CA2031436A1 - Stabilized, chlorine-containing composition - Google Patents

Abstract

Stabilized, chlorine-containing composition Abstract of the disclosure Compositions containing a) at least one chlorine-containing polymer, b) at least one blowing agent or foaming agent, c) at least one sterically hindered amine, and d) at least one zinc, calcium/zinc and/or barium/zinc compound, and foamed articles obtained by expanding the compositions, have good thermostability.

Description

~3:L !~3 3 - 1- ' A-17863/+/CGM 365 Stabilized, chlorine-containing composition The invention relates to stabilized, foarnable, chlorine-containing polymer compositions and to the foams obtainable therefrom.

It is known that chlorine-containing polymers tend to discolour even at moderatetemperatures and therefore can only be processed as thermoplastics with addition of -stabilizers. While basic additives, such as organic amines, generally increase the discoloration, specific sterically hindered amines have recently been disclosed which can act both as light screens and as therrnal stabilizers, as described, for example, in JP-~
82/168 933 and JP-A 86/163 965.

In the production of foams from chlorine-containing polymers, the risk of discoloration is particularly high due to the high foaming temperatures and due to the basic foaming agents or catalysts (kickers) which are frequently present. It has surprisingly been found that sterically hindered amines of this type can also be used for the production of foams ` ~`
from chlorine-containing polymers if, in addition, certain thermostabilizers or costabilizers are additionally employed. In the foam, the hindered amines act not only as a light screen, but also as n so-called long-term thermal stabilizer.

This is aellieved nccording to the invention using compositions containing n) nt lenst one chlorine-contnining polymer, b) nt least one blowing agent or foaming agent, c) at least one sterically hindered amine, and d) at least one zinc, calcium/zinc and/or barium/zinc compound.

The compositions according to the invention may contain, for example, as the chlorine-containing polymer:
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 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 ' ~ ' ,' ' `:

' :- :
.. ~ . ... - . ..
.. . . .
:-2~31l~$

dicarboxylic acids or anhydrides thereof, such as copolymers 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.

This also includes 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, polylactones and nitrile rubber.

particul,lrly preferred chlorine-containing polymer is polyvinyl chloride, in particular as a suspension polymer, emulsion polymer or bulk polymer.

Vario~ls processes which are known per se are suitable for producing foam articles or expnncled articles from the composition according to the invention.

ï'he compositions can be expanded by means of finely divided gases, it being possible to use various types of gases. For example permanent gases, usually nitrogen, can be incorporated into PVC melts at a pressure of about 200 bar. For expansion, the mouldings cooled in a press mould under pressure are, for example, heated in the open in a two-step process. For example, soft foams are also produced from corresponding plastisols, ie.
mixtures of polymers and plasticizers, with addition of surface-active foaming agents and compressed air or CO2 as blowing gas or foaming agent, for example by continuousextrusion.
Other processes use physical blowing agents, such as readily evaporating hydrocarbons, 2a311 ~

eg. pentane to heptane, or chlorinated hydrocarbons, such as methyl chloride, methylene chloride, trichloroethylene or chlorofluoroalkanes. For example, the physical blowing agents are dissolved in the raw materials or precursors or added under pressure during processing. The formation of closed pores can be promoted by crosslinking.

Also known per se are chemical blowing agents. These are substances which decompose at elevated temperatures to form inert gases. These are inorganic blowing agents, such as NaHCO3, or organic blowing agents, eg. azo compounds, N-nitroso compolmds and sulfonyl hydrazides, for example having initiation temperatures of between 90 and 275C, from 100 to 300 ml of nitrogen being eliminated per gram.

Examples of such blowing agents are azodicarbonamide; modified azodicarbonamide;4,4'-oxybis(benzenesulfohydrazide), diphenyl sulfone 3,3'-disulfohydrazide, diphenylene - ` -oxide 4,4'-disulfohydrazide; trihydrazinotriazine; p-tolylenesulfonyl semicarbazide;
5-phenyltetrazole and isatoic anhydride. A particularly preferred blowing agent is azodicarbonamide, for example having an initiation temperature of 200-235C or areduced initiation temperature of 155-200C. In order to reduce the initiation temperature, so-called kickers, eg. Zn stabilizers present in the polymer mixture, can be used. The kicker can also be used in the form of zinc oxide/stearic acid. Other kickers which can be used are alkali metal compounds, for example sodium compounds or potassium compounds, such as alkali metal bicarbonates, preferably Na~ICO3, or alkali metal compounds from the series comprising the aliphntic, saturated Cl-C22carboxylates, aliphatic, olefinic C2-C22carboxylates, aliphatic C2-C22carboxylates which are substituted by at least one O~l group, cyclic and bicyclic carboxylates having S-22 carbon atoms, ~romntic C6-C22carboxylatc9, aromatic C6-C22carboxylates which are substituted by at least one O~l group, Cl-Cl6alkyl-substituted phenylcarboxylates, phenyl Cl-CI6alkylcarboxylates, C6-CI8phenolates, dehydroacetic acid and derivatives thereof, mercaptides based on mercaptocarboxylates, and glycinates.

The alkali metal compounds from the series comprising the carboxylates are preferably salts of carboxylic acids having from 7 to 20 carbon atoms, for exarnple benzoates, alkenoates or alkanoates, preferably stearates, oleates, laurates, palmitates, hydroxystearates or 2-ethylhexanoates. Particular preference is given to stearates, oleates and p-tert-butylbenzoates. The potassium compounds are particularly preferred here, and potassium 2-ethylhexanoate is very particularly preferred.

, -.

2~3~ ~3~

The compositions may also contain nucleating agents and pore regulators which are known per se. Examples of nucleating agents and pore regulators added to the foam mixtures are small amounts of finely divided solids or C02-eliminating mixtures of NaHCO3 and solid organic acids.

The compositions of the present invention may be blowing agent-containing PVC
moulding compositions which are ready for processing, for example for extrusion of structural foarned pipes and profiles or for therrnoplastic foam casting. Or they may be plastisols for conversion into foamed soft PVC articles.

Foamed articles can also be obtained from the compositions of the present invention by the high-pressure processes which are known per se for the production of hard and soft PVC foarns.

The compositions according to the invention can be used to produce PVC foams, for example soft PVC foams, by the low-pressure process, which is known per se. In addition, the compositions according to the invention can be employed, for example, in thepressureless process, which is known per se.

The said processes are described, for example, in Hansjurgen Saechtling, Kunststoff-rraschenbuch [Pocketbook of Plastics], 22nd Edition, Carl Hanser Verlag, Munich. :

Component tc) in the composition according to the invention can be any cyclic ornoncyclie sterically hindered amine. te) is preferably a compound which contains at least one ~roup of the formula III

-N~ (III) in which R is hydrogen or methyl. R is preferably hydrogen. These are derivatives of polyalkylpiperidines, in particular of 2,2,6,6-tetramethylpiperidine. These polyalkylpiperidines preferably carry one or two polar substituents or a polar spiro ring .~ ~

~3~3~

system in the 4-position.
The following classes of polyalkylpiperidines are of particular importance.
a) Compounds of the formula IV
~ ., RCH2~R

Rl,-N~O---R12 (IV), RCH2 CH3 n in which n is a number from 1 to 4, preferably 1 or 2, R is hydrogen or methyl, Rl1 is hydrogen, oxyl, hydroxyl, Cl-Cl2alkyl, C3-C8alkenyl, C3-C8aL~cynyl, C7-CI2aralkyl, Cl-Cl8alkoxy, C5-C8cycloalkoxy, C7-CgphenylaL1coxy, Cl-C8aL~anoyl, C3-CsaLtcenoyl, C1-Cl8alkanoyloxy, benzyloxy, glycidyl or a -CH2CH(OH)-Z group, in which 7. is hydrogen, methyl or phenyl, Rll preferably being H, C1-C4alkyl, allyl, benzyl, acetyl or acryloyl, and Rl2, if n is 1, being hydrogen, Cl-Cl8alkyl which is uninterrupted or intermpted by one or more oxygen atoms, cyanoethyl, benzyl, glycidyl, a monovalent rndicnl of nn aliphatic, cycloaliphatic, arnliphatic, unsaturated or aromatic carboxylic acid, cnrbamic slcid or pllosphorlls-containing acid or a monovalent silyl radical, preferably a rndicnl of nn nliphsltic carboxylic acid having from 2 to 18 carbon atoms, of a cyclonliphntic carboxylic ncid having from 7 to 15 carbon atoms, of an a,~-unsaturated cnrboxylic ncid hnving from 3 to 5 carbon atoms or of an aromatic carboxylic acid having from 7 to 15 carbon ntoms, Rl2 being, if n is 2, Cl-CI2alkylene, C4-C12alkenylene, xylylene, n divalent rndicnl of an aliphatic, cycloaliphatic, araliphatic or aromatic dicnrboxylic acid, dicarbamic acid or phosphorus-containing acid, or a divalent silyl rndical, prefernbly a radical of an aliphntic dicarboxylic acid having from 2 to 36 carbon atoms, of n cycloaliphatic or aromatic dicarboxylic acid having from 8 to 14 carbon atoms or of an aliphatic, cycloaliyhatic or aromatic dicarbamic acid having from 8 to 14 carbon atoms, Rl2 being, if n is 3, a trivalent radical of aliphatic, cycloaliphatic or aromatic tricarboxylic acid, of an aromatic tricarbamic acid or of a phosphorus-containing acid, or a trivalent silyl radical, and Rl2 being, if n is 4, a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid~

.
' :, .
: ' . . ' . -î $ ~ q ~

If any substituents a~e Cl-Cl2alkyl, they are, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.

