AU696585B2 - Stabilized halogen-containing polymers - Google Patents

Description

Our Ref: 546003 P/00/011 Regulation 3:2

AUSTRALIA

Patents Act 1990

ORIGINAL

COMPLETE SPECIFICATION STANDARD PATENT rr o a Applicant(s): Ciba ociy AG 6 -Kyteekstrasse 4 14 4002 BfASfLE-

SWITZERLAND

C"LCCc4I ClR P~ K 6 c- C'4s~ c ecos BojP Su 3e-ano Address for Service: Invention Title: DAVIES COLLISON CAVE Patent Trade Mark Attorneys Level 10, 10 Barrack Street SYDNEY NSW 2000 Stabilized halogen-containing polymers The following statement is a full description of this invention, including the best method of performing it known to me:- 5020 A-19914/A/CGM 435 -1- Stabilized halogen-containing polymers The invention relates to stabilized halogen-containing polymers or recyclates thereof, preferably polyvinyl chloride (PVC) or recyclates thereof, and a stabilizer mixture comprising an alumo salt compound, a magadiite or a kenyaite or a kanemite, and to a process for the preparation of stabilized halogen-containing polymers.

In addition to compounds of tin and lead, PVC can also be stabilized using fatty acid salts, known as metal soaps, where the metals are usually barium, cadmium, zinc, magnesium or calcium. In view of the different stabilization properties (initial colour, colour retention and long-term stability), a combination of two different metal soaps, for example Ba/Cd soaps, is in each case employed in order to achieve balanced stabilization. In order to avoid the use of barium-, lead- or cadmium-containing compounds, Ca/Zn soaps have also been proposed; cf. in this respect, for example, "Taschenbuch der Kunststoff-Additive" [Handbook of Plastics Additives], editors R. Gachter and H. Miiller, Hanser Verlag, 3rd Edition, 1990, pages 308-309, and "Kunststoff-Handbuch PVC" [Plastics Handbook PVC], Volumes 1 and 2, Beck/Braun, Carl Hanser Verlag, 2nd Edition, 1985/1986.

It has also been proposed, inter alia, to use, as costabilizer for PVC, a compound from the series consisting of the zeolites and hydrotalcites; examples are given in EP 0 062 813 and EP 0432 495.

i.: However, there continues to be a demand for a physiologically acceptable stabilizer system which at the same time enables a high degree of stabilization. In particular, stabilizer systems containing barium, lead or cadmium should be avoided.

It has now been found that certain alumo salt compounds or a magadiite or a kenyaite or a kanemite mixed with a zinc, aluminium or rare-earth compound give halogen-containing polymers excellent long-term stability with good initial colour and colour rc.ntion.

Surprisingly, the proportion of the zinc, aluminium or rare-earth compound can remain low on use of these alumo salt compounds or a magadiite or a kenyaite or a kanemite. In addition, plasticized PVC stabilized in accordance with the invention has significantly improved transparency compared with PVC stabilized by means of other inorganic compounds, for example zeolites.

The invention thus relates to a stabilized halogen-containing polymer comprising a halogen-containing polymer or a recyclate thereof, r P an alumo salt compound of the formula ((MtzO)m.(Al20 3 )n-Z-pH 2 0) in which Mt is H, Na, K, Mgl/, Cal z Sr 12 or Znt2; Z is CO 2

SO

2 (C120 7 )12, B 4 0 6

S

2 0 2 (thiosulfate) or C 2 0 2 (oxalate); m, if Mt is Mg 1 /2 or Ca/2, is a number from 1 to 2, and in all other cases m is a number from 1 to 3; is a number from 1 to 4, o is a number from 2 to 4; and p is a number from 0 to or.a magadiite of the formula Na 2 Si 1 40 29 -n H20 or Na 2 Si g

O

1 7 .n H20, in which n is a number from 0 to or a kenyaite of the formula Na 2 Si220 45 -n H 2 0, in which n is a number from 0 to or a kanemite of the formula Na 2 Si 2 zO5n H 2 0,NaHSi 2

O

5 -n H20 or Na 2 Si409-n H2O, in which n is a number from 0 to 30; and an inorganic or organic zinc, aluminium or rare-earth compound other than of the formula where, if is an alumo salt compound of the formula no organotin-Pdiketonate and no (y-hydroxyalkyl)polyorganosiloxane oil is present.

A halogen-containing polymer stabilized in this way preferably contains no compounds of barium, lead or cadmium.

The halogen-containing polymers or recyclates thereof are preferably chlorine-containing, for example 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, in S particular 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 anhydrides thereof, such as copolymers S of vinyl chloride with diethyl maleate, diethyl fumarate or maleic 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 polymerizable 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 rubbers; chlorinated polymers of ethylene; polymers and post-chlorinated polymers of chlorobutadiene and copolymers thereof with vinyl chloride, rubber hydrochloride and chlorinated rubber hydrochloride; and mixtures of said polymers with one another or with other.polymerizable compounds.

c Also suitable are graft polymers of PVC with EVA, ABS and MBS. Preferred substrates are also mixtures of the abovementioned homopolymers and copolymers, in particular vinyl chloride homopolymers, with other thermoplastic and/or elastomeric polymers, in particular blends with ABS, MBS, NBR, SAN, EVA, CPE, MBAS, PMA, PMMA, EPDM and polylactones.

Also preferred are suspension, bulk and emulsion polymers.

The particularly preferred chlorine-containing polymer is polyvinyl chloride, in particular suspension or bulk polyvinyl chloride.

For the purposes of this invention, PVC is also taken to mean copolymers or graft polymers of PVC with polymerizable compounds, such as acrylonitrile, vinyl acetate or ABS, it being possible for these to be suspension, bulk or emulsion polymers. Preference is given to PVC homopolymer, also in combination with polyacrylates.

For the purposes of the present invention, is also taken to mean, in particular, recyclates of halogen-containing polymers, these being the above-described polymers which have experienced damage due to processing, use or storage. Particular preference is .given to PVC recyclate. The recyclates can also contain small amounts of foreign substances, for example paper, pigments and adhesives, which are frequently difficult to remove. These foreign substances can also originate from contact with diverse substances during use or treatment, for example fuel residues, paint remnants, metal traces, initiator residues or water traces.

The alumo salt compounds of the formula which can be used in accordance with the invention can be naturally occurring minerals or synthetic compounds. The metals may have been, in part, replaced by one another. Said alumo salt compounds are crystalline, partially crystalline or amorphous or in the form of a dried gel. The aiumo salt compounds can also be in rarer crystalline modifications. A process for the preparation of such compounds is given in EP 0 394 670. Examples of naturally occurring alumo salt compounds are indigirite, tunisite, alumohydrocalcite, para-alumohydrocalcite, strontiodresserite and hydro-strontiodresserite. Other examples of alumo salt compounds are potassium alumocarbonate ((K20).(A1 2 0 3

).(CO

2 2 .2H 2 sodiuni alumothiosulfate ((Na 2 O) (Al 2 0 3 2 0 2 2 -2H 2 0 potassium alumosulfite (A1 2 0 3 (SO2) 2 2H 2 0 calcium alumooxalate {(CaO).(A1 2 0 3 2 0 2 2 5H20), magnesium alumotetraborate I 8 L L_ I ((MgO).(Al 2 0 3 4 0 6 2 .5H 2 0 (([Mg0.

2 Nao.6]20)'(A1203)'(C0 2 2 -4.1H 2 0), {([Mg0.

2 Nao.61 2 0)-(A1 2 0 3 ).(C0 2 2 .4.3H 2 0) and (([Mg0.

3 Nao.4]20) (A1 2 0 3

)'(CO

2 2 .2-4.9H 2 0).

Some of the mixed alumo salt compounds are novel and can be obtained by processes known per se by cation exchange, preferably from the alkali metal alumo salt compounds, or by combination precipitation (see, for example, US 5 055 284).

The magadiites, kenyaites and kanemites which can be used in accordance with the invention can be naturally occurring minerals or synthetic compounds. A process for the preparation of such compounds is given, for example, in EP 0 472 144, EP 0 615 955, EP 0 615 956, EP 0 627 383 andDE 41 07 955.

Preference is given to alumo salt compounds of the formula in which Mt is Na or K; Z is C0 2 S02 or (C120 7 1 2; m is 1-3; n is 1-4; o is 2-4 and p is 0-20. Z is particularly preferably CO 2 Further preferred compounds are those which can be represented by the following e" Bformulae: *4 0 0 Mt 2 0-A1 2 0 3 -(C0 2 2 pH 2 0 (la) 2 .(A1 2 0 3 2 -(C0 2 2 pH P 2 0 (Ib) Mt20.(A 2 0 3 2 -(C0 2 2

PH

2 0 (Ic) where Mt is a metal, such as Na, K, Mgl/2, Cal2, Sr/2 or Znlz and p is a number from 0 to 12.

Also preferred is a magadiite of the formula Na 2 Si 1 4029-6 and a kenyaite of the formula Na 2 Si 22 0 45 .7 Component can be used in an amount of, for example, from 0.01 to 5 parts by weight, expediently from 0.1 to 3 parts by weight, particularly preferably from 0.1 to 2 parts by weight, based on 100 parts by weight of halogen-containing polymer.

Preference is given to a stabilized halogen-containing polymer, as described above, in which is at least one inorganic zinc compound other than of the formula for example zinc oxide, hydroxide, chloride or sulfide, or superbasic zinc oxide/hydroxide addition compounds, or an organic zinc compound from the series consisting of aliphatic, saturated C 2

-C

22 carboxylates, aliphatic, unsaturated C 3

-C

22 carboxylates, aliphatic

C

2

-C

22 carboxylates which are substituted by at least one OH group or whose chain is interrupted by at least one O atom (oxa acids), cyclic and bicyclic carboxylates having 5-22 carbon atoms, phenyl carboxylates which are unsubstituted, are substituted by at least one OH group and/or are C 1

-C

16 alkyl-substituted, naphthyl carboxylates which are unsubstituted, are substituted by at least one OH group and/or are Cl-C 16 alkyl-substituted, phenyl-C 1

-C

16 alkyl carboxylates, naphthyl-C 1

-C

16 alkyl carboxylates, or unsubstituted or

C

1

-C

1 2 alkyl-substituted phenolates.

Examples which may be mentioned by name are 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, 2-ethylhexanoic acid, pelargonic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanAc acid, myristic acid, palmitic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, 9,10-dihydroxystearic acid, 3,6-dioxaheptanoic acid, 3,6,9-trioxadecanoic acid, behenic acid, benzoic acid, p-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-di-tert-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, n-propylbenzoic acid, salicylic acid, p-tert-octylsalicylic acid, and sorbic acid; 7inc salts of monoesters of divalent carboxylic acids, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, -cntane-1,5-dicarboxylic acid, hexane-1,6-dicarboxylic acid, heptane-1,7-dicarboxyiic acid, octane-1,8-dicarboxylic acid, 3,6,9-trioxadecane-1,10-dicarboxylic acid, polyglycoldicarboxylic acid (n=10-12), phthalic acid, isophthalic acid, terephthalic acid and hydroxyphthalic acid; and diesters or triesters of trivalent or tetravalent carboxylic acids, such as hemimellitic acid, trimellitic acid, pyromellitic acid and citric acid, and zinc salts of mono- and diesterified phosphoric acid or of ronoesterified phosphorous acid, as described in JP 3 275 570.

Preference is given to compositions as described above in which is an organic zinc compound, in particular an organic zinc carboxylate of a carboxylic acid having 7 to 18 6 carbon atoms (zinc soaps), for example benzoates or alkanoates, preferably stearate, oleat, laurate, palmitate, behenate, hydroxystearates, dihydroxystearates or (iso)octanoate. Particular preference is given to stearate, oleate, benzoate and 2-ethylhexanoate.

In addition to said zinc compounds, component can also be inorganic or organic aluminium compounds other than of the formula to which the abovesaid relating to the zinc compounds also applies. Further information on the preferred aluminium compounds which can be used is given in US 4 060 512.

In addition to said zinc compounds, component can also be inorganic or organic rare-earth compounds, to which the abovesaid regarding the zinc compounds also applies.

The term rare-earth compounds is taken to mean, in particular, compounds of the elements cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, lanthanum and yttrium, preference being given to mixtures, in particular with cerium. Further pieferred rare-earth compounds are given in EP-A 0 108 023.

It it also possible to employ a mixture of zinc, aluminium, lanthanum or lanthanoid compounds of different structures. Organic zinc, aluminium, lanthanum or lanthanoid compounds can also be coated onto an alumo salt compound of the formula cf.

DE-A 4 031 818.

The inorganic or preferably organic zinc, aluminium or rare-earth compound can be used in an amount of, for example, from 0.001 to 5 parts by weight, expediently from 0.01 to 3 parts by weight, particularly preferably from 0.1 to 2 parts by weight, based on 100 parts by weight of PVC.

The proportion by weight of the zinc, aluminium or rare-earth compound, calculated as stearate, is preferably less than the proportion by weight of the alumo salt compound; it is particularly preferably at most two-thirds of the proportion by weight of the alumo salt compound of the formula I.

