CA2026899A1 - Stabilized chlorine-containing polymer compositions - Google Patents

Abstract

A-17782/=/CGM 353 Stabilized chlorine-containing polymer compositions Abstract of the disclosure Stabilized chlorine-containing polymer compositions, containing a chlorine-containing polymer and a stabilizer mixture, containing:
a) at least one cyclic or acyclic sterically hindered amine, b) at least one organic zinc compound and/or inorganic zinc compound from the series comprising carbonates, chlorides, sulfates, oxides, hydroxides, basic oxides and mixed oxides, and c) at least one compound from the series of hydrotalcites and, if desired, d) at least one 1,3-diketone and/or e) at least one organic or inorganic calcium compound.

Polymer compositions of this type are preferably used for slush mould and crash pad applications.

Description

~-17782/=/CGM 353 Stabilized chlorine-containin~ polymer compositions The invention relates to novel chlorine-containing polymer compositions and the use of the polymer compositions.

For example, it is known from JP-A 63/175,072 to stabilize plasticized polyvinyl chloride films for agricultural purposes by means of a sterically hindered amine and a hydrotalcite against the effect of pesticides.

In JP-A 63/178,155, rigid PVC mixtures are disclosed which are stabilized by means of a metal-containing stabilizer, an epoxy compound which is solid at norrnal tempelature, and a hindered piperidine compound.

In EP-A 0,237,485, stabilized rigid PVC compositions are disclosed which contain at least one 2,2,6,~tetraalkylpiperidine light stabilizer and at least one organotin stabilizer.

In EP-A 0,063,180, a stabilizer composition for halogen-containing polymers is disclosed which consists of ,~-diketones and a hydrotalcite.

The known stabilizers and stabilizer mixtures are incapable of meeting in the polymers all the demands made on them.

It has now been found that the chlorine-containing polymer compositions stabiliæd according to the presen~ invention have ~urther improved properties with respect to heat and light stability.
. .
According to the invention, this is achieved by a polymer composition with or without plasticizer, containing a chlorine-containing polymer and a stabilizer mixture, containing:
.
a) at least one cyclic or acyclic sterically hindered amine, with the exception of the compound of the formula fH2-COOR H3C CH3 CH~OOR /~
, whereRis ( NH
CH-COOR

in plasticizer-containing polymer compositions, b) at least one organic zinc compound and/or inorganic zinc compound from the series comprising carbonates, chlorides, sulfates, oxides, hydroxides, basic oxides and mixed oxides, and c) at least one compound from the series of hydrotalcites.
The polymer compositions according to the invention can contain further components.

Thus, the polymer composition can contain, as further stabilizer, d) at least one 1,3-diketone.

The polymer composition can contain, as further stabilizer, e) at least one organic or inorganic ealcium compound.

Accordingly, for example, polymer compositions, as described above, which contain one or both of components d) and e) in the stabilizer mixture are also within the scope of the present invention~ Accordingly, polymer eompositions whieh contain, in the stabilizer mixture, components a), b) and e) or, for example, a), b), e) and d) or a), b), e) and e) or a), b), e), d) and e) are ineluded in the present invention.

Polymer eompositions, as deseribed above, eontaining, in the stabiliær mixture as a), at least one cyelie sterically hindered amine, in particular a compound from the series of derivatives of polyalkylpiperidines containing at least one group of the ~ormula lII
~' - ,, - . . - .
: ~ ',' ,' :
.
- , ., ,, , ., ~, :

2~2~

N~)< (III) in which R is hydrogen or methyl are advantageous; preferably, the polyalkylpiperidine groups of the formula III are substituted in the 4 position by one or two polar substituents or a polar spiro ring system.