Cl-CI8ALl~yl Rll or Rl2 may be, for example, the abovementioned groups and additionally, ~or example, n-tridecyl, n-tetradecyl, n-hexadeeyl or n-octadecyl.
C3-C8ALIcenyl Rll may be, for example, 1-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl or 4-tert-butyl-2-butenyl.

C3-C8Alkynyl Rll is preferably propargyl.

C7-CI2Aralkyl Rll is in particular phenethyl and especially benzyl.

Cl-C8Alkanoyl Rll is, for example, formyl, propionyl, butyryl or octanyl, bu~ preferably aeetyl and C3-Csalkenoyl Rl1 is in particular aeryloyl.

A monovalent earboxylie aeid radieal Rl2 is, for example, an aeetie aeid, eaproic aeid, stearie aeid, aerylie aeid, methaerylic aeid, benzoie acid or p-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic aeid radieal.

A divnlent diearboxylie aeid radieal Rl2 is, for example, a malonie aeid, sueeinie aeid, ~lutarie aeid, adipie aeid, suberie aei(l, sebaeie acid, maleie aeid, itaconie acid, phthalie neid, dibutylmalonie aeid, dibenzylmalonie acid, butyl(3,5-di-tert-butyl-4~hydroxybenzyl)malonie aeid or bieyeloheptenediearboxylic acid radieal.

A trivalent triearboxylie aeid Rl2 is, for example, a trimellitie aeid, eitrie aeid or nitrilotriaeetie acid radieal.

A tetravalent tetraearboxylie aeid radical Rl2 is, for example, the tetravalent radical of butane- 1 ,2,3,4-tetraearboxylie aeid or of pyromellitie aeid.

A divalent diearbamie aeid radieal Rl2 is, for example, a hexamethylenediearbamie aeid or 2,4-tolylenediearbamie aeid radieal.

: ' , ' ~ . ~ '' ' " - ' . . .

2~3~3~ :

':
Preference is given tO compounds of the formula IV in which R is hydrogen, Rll is hydrogen or methyl, n is 2, and Rl2 is the diacyl radical of an aliphatic dicarboxylic acid having from 4 to 12 carbon atoms.

The following Gompounds are examples of polyalkylpiperidine compounds of this class:

1) 4-hydroxy-2,2,6,6-tetramethylpiperidine 2) 1-allyl-4-hydroxy-2,2,6,6-tetrarnethylpiperidine 3) 1-benzyl-4-hydroxy-2,2,6,6-tetrarnethylpiperidine 4) 1-(4-tert-butyl-2-butenyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine 5) 4-stearoyloxy-2,2,6,6-tetramethylpiperidine 6) 1-ethyl-4-salicyloyloxy-2,2,6,6-tetramethylpiperidine 7) 4-methacryloyloxy-1,2,2,6,6-pentarnethylpiperidine 8) 1 ,2,2,6,6-pentamethylpiperidin-4-yl ,B- (3 ,5-di-tert-butyl-4-hydroxyphenyl)propionat 9) di(l-benzyl-2,2,6,6-tetramethylpiperidin-4-yl) maleinate 10) di(2,2,6,6-tetramethylpiperidin-4-yl) succinate I l) di(2,2,6,6-tetramethylpiperidin-4-yl) glutarate 12) di(2,2,6,6-tetramethylpiperidin-4-yl) adipate 13) di(2,2,6,6-tetramethylpiperidin-4-yl) sebacate 14) di(l,2,2,6,6-pentamethylpiperidin-4-yl) sebacate 15) di(l,2,3,6-tetrnmethyl-2,6-diethyl-piperidill-4-yl) sebacate 16) di(1-allyl-2,2,6,6-tctramethylpiperidin-4-yl) phthalate 17) 1-hydroxy-4-,~-cyanoethyloxy-2,2,6,6-tetramethylpiperidine 18) 1-acetyl-2,2,6,6-tetrnmethylpiperidin-4-yl acetate 19) tri(2,2,6,6-tetramethylpiperidin-4-yl) trimellitate 20) 1-acryloyl-4-benzyloxy-2,2,6,6-tetramethylpiperidine 21) di(2,2,6,6-tetramethylpiperidin-4-yl) diethylmalonate 22) di(l,2,2,6,6-pentamethylpiperidin-4-yl) dibutylmalonate 23) di( 1 ,2,2,6,6-pentamethylpiperidin-4-yl) butyl(3,5-di-tert-butyl-4-hydroxybenzyl)malonate 24) di(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate 25) di(l-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate 26) hexan-l ',6'-bis-(4-carbarnoyloxy- 1 -n-butyl-2,2,6,6-tetramethylpiperidine)27) toluene-2',4'-bis-(4-carbamoyloxy-1-n-propyl-2,2,6,6-tetramethylpiperidine) 28) dimethylbis~2,2,6,6-tetramethylpiperidin-4-oxy)silane 29) phenyltris(2,2,6,6-tetramethylpiperidin-4-oxy)silane .

2 ~ 3 ~

30) ~is(1-propyl-2,2,6,6-tetramethylpiperidin-4-yl) phosphite 31) tris(1-propyl-2,2,6,6-te~ramethylpiperidin-4-yl) phosphate 32) phenyl[bis-(1,2,2,6,6-pentamethylpiperidin-4-yl)] phosphonate 33) 4-hydroxy-1,2,2,6,6-pentamethylpiperidine 34) 4-hydroxy-N-hydroxyethyl-2,2,6,6-tetramethylpiperidine 35) 4-hydroxy-N-(2-hydroxypropyl)-2,2,6,6-tetramethylpiperidine 36) 1-glycidyl-4-hydroxy-2,2,6,6-tetramethylpiperidine -b) Compounds of the formula (V) ~ .

RCH2~R

R, 1 - N~>--N ~ ~ R14 (V) RCH2 CH3 n in which n is the number 1 or 2, R and Rll are as defined under a), Rl3 is hydrogen, Cl-CI2alkyl, C2-Cshydroxyalkyl, Cs-C7cycloalkyl C7-C8aralkyl, C2-CI8alkanoyl, C3-Csalkenoyl, benzoyl or a group of the forrnula RCH2~R

R~l-N~}

and Rl4, if n is 1, is hydrogen, Cl-CI8alkyl, C3-C8alkenyl, Cs-C7eycloalkyl, Cl-C4alkyl whieh is substituted by a hydroxyl, eyano, alkoxyearbonyl or earbamide group, glycidyl, a group of the formula -CH~-CH(OH)-Z or of the formula -CONH-Z in which Z is hydrogen, methyl or phenyl; if n is 2, Rl4 is C2-CI2alkylene, C6-C12arylene, xylylene, a -CH2-CH(OH)-CH2- group or a -CH2-CH(OH)-CH2-O-D-O- group, in which D is C2-CI0alkylene, C6-CIsarylene, C6-CI2cycloalkylene or, as long as Rl3 is not alkanoyl, alkenoyl or benzoyl, Rl4 may alternatively be a divalent radieal of an aliphatie, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid or alternadvely the -CO-group, or Rl3 and Rl4 together, if n is 1, may be the divalent radical of a aliphatie, eyeloaliphatie or aromatie 1,2- or 1,3-dicarboxylie acid.

.
-~ -2 ~ 3 ~

g Any Cl-CI2 or Cl-Cl8alkyl substituents are as defined under a).

Any Cs-C~cycloaL~syl substituents are, in particular, cyclohexyl.
.

C7-C8AraL~yl Rl3 is, in particular, phenylethyl or especially benzyl. C2-CsHydroxyalkyl Rl3 is, in particular, 2-hydroxyethyl or 2-hydroxypropyl.

C2-CI8Alkanoyl Rl3 is, for example, propionyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl or octadecanoyl, but preferably acetyl and C3-CsaL~cenoyl Rl3 is, in particular, acryloyl.

C2-C8Alkenyl Rl4 is, for example, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl or 2-octenyl.

Hydroxyl-, cyano-, alkoxycarbonyl- or carbamide-substituted Cl-C4aLtcyl Rl4 may be, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl, methoxycarbonylmethy], 2-ethoxycarbonylethyl, 2-aminocarbonylpropyl or 2-(dimethylaminocarbonyl)ethyl.

~ny C2-CI2alkylene substituents are, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodccnmethylene.

Any C6-CIsnrylene subslitucnts are, for example, o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.

C6-CI2Cyclonlkylene D is, in particular, cyclohexylene.

Preferred compounds of the formula V are those in which n is 1 or 2, R is hydrogen, Rll is hydrogen or methyl, Rl3 is hydrogen, Cl-CI2alkyl or a group of the formula RCH2~R

R, 1 - N~

-. ` ` . . ` . . .

2a3~ ~3~

and Rl4 is, in the case where n = 1, hydrogen or Cl^Cl2aLI~yl, and, in the case where n = 2, is C2-C8alkylene.