The PVC stabilized in accordance with the invention may contain further additives. These are, for example, inorganic or organic calcium or magnesium compounds, zeolites, hydrotalcites, 1,3-diketo compounds, polyois and disaccharide alcohols, N-containing compounds, for example p-aminocrotonates, as mentioned in EP 0 465 405, p. 6, lines 9-14, c-phenylindole, pyrroles, sterically hindered amines (HALS), dihydropyridines and polymers thereof, perchlorates, epoxides, phenolic antioxidants (HANDBOOK OF PVC FORMULATING, E.J. Wickson, John Wiley Sons, Inc., 1993, pp. 505-515), naphthols, thiophosphates, plasticizers (HANDBOOK OF PVC FORMULATING, E.J. Wickson, John Wiley Sons, Inc., 1993, pp. 163-303), fillers (HANDBOOK OF PVC FORMULATING, E.J. Wickson, John Wiley Sons, Inc., 1993, pp. 393-449) and reinforcing agents (TASCHENBUCH DER KUNSTSTOFF-ADDITIVE, R. Gachter -7- H. MUller, Carl Hanser, 1990, pp. 549-615) (for example calcium carbonate, magnesium oxide, magnesium hydroxide, silicates, glass fibres, talc, kaolin, chalk, mica, metal oxides and hydroxides, carbon black or graphite), phosphites, chelators (TASCHENBUCH DER KUNSTSTOFF-ADDITIVE, R. Gachter H. Muiller, Carl Hanser, 1990, pp. 109-131), light stabilizers, UV absorbers (HANDBOOK OF PVC FORMULATING, E.J. Wickson, John Wiley Sons, Inc., 1993, pp. 355-369), lubricants (HANDBOOK OF PVC FORMULATING, E.J. Wickson, John Wiley Sons, Inc., 1993, pp. 369-393), impact modifiers (IMPACT MODIFIERS FOR PVC, J.T. Lutz D.L. Dunkelberger, John Wiley Sons, Inc., 1992) and processing auxiliaries (TASCHENBUCH DER KUNSTSTOFF-ADDITIVE, R. Gachter H. Miiller, Carl Hanser, 1990, pp. 505-524), fatty acid esters, paraffins, blowing agents (HANDBOOK OF PVC FORMULATING, E.J. Wickson, John Wiley Sons, Inc., 1993, pp. 525-551), optical brighteners (TASCHENBUCH DER KUNSTSTOFF-ADDITIVE, R. Gachter H. Miller, Carl Hanser, 1990, pp. 807-821), gelling auxiliaries, dyes (HANDBOOK OF PVC FORMULATING, E.J. Wickson, John Wiley Sons, Inc., 1993, pp. 449-475), pigments (TASCHENBUCH DER KUNSTSTOFF-ADDrITVE, R. Gachter H. Miller, Carl Hanser, 1990, pp. 663-735), flameproofing agents and smoke-reducing agents (HANDBOOK OF PVC FORMULATING, E.J. Wickson, John Wiley Sons, Inc., 1993, pp. 551-579), antistatics (HANDBOOK OF PVC FORMULATING, E.J. Wickson, John Wiley Sons, Inc., 1993, pp. 487-505), antifogging agents (HANDBOOK OF PVC FORMULATING, E.J. Wickson, John Wiley Sons, Inc., 1993, pp. 475-487), biocides, thiodipropionic acid and esters thereof, dialkyl disulfides (HANDBOOK OF PVC FORMULATING, E.J. Wickson, John Wiley Sons, Inc., 1993, pp. 515-525), mercaptocarboxylic acid esters, peroxide scavengers, modifiers and other complexing agents for Lewis acids.

Suitable inorganic or organic calcium and magnesium compounds are the analogous compounds mentioned under zinc compounds. Preference is given to organic calcium or magnesium co'mpounds, in particular calcium or magnesium soaps, and calcium oxide, calcium hydroxide and superbasic calcium compounds, as described, for example, in EP 0 446 685, 0 394 547 and 0 279 493.

In addition to components and of this invention, it is also possible to employ epoxy compounds, such as 1,2-epoxides and oxiranes, in amounts of, for example, up to 10 parts by weight, expediently up to 5 parts by weight, preferably from 0.01 to 2 parts by weight, based on 100 parts by weight of the composition. Examples thereof are epoxidized polybutadiene, epoxidized soybean oil, epoxidized linseed oil, epoxidized fish oil, I- L~epoxidized tallow, methylbutyl or 2-ethylhexyl epoxystearate, tris(epoxypropyl)isocyanurate, epoxidized castor oil, epoxidized sunflower oil, 3-(2-phenoxy)-l,2-epoxypropane, bisphenol A polyglycidyl ether, vinylcy lohexene diepoxide, dicyclopentadiene diepoxide and 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate.

The other epoxide compounds which can be used for the purposes of the invention can have an aliphatic, aromatic, cycloaliphatic, araliphatic or heterocyclic structure; th-y contain epoxide groups as side groups. The epoxide groups are preferably bonded to the remainder of the molecule as glycidyl groups via ether or ester bonds, or they are N-glycidyl derivatives of heterocyclic amines, amides or imides. Epoxide compounds of these types are known in general terms and are commercially available.

The epoxide compounds contain at least one epoxy radical, in particular of the formula II

O

CH- (CH 2 C- CH

(I)

R R 2

R

3 which is bonded directly to carbon, oxygen, nitrogen or sulfur atoms, where R 1 and R 3 are both hydrogen, R 2 is hydrogen or methyl, and n is 0, or in which R 1 and R 3 together are

-CH

2

-CH

2 or -CH 2

-CH

2

-CH

2

R

2 is then hydrogen, and n is 0 or 1.

Examples which may be mentioned of epoxide compounds are: *e I) Glycidyl and p-methylglycidyl esters obtainable by reacting a compound containing at least one carboxyl group in the molecule and epichlorohydrin or glycerol dichlorohydrin or p-methylepichlorohydrin. The reaction is preferably carried out in the presence of bases.

The compounds containing at least one carboxyl group in the molecule can be aliphatic carboxylic Lcids. Examples of these carboxylic acids are glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid or dimerized or trimerized linoleic acid, acrylic acid, methacrylic acid, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid and pelargonic acid, and the acids mentioned in the case of the organic zinc compounds.

I _I However, it is also possible to employ cycloaliphatic carboxylic acids, for example cyclohexanecarboxylic acid, tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid or 4-methylhexahydrophthalic acid.

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

It is likewise possible to use carboxyl-terminated adducts, for example of trimellitic acid and polyols, for example glycerol or 2,2-bis(4-hydroxycyclohexyl)propane.

Other epoxide compounds which can be used for the purposes of the present invention are given in EP 0 506 617.

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

Ethers of this 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-1,4-diol, poly(oxytetramethylen glycols, pentane-1,5-diol, hexane-1,6-diol, hexane-2,4,6-triol, glycerol, 1,1,1-trimethylolpropane, bistrimethylolpropane, pentaerythritol, sorbitol, and from polyepichlorohydrins, butanol, amyl alcohol, pentanol and from monofunctional alcohols .such as isooctanol, 2-ethylhexanol, isodecanol and C 7

-C

9 alkanol and C 9 -Cj 1 alkanol mixtures.

However, they are also derived, for example, from cycloaliphatic alcohols, such as 1,3- or 1,4-dihydroxycyclohexane, bis(4-hydroxycyclohexyl)methane, 2,2-bis(4-hydroxycyclohexyl)propane or 1,1-bis(hydroxymethyi)cyclohex-3-ene, or they S contain aromatic rings, such as N,N-bis(2-hydroxyethyl)aniline or p,p'-bis(2-hydroxyethylamino)diphenylmethane.

The epoxide compounds can also be derived from monocyclic phenols, for example from phenol, resorcinol or hydroquinone; or they are based on polycyclic phenols, for example on bis(4.-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 4,4'-dihydroxydiphenyl sulfone or on condensation products of phenols with formaldehyde obtained under acid conditions, such as phenol novola-ks.

Examples of other possible terminal epoxides are: glycidyl 1-naphthyl ether, olycidyl 2-phenyiphenyl ether, 2-biphenyl glycidyl ether, N-(2,3-epoxypropyl)phthalimide and 2, 3-epoxypropyl 4-methoxyphenyl ether.

111) N-Glycidyl compounds obtainable by dehydrochiorinating the products of the reaction of epic hlorohydrin with amnines, which contain at least one amino hydrogen atom. These amines are, for example, aniline, N-methylaniline, toluidine, n-butylamine, bis(4-aminophenyl)methane, m-xylylenediamine or bis(4-methylaminophenyl)methane, but also N,N,O-triglycidyl-m-aminophenol or N,N,O-triglycidyl-p-aminophenol.

However, the N-glycidyl compounds also include N,N',N"-tri- and N, N',N",N""'-tetraglycidyl derivatives of cycloallcyleneureas, such as ethyleneurea or 1 ,3-propyleneurea, and N,N'-diglycidyl derivatives of hydantoins, such as of or glycol uril and triglycidyl. isocyanurate.

IV) S-Glycidyl compounds, for example di-S-glycidyl derivatives derived from dithiols, for example ethane- 1,2-dithiol or bis(4-mercaptomethylphenyl) ether.

V) Epoxide compounds containing a radical of the formula II in which R, and R 3 together are -CH 2

-CH

2 and n is 0, are bis(2,3-epoxycyclopentyl) ether, 2,3-epoxycyclopentyl glycidyl ether or 1,2-bis(2,3-epoxycyclopentoxy)ethane. An epoxide compound containing a radical of the formula II in which R, and R 3 together are -CH 2

-CH

2 and n is 1 is for exanmple (3'4'-epoxy-6'-methylcyclohexyl)methyl 3,4-epoxy-6-methylcyclohexanecarboxylate.

Examples of suitable terminal epoxides are: a) liquid bisphenol A diglycidyl ethers, such as Araldit®GY 240, Araldit®GY 250, Araldit®DGY 260, Araldit®GY 266, Araldit®GY 2600, Araldit®MY 790; b) solid bisphenol A diglycidyl ethers, such as Araldit®DGT 607 1, Araldit®GT 707 1, Araldit®DGT 7072, Araldit®GT 6063, Araldit®GT 7203, Araldit®GT 6064, Araldit®GT 7304, Araldit®GT 7004, Araldit®GT 6084, Araldit®GT 1999, Arrldit®GT 7077,' Araldit@GT 6097, Araldit®GT 7097, Araldit®GT 7008, Araldit®GT 6099, Araldit®GT 6608, Araldit®GT 6609, Araldit®DGT 6610; c) iiquid bisphenol F diglycidyl ethers, such as Araldit®GY 281, Araldit®PY 302,

I

11 Araldit®PY 306; d) solid polyglycidyl ethers of tetraphenylethane, such as CG Epoxy Resin0 163; e) solid and liquid polyglycidyl ethers of phenol-formaldehyde novolak, such as EPN 1138, EPN 1139, GY 1180, PY 307; f) solid and liquid polyglycidyl ethers of o-cresol-formald.hyde novolak, such as ECN 1235, ECN 1273, ECN 1280, ECN 1299; g) liquid glycidyl ethers of alcohols, such as Shell® glycidyl ether 162, AralditDY 0390, AralditDY 0391; h) liquid glycidyl ethers of carboxylic acids, such as Shell®Cardura E terephthalates, trimellitates, AiralditPY 284; i) solid heterocyclic epoxy resins (triglycidyl isocyanurates), such as Araldit® PT 810; j) liquid cycloaliphatic epoxy resins, such as Araldit®CY 179; k) liquid N,N,O-triglycidyl ether of p-aminophenol, such as Araldit®MY 0510; 1) tetraglycidyl-4,4'-methylenebenzamine or N,N,N',N'-tetraglycidyldiaminophenylmethane, such as Araldit®MY 720, Araldit®MY 721.

Preference is given to epoxide compounds containing two functional groups. However, it is in principle possible for epoxide compounds containing one, three or more functional groups to be used.

Predominantly employed are diglycidyl compounds, having aromatic structures, for example phenyl radicals.

S If desired, a mixture of epoxide compounds of differe nt structures can also be employed.

Particularly preferred polyfunctional epoxide compounds are diglycidyl ethers based on bisphenols, fcr example on 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), bis(4-hydroxyphenyl)metbhane or mixtures of bis(ortho/para-hydroxyphenyl)methane (bisphenol F).

1,3-Diketo compounds which can be used can be linear or cyclic dicarbonyl compounds.

Preference is given to diketo compounds of the formula (III) R- -C -R3

(III)

I C~ I sssl -12in which R, is C 1

-C

22 a~kyl, C 5 -Cl 0 hydroxyalkyl, C 2 -Cl 8 alkenyl, phenyl, phenyl which is substituted by OH, CI-C 4 alkyl, CI-C 4 alkoxy or halogen, C 7 -Cl 0 phenylalkyl,

C

5

-CI

2 cycloalkyl, C 5

-C

12 cycloalkyl which is substituted by Cl-C 4 alkyl, or an -R 5

-S-R

6 Or

-RS-O-R

6 group, R 2 is hydrogen, Cl-C 8 alkyl, C- 2 -Cl 2 alkenyl, phenyl, C 7 -Cl 2 alkcylphenyl, C7-Clophenylalkyl or a -CO-R 4 group, R 3 has one of the meanings given for 11 1 or i*s Cl-Clgalkoxy, R 4 is Cl-C 4 alkyl or phenyl, R 5 is Cl-Cl 0 alkylene, and R 6 is Cl-Cl 2 alkyl, phenyl, C 7 -Clgalkylphenyl or C 7 -Cl 0 phenylalkyl.

