 0.3 0.3 1.0 YT Y Minutes 18.5 9.7 36.5 18.8 103 33.3 'fl-keto ester of the formula 11.4 15.6 21.9 28.3 46.0 59.2 0 N N

Y

O':kN11 Y (CH 2 2

-O-CO-CH

2

-CO-CH

3 It can be seen that combinations comprising 6-diketone or B-keto ester give good results.

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

C)

Mixture VIII VII2 VII3 VII4 VII5 VII6 VTI7 VII8 Evipol SH 6030 (PVC K value 60) CH 3003) Wax E 6 Epox. soya oil Ca stearate Zn stearate Synesal M Stavinor D 50719) Stabiliser 1 Stabiliser 29', Stabiliser 310) 100 100 100 0.8 0.8 0.8 0.4 0.4 0.4 5.0 5.0 5.0 0.550.55 0.55 0.25 0.25 0.25 1.0 1.0 1.0 YI YI YV 5.4 4.8 6.3 6.4 4.7 6.7 6.7 5.5 7.0 7.3 7.6 8.3 10.8 12.3 12.5 19.9 28.5 22.9 33.7 65.8 45.1 100 100 100 0.8 0.8 0,8 0.4 0-4 0.4 5.0 5.0 5.0 0.55 0.55 0.55 0.25 0.25 0.25 0.2 0.2 0.2 1.0 1.0 1.0 100 100 0.8 0.8 0.4 0.4 5.0 0.55 0.55 0.25 0.25 .0.2 0.2 .0 YI YI 2.9 4.4 3.7 4.9 4.5 6.7 6.3 8.2 11.3 11.9 23.8 21.3 62.6 38.4 Minutes 0

YI

2.9 3.5 4.4 5.4 8.9 18.0 31.8 YI YI 3.9 2.3 4.1 2.3 5.3 3.5 7.5 5.4 13.9 9.3 27.2 17.5 64.2 32.3 "8mThiodiethylene-bis(5-methoxy-carbonyl-2,6-dimethyl-1,4-dihydro-pyridine)-3carboxylate supplied by LAGOR ")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).

PAWPDDCSl|jwpcC 2CROMPTON D7.do27/03/03 Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", and variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.

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

Claims (9)

1. A stabiliser combination for chlorine-containing polymers comprising A) at least one compound of formula I N II (I) Y N NH 2 R* 2 wherein R*I and R* 2 are each independently of the other C 1 -C 1 2 alkyl, C 3 -C 6 alkenyl, C 5 C 8 cycloalkyl that is unsubstituted or substituted by from 1 to 3 Cz-C 4 alkyl, C 1 C 4 alkoxy, Cs-C 8 cycloalkyl or by hydroxy groups or chlorine atoms, or C 7 -Cgphenylalkyl that is unsubstituted or substituted at the phenyl ring by from 1 to 3 C 1 -C 4 alkyl, C 1 C 4 alkoxy, Cs-Cscycloalkyl or by hydroxy groups or chlorine atoms, and R*i and R*2 may additionally be hydrogen and C 1 -Cl 2 alkyl, and Y is 0, and B) an alkali aluminocarbonate (dawsonite) compound.

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

3. A stabiliser combination according to claim 1, wherein the compound of component A) is 6-amino-1,3-dimethyl-uracil,

6-amino-1,3-di-n-propyl-uracil or 6- amino-1,3-di-n-butyl-uracil. 4. A stabiliser combination according to any one of claims 1 to 3, which additionally comprises at least one epoxidised fatty acid ester. P:\WPDOC\Hjw'pc 2CROMPTON DT.duc-27/O/03 -67- A stabiliser combination according to any one of claims 1 to 4, which additionally comprises zinc and/or alkali metal and/or alkaline earth metal carboxylates or aluminium carboxylates. 6. A stabiliser combination according to any one of claims 1 to 5, which additionally comprises at least one further substance from the groups of the phosphites; antioxidants, beta-dicarbonyl compounds, plasticisers, fillers, glidants and pigments.

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

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

9. A stabiliser combination according to claim 6, wherein titanium dioxide is used as the pigment. A composition comprising a chlorine-containing polymer and a stabiliser combination according to any one of claims 1 to 9.

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

12. A method of stabilising chlorine-containing polymers, which comprises incorporating into the chlorine-containing polymers a stabiliser combination according to any one of claims 1 to 9. PAWPD0CS\HJW~sp- 2\CROMPTON D7.do.-29/lO/04 -68- Z 13. A stabiliser combination of claim 1, or a polymer containing the same substantially as hereinbef ore described with reference to the Examples. D~ATE[) this 29th day of October 2004 CROMPTON VINYL ADDITIVES GMBH By its Patent Attorneys DAVIES COLLISON CAVE