The following are examples of polyaL~cylpiperidine compounds of this class:

37) N,N'-bis(2,2,6,6-tehamethylpiperidin-4-yl)hexamethylene-1,6-diamine 38) N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylene-1,6-diacetamide 39) bis(2,2,6,6-tetramethylpiperidin-4-yl)amine 40) 4-benzoylamino-2,2,6,6-tetramethylpiperidine 41 ) N,N ' -bis (2,2,6,6-tetramethylpiperidin-4-yl)-N,N ' -dibutyladipamide 42) N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)-N,N'-dicyclohexyl-2-hydroxypropylen-1,3-diamine 43) N,N'-bi~(2,2,6,6-tetramethylpiperidin-4-yl)-p-xylylenediamine 44) N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)-succindiamide 45) di(2,2,6,6-tetramcthylpiperidin-4-yl) N-(2,2,6,6~Tetramcthylpiperidin-4-yl)-~-aminodipropionate 46) The compound of the formula -' ' ?

- ~

2~3~'~3~

CH3 - N~ N--CH2- CH(OH~ CH2-O

CH3 011, CH3~

CH3 ~ N ~ N--CH2- CH(OH)- CH2- 0 \~ C4Hg CH /\CH
47) 4-(bis-2-hydroxyethyl-amino)-1,2,2,6,6-pentamethylpiperidine 48) 4-(3-Methyl-4-hydroxy-5-tert-butyl-benzamido)-2,2,6,6-tetramethylpipendine 49) 4-methacrylamido- 1 ,2,2,6,6-pentnmethylpiperidine c) Compounds of the formula (VI) RCH2~R

R11 ~ N~< ~ R15 (VI) RCH2 CH3 n in which n is the number 1 or 2, R and Rl 1 are as defined under a), and Rls, if n is 1, is C2-C8alkylene or -hydroxyalkylene or C4-C22acyloxyalkylene, and, if n is 2, is the (-CH2)2C(CH2-)2 group.

C2-C8Alkylene or -hydroxyalkylene Rls is, for example, ethylene, 1-methylethylene, propylene, 2-ethylpropylene or 2-ethyl-2-hydroxymethylprowlene.

C4-C22Acyloxyalkylene Rls is, for example, 2-ethyl-2-acetoxymethylpropylene.

.~ - .

, 2~3~3~

The following are examples of polyalkylpiperidine compounds of this class:

50) 9-aza-8,8,10,10-tetramethyl-l,S-dioxaspiro[5.5]undecane Sl) 9-aza-8,8,10,10-tetramethyl-3-ethyl-l,S-dioxaspiro[5.5]undecane 52) 8-aza-2,7,7,8,9,9-hexamethyl-1,4-dioxaspiro[4.5]decane 53) 9-aza-3-hydroxymethyl-3-ethyl-8,8,9,10,10-pentarnethyl-1,5-dioxaspiro[S.S]undecane 54) 9-aza-3-ethyl-3-acetoxymethyl-9-acetyl-8,8,10,10-tetramethyl-1,5-dioxaspiro-[S.S]undecane SS) 2,2,6,6-tetramethylpiperidine-4-spiro-2'-(1',3'-dioxane)-S'-spiro-S"-(1 ",3"-dioxane)-2"-spiro -4"'-(2"',2"',6"',6"'-tetramethylpiperidine).

d) Compounds of the formulae VIIA, VIIB and VIIC

\~/ I ~ ' .
/~N--C _ O (VII~) ~/ C--N _ R~7 RCH~ CH3 n RCH2 CH3 R Tl R~ -N)~o_ I -T2 (VIIB) ~ ~ ~ C--N=O
RCH2 CH3 H ' ¦--FI N~ (VIIC) RCH2 CH3 0 _ n 2~3~3~

in which n is the number 1 or 2, R and Rll are as defined under a), Rl6 is hydrogen, Cl-Cl2alkyl, allyl, benzyl, glycidyl or C2-C6aL~oxyalkyl, and R17, if n is 1, is hydrogen, Cl-Cl2alkyl, C3-Csalkenyl~ C7-C9aralkyl, Cs-C7cycloalkyl, C2-C4hydroxyalkyl, C2-C6alkoxyalkyl, C6-C1Oaryl, glycidyl or a groap of the formula -(CH2)p-COO-Q or of the formula -(CH2)p-O-CO-Q, in which p is 1 or 2 and Q is Cl-C4alkyl or phenyl, and, if n is 2~ Rl7 is C2-Cl2alkylene, C4-C12alkenylene, C6-Cl2arylene, a -CH2-CH(OH)-CH2-O-D-O-CH2-CH(OH)-CH2- group in which D is C2-ClOalkylene, C6-Clsarylene, C6-Cl2cycloalkylene, or a -CH2CH(OZ')CH2-(OCH2-CH(OZ')CH2)2-group in which Z' is hydrogen, Cl-Cl8alkyl, allyl, benzyl, C~-C12aL~anoyl or benzoyl, T
and T2, independently of one another, are hydrogen, C1-Cl8aLkyl or C6-ClOaryl orC7-Cgaralkyl, each of which is unsubstituted or substituted by halogen or C1-C4aLkyl, or Tl and T2, together with the carbon atom connecting them, form a Cs-C12cycloaLkane ring.

Any Cl-Cl2alkyl substituents are, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.

Any Cl-Cl8alkyl substituents may be, for example, the abovementioned groups and in addition, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

Any C2-C6alkoxyalkyl substituents are, for example, methoxymethyl, ethoxymethyl,propoxymethyl, tert-butoxyrnethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl, tert-butoxyethyl, isopropoxycthyl or propoxypropyl.

C3-C5Alkcnyl Rl7 is, for cxarnple, 1-propenyl, allyl, methallyl, 2-butenyl or 2-pentenyl.

C7-CgAralkyl R17, T1 and T2 are, in particular, phenethyl or especially benzyl. If T1 and T2, to~ether with the carbon ntom, forrn a cycloalkyl ring, it may, for example, be a cyclopentane, cyclohexane, cyclooctane or cyclododecane ring.

C2-C4Hydroxyalkyl Rl7 is, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

C6-C1OAryl R17, T1 and T2 are, in particular, phenyl, a- or ~-naphthyl, which are unsubstituted or substituted by halogen or C1-C4alkyl.

~ .
' . . ' ~ , .
. .

,~3~3i~

C2-CI2Alkylene Rl7 is, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octa nethylene, decamethylene or dodecamethylene.
C4-CI2Alkenylene Rl7 is, in particular, 2-butenylene, 2-pentenylene or 3-hexenylene.

C6-Cl2Arylene R17 is, for example, o-, m- or p-phenylene, 1,4-naph.~hylene or 4,4'-diphenylene.

C2-Cl2AL~canoyl Z' is, for example, propionyl, butyryl1 octanoyl or dodecanoyl, but preferably acetyl.

C2-CIOAlkylene, C6-CIsarylene or C6-CI2cycloalkylene D is as defined under b). ~ -The following are examples of polyalkylpiperidine compounds of this class:

56) 3-benzyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4-dione 57) 3-n-octyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4-dione 58) 3-allyl-1,3,8-triaza-1,7,7,9,9-pentamethylspiro[4.5]decane-2,4-dione 59) 3-glyciclyl-1,3,8-t~iaxn-7,7,8,9,9-pentamethylspiro[4~5]decane-2,4-dione 60) 1,3,7,7,8,9,9-heptnmethyl-1,3,8-trillznspiro[4.5]decane-2,4-dione 61) 2 iso-propyl-7,7,9,9 tetrnmethyl-1-oxn-3,8-diaza-4-oxospiro[4.5]decane 62) 2,2-dibutyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane 63) 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodispiro[S.1.1 1.2]heneicosane 64) 2-butyl-7,7,9,9-tetramethyl-1-oxa-4,8-diaza-3-oxospiro[4,5]decane 65) 8-acetyl-3-dodecyl- 1 ,3,8-triaza-7,7,9,9-tetramethylspiro[4,5]-decane-2,4-dione or the compounds of the following formulae:

- . .
- ~

. .

, .
.
.

~3~

- 1s-)~\ HN-C=O O=C-NH ~--Y
66) CH3 - N X I I ~( N--CH3 CH3k~ C-N--CHzCH(OH)CH2-lOCH2-CH(OH)CH2]2 N ~C

)~ HN--C=O O=C--NH ~Y
67) CH3--N X ~ N--CH3 CH3k~ C--N--(CH2)6~ N - C \~

Y--~ HN--C=O O=C--NH ~--Y

C~ I kC~ ~ CH2~ o~3 0110 H3C~ CH2)l, 69) UN
>~ C--N--CH2CH2COOC12H2s c) Compounds of the ~ormula VIII

[R~ R~o (Vlll), in which n is the number 1 or 2 and Rl8 is a group of the for nula ~' .. . : ~. . :, . . : . :

2 ~ 3 ~

R~CH2R

-E-(A)~N - Rl, in which R and R,l are as de~lned under a), E is -O- or -NRll-, A is C2-C6alkylene or -(CH2)3-O-, x is the number O or 1, Rlg is identical with Rl8 or is one of the groups : :
-NR21R22, -OR23, -NHCH20R23 or -N(CH20R23)2, R20, if n is 1, is identical with Rl8 or Rlg and, if n i~ 2, is an -E-B-E- group in which B is C2-C6aLkylene which is uninterrupted or is intenupted by -N(R2,)-, Rll is Cl-Cl2alkyl, cyclohexyl, benzyl or Cl-C4hydroxyalkyl or is a group of the forrnula R~CH2R

~N-Rtl, R22 is Cl-CI2alkyl, cyclohexyl, benzyl or Cl-C4hydroxyalkyl, and R23 is hydrogen, Cl-Cl2alkyl or phenyl, or R21 and R22 together are C4-C5alkylenè or -oxaalkylene, for -CH2CH2~ -CH2CH2 exnmple / or n group of the formula N--R,l or alternatively R21 and Ræ

arc cnch a group of the formula CH3\/CH3 HN/~ HN--A--k ~
CH3 CH3 C4Hg--N
CH3 ~<CH3 ,~ . ` ` ' , ,:
.` . : . ` `-, . :

`

2~ l3~

Any Cl-Cl2alkyl substituents are, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, or n-dodecyl.