These include the hydroxyl-containing diketones of EP-A 346 279 and the oxa- and thiadiketones of EP-A 307 358.

Alkyl R, and R 3 can be, in particular, Cl-Clgalkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl or octadecyl.

Hydroxyalkyl R, and R 3 are, in particular, a -(CH 2 group, in which n is 5, 6 or 7.

ALkenyl R, and R 3 can be, for example, vinyl, allyl, methallyl, 1-butenyl, 1-hexenyl or oleyl, preferably allyl.

OH-, alkyl-, alkoxy- or halogen-substituted phenyl R, and R 3 can be, for example, tolyl, xylyl, tert-butylphenyl, methoxyphenyl, ethoxyphenyl, hydroxyphenyl, chlorophenyl or .dichlorophenyl.

Phenylalkyl R, and R 3 are, in particular, benzyl. Cycloalkyl or alkylcycloalkyl R, and R 3 are, in particular, cyclohexyl or methylcyclohexyl.

Alkyl R 2 can be, in particular, Cr-C 4 alkyl. C 2 -Cl 2 alkenyl R 2 can be, in particular, allyl.

Alkylphenyl R 2 can be, in particular, tolyl. Phenylalkyl R 2 can be, in particular, benzyl. R 2 is preferably hydrogen. Alkoxy R 3 can be, for example, methoxy, ethoxy, butoxy, hexyloxy, octyloxy, dodecyloxy, tridecyloxy, tetradecyloxy or octadecyloxy.

Cl-Cl 0 alkylene R 5 is, in particular, C 2

-C

4 alkylene. Alkyl R 6 is, in particular, C 4 -Cl 2 alkyl, for example butyl, hexyl, octyl, decyl or dodecyl. Alkylphenyl R 6 is, in particular, tolyl.

Phienylalkyl R 6 is, in particular, benzyl.

Examples of 1,3-dicarbonyl, compounds of the formula (111) are acetylacetone, acetylcyclopentanone, benzoylcyclopentanone, acetylbutyrolactone, 13 benzoylbutyrolactone, butanoylacetone, heptanoylacetone, stearoylacetone, palmitoylacetone, lauroylacetone, 7-tert-nonylthioheptane-2,4-dione, benzoylacetone, dibenzoylmethane, lauroylbenzoylmethane, palmitoylbenzoylmethane, stearoylbenzoylmethane, 5-hydroxycaproylbenzoylmethane, tribenzoylmethane, bis(4-methylbenzoyl)methane, benzoyl-p-chlorobenzoylmethane, his(2-hydroxybenzoyl)methane, 4-methoxybenzoylbenzoylmethane, bis(4-methoxybenzoyl)methane, 1-benzoyl- 1-acetNlnonane, benzoylacetylphenylmethane, stearoyl-4-methoxybenzoylmethano, bis(4-tert-butylbenzoyl)methane, benzoylformylmethane, benzoylphenylacetylmethane, bis(cyclohexanoyl)methane, di(pivaloyl)methane, methyl, ethyl, hexyl, octyl, dodecyl or octadecyl acetoacetate, ethyl, butyl, 2-ethyihexyl, dodecyl or octadecyl benzoylacetate, ethyl, propyl, butyl, hexyl or octyl stearoyl acetate and dehydracetic acid, and the magnesium, calcium, zinc or aluminium salts thereof.

Preference is given to 1,3-diketo compounds of the formula (III) in which R 1 is

C

1

-C

18 alkyl, phenyl, phenyl which is substituted by OH, methyl or methoxy,

C

7 -Clophenylalkyl or cyclohexyl, R 2 is hydrogen, and R 3 has one of the meanings given for R 1 Particular preference is given to magnesium acetylacetonate, calcium acetylacetonate, zinc acetylacetonate, aluminium acetylacetonate, stearoylbenzoylmethane, dibenzoylmethane, benzoyloctanoylmethane and the trisacetoacetic ester of trisethylisocyanurate, as described in US 4 339 383. A review of 1,3-diketo compounds is given in EP 6318, EP 0 046 161, EP 0 035 268 and EP 0 040 286.

The 1,3-diketo compounds can be used in an amount of, for example, from 0.01 to 10 parts by weight, preferably from 0.01 to 2 parts by weight, in particular from 0.05 to 1 part by weight, based on 100 parts by weight of halogen-containing polymer.

Other possible stabilizers which can be used in addition are 1,3-ketoesters of the formula

(IV)

O O R C-CH 2 X

(IV)

in which n is 1, 2, 3, 4 or 6 and, if n 1, R is phenyl and X is an alkyl group having 10 to -14carbon atoms, if n 2, R is alkyl having 1 to 4 carbon atoms or phenyl, and X is alkylene having 4 to 12 carbon atoms, alkylene having 2 to 12 carbon atoms which is substituted by at least one

C

1

-C

8 alkyl group, -CH 2

-CH

2

-S-CH,-CH

2

-S-CH

2

-CH

2 or -CH 2

-CH

2

-S-CH

2 -CH2-, if n 3, R is alkyl having 1 to 4 carbon atoms or phenyl, and X is CH3C 2

C(CH

2 3 if n 4, R is alkyl having 1 to 4 carbon atoms or phenyl, and X is

CH

2 CH2 I I H3C-(CH 2

O-C-(CH

2 )m-CH 3 I I CH2- CH 2 in which m is 0 or 1, and if n 6, R is alkyl having 1 to 4 carbon atoms or phenyl, and X is

CH

2

CH

2 I I

-CH

2

-C-O-C-CH

2 I I

CH

2

CH

2 R as alkyl having 1 to 4 carbon atoms is, for example, methyl, ethyl, propyl or butyl.

X as alkyl having 10 to 20 carbon atoms may be straight-chain or branched and is, for example, n-decyl, n-dodecyl or n-octadecyl.

X ag C 4

-C

1 2 alkylene or as C 2 12 alkylene which is substituted by at least one C 1 -Cgalkyl group is, for example, 1,2-di-tert-butyldimethylene, tetramethylene, hexamethylene, 2,2-dimethyltrimethylene, 2-ethyl-2-butyltrimethylene, 2-methyl-2-propyltrimethylene, octamethylene, nonamethylene, decamethylene or dodecamethylene.

The variable n is preferably 1, 2 or 3, as described in EP 0 433 230.

Oe Oi..sh Other possible stabilizers which can be used in addition are compounds of the formula (V)

I-

R

3

X-R

2 /43\

(V)

R,

N

H

in which X is 0

II

or II II II O O O

R

1 and R 2 independently of one another, are C 1

-C

20 alkyl, hydroxy- and/or halogen-substituted C 1 -Cloalkyl, C 3

-C

20 alkenyl, C 5

-C

12 cycloalkyl, C 1

-C

4 alkyl-substituted

C

5 -Cgcycloalkyl, phenyl or phenyl which is monosubstituted to trisubstituted by A 1 where the radicals A 1 are, independently of one another, C 1 -Cloalkyl, halogen, hydroxyl, methoxy or ethoxy, RI and R 2 are furthermore C 7 -Clophenylalkyl which is unsubstituted or monosubstituted to trisubstituted on the phenyl ring by A 2 where the radicals A 2 are, independently of one another, C 1

-C

20 alkyl, halogen, hydroxyl, methoxy or ethoxy, and

R

3 is phenyl or phenyl which is monosubstituted to trisubstituted by A 3 where the radicals

A

3 are, independently of one another, C 1

-C

10 alkyl, halogen, hydroxyl, methoxy, ethoxy or (Ci-Cgalkyl)oxycarbonyl, with the provisos that at least one of the radicals R 1 and R 2 is phenyl or phenyl substituted as defined, and R 1 is not methyl if R 2 is phenyl.

The compounds of the above formula have a very good stabilizing action against both thermal and light-induced degradation. The long-term stabilizing action against thermal degradation is particularly noteworthy.

R

1 is preferably not C 1

-C

3 alkyl, in particular C 1 -Co 2 alkyl, if R 2 is phenyl.

Halogen is preferably chlorine.

Alkyl having up to 20 carbon atoms is, for example, methyl, ethyl, propyl, butyl, t-butyl, pentyl, hexyl, heptyl, octyl, i-octyl, i-nonyl, decyl, dodecyl or octadecyl.

Hydroxy- and/or halogen-substituted C 1 -Cl 0 alkyl is, for example, 2,3,5-trihydroxypentyl or

C

3

-C

20 )alkenyl is, for example, allyl, 2-methallyl, 3-methylbut-2--enyl, 3-methylbut-3-enyl, hexenyl, decenyl, undecenyl, hepladecenyl or oleyl. Preference is given to allyl, methallyl and oleyl.

C

5

C

12 cycloalkyl is, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl or cyclododecyl. C 5

-C

7 Cycloalkyl, in particular cyclohexyl, is preferred.

C

5 -Cscycloalkyl which is substituted by Cl-C 4 alkyl, in particular methyl, is, for example, methylcyclohexyl or tert-butylcyclohexyl.

Examples of phenyl which is monosubstituted to trisubstituted by radicals as defined are m- and p-methylphenyl, 2,3-dimethyiphenyl, 2,4-dimethyiphenyl, 2,6-dimethyiphenyl, 3,4-dimethylphenyl, 3,5-dimethyiphenyl, 2-methyl-6-ethylphenyl, 2-methyl-4-tert-butylphenyl, 2-ethyiphenyl, 2,6-diethylphenyl, 2,6-diethyl-4- ~:methyiphenyl, 2,6-diisopropylphenyl, 4-tert-butylphenyl, p-nonylphenyl, m- and p-chlorophenyl, 2,3-dichlorophenyl, 2,4-dichlorophenyl, 2,5-dichiorophenyl, 2,6-dichlorophenyl, 3,4-dichlorophenyl, 2,4,5-trichiorophenyl, 2,4,6-trichlorophenyl, m- and p-hydroxyphenyl, m- and p-methoxyphenyl, o- and p-ethoxyphenyl, 2,4-dimethoxyphenyl, 2,5-climethoxyphenyl, 2,5-diethoxyphenyl, m- and p-methoxycarbonyl, 2-chloro-6-methylphenyl, 3-chloro-2-methylphenyl, 3-chloro-4-methylphenyl, 4-chloro-2-methylphenyl, 5-chloro-2-methylphenyl, 2,6-dichloro-3-methylphenyl, 2- hydroxy-4-methylphenyl, 3-hydroxy-4-methylphenyl, 4-methoxy-2-methylphenyl, 3-chloro-4-methoxyphenyl, 3-chloro- 6-mnethoxyphenyl, 3-chloro-4,6-dimethoxyphenyl and 4-chloro-2,5-dimethoxyphenyl.

C

7 -Cl 0 Phenylalkyl is, for example, benzyl or 2-phenylethyl. Benzyl is preferred. If the phenyl group in these radicals is monosubstituted to trisubstituted by groups as defined, it can be as defined above. C 7 -Cl 0 Phenylalkyl which is substituted on the phenyl group by Cl-C 20 alkyl, preferably C 8 -Cl 4 alkyl, is as defined above. A further example which may be mentioned la dodecylbenzyl. A more precise list is given in EP 0 465 405.

Other possible stabilizers which can be used in addition are pyrroles of the formula (VI) 17 I I (VI) N

R

H

in which R, is hydrogen, alkyl, cycloalkyl, aryl, alkoxycarbonylmethyl, c-hydroxyalkyl, esterified (x-hydroxyalkyl, ca-hydroxycycloalkylmethy1, esterified xC-hydroxycycloalkylmethyl, c-hydroxyaralkyl, esterified ax-hydroxyaralkyl, alkoxymethyl, alkylthiomethyl, aryloxymethyl, aryithiomethyl, cycloalkoxymethyl, cycloalkyithiomethyl, aralkoxymethyl, aralkyithiomethyl, alkoxy, alkylthio, cycloalkoxy, cycloalkyithio, araiLcoxy, arylalkylthio, aryloxy, arylthio, halogen, mercapto, mercaptomethyl or hydroxyl,

R

2 is hydrogen, alkyl, cycloalkyl, aryl, o-hydroxyalkyl, esterified cc-hydroxyalkyl, the ailkyl moiety of which, together with R 1 can be. alkylene, c-hydroxycyckoalkylmethyl, esterified a-hydroxycycloalcylmethyl; a-hydroxyaralkyl, esterified o ta%! -,'aralkyl, alkoxy, cycloalkyloxy, aralkoxy, aryloxy, alkylthio, cycloalkylthio, aiwt:.,arylthio, alkoxymethyl, alkyithiomethyl, aryloxymethyl, arylthiomethyl, cycloalkoxymethyl, cycloalkyithiomethyl, aralkoxymethyl, arylalkylthiomethyl, hydroxyl, cyano, carboxyl, salted, esterified or amidated carboxyl or acyl, where, acyl, together with RI, can be -COalkylene, in which -CO- is bonded in the 3-position, or halogen, mercapto or mercaptomethyl, and R 3 is alkyl, cycloalkyl, aralkyl, aryl, hydroxymethyl, esterified hydroxymethyl, alkoxymethyl, alkyithiomethyl, cycloalkoxymethyl, cycioalkylthiomethyl, aralkoxymethyl, arylalkyithiomethyl, aryloxymethyl or aryithiomethyl, alkoxy, alkylthio, cycloalkoxy, cycloalkylthio, aralkoxy, aralkylthio, aryloxy, arylthio, halogen, mercapto or mercaptomethyl, or, if R 2 is salted carboxyl, R 3 is hydrogen and R, is as defined above, or in which R 3 is hydroxyl, and R, is hydrogen, alkyl or aryl, and R 2 is hydrogen, alkyl, aryl or acyl, or a salt thereof. A list of these is given in EP 0 022 087.