Any Cl-C4hydroxyalkyl substituents are, for example, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

C2-C6AL'cylene A is, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene or hexarnethylene.

If R2l and R22 ~ogether are C4-Csalkylene or -oxaaL1cylene, this is, for example, tetramethylene, pentamethylene or 3-oxapentamethylene.

The following are examples of polyalkylpiperidine compounds of this class:

H3CyN yCH3 H3C I~J CH3 N--C4Ho NJ~N

(CH3CH2)2N ~ N N(CH2CH3)2 CH3~ Ho)2 71) C2H~--N )'--Nl ~ ,~LN ( N--C2H5 k C2~,5 C2Hs 7~
CHa CH3 CHa CH3 72) N~N whereR= NH-c~2cl~2c~2-o~;_CH

'~'. '~ "' ~' '''- ' ' ' ` .

2 ~ 3 ~

,~CH3 CH2 CH2~NH
NH
CH3~ ~ CH3CH3~CH3 HN ,~CH2-CH2-NH 1~ J NH-CH2-CH?.--~ NH

74) HN~ NHCHzC~CH2CH~NH --CH3 h CH3 ~N~N~ N,C4Hg ~
CH3~N~CH3 l l CH3l ~CH3 H J~ ~-- CH3~N CH3 CH3 ~ CH3 CH3 ~ <CH3 H
CH3 N CH3 CHa N CH3 H H

7~i) R N~I-(C~12)3-N-(CI-12~2-N-(CH2)3-NH.R

_~N~

N~N
C4Hg--N CH3 CH3 CH3~<CH3 R R
76) R-NH-(cH2)3-l~-(cH2)2-~-(cH2)3-NH R

,~ ' `' ~' ' ' ' .
, . , ' . ~, ~'~ ,' `
, .

2~3~1~3~

C4HD~y N ~ N - CH3 N ~ N ~
where R = C4H9 - N CH3 CH3 CH3 ~ CH3 CIH3 IR R ~H3 77) R-N-(cH2)3-N-(cH2)2-~-(cH2)3-~-R

N ~ N - CH3 N ~ N ~
where R = C4HD - N CH3 CH3 CH3~<CH3 C ~ CH3 C8H17--N ~ NH
78) N N CH3 CH3 C~H~7 - N N NH(CH2)3 CH3 ~ CH3 .

- ` ' ~ ''`: .

.
:

` ~3~3l3 CH2CH;~OH

H3C>~<CH3 N C4H3 .

79)CH3~;1 ~1 /~<
HO-CH2CH2--N ~ N N N ~ N--CH2CH2-OH
k-- C4H9C4Hs 7~ ~ .

CH2-CH=C~2 H3C~N~",,CH3 H3C1 T~CH3 \I~ :, N--C4Hs 80)H3C~ NJ~N C~CH3 H2C~HC-H2C--N )--NlNlN_~\N--CH2-CH.CH2 ~ C4H8 C4H9 7~ `
H3C CH3 CHa CH3 :.

Preference is given to f) oligomers or polymeric compounds whose recurring structural unit contnins a 2,2,6,6-tetraalkylpiperidine radical of the formula III, in particular polyesters, polyethers, polyamides, polyamines, polyurethanes, polyureas, polyaminotriazines, poly(meth)acrylates, poly(meth)acrylamides and copolymers thereof which contain such radicals.

The following are examples of 2,2,6,6-polyalkylpiperidine light screens of this class, where m is a number from 2 to about 200.

O O ~
81 ) -E C--CH2-CH2 - C--O-CH2-CH2 - Nj~ }m .~:

,, . -. - , . . . .

- 2~ '13~

CH3>~ 0 ~CH3 0 0 82) ~CH2-CH2--Nk~O'C--(CH2)4--C-O~N-CH2-CH2-O--C- (CH2)4--C~

83) tNH(cH~ NH-c~o-N~cH~)~NH-o~3--C~

84) the particularly preferred compound of the forrnula Cl H3 Cl H3 J~ CH3 CH3 f~ JLN (CH2)~ ]m CH~>~ J<CH3 CH3>~ CH3 CH3 N CH ~ CH3 N CH3 H H

[ N - cH2-cH(oH) c~l2~i~
85) CH3~CH3 H

~CH3 CH3~ o C4Hs 1l 86) ~0~7~N--CH2-CH=CH CH2-Nk~o-C-C--C~m ~3~

N ~I N (CH2)6 N - - ]m~
~ CH3~<CH3 CH3~CH3 87) -C4HE, CH3 N CH3 CH3 N CH3 C~13~ CH3 88) E~ CWz~C~o-C-(CHz)~-~

Ct C2Hs o H3C~;
89) ~ C - C----C ~CH2-CH2 - N. ~-- ~i~t C2Hs H3CCH3 90) t C--CH2~
~CH3 ~.
O~<N-CH3 C~113 91 ) [ C--CH2~
~CH3 CsHt3--N ~N CH3 : . ' ~ ' - -2 ~ 3 ~

'?
92) ~N~N tCH2)6 N }m CH3 >~J)<CH3 CH3 '>~CH3 C~3 N CH3 CH3 N CH3 93) [ - N _ (CH2)6----N--CH2-CH2--3jj;~
CH3 >~)<CH3 CH3 >~<CH3 94) [ ~ - N _ (CH2)6--N--CH2--C ~;;~
CH3~)<CH3 CH3~)<cH3 g) Compounds of the forrmlla IX

RCH2~ R

Rl 1 N ~= O (Ix) ~r in which R and R11 are as defined under a).

Preferred compounds of the formula IX are those in which R is hydrogen or methyl, and R11 is hydrogen or methyl.

Examples of such compounds are:
95) 2,2,6,6-tetramethyl-4-piperidone (aminotriacetone) . : , - .
' : .

- :.

3 ~

96) 1 ,2,2,6,6-pentamethyl-4-piperidone 97) 2,2,6,6-tetramethyl-~-piperidone 1-oxide 98) 2,3,6-trimethyl-2,6-diethyl-4-piperidone.

Expedient compositions are those as described above which contain, as d), at least one organic zinc compound andlor at least one inorganic zinc compound from the series comprising the carbonates, chlorides, sulfates, oxides, hydroxides, basic oxides and mixed oxides.

Examples of organic zinc compounds are those from the series comprising the aliphatic, saturated Cl-C22carboxylates, aliphatic, olefinic C2-C22carboxylates, aliphatic C2-C22carboxylates which are substituted by at least one OH group, cyclic and bicyclic carboxylates having 5-22 carbon atoms, aromatic C6-C22carboxylates, aromatic C6-C22carboxylates which are substituted by at least one OH group, Cl-Cl6alkyl-substituted phenylcarboxylates, phenyl-CI-Cl6alkylcarboxylates, C6-CI8phenolates, Cs-C26chelates of 1,3-diketones or p-ketocarboxylates, dehydroacetic ncid and derivatives thereof~ mercaptides based on mercaptocarboxylates, and glycinates.

Preference is given to polymer compositions containing, as d), an organic zinc compound, the zinc compollnd being a salt of carboxylic acid having from 7 to 20 carbon atoms or a C7-C20alkylphcnolate.

The zinc compounds from the series comprising the carboxylates are preferably salts of carboxylic acids having from 7 to 20 carbon atoms, for example benzoates, alkenoates or alkanoates, preferably stearates, oleates, laurates, palmitates, hydroxystearates or 2-ethylhexanoates. Particular preference is given to stearates, oleates and p-tert-butylbenzoates.

A Zn phenolate component d) is, in particular, a C7 C20alkylphenola~e, for example nonylphenolate.

Compounds which may be mentioned by name as examples are zinc salts of monobasiccarboxylic acids, such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, neodecanoic acid, 2-ethylhexanoic acid, pelargonic acid, '' ' ': ' .' ' :

. . . ~ .
,. . -: . : . ~ :

. . - . ~ . . -3 ~

capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmilic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, benzoic acid, monochlorobenzoic acid, p-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-di-tert-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, cumic acid, n-propylbenzoic acid, aminobenzoic acid, N,N-dimethylbenzoic acid, acetoxybenzoic acid, salicylic acid, p-tert-octylsalicylic acid, oleic acid, elaidic acid, sorbic acid, linoleic acid, linolenic acid, thioglycolic acid, mercaptopropionic acid and octylmercaptopropionic acid; monoesters and monoamides of dibasic carboxylic acids, such as oxalic acid, malonic acid, succinic acid, glutamic acid, adipic acid, pimelic acid, suberic acids azelaic acid, sebacic acid, phthalic acid, isophthalic acid,~terephthalic acid, hydroxyphthalic acid, chlorophthalic acid, aminophthalic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, haconic acid, aconitic acid and thiodipropionic acid; and diesters or triesters of tribasic or tetrabasic carboxylic acids, such as hemimellitic acid, trimellitic acid, mellophanic acid, pyromellitic acid and mellitic acid.

Examples of chelates of 1,3-diketones and p-ketocarboxylates are compounds of the formula Zn~R ~-CR R ~ R )2 in whicll R, R', R" and R"' are alkyl having from 1 to 18 carbon atoms, alkenyl having from 2 to 18 carbon atoms, cycloalkyl having from 5 to 12 ring carbon atoms, mono- to tri-CI-C4alkyl-substituted cycloalkyl having from 5 to 12 carbon atoms, alkyl having from I to 18 c~rbon atoms which is substitllted by cycloalkyl having from 5 to 12 ring carbon atoms, phenyl-CI-C18alkyl, Cl-CI8alkylphenyl, phenyl, alkoxyalkyl or alkylenedioxyalkyl or -phenyl~

Examples of R, R', R" and R"' are methyl, ethyl, propyl, isopropyl, isobutyl, n-butyl, sec-butyl, tert-butyl, 1-pentyl, 3-pentyl, 1-hexyl, 1-heptyl, 3-heptyl, l-octyl,2,4,4-trimethylphenyl, tert-octyl, nonyl, decyl, tridecyl, pentadecyl, heptadec-8-en-1-yl, n-octadecyl, allyl, methallyl, 2-hexenyl, 1-methylcyclopentyl, cyclohexyl, cyclohexylpropyl, phenyl, m-tolyl, p-ethylphenyl, tert-butylphenyl, benzyl, phenylpropyl and nonylbenzyl.

Alkoxyalkyl may be ethoxymethyl, n-butoxymethyl, 2-methoxyethyl, 2-methoxyphenyl or 2~ 3~

4-n-octoxyphenylbenzyl Alkylenedioxyalkyl or -phenyl may be, for example, 3-(ethylenedioxypropyl) or 3,4-methylenedioxyphenyl~.

Analogously, for example, all 1,3-diketones mentioned below which are not covered by the above list may also be employed in their zinc chelate form as the organic zinc compound.

The polymer compositions may contain, as component d), inorganic Ca/Zn and/or Ba/~Zn compounds from the series comprising carbonates, chlorides, sulfates, oxides, hydroxides, basic oxides and mixed oxides. Preference is given to calcium/zinc compounds.

In addition, organic Ca/Zn or BatZn compounds may be used as component d), for example those from the series comprising the aliphatic Cl-C22carboxylates, olefinic C2-C22carboxylates, aliphatic C2-C22carboxylates which are substituted by at least one OH
group, cyclic and bicyclic carboxylates having 5-22 carbon atoms, aromatic C6-C22carboxylates, aromatic C6-C22carboxylates which are substituted by at least one OH group, Cl-CI6alkyl-substituted phenylcarboxylates, phenyl-CI-C16aLtcylcarboxylates, C6-CI8phenolates, Cs-C26chelates of 1,3-diketones or ~-ketocarboxylates, dehydroacetic acid and derivatives thereof, mercaptides based on mercaptocarboxylates, glycinates, phosphates, phosphites, phosphonites, phosphonates, partial esters of phosphonates, sulfonates and sulfinates. -Componellt d) in the composition according to the invention is particularly preferably a ~n, Ca/Zn or Ba/Zn cnrboxylnte. The cnrboxylates are preferably salts of carboxylic acids hnvillg frorn 7 to 20 cnrbon atoms, eg. benzoatcs, alkanoates or alkenoates, preferably stenrates, olcates, lnurates, palmitates, hydroxystearates or 2-ethylhexanoates. Pal~icular prefcrence is given to octanoates, stearates, caprylates, oleates and p-tert-butylbenzoates.

~ixtures of Ba/Zn or Ga/Zn carboxylates are particularly preferred as component d), the C.llZn carboxylates being very particularly preferred.

Zinc octanoate or zinc caprylate is likewise particularly preferred as component d).

A Ca/Zn or Ba/Zn phenolate component d) is, in particular, a C7-C20alkylphenola~e, for example nonyl phenolate.
, . , . -, . . ~ .
:. ' . . , .

3 ~

The present compositions may also contain further stabilizers or stabilizer mixtures whichimprove the processing or service properties of such compositions and the articles produced therefrom.

Stabilizers of this type include Mg, Al, Mg/Al and Mg/Zn compounds, the individual compounds mentioned for inorganic and organic zinc compounds being suitable. In each of these, the zinc may be replaced by Mg, Al, Mg/A1 or Mg/Zn.

Further stabilizers which may be used in sorne cases are compounds which are known per se, such as 1,3-diketones.

The 1,3-diketones may have the general formula II

Ra-e-CHRb ~ RC ~ :
where Rn iS alkyl having from 1 to 22 carbon atoms, Cs-Cl0alkoxyalkyl, alkenyl having from 2 to 22 carbon atoms, phenyl, phenyl which is substituted by from 1 to 3 groups from the series comprising -OH, Cl-C4alkyl, Cl-C4alkoxy or halogen, or is phenyl-CI-C4alkyl, a group of the formula f ~. cycloalkyl having from S to 12 ring carbon atoms, or mono- to tri-CI-C4alkyl-substituted cycloalkyl having from 5 to 12 ring carbon atoms;
Rc is alkyl having from 1 to 22 carbon atoms, Cs-CI0hydroxyalkyl, alkenyl having from 2 ~o 22 carbon atoms, phenyl, phenyl which is substituted by from 1 to 3 groups from the series comprising -O~l, Cl-C4alkyl, Cl-C4alkoxy or halogen, or is phenyl-CI-C4alkyl, a grollp of the formula 1 ~, cycloalkyl having from 5 to 12 ring carbon atoms, or mono- to tri-CI-C4alkyl-substituted cycloalkyl having from 5 to 12 ring carbon atoms, and Rb is -H, alkyl having from 1 to 18 carbon atoms, alkenyl having from 2 to 12 carbon atoms, phenyl, Cl-C4alkyl-substituted phenyl, phenyl-CI-C4alkyl, or a group of the formula p~d .
.,., , : . , -., . :

where Rd is -CH3, -C2Hs or phenyl, or in which Ra and Rb together are a tetramethylene radical or a tetramethylene radical which is fused to a benzo radical, or Ra and Rc together are a trimethylene radical or a mono- to tri-CI-C4alkyl-substituted trimethylene radical, or Ra and Rc together are a ~rirnethylene radical, and form a compound of the formula Ila [ 3~x (lla), where Rb is as defined above, and X is alkylene having from 1 to 4 carbon atoms.
Cl-C22Alkyl Ra and Rc may be, for example, methyl, ethyl, propyl, n-butyl, tert-butyl, ~ -pentyl, hexyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, octadecyl or eicosyl, and Cl-Cl8alkyl Rb may be, for example, as defined above with the exception of eicosyl.
~ .
Examples of Cs-Cl0hydroxylalkyl R~ and Rc are S-hydroxypentyl, 6-hydroxyethyl and 7-hydroxyheptyl.

Examples of C2-C22alkenyl Rn and Rc are vinyl, propenyl, allyl, butenyl, methallyl, hexenyl, decenyl nnd heptndccenyl. Corresponding examples of C2-CI2alkenyl Rb can be tnken annlo~ously from the nbovc list.

Phcnyl grollps, which are preferllbly substituted from one to three groups from the series comprising -OH, Cl-C4nlkyl, Cl-C4alkoxy or halogen, as mentioned for Rn and RC, may be 4-hydroxypllenyl- or 4-hydroxy-3,5-di-CI-C4alkylphenyl where Cl-C4alkyl is, for example, methyl or t-butyl, or methylphenyl, dimethylphenyl, ethylphenyl, n-butylphenyl, tert-butylphenyl, methyl-tert-butylphenyl, di-tert-butylphenyl, methoxy, ethoxyphenyl or monochlorophenyl.

Cl-C4Alkyl-substituted phenyl Rb is, for example, methylphenyl, ethylphenyl or tert-butylphenyl.

Phenyl-CI-C4alkyl Ra, Rb and Rc is, for example, benzyl or methylbenzyl.

' ' -3 ~

Ra and Rc may also be cycloalkyl having from S to 12 ring carbon atoms or mono- to tri-C1-C4alkyl-substituted cycloalkyl having from 5 to 12 ring carbon atoms. Examples of these are cyclopentyl, cyclohep~yl, cyclobutyl, cyclononyl, cyclododecyl, etc., and methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl and tert-butylcyclohe~yl.

Examples of 1,3-diketones are: dehydroacetic acid, dehydropropionylacetic acid, dehydrobenzoylacetic acid, cyclohexane-1,3-dione, dilttedone, 2,2'-methylenebiscyclohexane-1,3-dione, 2-benzylcyclohexane-1,3-dione, acetyltetralone, palrnitoyltetralone, stearoyltetralone, benzoyltetralone, 2-acetylcyclohexanone,2-benzoylcyclohexanone, 2-acetylcyclohexane-1,3-dione, benzoyl-p-chlorobenzoylmethane, bis(4-methylbenzoyl)methane, bis(2-hydroxybenzoyl)methane, benzoylacetone, t~ibenzoylmethane, diacetylbenzoylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane, lauroylbenzoylmethane, dibenzoylmethane, 4-methoxybenzoylbenzoylmethane, ;
bis(4-methoxybenzoyl)methane, bis(4-chlorobenzoyl)methane, bis(3,4-methylenedioxybenzoyl)methane, benzoylacetyloctylmethane, benzoylacetylphenylmethane, stearoyl-4-methoxybenzoylmethane, bis(4-t-butylbenzoyl)methane, butanoylacetone, heptanoylacetone, distearoylmethane, acetylacetone, stearoylacetone, palmitoylacetone, lauroylacetone, benzoylformylmethane, bellzoylphenylacetylntethnne, bis(cyclohexanoyl)methane and dipivaloylmethane.