Other possible stabilizers which can be used in addition are compounds of the formula (VII) R2 NH -R 3

(VID)

[R N'i 18 ,n which n is 1 or 2, R, is Cl-C 4 alcyl, R 2 is a group of the formula Ila, JIb, l1c or ld

-CNHX

2

-CNHX

2

,-CX

3 o0 S0 (Iha) (Ilb) (le) (Ild) X, is hydrogen, CI-C 20 allcyl, C 3

-C

6 alkyl which .i.terrupted by one or two oxygen atoms or sulfur atoms and/or is substituted by OH, C f 'tceay1, C 5

-C

12 cycloalkYl,

C

1 -C~alkyl-substituted C 5

-C,

2 cycloai kyl, phe!,A:. 'Cicallcyl-, chlorine-, hydroxyl-, methoxy- and/or ethoxy-substituted phenyl, iylalkyl or C 7 -Cl 0 phenylalkyl which is substituted on the phenyl. radical by CIJ-Q., .yl, chlorine, hydroxyl, methoxy and/or ethoxy, X 2 is phenyl which is unsubstitutced or inonosubstituted to trisubstituted, where the; substituents are selected from the group consisting of Cl-C 4 alkyl, chlorine, hydroxyl, rnethoxy, ethoxy and acetylamino, X 3 is Cl-C 3 alkyl or phenyl, R 3 if n is 1, is a group of the formulae lIla to M~g YJ 0 -CH=C ,_Y2 C1Y 3

-CY

4

-CX

0

Y

5

,-C-CY

6

,-SY

7 0 0 S 0 0

Y

8

X

0 is an oxygen or sulfur atom, Yj and Y 2 independently of one another, are -CN, benzoyl, C 2

-C

4 alkanoyl or C 2

-C

4 alkoxycarbonyl, Y 3 is C 1

-C

20 alkyl, C 3

-C

20 alkenyl, phenyl, Cl-C 4 alkyl-, chlorine-, NO 2 methoxy- and/or ethoxy-substituted phenyl., 2-phenylethenyl, di(Cj-C 4 alkyl)amino, diplienylamino, Cl-C 2 V.lkylamino,

C

3

-C

8 cycloalkylamino, phenylamino, phenylamino which is substituted on the phenyl. ring by Cl-C 4 alkyl, chlorine, hydroxyl, methoxy and/or ethoxy, benzylamino, benzenesulfonamido or toluenesulfonamido, Y 4 is di(C 1

-C

4 alkyl)amino, diphenylamino, Cl-C 8 alkylamino, phenylamino, phenylamino which is substituted on the phenyl ring by 19 Cl-C 4 alkyl, chlorine, hydroxyl, methoxy and/or ethoxy, or benzyiamino, Y 5 is Cj-C 20 aLkyl, C 3

-C

6 a~kyl which is interrupted by one or two oxygen atoms,

C

5

-C

12 cycloalkyl, G 1

-C

4 alkyl- subs tituted C 5

-C

12 CYCloalkyl, phenyl, C 7 -Cl 0 phenylalkyl or

C

7 -Cl 0 phenylalkyl which is substituted on the phenyl radical by C 1

-C

20 alkyl, Y 6 is

CI-C

4 alkoxy, phenylamino or phenylamino which is substituted on the phenyl group by

CI-C

4 alkyl, chlorine, hydroxyl, methoxy and/or ethoxy, Y 7 is Cl-C 4 allcyl, phenyl or Cl-C 4 allcyl-, chlorine-, -NO 2 (Cl-Cl 2 alkyl)oxycarbonyl- and/or phenoxycarbonyl-substituted phenyl, the radicals Y 8 independently of one another, are

CI-C

4 alkoxy or allyloxy, and, if n is 2, R 3 is a group of the formula IVa, IVb, TVc or IVd -tCO-Z 2 -OC- CNI{-Z 3 -NHC- I II I I 1 N~ N X0X 0 0 (IVa) (IVb) (IVd)

Z

(IVd)

X

0 is as defined above, Z, is a, direct bond, Cl-Cl 2 alkylene or phenylene, Z2 is

C

2 -Cl 2 alkylene or 3-oxapentylene, Z3 is C 4

-C

8 alkylene or phenylene, and Z 4 is Cj-C 4 alkoxy or allyloxy.

CI-C

20 alkyl is, for example, methyl, ethyl, propyl, butyl, t-butyl, pentyl, hexyl, heptyl, octyl, i-octyl, i-nonyl, decyl, dodecyl or octadecyl.

R, is preferably straight-chain Cl-C 4 alkyl, in particular methyl.

A preferred meaning of X, is Cl-C 15 alkyl, in particular Cl-Cl 2 alkyl, for example mnethyl or ethyl.

Alkyl X 3 is preferably methyl or ethyl, in particular methyl.

Alkyl Y 5 preferably has 1 to 4 carbon atoms. Methyl and ethyl are particularly preferred meanings Of Y 5

CI-C

4 alkoxy is, for example, methoxy, ethoxy, propoxy or butoxy.

C

3

-C

6 allcyl which is interrupted by 1 or 2 oxygen atoms is, for example, 3-oxabutyl, 20 3-oxapentyl, 3-oxaheptyl, 3,6-dioxaheptyl or 3,6-dioxaoctyl.

C

3

-C

6 alkyl which is interrupted by 1 or 2 oxygen atoms or s corns and/or is substituted by OH can be, for example, addition to the radicat.. ientioned in the preceding paragraph, 3-thiabutyl, 3-thiapentyl, 3,6-dithiaheptyl, 3,6-dithiaoctyl, 5-hydroxy-3-oxapentyl, 5-hydroxy-3-thiapentyl or 4-hydroxybu tyl.

C

3

-C

20 alkenyl is, for example, allyl, 2-methallyl, 3-methylbut-2-enyl, 3-methylbut-?' enyl, hexenyl, decenyl, undecenyl, heptadecenyl or oleyl. Preferred meanings are allyl, methallyl and oleyl.

C

5 -Cl 2 CYCloalkyl, which may be substituted by Cl-C 4 alkyl, in particular methyl, is, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclododecyl or methylcyclohexyl. Unsubsti'tuted or substituted C 5

-C

8 cycloalkyl, in particular cyclohexyl, is preferred.

Examples of phenyl which is substituted, preferably monosubstituted to trisubstitited, by radicals as defined are mn- and p-chlorophenyl, 2,3-dichiorophenyl, 2,4-dichiorophenyl, 2,5-dichlorophenyl, 2,6-dichlorophenyl, 3,4-dichiorophenyl, 2,4,5-trichlorophenyl, 2,4,6-trichiorophenyl, mn- and p-methylphenyl, 2,3-dimethyiphenyl, 2,4-dimethylphenyl, 2,5-diinethylphenyl, 2,6-dimethylphenyl, 3,4-dim ethylphenyl, phenyl, 2-methyl-6-ethylphenyl, 2-inethyl-4-tert-butylphcnyl, 2-ethylphenyl, 2,6-diethylphenyl, 2,6-diethyl-4-methylphenyl, 2,6-diisopropylphenyl, 4-tert-butylphenyl, p-nonylphenyl, 2-chloro-6-methylphenyl, 3-chloro-2-methylphenyl, 3-chloro .4-methylphenyl, 4-chloro-2-methylphenyl, 5-chloro-2-m-ethylphenyl, 2,6-dichloro-3-raethylphenyl, mn- and p-methoxyphenyl, o- and p-ethoxyphenyi, 2,4-dimethoxyphenyl, 2,5 -diethoxyphenyl, 2-niethoxy-5-methylphenyl, 4-methoxy-2methylphenyl, 3-chloro-4-methoxyphenyl, 3-chloro-6-methoxyphlenyl, 3-chloro-4,6dimethoxyphenyl, 4-cliloro-2,5-dimethoxyphenyl, and p-hydroxyphenyl, 2-hydroxy-4-methiylphenyl, 3-hydroxy-4-methylphenyl, m- and p-acetylaminophenyl, m- and p-nitrophenyl, p-(CI-Cl 2 alkyl)oxycarbonylphenvl and p-phenyloxycarbonylphenyl.

If Y 3

Y

4 and Y 6 are phenylamino which is substituted, preferably monosubstituted to trisubstituted, on the phenyl radical by radicals as defined, the substituted pheniyl radical can, for example, be as defined above.

-21-

C

7 -Clophenylalkyl is, for example, benzyl or 2-phenylethyl. Benzyl is preferred. If the phenyl group in these radicals is substituted, preferably monosubstituted to trisubstituted, by groups as defined, they can be as defined above. C 7 -CloPhenylalkyl which is substituted on the phenyl group by C 1

-C

20 alkyl, preferably C 8

-C

14 alkyl, is one of the preferred meanings. Dodecylbenzyl may be mentioned as a further example.

C

2

-C

4 alkanoyl is, for example, acetyl, propanoyl or butanoyl. Acetyl is preferred.

C

2

-C

4 alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl or propoxycarbonyl. Methoxycarbonyl and ethoxycarbonyl are preferred.

Di(C 1

-C

4 alkyl)amino is, for example, dimethylamino, diethylamino, dipropylamino or dibutylamino.

C

1

-C

20 alkylamino, preferably C 1 -Cgalkylamino, in particular C 4

-C

8 alkylamino, is, for example, butylamino, pentylamino, hexylamino, heptylamino or octylamino.

C

3

-C

8 cycloalkylamino is, for example, cyclopropylamino, cyclohexylamino or cyclooctylamino.

Alkylene having up to 12 carbon atoms is, for example, methylene, dimethylene, trimethylene, butylene, pentamethyk.ne, hexamethylene, octamethylene, decamethylene or dcdecamethylene. Alkylene having up to 8 carbon atoms is preferred. US 5 155 152 contains a review.

S Other possible stabilizers which can be used in addition are compounds of the formulae a and b HR, H R 1 -O-CO-O H R2 F1R--O0\ /H C=C C=C RI--CO--O CO-R 3 R, CO-R 3 in which R' is C 1

-C

22 alkyl, phenyl, mono- or di(C 1

-C

9 alkyl)-substituted phenyl,

C

5

-C

7 cycloalkyl or a group of the formula A or B

I

22 02\ R2\0= C0 O R

CO-R

3

H

or RI is a group of the formula ca or cb R2\ /H /0=C0 (ca),

-R

4 -O-CO-O-0 CO-R 3 R2\C/ O R (cb),

-R

4 -O-CO-O-C

H

R 2 and R 3 independently of one another, are Cl-C 20 alkyl, phenyl, mono- or di(Cl-Cgalkyl)-substituted phenyl or C 5

-C

7 cycloalkyl, and R 4 is C 2 -Cl 2 alkylene. More detailed explanations, examples and preferences are given in EP 224 438.

Further stabilizers are triazoles of the formula R, R 1 N (OH 2 or R, )N'I R 4 H n

H

in which R, is hydrogen, hydroxyl, C 1

-C

6 alkoxy, carboxyl, C 2

-C

6 alkoxycarbonyl, mercapto, CI-C 6 atkylthio, -S-CH 2 -COOH or -S-CH 2

-COO-(C

1

-C

6 )alkyl, X is thio, methylene, -COO- or -S-CH 2 -COO-, in each case bonded to the alkyl via the ester oxygen atom, m is an integer from i to 20, n is 1 or 2, R 2 if monovalent, is hydrogen, hydroxyl. or mercapto and, if divalent, is a direct bond, imino, Cl-C 6 alkylimino, oxy, thio or methylrcne, R 3 is hydrogen, amino, mercapto or C 1 -Cl 2 alkylthio, and, if R 3 is hydrogen, R 4 is hydrogen, -COOR 5 in which R 5 is hydrogen, C 1

-C

8 alkyl or -,CH 2 -COO .(Cl-C 8 )alkyl, or -S-R 6 where R 6 is hydrogen, C 1

-C

12 a1.kyl, -CH 2 -COO-(Cl-C 8 )alkYl Or Cl-C 12 alkylthio, N- N or ,in which X' is -CO-NH-alkylene-NI-I-CO-,

H

-CO-alkylenie-S-alkylene-CO, in each case having 1-12 carbon atoms in the alkylene chain, or (Cl-C 12 )alkylene, if R 3 is N11 2

R

4 is Cl-C 4 ,ilkyl, mer.capto, Cl-C 4 alkylthio or -23- N N -S-alkylene-S- N having 1-12 carbon atoms in the alkylene chain, if R 3 is N

NH

2

H

mercapto, R 4 is unsubstituted or substituted phenyl, and if R 3 is C 1

-C

1 2 alkylthio, R 4 is Cl-C 4 alkyl, C 1

-C

12 alkylthio or unsubstituted or substituted phenyl.

These stabilizers, further embodiments, examples and preferences are given in DE 3 048 639.