I ,3-Diketo compounds which can be used as costabilizers are also those described in DE-B 2 600 516 and EP-A 35 268, for example those of the forrnula given in the patent clnim of DE-B 2 600 516. Other 1,3-diketo compounds are benzoylstearoylmethane, nlkyl(f;~r cxnmple ethyl) 2-benzoylacetoacetate and triacylmethanes.

Other 1,3-diketo compoun~s which cnn be used have the formula lIb Rl -~-cH2 ~-R2 (IIb), in which Rl is Cl-CI0atkyl, Cs-CI0hydroxyalkyl, phenyl, hydroxyphenyl, C7-CI0phenylalkyl or C7-CI0phenylalkyl which is substituted on the phenyl ring by an OH
group, and R2 is C~;-CIOhydroxyalkyl, hydroxyphenyl or C7-CIOphenylalkyl which is substituted on the phenyl ring by an OH group, with the proviso that R2 is not hydroxyphenyl if Rl is phenyl or hydroxyphenyl.

, -. . . .

2 ~ 3 ~

C1-CloAlkyl R1 is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl or n-decyl. C1-C4Alkyl, in particular methyl or tert-butyl, is preferred.

Examples of Cs-ClOalkoxyalkyl R1 and R2 are 5-hydroxypenytyl, 1,1-dimethyl-3-hydroxypropyl, 6-hydroxyhexyl, 8-hydroxyoctyl and 10-hydroxydecyl.
S-Hydroxypentyl, 6-hydroxyhexyl and 7-hydroxyheptyl are preferred. The hydroxyaLIcyl group is preferably not in the -position. R2 is, in particular, a group of the forrnula -(CH2)n-OH in which n is an integer from 5 to 7. 5-Hydroxypentyl R2 is of particular interest. ~ ~ -If R1 and R2 are hydroxyphenyl, the OH group may be in the ortho-, me~a- or para-position. o-Hydroxyphenyl is preferred.

Examples of C7-ClOphenylalkyl Rl are benzyl and 2-phenylethyl.

R1 and R2 as C7-Cl0phenylalkyl which is substituted on the phenyl ring by an OH group are, for example, (2-hydroxyphenyl)methyl, (3-hydroxyphenyl)methyl, t4-hYdroxyphenyl)methyl~ 2-(2-hydroxyphenyl)ethyl and 2-(4-hydroxyphenyl)ethyl.

Within this group of stabilizcrs, preferred compounds are those of the above forrnula IIb in which R1 is Cl-Cl0alkyl, Cs-CI0hydroxyalkyl, phenyl, hydroxyphenyl, C7-C10phenylalkyl or C7-C10phenylalkyl which is substitllted on the phenyl ring by an OH group, and R2 is Cs-ClOhydroxyalkyl, hydroxyphcnyl or C7-ClOphenylalkyl which is substituted on the phcnyl ring by an OH group, with the proviso that R2 is not hydroxyphenyl if Rl is phenyl or hydroxyphenyl.

P~urticularly preferred compounds of the above forrnula IIb are those in which Rl is Cl-CIOalkyl, Cs-CI0hydroxyalkyl or phenyl, and R2 is C5-C10hydroxyalkyl or hydroxyphenyl, and very particularly preferred compounds of the forrnula IIb are those in which Rl is C1-C4alkyl or phenyl, and R2 is Cs-C10hydroxyalkyl or hydroxyphenyl,furtherrnore those in which R2 is a -(CH2)n-OH group where n is an integer from S to 7.

Further examples of particularly preferred compounds of the above formula IIb are those in which R1 is rnethyl, butyl or phenyl, and R2 is ~-hydroxypentyl, 6-hydroxyhexyl, , ` . , - . .

2~3;~3~

7-hydroxyheptyl or ortho-hydroxyphenyl.

Preferred compounds of the formula IIb which should be mentioned by name are stearoylbenzoylmethane, dibenzoylmethane, l-phenyl-8-hydroxyoctane-1,3-dione, 1-t-butyl-8-hydroxyoctane-1,3-dione, 1-methyl-8-hydroxyoctane-1,3-dione and 1-(o-hydroxyphenyl)butane-1,3-dione.

Other suitable compounds have the formula IIc R~ H'&-R2-S-R3 (IIc) in which R1' and R3', independently of one another, are Cl-C12alkyl, phenyl, mono- to tri-CI-Cl2alkyl-substituted phenyl, C7-CI0phenylalkyl or mono- to tri-Cl-CI2aLlcyl-substituted C7-CI0phenylalkyl, and Rl' is additionally -R2'-S-R3', R2' is Cl-CIOalkylene, and R4' is hydrogen, C2-CsaL~coxycarbonyl or C2-CsaL~canoyl. Further ~ ;
details on these compounds, and examples and preferences are given in EP 307 358.

Expedient compositions are those as described above which contain, based on 100 parts by weight of thc composition, from 0.0001 to 8 parts by weight of blowing agent or foaming ngent, from 0.01 to 3.0 pnrts by wcight of sterically hindered amines, and from 0.01 to 8 parts by wcight of a zinc, Ca/Zn or Ba/Zn compound.

Prcfcrred rangcs for the amaunt of blowing agent or foaming agent are from 0.01 to S
parts by weight, particularly preferably from 0.1 to 3 parts by weight, very particularly preferably from 0.1 to 2 parts by weight, in each case based on 100 parts by weight of the composition.

Preferred ranges for the amaunt of sterically hindered amines in the composition are from 0.05 to 1.0 parts by weight, based on 100 parts by weight of the composition. An arnount of from 0.1 to 0.5 part by wcight is particularly preferred.

Preferred ranges for the amount of the zinc, Ca/Zn or Ba/Zn compound in the composition are from 0.05 to 3 parts by weight, particularly preferably from 0.1 to l.S parts by weight, .

.

. ~ ,. ~ : . . .

.. . . . ~ ~. -. ~ ' . ..

2~33 ~

in particular from 0.5 to 1.0 part by weight, in each case based on 100 parts by weight of the composition.

Preferred ranges for the amount of so-called kickers in the composition are from 0.01 to 5 parts by weight, particularly preferably from 0.05 to 3 parts by weight, based on 100 parts by weight of the composition.

If the composition also contains a 1,3-&etone, it preferably does so in an amount of from 0.05 to 5 parts by weight, in particular from 0.1 to 1 part by weight based on 100 parts by weight of the composition.

The chlorine-containing polymer may contain a plasticizer.

Suitable plasticizers may come, for example, from the following groups:
A) Phthalates (phthalic acid esters) Examples of plasticizers of this type are dimethyl, diethyl, dibutyl, dihexyl, di-2-ethylhexyl, di-n-octyl, diisoortyl, diisononyl, diisodecyl, diisotridecyl, dicyclohexyl, dimethylcyclohexyl, dimethyl glycol, dibutyl glycol, benzylbutyl and diphenyl phthalate, and mixtures of phthalates such as C7-Cg- and C9-Cllalkyl phthnlates comprising prcdominantly linear alcohols, C6-C1O-n-alkyl phthalates and C8-C1O-n-alkyl phthalates. Of these, preference is given to dibutyl, dihexyl, di-2-ethylhexyl, di-n-octyl, diisooctyl, diisononyl, diisodecyl, diisotridecyl and benzyl butyl phthalate, and said mixtures of alkyl phthalates. Particular preference is given to di-2-cthylhcxyl phtllalate (I)OP).

U) Estcrs of aliphatic dicarboxylic acids, in pMticular esters of adipic, azelaic and sebacic acid.
Examples of plasticizers of this type are di-2-ethylhexyl adipate, diisooctyl adipate (mixture), diisononyl adipate (mixtllre), diisodecyl adipate (mixture), benzyl butyl adipate, benzyl octyl adipate, di-2-ethylhexyl azelate, di-2-ethylhexyl sebacate and diisodecyl sebacate (mixture). Preference is given to di-2-ethylhexyl adipate and diisooctyl adipate.

C) Trimellitic acid esters, for example tri-2-ethylhexyl trimellitate, triisodecyl trimellitate (mixture), triisotridecyl trimellitate, triisooctyl trimellitate (mixture) and tri-C6-C8alkyl, tri-C6-ClOalkyl, tri-C7-Cgalkyl and tri-Cg-Cllalkyl trimellitates. The last-mentioned trimellitates are produced by esterifying trimellitic acid with the corresponding alkanol - ' 2 ~ 3 ~L ~ 3 ~

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

D) Pol~mer plasticizers A definition of these plasticizers and examples thereof are given in "Plastics Additives Handbook", editors H. Gachter and H. Muller, Hanser Publishers, 1985, page 284, chapter 5.7.10, and in "PVC Technology", editor W.V. Titow, 4th Ed., Elsevier Publ., 1984, pages 165-170. The most common starting materials for the preparation of polyester plasticizers are: dicarboxylic acids, such as adipic, phthalic azelaic and sebacic acid; 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 C7-CgaL~canol and Cg-C1laLtcanol mixtures.
Pa~ticularly advantageous polyester plasticizers are those made from said dicarboxylic acids and monofunctional alcohols.