Stabilizer mixtures comprising a thioether of the formula (VIII)

R,

R-CO-CH-CO-O-Y-CH-

(VIII)

in which n is zero or 1, R is C 1

-C

18 alkyl, C 5 -Cgcycloalkyl, or unsubstituted or C 1

-C

4 alkyl-substituted

C

6

-C

10 aryl, and RI is hydrogen or C 1

-C

4 alkyl, each X, as a recurring symbol, is identical to or different from the others and is hydrogen or a group of the formula

RI

R-CO-CH-CO-O-Y-,

each Y, as a recurring symbol, is identical to or different from the others and is Ci-C 6 alkylene or a group of the formula H -H-+-CH2 ORz where the -(-CH 2 group is bonded to the oxygen atom and in which R 2 is hydroge.

or a group of the formula -24-

R-CO-CH-CO-,

R,

n is 1 to 4, and p is zero to 3, Z is C 1

-C

6 alkylene or a group of the formula

-CH

2

-CH-CH

2 and

OR

2 b) a stabilizer comprising a metal from the group consisting of zinc, calcium, magnesium and antimony, or furthermore zinc combined with at least one of the abovementioned metals.

Further details in this respect, examples and preferences are given in EP 19 576.

Compounds of the formula (IX)

X

n mH)

(IX)

(Y-NHR)p in which m is 0, 1 or 2, n is 0, 2 or 3 and p is i or 2, Hal is -Cl, -Br or -I, X is -NH 2

-NHCH

3 and/or -OCH 3 or OC 2

H

5 Y is -CO- or -SO 2 and R is -OH, -NI-I 2

C

1

-C

18 alkyl which is unsubstituted or substituted by, for example, one to three HO- and/or C 1

-C

4 alkoxy or phenoxy groups, phenyl, benzyl or phenethyl, or R furthermore is a group of the formula

-OY

(Hal)m where X, Y, m, n and Hai are as defined above. Detailed descriptions, examples and preferences are given in EP 122 228 and EP 174 412.

Stabilizer mixtures obtainable by mixing at least one compound of the formula (X) [ROOC-CnH2S-]3 PX,

(X)

in which X is O or S, n is an integer from 1 to 5, and R is straight-chain or branched

C

1

-C

18 alkyl or substituted or unsubstituted cyclohexyl, and at least one PVC stabilizer of the Me(II) carboxylate and/or Me(H) phenoxide type, where Me(II) is one or more metals from the series consisting of Ba, Sr, Ca, Mg, Zn and Cd, and where, based on the halogen-containing polymer, from 0.01-2 by weight of the compound of the formula I and 0.1-4 by weight of the Me(II) carboxylate and/or Me(II)phenoxide are employed.

Such stabilizer mixtures are described in greater detail in EP 90 770, which also gives examples and preferences.

Examples of suitable organic plasticizers are those from the following groups: A) Phthalates (esters of phthalic acid) Examples of these plasticizers are dimethyl, diethyl, dibutyl, dihexyl, di-2-ethylhexyl, di-n-octyl, di-isooctyl, di-isononyl, di-isodecyl, di-isotridecyl, dicyclohexyl, dimethylcyclohexyl, dimethyl glycol, dibutyl glycol, benzyl butyl and diphenyl phthalates, and mixtures of phthalates, such as C 7

-C

9 and C 9 -Cllalkyl phthalates made from predominantly linear alcohols, C 6 -Clo-n-alkyl phthalates and Cs-Clo-n-alkyl phthalates.

Preference is given to dibutyl, dihexyl, di-2-ethylhexyl, di-n-octyl, di-isooctyl, di-isononyl, di-isodecyl, di-isotridecyl and benzyl butyl phthalates, and said mixtures of alkyl phthalates. Particular preference is given to di-2-ethylhexyl, di-isononyl and di-isodecyl phthalate.

B) Esters of aliphatic dicarboxylic acids, in particular esters of adipic, azelaic and sebacic acids Examples of these plasticizers are di-2-ethylhexyl adipate, di-isooctyl adipate (mixture), -26di-isononyl rdipate (mixture), di-isodecyl adipate (mixture), benzyl butyl adipate, benzyl octyl adipate, di-2-ethylhexyl azelate, di-2-ethylhexyl sebacate and di-isodecyl sebacate (mixture). Preference is given to di-2-ethylhexyl adipate and di-isooctyl adipate.

C) Esters of trimellitic acid, for example tri-2-ethylhexyl trimellitate, tri-isodecyl trimellitate (mixture), tri-isotridecyl trimellitate, tri-isooctyl trimellitate (mixture) and tri-C 6 -Cgalkyl, tri-C 6

-C

1 0 alkyl, tri-C 7

-C

9 alkyl and tri-C 9

-C

11 alkyl trimellitates. The last-mentioned trimellitates are formed by esterifying trimellitic acid by means of the appropriate alkanol mixtures.

Preferred trimellitates are tri-2-ethylhexyl trimellitate and said trimellitates made from alkanol mixtures.

D) Epoxy plasticizers, such as 1,2-epoxides and oxiranes; examples thereof are epoxidized polybutadiene, epoxidized soybean oil, epoxidized linseed oil, epoxidized fish oil, epoxidized tallow, methylbutyl and 2-ethyihexyl epoxystearate, tris(epoxypropyl) isocyanurate, epoxidized castor oil, epoxidized sunflower oil, 3-(2-phenoxy)-1,2-epoxypropane, bisphenol A polyglycidyl ether, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide and 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate.

E) Polymer plasticizers A definition of these plasticizers and examples thereof are given in "Taschenbuch der Kunststoff-Additive" [Handbook of Plastics Additives], edited by R. Gichter and H. MiUller, Hanser Verlag, 10, page 412, chapter 5.9.6, and in "PVC Technology", edited by W.V. Titow, 4th Ed., Elsevier Publ., 1984, pages 165-170. The most usual starting materials for the preparation of polyester plasticizers are: dicarboxylic acids, such as adipic, phthalic, azelaic and sebacic acids; diols, such as 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and diethylene glycol; monocarboxylic acids, such as acetic, caproic, caprylic, lauric, myristic, palmitic, stearic, pelargonic and benzoic acids; monofunctional alcohols, such as isooctanol, 2-ethylhexanol, isodecanol and C 7

-C

9 alkanol and C 9 -Cj 1 alkanol mixtures. Particularly advantageous are polyester plasticizers made from said dicarboxylic acids and monofunctional alcohols.

F) Esters of phosphoric acid A definition of these esters is given in the abovementioned "Taschenbuch der Kunststoff-Additive" on page 408, citapter 5.9.5. Examples of these phosphates are -27tributyl phosphate, tri-2-ethylbutyl phosphate, tri-2-ethylhexyl phosphate, trichloroethyl phosphate, 2-ethylhexyl diphenyl phosphate, cresyl diphenyl phosphate, triphenyl phosphate, tricresyl phosphate and trixylenyl phosphate. Preference is given to tri-2-ethylhexyl phosphate and ®Reofos G) Chlorinated hydrocarbons or chlorinated paraffins H) Hydrocarbons (paraffins) I) Monoesters, for example butyl oleate, phenoxyethyl oleate, tetrahydrofurfuryl oleate and esters of alkylsulfonic acids.

J) Glycol esters, for example diglycol benzoates or polyol full or partial esters in general.

Definitions and examples of plasticizers from groups G) to J) are given in the following handbooks: "Taschenbuch der Kunststoff-Additive" [Handbook of Plastics Additives], edited by R. Gachter and H. Miller, Hanser Verlag, 1990, page 422, chapter 5.9.14.2 (group and chapter 5.9.14.1 (group "PVC Technology", edited by W.V. Titow, 4th Ed., Elsevier Publishers, 1984, pages 171-173, chapter 6.10.2 (group page 174, chapter 6.10.5 (group page 173, chapter 6.10.3 (group and pages 173-174, chapter 6.10.4 (group Particular preference is given to plasticizers from groups A) to in particular A) to D) and especially the plasticizers in these groups which have been mentioned as preferred.

It is also possible to use mixtures of different plasticizers.

The plasticizers can be used in an amount of, for example, from 1 to 120 parts by weight, preferably from 1 to 100 parts by weight, in particular from 2 to 70 parts by weight, based on 100 parts by weight of halogen-containing polymer.

Suitable dihydropyridines are monomeric and oligomeric compounds, for example as described in EP-A-0 362 012, EP-A-0 286 887 and EP-A-0 024 754.

L_ 19~ Is 28 Suitable perchiorates are alkali metal and alkaline earth metal perchlorates and zinc and aluminium. perchlorates or perchiorates whose cation comprises a surfactant ammonium or phosphonium cation, possibly also applied to supports, for example as described in US 5 034 443. It is also possible to use adducts of these perchiorates with monohydric and polyhyciric alcohols.

Examples of suitable antioxidants are: 1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(c-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenoi, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymet.'iylphenol, 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6-(l1'-methylund ,c-l1'-yl)phenol, 2,4-dimethyl-6- (1 '-methylheptadec- 1 '-yl)phenol, 2,4-dimethyl-6-( 1'-methyltridec- 1 '-yl)phenol, octyiphenol, nonylphenol and mixtures thereof.

2. Alkylthiomethylphenols, for example 2,4-dioctylthiomethyl-6-teft-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4.-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol.

3. Hydroguinones and alkylated hydroquinones, for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-amyl-hydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butyl-hydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydrc.-xyaniisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

4. Hydroxylated. diphenyl thioethers, for example 2,2 '-thiobis(6-tert-,butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 4,4 '-thiobis(6-tert-butyl-3-methylphenol), 4,4' -thiobis(6-tert-butyl-2-methylphenol), 4,4 '-thiobis(3 ,6-di-sec-amylphenol), 4,4' -bis (2,6-dimethyl-4-hydroxyphenyl) disalfide.

Allcylidenebisphenols, for example 2,2'-methylene-bis(6-tert-butyl-4--Iethylphenol), 2,2' -methylene-bis(6-tert-butyl-4-ethylphenol), 29 2,2 '-methylene-bis[4-methyl-6-(cx-methylcyclohexyl)phenol], 2,2'-methylene-bis(4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis(6-nonyl-4-methylphenol), 2,2' -methylene-bis(4,6-.di-tert-butylphenol), 2,2'-ethylidene-bis(4,6-di-tert-butylphenol), 2,2'-ethylidene-bis(6-tert-butyl-4-isobutylphenol), 2,2'-methyiene-bis [6-((x-methylbenzyl)-4-nonylphenol], 2,2'-methylene-bis[6-(cz,a-dimethylbenzyl)-4-nonylphenol], 4,4'-methylene-bis(2,6-di-tert-butylphenol), 4,4'-methylene-bis(6-tert-butyl-2-methylphenol), 1, 1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-buityl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1, 1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1, 1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3 '-tert-butyl-4'-hydroxyphenyl) butyrate], bis (3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene, bis '-tert-butyl-2'-hydroxy-5 '-methylbenzyl)-6-tert-butyl-4-methyl-phenyl] terephthalate, 1, 1-bis(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-.di-tert-butyl-4-hyclroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane, 1, 1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

6. N- and S-benzyl compounds, for example 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl 4-hydlroxy-3,5-dimethylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hyclroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

7. Hydroxybenzylated malonates, for example dioctaidecyl 2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, dioctadecyl 2- (3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, didodecylmercaptoethyl 2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, di[14-( 1,1 ,3,3-tetramethylbutyl)phenylj 2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

8. H-ydroxybenzyl aromatic compounds, for example 30 1,3,5-t-is (3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1 ,4-bis(3,.r-u., tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3 bu tyl-4-hydroxybenzyl)phenol.

9. Triazine compounds, for example 2,4-bisoctylmercapto-6-(3,5-di-tert-butyl-4-hydroxyanilino)- 1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)- 1,3,5-triazine, 2-octylmercapto-4,6-bis(3 ,5-di-tert-butyl-4-hydroxyphenoxy)-l1,3,5-triazine, 2,4,6tris(3,5-di-tert-butyl-4-hydroxyphenoxy)- 1,2,3-triazine, 1 ,3,5-tris(3,5-di-tert-butyl- 4-hydroxybenzyl) isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxypheniylethyl)- 1,3,5-triazine, 1, 3,5-t-is (3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexahydro- 1,3,5-triazine, 1 ,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

Phosphonates, phosphites and phos-phonites, for example dimethyl 2,5-di-tert-butyl-4hydroxybenzylphosphonate, diethyl 3,5-di-tertbutyl-4-hydroxybenzylphosphonate, 5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of monoethyl 3,5-di-tert-butyl-4-hydroxybenzyl phosphonate, triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythrityl diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythrityl diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythrityl diphosphite, bis(2,6-di-tert-butyl-4-methiylphenyl) pentaerythrityl *diphosphite, bisisodecyloxy pentaerythrityl diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl) pentaerythrityl diphosphite, bis(2,4,6-tri-tert-butylphenyl) pentaerythrityl diphosphite, tristearyl sorbityl triphosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,1Otetra- tert-butyl- 12H-dibenz[d,gI- 1 ,3,2-dioxaphosphocine, 6-fluoro-2,4,8, lO-tetra-tertbutyl- 12-methyldibenz[d,g]- 1,3,2-dioxaphosphocine, bis (2,4-di-tert-bu tyl-6-rnethylphenyl) methyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite,

(C

9

H

19

-C

6

H

4 1 5 -P-(O-Cl 2 13

H

25 27 11. Acylaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N- (3,5-di-tert- butyl-4-hydroxyphenyl)carbam ate.