E) Phosphoric acid esters A definition of these esters is given in the abovementioned "Plastics Additives Handbook"
on page 271, chapter 5.7.2. Examples of such phosphoric acid esters are tributylphosphate, tri-2-ethylbutyl phosphate, ~i-2-ethylhexyl phosphate, trichloroethylphospllate, 2-ethylhexyldiphenyl phosphate, cresyldiphenyl phosphate, triphenyl phosphate, tricresyl phosphate and trixylenyl phosphate. Preference is given to tri-2-ethylhexyl phosphnte.

F) Chlorinatcd hydroc,lrbons (paraffins) G) Hydrocnrbons H) Monoesters, for example butyl oleate, phenoxyethyl oleate, tetrahydrofurfuryl oleate and alkylsulfonic acid esters.

I) Glycol esters, for example diglycol benzoates.

Definitions and examples of group F) to I) plasticizers are given in the following handbooks:

~, . . . .
~: .
. . :
:' . ~": . , ~:~

~03~ ~3~

"Plastics Additives H~mdbook", editors H. Gachter and H. Muller, Hanser Publishers, 1985, page 284, chapter 5.7.11 (group F)) and chapter 5.7.13 (group G)).

"PVC Technology", editor W.V. Titow, 4th Ed., Elsevier Publishers, 1984, pages 171-173, chapter 6.10.2 (group P)), page 174, chapter 6.10.5 (group G)), page 173, chapter 6.10.3 (group H)) and pages 173-174, chapter 6.10.4 (group I)).

Particularly preferred plasticizers are those from groups A) to E), in particular A) to C), in particular those emphasized as being preferred in these groups. Di-2-ethylhexyl phthalate (DOP) is particularly favourable.

The plasticizers may be used in an amount of, for example, from 15 to 100 parts by weight, expediently from 15 to 70 parts by weight, in particular from 20 to 50 parts by weight, based on 100 parts by weight of the chlorine-containing polymer.

The compositions according to the invention may also conta;n further stabilizers which are customary for chlorine-containing thermoplastics, for example organic phosphites. Such phosphites may be present, for example, in an amount of from 0.01 to 3 parts by weight, in particular from 0.01 to 1.5 parts by weight, preferably from 0.1 to 0.6 part by weight.
Exnmples of phosphites of this type are, for example, those of the forrnulae Rl Q~ / ~ \
R2"~7P nnd R~ O-P~ _)CO~P_OR2"

in WiliCh Rl", R2" and R3" nre idcntical or different and are C6-C18alkyl and C6-Cl8alkcnyl, substituted or unsubstituted phenyl or Cs-C7cycloalkyl.

C6-Cl8Alkyl Rl", R2" and R3" are, for example, n-hexyl, n-octyl, n-nonyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl. Preference is given to alkyl groups having from 8 to 18 carbon atoms.

Substituted phenyl Rl", R2" and R3" are, for example, tolyl, ethylphenyl, xylyl, cumyl, cymyl, cresyl, 4-methoxyphenyl, 2,4-dimethoxyphenyl, ethoxyphenyl, butoxyphenyl,p-n-octylphenyl, p-n-nonylphenyl or p-n-dodecylphenyl.

.

2~3~3~

Particularly suitable phosphites are trioctyl, tridecyl, tridodecyl, tritetradecyl, tristearyl, trioleyl, triphenyl, tricresyl, tris-p-nonylphenyl and tricyclohexyl phosphite, particularly preferably ar,vldialkyl and alkyldiaryl phosphites7 for example phenyldidecyl, (2,4-di-tert-butylphenyl)didodecyl and (~,6-di-tert-butylphenyl)didodecyl phosphites and dialkyl- and diarylpentae.~thritol diphosphites, such as distearylpentaerythritol diphosphite.

Prefcrred organic phosphites are distearylpentaerythritol diphosphite, trisnonylphenyl phosphite and phenyldidecyl phosphite.

The compositions according to the invention may furthermore contain further known costabilizers. Examples of costabili7ers of this type which may be mentioned areaminocrotonic acid esters, 2,4-dihydroxybenzophenone, 2,4-dihydroxy-4'-tert-butylbenzophenone and pyrrole deAvatives. The amounts of such costabilizers may be, for example, 0.01 to 1.5 parts by weight, preferably from 0.1 to 1 part by weight, based on the composition.

Suitable aminocrotonic acid esters are, in particular, those with monohydric, straight-chain C8-C20, in particular Cl2-Cl8alcohols andlor with 1,3- or 1,4-butanediol and/or 1,2-dipropylene glycol and/or thiodiethylene glycol.

P;urticularly suitable pyrrolc costnbilizers are those described in EP-A 22 087 and GB-A
2,078,761. ~n exnmple which may be mentioned is 2-mcthyl-3-cyclohexyloxycnrbonyl-4-phenyl- lH-pyrrole.

'I'hc compositions according to the invention may furthermore contain further optional constitucnts, eg. organic antimony compounds, such as antimony tris[isooctylthioglycolate] .

Other stabilizers which can be used in the compositions according to the invention are polyols. The amounts to be used are, for example, up to 3 parts by weight, based on 100 parts by weight of the composition, expediently up to 2 parts by weight and preferably from 0.01 to 1 part by weight. Typical examples of polyols are pentaerythritol, dipentaerythritol, trimethylolpropane, ditrimethylolpropane, tris(2-hydroxyethyl) isocyanurate (THEIC), the latter being preferred, sorbitol, mannitol and inositol.

' ' , ': :
' .

2~3~3~

In addition to said stabilizers and costabilizers, it is also possible to use epoxy compounds, such as 1,2-epoxides and oxLranes, in amounts of, for example, up to 10 parts by weight, based on 100 parts by weight of the composition, expediently up to 5 parts by weight and preferably from 0.01 to 2 parts by weight. ~xamples of these are epoxidized polybutadienf~, epoxiclized soybean oil, epoxidized linseed oil, epoxidized fish oil, epoxidized tallow, methylbutyl or 2-ethylhexyl epoxystearate, tris(epoxypropyl) isocyanurate, epoxidized castor oil, epoxidized sunflower oil, 3-(2-xenoxy)-1,2-epoxypropane, bisphenol ~ polyglycidyl ether, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide and 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate.

The compositions according to the invention may furthermore contain conventionalantioxidants, light stabilizers and UV adsorbers. Examples of these are:

1. Antioxidants 1.1. Alkvlated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-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-i-butylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(a-methylcyclohexyl)-4?6-dimethylphenol?
2,6-dioctndccyl-4-methylphenol, 2,4,6-tricyclohexylphenol, ~,6-di-tcrt-butyl-4-methoxymethylphenol and 2,6-dinonyl-4-methylphenol.

1.2. Alkylate(l hvdroquinones, for example 2,6-di-tert-butyl-4-methoxyphenol, 2,S-di-tcrt-butylhydroqllinone, 2,5-di-tert-amylhydroquinone and 2,6-diphcnyl-4-octadecyloxyphenol.

1.3. ~IYdroxylatèd 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) and 4,4'-thiobis(6-tert-butyl-2-methylphenol).

1.4. Alkvlidenebisphenols, for example 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(a-methylcyclohexyl)phenol], 2,2 '-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4-methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), .
:

2 ~ 3 ~

2,2'-ethylidenebis(4,6-di-tert-butylphenol), 2,2 '-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-(~-methylbenzyl)-4-nonylphenol], 2~2~-methylenebis[6-(a~-dimethylbenzyl)-4-nonylyhenol]~
4,4'-methylenebis(2,6-di-tert-butylphenol~, 4,4 '-methylenebis(6-tert-butyl-2-methylphenol), 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-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)bicyclopentadiene and bis[2-(3 ' -tert-butyl-2 '-hydroxy-5 '-methylbenzyl)-6-tert-butyl-4-methylphenyl]
terephthalate.

1.5 Benzyl compounds, for example 1 ,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, 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, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, the calcium salt of monoethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, and 1,3,S-tris(3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

1.6 ~cYlaminophenols, for cxample 4-hydroxylauranilide, 4-hydroxystearanilide, 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-s-triazine and octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamale.

1.7. Esters of ~-(3.5-di-tert-butYI-4-hYdroxYphenYl)propionic acid with monohydric or polyhydric alcohols, eg. with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate or N,N'-bis(hydroxyethyl)oxalamide.

1.8. Esters of ~-(S-tert-butYI-4-hYdroxY-3-methYlphenvl)propionic acid with monohydric .
.: .. . . . .

20~ ~3~

or polyhydric alcohols, e~. with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxy)ethyl isocyamlrate or N,N'-bis(hydroxyethyl)oxalamide.

1.9. Esters of ~-(3,5-dicyclohexYI-4-hYdroxYphenYl)yropionic acid with monohydric or polyhydric alcohols, eg. with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxy)ethyl isocyanurate or N,N'-bis(hydroxyethyl)oxalamide.

1.10. Amides of ~-(3,5-di-tert-butyl-4-hvdroxYphenvl)propionic acid, forexample N,N '-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine and N,N '-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine.

2. UV absorbers and light screens 2.1. 2-(2'-Hvdroxyphenyl)benzotriazoles, for example the 5'-methyl, 3',5'-di-tert-butyl, S'-tert-butyl, 5'-(1,1,3,3-tetramethylbutyl), S-chloro-3',5'-di-tert-butyl, S-chloro-3'-tert-butyl-S'-methyl, 3'-sec-butyl-S'-tert-butyl, 4'-octoxy, 3',5'-di-tert-amyl and 3',5'-bis(~,a-dimethylbenzyl) derivatives.