12. Esters of B-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with monohydric or polyhydric alcohols, for example with methanol, ethanol, octanol, octadecanol, 31 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaeryvthritol, tris(hydroxyethyl) isocyanurate, N,N' -bis(hydroxyethyl)oxalamide, 3-thiaundecanol, 3-thiapentadecanol, trimethyihexanediol, trimethyloipropane, 4- hydroxymethyl- 1 -phospha-2,6,7-trioxabicyclo- -octane.

13. Esters of !-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with monohydric or polyhydric alcohols, for example with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxalamide, 3 -thi~aundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl- 1-phospha-2,6,7-trioxabicyclo [2.2.2]-octane.

14. Esters of 1-(3,5-dicyclohexyl-4-hydroxyphenyl),propionic acid with monohydric or polyhydric alcohols, for example with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxalamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylbexanediol, trimethyloipropane, 4-hydroxymethyl- 1 -phospha-2,6,7-trioxabicyclo- -octane.

Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with monohydric or polyhydric alcohols, for example with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethy1)oxalamide, 3-thiaundecanol, 3-thia.Dentadecanol, trimethyihexanediol, trimethyloipropane, 4- hydroxymethyl- 1-phospha-2,6,7-trioxabicyclo- [2.2.23-octane.

16. Amides of -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, for example N,N '-bis (3,5-di-tert-butyl-4-hydrcxy3phenylpropionyl)hexametiylenediahine, bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethyleiiediamine, N,N' *-bis (3 ,5-di-tert-butyl-4-hydroxyphenylpropioniyl)hydrazine.

17. Esters of thiodiacetic acid and thiodipropionic acid 32 Preference in given to antioxidants from groups 5, 10 and 14, in particular 2,2-bis(4-hydroxyphenyl)propane, esters of 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid with octadecanol or pentaerythritol, and tris(2,4-di-tert-butylphenyl) phosphite.

If desired, a mixture of antioxidants of different structures can be employed.

The antioxidants can be used in an amount of, for example, 0.01 to 10 parts by weight, preferably from 0. 1 to 10 parts by weight, in particular from 0. 1 to 5 parts by weight, based on 100 parts by weight of halogen-containing polymer.

Examples of suitable UV absorbers and light stabilizers are: 1. 2-(2'-Hydroxyphenyl)benzotriazoles, for example 2-(2'-hydroxy-5'methylphenyl)benzotriazole, 2-(3 '-di-tert-butyl-2 '-hydroxyphenyl)benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, -hydroxy-5 (1,1 ,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3 '-di-tertbutyl-2'-hydroxypheny1)-5-chlorobtnzotriazole, 2-(3 '-tert-butyl- 2'-hydroxy-5 2-(3 '-sec-butyl-5 '-tert-butyl-2 '-hydroxyphenyl)bonzotriazole, 2-(2 '-hydroxy-4 -octoxyphenyl)benzotriazole, 2-(3 '-di-tertamyl-2'-hydroxyphenyl)benzotriazole, 2-(3 ',5'-bis(cc-dimethylbenzyl)-2'hydroxyphenyl)benzotriazole, mixture of 2-(3'-tert-butyl-2'-hydroxy-5'- 2-(3'-tert-butyl-5'- [2-(2-ethylhexyloxy)carbonylethyl] 2-(3 '-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonyiethl)phenyl)-5-cllorobelzotriazole, 2-(3 -etbtl2-yrx-5-2mtoyabnlt ~hnlbnoraoe 2-(3'-tert-butyl-2 '-hydroxy-5 '-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3 '-tert-butyl-5'-[,2-(2-ethylhexyloxy)carbonylethyl]- 2 '-hydroxyphenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5 '-methylphenyl)benzotriazole, and 2-(3'-tert-butyl-2'-hydroxy- 5'-(2-isooctvloxycarbonylethyl)phenylbenzotriazole, 2,2'-methylenebisll4-( 1,1,3,3tetramethylbutyl)-6-benzotriazol-2-yl phenol]; transesterification product of 2-[3'-tertbutyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl] benzotriazole with polyethylene glycol 300; [R-CH 2

CH

2

-COO(CH

2 3 where R- 'ttbty4-hdoy52benzotriazol-2-yl phenyl.

2. 2-Hydroxybenzophenones, for example the 4- hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.

-33 3. Esters of unsubstituted or substituted benzoic acids, for example 4-tert-butyl-phenyl salicylate, phenyl salicylate, octyiphenyl. salicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol, 2,4-di-tert-butyiphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-rnethyl-4,6-di-tert-butylphenyl.

3 ,5-di-tert-butyl-4-hydroxybenzoate.

4. Apgy-'te, for example ethyl and isooctyl a-cyano-f3,[-diphenylacrylate, methyl a-carbomethoxycinnamate, methyl. and butyl. (x-cyano-f-methyl-p-methioxycinnamate, methyl. a-carbomethoxy-p-methoxycinriamate and N-(f-carbomethoxy-f-cyanovinyl)-2-methylindoline.

Nickel compounds, for example nickel complexes of :2,2'-thiobis[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 and 1:2 complexes, if o desired with additional ligands, such as n-butylamine, triethanolamnine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of monoalkyl esters, such as the methyl or ethyl esters, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complL xes of ketoximes, such as of 2-hydroxy-4-methylphenyl undecyl ketoxime, and nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, if desired with additional ligands.

6. Sterically hindered amines, for example bis(2,2,6,6-tetramethylpiperidyl) sebacate, bis(2,2,6,6-tetramethylpiperidyl) succinate, bis( 1,2,2,6,6-pentamethylpiperidyl) sebacate, bis( 1,2,2,6,6-pentamethylpiperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the product of the condensation of l-hydroxyethyl-2,2,6,6-tetramnethyl-4-hydroxypiperidine and succinic acid, the product of thle condensation of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexanmethylenediamine and 4-tert-octylami, o-2,6-dichloro- 1,3 ,5-s-triazine, tis (2,2,65,6- tetraxethyl-4-pipeiidyl) nitrilDtriacetate, tetrakis(2,2,6,6-tetramethyl-4-pipeiidyl!) 1,2,3 ,4-butanetetraoate, 1,1 ,2-ethanediyl)bis-(3 ,3,5,5-tetramnethylpiperazinone), 4-benizoyl- 2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethiylpiperidine, bis( 1,2,2,6,6pentamethylpiperidyl) 2-n-butyl-2-(2-hydroxy-3 3-n-octyl-7,7 ,9,9-tetramethyl- 1,3,8-triazaspiro[4.5]decane-2,4-dione, bis( t-octyloxy- 2,2,6,6-tetramethylpiperidyl) sebacate, bis( 1-oclyioxy-2,2,6,6-tetramethylpiperidyl) succinate, the product of the condensation of N,N'-bis(2,2,6,6-tetramethyl- 4-piperidyl)hexamethylene diamine and 4-morpholino-2,6-dichloro- 1,3,5-triazine, the 34 product of the condensation of 2-chloro-4,6-di(4-n-butylamino-2,2,6,6-tetramethylpiperidyl) 1,3,5- triazine and 1 ,2-bis(3-aminopropylamino)ethane, the product of the condensation of 2-chloro-4,6-di(4-n-butylamino- 1,2,2,6,6-pentamethylpiperidyl)- 1,3 ,5-triazine and 1 ,2-bis(3-aminopropylamino)ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl- 1,3 ,8-triazaspiro[4.5]decane-2,4-dione, 3-dodecyl-l1-(2,2,6,6-tetramethyl-4- 3-dodecyl- I-(l,2,2,6,6-pentamethyl- 4-piperidyl)pyrrolidine-2,5-dione and Chimassorb 966.

7. Oxalamides, for example 4,4'-dioctyloxyoxanilide, 2,2'-dioctyloxy-5,5 '-di-tert-butyloxanilide, 2,2'-didodecyloxy-5,5 '-di-tert-butyloxanilide, 2-etthoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminiopropyl)oxalamide, 2-ethoxy-5-ter-butyl-2'-ethyloxainilide and mixtures thereof with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide, and mixtures of o- and p-methoxy- and of o- and p-ethoxy-disubstituted oxanilides.

8. 2-(2-Hydroxyphenyl)- 1,3,5-triazines, for example 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)- 1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)- 1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)- 1 2,~4 -bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)- 1 2-2hdoy4otyoyhn *06bi( mtypeyl-,,-raie :2-(2-hydroxy-4-ocyloxyphenyl)-4,6-bis(4-thylhnpny)- 1 2- [2-hydroxy-4-(2-hydroxy-3-butoxypropoxy)phenyl]-4,6-bis(2,4-dinethylphenyl)- 1,3,5triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropoxy)phenyl]- 4,6-bis(2,4-dimethylphenyl)- 1,3,5-triazine.

Examples of suitable peroxide scavengers are: esters of P-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl. esters, mercaptobenzimidazole, the zinc salt of 2-mnercaptobenzimidazole, zinc dibut-yldithiocarbam ate, dioctadecyl disulfide, pentaerythrityl tetraks(f3-dodecylmercapto)propioniate and ethylene glycol bismercaptoacetate.

Examples of suitable lubricants are: montan wax, fatty acid esters, PE waxes, amide waxes, polyol partial esters, partially hydrolysed PE waxes, so-called complex esters, chlorinated paraffins, glycerol esters, alkaline earth metal soaps and fatty ketones, as described in DE 4 204 887. L.:1iricants which can be used are also described it "Tscenuc der Kunststoff-Additive" [Handbook of Plastics Additives], editors R. Gachter and H. Miller, Hanser Verlag, 3rd Edition, 1990, pages 443-503. Other lubricants, in particular combinations, are given in EP 0 062 813 and EP 0 336 289.

Examples of suitable polyols are: pentaerythritol, dipentaerythritol, tripentaerythritol, trimethylolethane, bistrimethylolethane, trimethylolpropane, bistrimethylolpropane, sorbitol, mannitol, -:ylitol, lactose, leucrose, tris(hydroxyethyl) isocyanurate, tris(dihydroxypropyl) isocyanurate, inositol, tetramethylolcyclohexanol, tetramethylolcyclopentanol, tetramethylolcyclopyranol, glycerol, diglycerol, polyglycerol, thiodiglycol, thiodiglycerol, bishydroxyethyltartaramide, hexakis(hydroxyethyl)melamin, bistrihydroxymethyloxamide, tristrihydroxymethylcitramide and P- and y-cyclodextrins. Suitable disaccharide, alcohols are: maltitol, malbitol, lactitol, palatinitol, isomaltitol, isomaltol, l.ucrose, dihydroleucrose, glucopyranosylsorbitol, glucopyranosylmannitol and lycasine (dehydrated).

The polyols can be used in an amount of, for example, from 0.01 to 20 parts by weight, preferably from 0.1 to 20 parts by weight, in particular from 0.1 to 10 parts by weight, particularly preferably from 0.1 to 3 parts by weight, based on 100 parts by weight of halogen-containing polymer.

Suitable compounds from the series consisting of the hydrotalcites or zeolites are both naturally occurring minerals and synthetic compounds.

Compounds from the series consisting of the hydrotalcites can be described by the general formula I

M

2 +1-X M 3 +x '(OH) 2 mH 2 0 where M2+ Mg, Ca, Sr, Zn and/or Sn,

M

3 =A1,BorBi, Al- is an anion having the valency n, n is a number from 1 to 4, x is a number from 0 to 0.5, and m is a number from 0 to 2.

L~ I C ~s I -36is preferably OH-, Cl-, Br-, C10 4

HCO

3

CI-

3 C00-, C 6 1 5 CO0O, C0 3 ,S0, C 00O, (CHOHCOO) 2 2

(CHOH)

4

CH-

2 OHCOO-. CAH 4

(COO)

2 2 (cH 2 COO) 2 2

CH

3 CIIOHCOO-, SiO 3 2 Sio 4 4, Fe(CN) 6 3 Fe(CN) 6 4

HPO

3 2 or Hp0 4 2 Further examples of hydrotalcites are given in DE 41 06 403.

Other hydrotalcites which can preferably be used are compounds having the general formula Ia where M 2 1 is at least one metal from the series consisting of Mg and Zn, preferably Mg, V. An- is an anion, preferably from the series consisting Of C0 3 2 COO} OH-andS, where n is the valency of the anion, mn is a positive, number, preferably from 0.5 to 5, and x and z are positive numbers, x preferably being from 2 to 6 and z preferably being less than 2.

*Prefc. ,is given to compounds from the series consisting of the hydrotalcites of the general formula I where M 2 is Mg or a solid solution of Mg and Zn, An- is C0 3 2 x is a number from 0 to and m is a number from 0 to 2.

Very particular prefference is given to hydrotalcites of the formulae A1 2 0 3 .6MgO.C0 2 12H20, Mg 4 5 A1 2 (OH) 13 CO 3 3.5H-20, 4MgO-Al 2 O3yCO 2 *9H 2

O,

-37- 4MgO-Al 2 03-CO 2 -6H 2 0, ZnO-3MgO-Al 2 0 3 -C02-8-9H 2 0 or ZnO-3MgO-Al203-CO 2 -5-6H 2 0.

Zeolites can be described by the general formula (X)

M

4 [(AlO 2 )x(SiO 2 )y]-wH20 (X) where n is the charge of the cation M, M is an element from the first or second main group, or zinc, y:x is a number between 0.8 and infinity, preferably between 0.8 and 10.5, and w is a number between 0 and 300.

*Furthermore, zeolites which can be used are disclosed in "Atlas of Zeolite Structure Types", W.M. Meier and D.H. Olson, Butterworths, 3rd Edition, 1992.

Zeolites in a broader sense also include aluminium phosphates having a zeolite structure.

The preferred zeolites which are known per se have an average effective pore diameter of 3-5 A and can be prepared by known methods. Particular preference is given to zeolites of type NaA which have an average effective pore diameter of 4 A, and are therefore known as zeolites 4A.

Particular preference is given to crystalline sodium alumosilicates whose particle size is at least predominantly in the range from 1-10 im.

In a preferred embodiment of the invention, sodium alumosilicates having rounded corners and edges can also be used.

Preference is given to compounds of the formulae Na 1 2 A1 1 2 Si 1 204 8 27 H20 [zeolite A], Na 6 A1 6 Si60 24 2 NaX 7.5 H 2 0, X= OH, halogen, C10 4 [sodalite] 38 Na 6 A1 6 Si 30 0 72 24 H 2 0, Na 8 A1 8 S1 40

O

96 24 H 2 0, Nal 6

AI

16 Si2A0 80 16 H120, Nal 6

A

16 S3i 32 0 96 16 H 2 0, Na 56 A1 56 SiI 36 0 384 2501120, [zeolite Y] Na 86 A1 86 Sil 06 0 384 2641120 [zeolite X] or the zeolites which can be prepared by replacement of all or some of the sodium atoms by lithium, potassium, magnesium, calcium, strontium or zinc atoms, such as (Na,K), 0 AlSI 2 0 20 1120.

Ca 4 5 Na 3 [(A10 2 12 (SiO 2 1 2 301120

K

9 Na 3 [(A10 2 12 (SiO 2 12 27 1120.

:Prefercnce is given to a stabilized halogen-containing polymer comprising PVC or recyclate thereof, an alumo salt compound of the formula (Mt 2 0)m- (A 2 0 3 ),'Z,'PH1 2 01 in which Mt is Na, rMgj 1 2, Ca Sr/ or Znj 2; Z is CO 2 S 02, (C1 2 0 7 1

B

4 0 6

S

2 0 2 (thiosulfate) or C 2 0 2 (oxalate); m, if Mt is Mgj 1 2 or Cal 1 is a number from 1 to 2, in all other cases a number from 1 to 3; n is a number from 1 to 4; o is a number from 2 to 4; and p is a number from 0 to or a magadiite of the formula Na 2 Si 14

O

29 *n 1120 or Na 2 Si 8 Ol 7 .n 1120, in which n is a number from 0 to or a kenyaite of the fortnala Na 2 Si 22

O

4 5yn 1120, in which n is a number from 0 to or a kanemite of the formula Na 2 Si 2

O

5 .n 1120, NaI-1Si 2 0 5 .n 1120 or Na 2 Si 4

O

9 *n 1120, in which n is a number from 0 to and 0.001-5.0 parts by we~ght, per 100 parts by weight of PVC, of an inorganic or organic zinc compound other than of the formula where the proportion by weight of zinc compound, calculated as stearate, is less than the proportion by, weight of the alumo salt compound; -39and, if desired, a phenolic antioxidant, in particular 0.1-5.0 parts by weight per 100 parts by weight of PVC.

Particular preference is given to a stabilized halogen-containing polymer in which component is an alumo salt compound of the formula {(Mt20)m.(Al20 3 )nZo-pH 2 0) in which Mt is Na or K; Z is CO 2

SO

2 or (C120 7 )12; m is a number from 1 to 3; n is a number from 1 to 4; o is a number from 2 to 4; and p is a number from 0 to Preference is furthermore given to a stabilized halogen-containing polymer which additionally comprises a p-diketone and/or an Mg, Ca or Zn salt thereof, or a P-ketoester.

Preference is furthermore given to a stabilized halogen-containing polymer which additionally comprises an epoxide.

Preference is furthermore given to a stabilized halogen-containing polymer which additionally comprises a monomeric, oligomeric or polymeric dihydropyridine.

Preference is furthermore given to a stabilized halogen-containing polymer which additionally comprises, an inorganic or organic calcium compound.

0 Preference is furthermore given to a stabilized halogen-containing polymer which additionally comprises a phosphite, a perchlorate compound, a polyol or a disaccharide .0 alcohol.

Particular preference is given to a stabilized halogen-containing polymer which, in addition to and comprises a p-diketone and/or an Mg, Ca or Zn salt thereof, or a 0-ketoester and a monomeric, oligomeric or polymeric dihydropyridine.

Particular preference is furthermore given to a stabilized halogen-containing polymer which, in addition to and comprises a P-diketone and/or an Mg, Ca or Zn salt thereof, or a p-ketoester and a polyol or a disaccharide alcohol.

Particular preference is furthermore given to a stabilized halogen-containing polymer which, in addition to and comprises a perchlorate compound and a polyol or a disaccharide alcohol.

Particular preference is furthermore given to a stabilized halogen-containing polymer which, in addition to and comprises an epoxide and a perchlorate compound.

The.two last-mentioned combinations may additionally comprise a p-Diketone, an Mg, Ca or Zn salt thereof or a P-ketoester, or mixtures thereof.

All combinations may additionally comprise a calcium soap and/or a lubricant.

The present invention furthermore relates to a stabilizer mixture comprising an alumo salt compound of the formula a magadiite, a kenyaite or a kanemite and an inorganic or organic zinc, aluminium or rare-earth compound other than of the formula where, if the stabilizer mixture comprises an alumo salt compound of the formula no organotin-P-diketonate and no (y-hydroxyalkyl)polyorganosiloxane oil is present.

The abovementioned preferences apply to the individual mixture S constituents, and the stabilizer mixture can also contain the other constituents described Sabove.

The present invention furthermore relates to the use of an alumo salt compound of the formula a magadiite, a kenyaite or a kanemite in combin'n with an inorganic or organic zinc, aluminium or rare-earth compound other tha: *f ihe formula where, if the stabilizer mixture comprises an alumo salt compound of the formula no organotin-P-diketonate and no (y-hydroxyalkyl)polyorganosiloxane.oil is present.

for the stabilization of a halogen-containing polymer or polymer recyclate. The abovementioned preferences apply to the individual stabilizers and to the halogen-containing polymer itself, and in addition one of the other constituents described above can also be used.

The halogen-containing polymer stabilized according to the invention can be prepared in a manner known per se, to which end said stabilizers and, if desired, further additives are mixed with the halogen-containing polymer using equipment known per se, such as calenders, mixers, compounders, extruders and the like.

The halogen-containing polymer stabilized in accordance with the present invention can be converted into the desired shape in a known manner. Methoc, uf this type are, for example, grinding, calendering, extrusion, injection moulding, sintering or spinning, I s s=l II -41furthermore extrusion blow moulding or conversion by the plastisol process. The stabilized halogen-containing polymer can also be converted into foams.

The halogen-containing polymer according to the invention is particularly suitable for semirigid and flexible formulations, in particular in the form of flexible formulations for wire sheaths and cable insulations, which is particularly preferred. In the form of semirigid formulations, the halogen-containing polymer according to the invention is particularly suitable for decorative films, foams, agricultural sheeting, tubes, sealing profiles and office films.

In the form of rigid formulations, the halogen-containing polymer stabilized according to the invention is particularly suitable for hollow articles (bottles), packaging films (thermoformed films), blown films, crash-pad films (automobiles), tubes, foams, heavy profiles (window frames), light-wall profiles, building profiles, sidings, fittings, office films and equipm, t housings (computers and domestic applicances).

Examples of the use of the halogen-containing polymer according to the invention as Splastisols are artificial leather, floor coverings, textile coatings, wall coverings, coil coatings and automobile underseal.

ooooe Examples of sintered applications of the halogen-containing polymer stabilized according to the invention are slush, slush mould and coil coatings.

The examples below illustrate the invention in greater detail without representing a limitation. Parts and percentages are, as in the remainder of the description, by weight, unless stated otherwise. The yellowness index (YI) is determined in accordance with o•• ASTM D 1925-70 and the contrast ratio (CR) is determined in accordance with ASTM 2805-70 and 589-65.

Example 1: A PVC composition is prepared by mixing the individual components as shown in Table 1 below (amounts in parts by weight).

The constituents are homogenized for 5 minutes in mixing rolls at 190 0 C giving a film with a thickness of 0.3-0.5 mm.

The long-term stability is determined in accordance with DIN 53381, in which the sample -42is stored in a test oven at 190 0 C and the time taken for the sample to blacken is determined.

Table 1: PVC 1 100 Zinc laurate 0.4 DASC (dihydroxyaluminium sodium carbonate) 1.1 Dioctyl phthalate 18 Recplast 39 (epoxidized soybean oil) 2 After 45 minutes, the sample has darkened in colour, whereas a sample containing no DASC darkens only after 15 minutes.

Examples 2 and 3: A PVC composition is prepared by mixing the individual components as shown in Table 2 below (amounts in parts by weight).

The constituents are homogenized for 5 minutes in mixing rolls at 190 0 C giving a film with a thickness of 0.3-0.5 mm.

The long-term stability is determined in accordance with DIN 53381, in which the sample is stored in a test oven at 190 0 C and the time taken for the sample to blacken is determined.

Table 2: Comparison Ex. 2 Ex. 3 PVC 1 100 100 100 S" Zinc laurate 1.6 0.6 0.6 DASC 1.0 Dioctyl phthalate 18.0 18.0 18.0 Reoplast 39 (epoxidized soybean oil) 2.0 2.0 Antioxidant 1 0.2 0.2 0.2 Calcium acetylacetonate 0.3 0.3 0.3 Lubricant 1 0.3 0.3 0.3 The sample of Example 2 darkens after 45 minutes and that of Example 3 after minutes, whereas the comparison sample containing no DASC darkens after only 9 minutes.

-43- Example 4: A PVC composition is prepared by mixing the individual components as shown in Table 3 below (amounts in parts by weight).

The constituents are homogenized for 5 minutes in mixing rolls at 190 0 C giving a film with a thickness of 0.3-0.5 mm.

The thermal stability is determined in accordance with DIN 53381, in which the sample is stored in a test oven at 180 0 C and the yellowing (yellowness index YI value) is measured.

Table 3: Components Comp. 1 Comp. 2 Ex. 4 PVC 2 100 100 100 Zinc stearate 1.0 0.4 DASC 1.0 0.6 S Impact modifier 1 10.0 10.0 10.0 Reoplast 39 (epoxidized soybean oil) 5.0 5.0 Diketone 1 0.2 0.2 0.2 Calcium stearate 0.2 0.2 0.2 Lubricant 2 1.2 1.2 1.2 The sample of Example 4 darkens after 70 minutes, whereas comparative sample 1 (comp, 1) containing no DASC darkens after only 25 minutes and comparative sample 2 (comp. 2) containing no zinc stearate is dark brown from the beginning.

Examples 5 and 6: Preparation of the PVC composition and performance of the heat test as described in Example 4 (see Table 4).

I

-44- Table 4: Components Comp. 3 Comp. 4 Ex. 5 Ex. 6 PVC 3 100 100 100 100 Dioctyl phthalate 18 18 18 18 Reoplast 39 (epoxidized soybean oil) 2 2 2 2 Zinc stearate 0.7 0.3 0.3 DASC 0.7 0.4 0.7 Diketone 1 0.2 The sample of Example 5 darkens after 35 minutes and that of Example 6 after minutes, whereas comparative sample 3 (comp. 3) containing no DASC darkens after only 5 minutes and comparative sample 4 (comp. 4) containing no zinc stearate is brown from the beginning.

Examples 7 and 8: Preparation of the PVC composition and performance of the heat test as described in S Example 4 (see Table 5) (roll temperature: 180 0 C, test temperature: 190 0

C).

Table Components Comp. 5 Ex. 7 Ex. 8 PVC 3 100 100 100 S Dioctyl phthalate 18 18 18 Reoplast 39 (epoxidized soybean oil) 2 2 2 Zinc laurate 1.6 0.6 0.6 DASC 1.0 DAPC (dihydroxyaluminium potassium carbonate) 1 Antioxidant 1 0.2 0.2 0.2 Calcium acetylacetonate 0.3 0.3 0.3 The sample of Example 7 darkens after 35 minutes and that of Example 8 after minutes, whereas comparative sample 5 (comp. 5) containing no DASC and no DAPC darkens after only 25 minutes.

Examples 9-12: The mixing of the PVC composition and the determination of the thermal stability are ps Iq carried out as in Example 4. The compositions are shown in Table 6 (roll temperature: 180 0 C, test temperature: 180 0

C).

Table 6: Components Ex. 9 Ex. 10 Ex. 11 Ex. 12 PVC 2 100 100 100 100 Dioctyl phthalate 18 18 18 18 Reoplast 39 (epoxidized soybean oil) 2 2 2 2 Zinc stearate 0.3 0.3 0.2 0.3 DASC 0.6 0.5 0.6 0.6 Diketone 2 0.2 0.2 0.2 Ketoester 1 0.3 The samples of Examples 9-12 darken after 75, 65, 95 and 90 minutes respectively, confirming that good thermal stabilization occurs in the presence of P-diketone or P-ketoester in formulations containing DASC/zinc stearate.