2.2. 2-~1YdroxYbenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octoxy, 4-dccyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.

2.3. Esters of substituted or llnsubstitllted benzoic acids, for example 4-tert-butylphenyl snlicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate and hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrvlates, for example ethyl and isooctyl a-cyano-~,p-diphenylacrylate, methyl a-carbomethoxycinnamate, methyl and butyl a-cyano-p-methyl-p-methoxycinnamate~
methyl a-carbomethoxy-p-methoxycinnamate and N-(p-carbomethoxy-p-cyanovinyl)-2-methylindoline.

2.5. Nickel compounds, for example nickel complexes of . -, .
: ;:.

2~3~3~

2,2'-~hiobis[4-(1,1,3,3-tetramcthylbutyl)phenol], such as the 1:1 or 1:2 complex, if desired with additional ligands, such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of monoalkyl 4-hydroxy-3,5-di-tert-butylbenzylphosphonates, such as of the methyl or ethyl esters, nickel complexes of ketoximes, such as of 2-hydroxy-4-methylphenylundecylketoxime, and nickel complexes of 1-phenyl-4-lauroyl-S-hydroxypyrazole7 if desired with additional ligands.

2.6. Oxalamides, for example 4,4'-dioctyloxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyloxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butyloxanilide, 2-ethoxy-2'-ethyloxanilide, N,N-bis(3-dimethylaminopropyl)oxalamide.
2-ethoxy-5-tert-butyl-2'-ethyloxanilide and rnixtures thereof with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide, and rnixtures of o- and p-methoxy- and of o-and p-ethoxy-di-substituted oxanilides.

2.7. 2-(2-Hydroxvphenyl)-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)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propoxyphenyl)-6-(2,4-dimethylphenyl)- 1 ,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)- 1 ,3,5-triazine and 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

Depending on the intended use, the compositions according to the invention may also contain other customary additives, for example fillcrs and rcinforcing agents, eg. calcium carbonate, silicates, glass ~lbres, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black and graphite;

lubricants, pigments, flameproofing agents, antistatics, processing aids, impact modifiers (polyacrylates) or biocides.

The compositions may also contain a compound from the series comprising the hydrotalcites, in particular compounds having the general formula I

M2~ -M3+x-(OH)2-(An-)xln-mH2o (I), :
, : . : . : , . . .
., 3 ~

where M2+ is Mg" Ca, Sr, Ba, Zn, Cd, Pb, Sn and~or Ni, M3+ is Al, B or Bi, An is an n-valent anion, n is a number from 1 to 4, x is a number from O to û.5, m is a number from O to 2, and COO~
A is OH-, Cl-, Br~, I-, C104-, HC03-, (:H3COO-, C6EI5COO-, co32--, S042-, COO~
(CHOHCO0)22-,(CHOH)4CH20HCOO-.C2H4(coo)22-~(CH2C00)22--CH3CHOHCOO-, SiO32-, sio44-, Fe(CN)~;3~, Fe(CN)64- or HPo42-.

Other hydrotalcites which can be employed are compounds having the general formula Ia M2+xAI2(0H)2X+6nz(An-)2 mH20 (la) where M2 ~ is at least one metal from the series comprising Mg and Zn, preferably Mg, An-is an anion, for example from the series comprising co32-, ( l 0~ , OH- and S2-, where CO
n is the valency of the anion, m is a positive number, preferably from 0.5 to 5, and x and z are positive numbers, where x is preferably from 2 to 6 and z is less than 2.

Prefcrred polymer compositions are those as described above which contain at least one cornpound from tlle series comprising the hydrotalcites, of the general formula Ib M2~l~X Alx (OH)2 tAn~)xl2 H~O~ (Ib), wherc M2 ~ is Mg or a solid solution of Mg and Zn, An- is co32-, x is a number from O to 0.5 and rn is a number from O to 2.

Examples of hydrotalcites of this type are the compounds of the formulae 4MgO Al203 CO2 9H20~

4MgO Al203 C02 6H20.

ZnO 3MgO Al203 CO2-8-9H20 or . ' ' ' . . ' .

' ~,~3~ ~3~

ZnO 3MgO Al2O3 CO2 5-6H2O.

Expedient ranges for the amounts of hydrotalcite as mentioned above are from 0.1 to 3 parts by weight, preferably from 0.3 to 2 parts by weight, in particular from 0.4 to I part by weight, in each case based on 100 parts by weight of the composition.

The present invention also relates to foarned articles obtainable by expanding acomposition according to the invention, as described above.

The articles may be, ~or example, amongst many further applications, tubes or profiles, such as door frames, shutter boxes, window sills and furniture parts, sealing profiles, furtherrnore shoe soles, buffers, shock absorbers, mats, webs, furs, blocks, carpeting, foamed leathercloth, wall and floor coverings, cushioning materials and the like.

Examples of foamed articles which can be obtained according to the invendon are a) a closed-cell soft PVC foam hnving a density d of from 0.05 to 1.0 glem3, which ean be used as a highly elastic material in gymnastie mats, as an impact-protecting insert in helmets, for absorbing machine vibrations and as a wall and floor covering, b) an open cell soft PVC foam having a density d of from 0.07 to 0.33 g/cm3, which can be used as n materi;ll in soundproofing technology and for breathable cushioning, e) a hard PVC
struetllral foam having a density d of from 0.5 to 1.0 g/cm3, which ean be used as a light ~hermoforrnable interior or exterior construetion material, or d) a elosed-cell hard PVC
foam hnving a density d of from 0.04 to 0.13 g/em3, which ean be used as a sandwich core material, for net floats and life rafts or for low-temperature eontainers for liquid gases.

Example 1:

The following mixture is prepared for a hard foam:

Parts by weight~
Suspension PVC having a K value of ~8 100 PYC proeessing aid based on polymethyl methaerylate 8 Chalk 2 Titanium dioxide pigment 2 . . .

. ~ . ;
.. , -. .
. .
. . ~ . , .. . . .
~ - ~ , . . .

2 ~ l 3 ~

Diisodecylphenyl phosphite 0.5 Epoxidized soybean oil 0.8 Polyethylene wax (external lubricant) 0.3 Glycerol monooleate (internal lubricant) 1.0 Azodicarbonamide (chemical blowing agent for foaming 0.5 ~alcium stearate 0.8 Zinc stearate 2.0 Sterically hindered amine (Example 84 froM the description) 0.4 The mixture is subjected to the Brabender test, at a test temperature of 175C and a speed of 35 rpm. The yellowness index (YI) is determined on the sheeted-out compound as a function of time.

Table Time . 5' 10' 15' 20' YI 16.6 23.1 40.1 65.1 Example 2:
The following mixture was prepared for a sof~ foam:

Parts by weight:
Fincly divided emulsion homopolymer having n K value of 67 100 9,11-Phthalate plasticizer B0 Potassium 2-ethylhexanoate 0.35 Basic zinc 2-ethylhexanoate 0.9 Aromatic hydrocarbons (solvent) 0.5 Tripropylene glycol monomethyl ether 0.25 Sterically hindered amine (Example 84 from the description) 0.1 Azodicarbonamide (chemical blowing agent for foaming) 4 The mixture was subjected to the following test methods:

~3~3~

I'he Mathis test, in which the mixture is cast onto a substrate and gelled at 160C for 30 seconds. The sheeted-out compound produced is heat-treated at 200C, a fully expanded material having a good foam structure being obtained after 60 seconds.

In another test using the Mathis ThermoSakter, ~he gelled mixture is loaded statically at 190C, the foam material produced exhibiting a clear colour change to brown after heating for 28 minutes.

Example 3: A mixture is prepared as in Example 2, the 0.1 part by weight being replaced by 0.3 part by weight of sterically hindered amine. In the same test method, a fully expanded material having a good foam structure is obtained after 60 seconds, and the clear colour change to brown on heating takes place after 32 minutes.

.
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: ~ ' ' ' '. , ' - . .

Claims (12)

1. A composition containing a) at least one chlorine-containing polymer, b) at least one blowing agent or foaming agent, c) at least one sterically hindered amine, and d) at least one zinc, calcium/zinc and/or barium/zinc compound.

2. A composition according to claim 1, containing, as b), azodicarbonamide.

3. A composition according to claim 1, containing, as c), at least one compound which contains at least one group of the formula III

(III) in which R is hydrogen or methyl.

4. A composition according to claim 1, containing, as c), at least one oligomeric or polymeric compound whose recurring structural unit contains a 2,2,6,6-tetraalkylpiperidine radical of the formula III, in particular a polyester, polyether, polynmido, polyamine, polyaminotriazine, poly(meth)acrylate, poly(meth)acrylamide or copolymer thereof which contnins a radical of this type.

5. A composition according to claim 1, containing, as c), at least one compound of the formula below, where m is a number from 2 to about 200:
, , , , , , , , , , , , or .

6. A composition according to claim 1, containing, as c), a sterically hindered amine of the formula , where m is n number from 2 to about 200.

7. A composition according to claim 1, containing, as an additional component, at least one alkali metal compound as kicker.

8. A composition according to claim 7, containing potassium 2-ethylhexanoate.

9. A composition according to claim 1, containing, as an additional component, a1,3-diketone.

10. A composition according to claim 1, containing, as an additional component, an organic phosphite.

11. A composition according to claim 1, containing, as an additional component, an epoxy compound.

12. A foamed article obtainable by expanding a composition according to claim 1.