The following values for yellowing (YI) and transparency (contrast ratio CR) are obtained "e if the films are pressed at 150 bar and 180 0 C for 2 minutes to give sheets with a tlhckness of 2 mm: S Table 7 No. YI value CR value Ex. 9 17.0 2.6 Ex. 10 15.7 2.1 Ex. 11 15.1 1.8 Ex. 12 18.6 2.8 Table 7 shows that these formulations also give pressed sheets having very good service properties.

Examples 13-15: A PVC composition is prepared by mixing the individual components as shown in Table 8 below (amounts in parts by weight).

-46- The constituents are homogenized for 5 minutes in mixing rolls at 180 0 C, giving a film with a thickness of 0.3-0.5 mm.

The thermal stability is determined in accordance with DIN 53381, in which the sample is stored in a test oven at 190 0 C and the yellowing (yellowness index YI value) is measured.

Table 8: Components Comp. 6 Ex. 13 Ex. 14 Ex. PVC 3 100 100 100 100 Dioctyl phthalate 43 43 43 43 Reoplast 39 (epoxidized soybean oil) 2 2 2 2 Zinc oleate 0.9 0.9 0.9 0.9 Calcium stearate 0.2 0.2 0.2 0.2 Antioxidant 1 0.1 0.1 0.1 0.1 Magadiite 0.9 Kenyaite 0.9 Kanemite 0.9 The samples of Examples 13-15 darken after 45, 30 and 40 minutes, whereas comparative sample 6 (comp. 6) containing no magadiite, no kenyaite and no kanemite darkens after only 25 minutes.

The following substances are employed in the above examples: PVC 1: Corvic S 71/102 (S-PVC, K value 71) e PVC 2: Corvic S 57/116 (S-PVC, K value 57) PVC 3: Evipol SH 7020 (S-PVC, K value 71) Antioxidant 1: IRGANOX 1010 (pentaerythritol ester of P-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid) Diketone 1: Rhodiastab 50 (Stearoylbenzoylmethane) Diketone 2: 78 of diketone 1 12 stearic acid Lubricant 1: Loxiol G21 (12-hydroxystearic acid) Lubricant 2: Loxiol G15/PE 190 (glyceryl hydroxystearate/linear, unbranched, high molecular weight PE wax) Impact modifier 1: Kane ACE B22 (methylbutadiene-styrene-based impact modifier) Ketoester 1: trisacetoacetic ester of trishydroxyethyl isocyanurate -47- Kanumite: NaHSizO 4

(OH)

2 2hz 2 0 Kenyait: Na 2 Si220 45 -0-7H 2 0 Magadiite: Na 2 Si 1 40 29 -7H20 Preparation example: 100 g of DASC are slurried in 700 g of an aqueous 33 Mg(N0 3 2 6 H20 solution, and the mixture is stirred at 20 C for 3 hours and filtered. This operation is repeated twice.

The mixture is subsequently washed three times with 500 ml of H20, filtered and dried to constant weightin a drying cabinet at 110 0 C. Analysis gives 13.0 Na, 20.2 Al and 2.2 Mg, corresponding to the formula ((Nao.

7 5 Mgo 0 .250) 2 '(Al 2 0 3

)(CO

2 2 1 and confirms approximately 25 Na exchange.

Throughout this specification and the claims which follow, unless the context requires otherwise, S the word "comprise", and variations such as "comprises" and "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.

0 0 ft s

Claims (14)

1. A stabilized halogen-containing polymer comprising a halogen-containing polymer or a recyclate thereof, an alumo salt compound of the formula ((Mt 2 O)m-(Al 2 O 3 )n.-ZpH 2 zO in which Mt is H, Na, K, Mg 1 Cal/, Srl2 or Znl2; Z is CO 2 SO 2 (C1 2 0 7 1 2 B 4 0 6 S202 (thiosulfate) or C 2 0 2 (oxalate); m, if Mt is Mgl/2 or Cai/2, is a number from 1 to 2, and in all other cases m is a number from 1 to 3; n is a number from 1 to 4, o is a number from 2 to 4; and p is a number from 0 to or a magadiite of the formula Na 2 Sil 4 0 ,9-n H 2 0 or Na 2 Si 8 gO 1 -n H20, in which n is a number from 0 to or a kenyaite of the formula Na 2 Siz 2 0 45 .n H20, in which n is a number from 0 to or a kanemite of the formula Na 2 Si 2 05sn H 2 0,NaHSi2Os-n H20 or Na 2 Si 4 0 9 n H 2 0, in which n is a number from 0 to 30; and an inorganic or organic zinc, aluminium or rare-earth compound other than of the formula where, if is an alumo salt compound of the formula no organotin-P-diketonate and no (y-hydroxyalkyl)polyorganosiloxane oil is present.

2. A stabilized halogen-containing polymer according to claim 1, wherein component (a) is PVC or recyclate thereof.

3. A stabilized halogen-containing polymer according to claim 1, wherein component (a) is PVC or recyclate thereof and component is 0.001-5.0 parts, per 100 parts of PVC, of an inorganic or organic zinc compound other than of the formula where the proportion by weight of the zinc compound, calculated as stearate, is less than the proporion by weight of the alumo salt compound; and, if desired, a phenolic antioxidant, in particular 0.1-5.0 parts per 100 parts of PVC.

4. A stabilized halogen-containing polymer according to claim 1, wherein component (b) is an alumo salt compound of the formula ((MtzO)m-(Al 2 0 3 ),-Zo-pH 2 O) in which Mt is Na or K; Z is CO 2 SO 2 or 7 )112; m is a number from 1 to 3; n is a number from 1 to 4; o is a number fromn 2 to 4; and p is a number from 0 to V C j -49- A stabilized halogen-containing polymer according to claim 1, wherein component (b) is an alumo salt compound of the formula {(Mt 2 0)m-(A1 2 0 3 )n-Zo pH20) in which Mt is Na or K; Z is CO 2 m is a number from 1 to 3; n is a number from 1 to 4; o is a number from 2 to 4; and p is a number from 0 to

6. A stabilized halogen-containing polymer according to claim 1, which additionally comprises a p-diketone and/or an Mg, Ca or Zn salt thereof or a P-ketoester.

7. A stabilized halogen-containing polymer according to claim 1, which additionally comprises ar, epoxide.

8. A stabilized halogen-containing polymer according to claim 1, which additionally comprises a monomeric, oligomeric or polymeric dihydropyridine.

9. A stabilized halogen-containing nolymer according to claim 1, which additionally comprises an inorganic or organic calcium compound.

10. A stabilized halogen-containing polymer according to claim 1, which additionally comprises a phosphite, a perchlorate compound, a polyol or a disaccharide alcohol.

11. A stabilized halogen-containing polymer according to claim 1, which additionally S comprises a P-diketone and/or an Mg, Ca or Zn salt thereof or a [-ketoester and a monomeric, oligomeric or polymeric dihydropyridine.

12. A stabilized halogen-containing polymer according to claim 1, which additionally "comprises a p-diketone and/or an Mg, Ca or Zn salt thereof or a p-ketoester and a polyol or a disaccharide alcohol.

13. A stabilized halogen-containing polymer according to claim 1, which additionally comprises a perchlorate compound and a polyol or a disaccharide alcohol.

14. A stabilized halogen-containing polymer according to claim 1, which additionally comprises an epoxide and a perchlorate compound. A stabilizer mixture comprising an alumo salt compound of the formula {(Mt 2 O)m-(Al20 3 )n'Zo'pH20) in which Mt is s LUI'CI H, Na, K, Mlgl2, Ca 1 Srlt2 or Zn 1 Z is C0 2 S0 2 (Cl 2 Q,) 1 t2, B 4 0 6 S202 (thiosulfate) or C 2 0 2 (ox alate); m, if Mt is Mgj/2 or Cal/2, is a number from 1 to 2, and in all other cases m is a number from 1 to 3; n is a number from 1 to 4, o is a number from 2 to 4; and p is a number from 0 to or a magadiite of the formula Na 2 Sil 4 O29'n H120 or Na 2 Si 8 Oir-n 1120, in which a is a number from 0 to or a kenyaite of the formula Pla 2 Si 22 O 45 -n H120, in which n is a number from 0) to or a kanemite of the formula Na 2 Si 2 Q 5 .n H 2 O,NaHSi 2 Q 5 .n H 2 0 or Na 2 Si 4 0 9 'n M120, in which n is a number from 0 to and an inorganic or organic zinc, aluminium or rare-earth compound other than of the formula where, if the stabilizer mixture comprises an alumo salt compnound of the formula no organotin-p-diketonate and no (y-hydroxyalkyl)polyorganosiloxane oil is present.

16. The use of a stabilizer mixture comprising an alumo salt compound of the formula ((Mt 2 O)m-(A1 2 0 3 )n*Zo*pH 2 0) in which Mt is H, Na, K, Mg 1 j, Ca/, Srlt2 or Znw1; Z is GO 2 SO 2 (C1 2 0 7 )lt2, B 4 0 6 S202 (thiosulfate) or C 2 0 2 (oxalate); m, if Mt is Mgj/2 or Cajt2, is a number from i to 2, *and in all other casesrmuis a number from 1 to 3; nis a number from 1 to 4, o is a V. number from 2 to 4; and p is a number from 0 to or a magadite of the formnula Na 2 Si 1 4 rO 29 ?gn 1120 or Na 2 Si 8 O 17 1120, in which n is a number from 0 to or a kenyaite of the formula Na 2 Si 22 O 45 -n H 2 0, in which n is a number from 0 to or a kanemite of the for-mula Na 2 Si,,O 5 *n H 2 O,NaHSi 2 O 5 .n 1120 or Na 2 Si 4 O 9 .n 1120, in which n is a number from 0 to and an inorganic er organic zinc, aluminium or rare-earth compound other than of the formula where, if the stabilizer mixture comprises an alumo salt compound of the formula no organotin-p-diketonate and no (y-hydroxyalkIylI)poly 9rganos iloxane oil is present; for the stabilization of a halogen-containing polymer or polymer ilecyclate. Nl17. A process for the preparation of a stabilized halogen-containing polymer or polymer ~recyclate, which comprises mixing a stabilizer mixture comprising Vx IT OY' -51- an alumo salt compound of the formula ((Mt20)m-(A1 2 0 3 )n-ZopH20) in which Mt is H, Na, K, Mglt2, Cajt2, Sr./2 or Znl2; Z is CO2, SO 2 (C120 7 )12, B 4 0 6 S 2 0 2 (thiosulfate) or C 2 0 2 (oxalate); m, if Mt is Mglt or Ca 1 is a number from 1 to 2, and in all other cases m is a number from 1 to 3; n is a number from 1 to 4, o is a number from 2 to 4; and p is a number from 0 to or a magadiite of the formula Na 2 Si 1 4 0 9 -n H 2 0 or Na 2 SigOl-n H 2 0, in which n is a number from 0 to or a kenyaite of the formula Na 2 Si220 45 '20, in which n is a number from 0 to or a kanemite of the formula Na 2 Si 2 O 5 -n H 2 0,NaHSi 2 O-n H 2 0 or Na 2 Si 4 09-n H 2 0, in which n is a number from 0 to and an inorganic or organic zinc, aluminium or rare-earth compound other than of the formula where, if the stabilizer mixture comprises an alumo salt compound of the formula no organotin-P-diketonate and no (y-hydroxyalkyl)polyorganosiloxane oil is present as such or in the form of its individual constituents, and, if desired, further additives with a halogen-containing polymer using devices such as calenders, mixers, compounders, extruders and the like. S 18. A stabilized halogen-containing polymeraccording to any one of claims 1 to 14 or processes for preparing the same substantially as hereinbefore described with reference to the examples. DATED this 7th day of April 1995, CIBA-GEIGY AG By Its Patent Attorney DAVIES COLLISON CAVE "VT 0 Stabilized halogen-containing polymers Abstract of the disclosure Use of an alumo salt compound of the formula {(Mt 2 O)m(Al 2 0 3 )n-Zo-pH 2 O} in which Mt is H, Na, K, Mgl 2 Cal/, Sr/2 or Znl/; Z is CO2, SO 2 (C1 2 0 7 )1 2 B 4 0 6 S 2 0 2 (thiosulfaij or C 2 0 2 (oxalate); m, if Mt is Mgl/ 2 or Cal 2 is a number from 1 to 2, and in all other cases m is a number from 1 to 3; n is a number from 1 to 4, o is a number from 2 to 4; and p is a number from 0 to 30; or a magadiite of the formula Na 2 Si 1 4029On H20 or Na 2 SigO 1 7 -n H20, in which n is a number from 0 to S or a kenyaite of the formula Na 2 Si 22 0 45 -n H 2 0, in which n is a number from 0 to 30; or a S: kanemite of the formula Na 2 Si 2 Os 5 n H 2 0, NaHSizO2 5 n H20 or Na 2 Si 4 0 9 -n O20, in which S n is a number from 0 to and an inorganic or organic zinc, aluminium or rare-earth compound other than of the lonnula allows a high degree of stabilization of a halogen-containing polymer or polymer recyclate.