Polymer compositions, as described above, containing as b) at least one organic ~inc compound from the series ~f aliphatic saturated C2-C22 carboxylates, aliphatic olefinic C3-C22 carboxylates, aliphatic C2-C~2 carboxylates, which are substituted by at least one OH group, cyclic and bicyclic carboxylates having 5-22 C atoms, aromatic C7-C22 c~rboxylates, aromatic C7-C22 carboxylates which are substituted by at least vne OH
~roup, Cl-Cl6alkyl-substituted phenylcarboxylates, phenyl-Cl-Cl6alkyl carboxylates, C6-Cl8 phenolates, Cs-C26 chelates of 1,3-diketones or ~-ketocarboxylic esters or dehydroacetic acid derivatives and mercaptides based on mercaptocarboxylic esters and glycinates are advantageous.

Polymer compositions, as described above, which contàin as c) at least one compound ~m the series of hydrotalcites of the general formula I

M2+ 1~ M3+X-(oH)2-(An ~X umH20 (I~
/n in which 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 1-4, x is a number from ~0.5, m is a number from 0-2, and A is OH-, Cl-, Br^, I-, C104-, HCO3-, CH3~00-, ( ~6H5COO-~ Co32-~ So42-~

..
, . ~

.

g ~ ~ ~

coo -coo -, (CHOHCO0)22-, (CHOH)4CH20HCOO-, C2H4(coo)22-~ (C~2c0o)22-~CH3CHOHCOO-, SiO32-, sio44-, Fe(CN)63-, Fe(CN)64~ or HPo42-, are advantageous.

Other hydrotalcites which can advantageously be used in polymer compositions, such as described above, are compounds having the general formula Ia M2x+AI2(oH)2~6~(An-)2omH2o (Ia) in which in the present formula Ia M2+ is at least one metal from the series comprising Mg and Zn and Mg is preferred, An- is an anion, for exarnple from dle series comprising ~ ~2-co32-, ( I ~, OH- and S2-, n being ~he valence of the anion, m a positive number, ~ coo,~
preferably from 05 to 5, and x and z are positive numbers, x being preferably 2 to 6 and being less than 2.

Polymer compositions, as described above, which contain as d) at least one 1,3-diketone of the general formula II or IIa o o R a _ C--CHRb C--R (II), ¦ I~X (lla) in which Ra is aL~cyl of 1 to 22 C atoms, Cs-ClOhydroxyalkyl, aL~cenyl of 2 to 22 C atoms, phenyl, phenyl substituted by 1 to 3 groups from the series comprising -OH, Cl-C4alkyl, Cl- to C4alkoxy or halogen, phenyl-Cl-C4alkyl, a group of the forrnula 2~2~

cycloalkyl of S to 12 ring C atoms~ or cycloalkyl of 5 to 12 ring C atoms substituted by 1 to 3 Cl-C4alkyl groups, Rc is alkyl of 1 to 22 C atoms, Cs-CIOhydroxyaLlcyl, allcenyl of 2 to 22 C atoms, phenyl, phenyl substituted by 1 to 3 groups from the series comprising -OH, Cl-C4alkyl? Cl- to C4alkoxy or halogen, or phenyl-CI-C4a1~cyl, a group of the fonnula T~

cycloaL~cyl of ~ to 12 ring C atoms, or cycloalkyl of 5 to 12 ring C atoms substituted by 1 to 3 Cl- to C4alkyl groups, Rb is -H, alkyl of 1 to 18 C atoms, aLIcenyl of 2 to 12 C atoms, phenyl, phenyl substituted by Cl-C4alkyl, phenyl-Cl-C4alkyl, or a group of the formula --C--Rd ll in which Rd is -CH3, -C2Hs or phenyl, or in which R~ and Rb together are a tetramethylene radical or a tetramethylene radical fused with a benzo radical, or Ra and Rc together are a trimethylene radical or a ~rimethylene radical substituted by 1 to 3 Cl-C4alkyl groups, and X is aL~cylene of 14 C atoms, are advantageous.

Ra and Rc as aLIcyl of 1 to 22 C atoms can be, for example, methyl, ethyl, propyl, n-butyl, tert-butyl, pentyl, hexyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecylj ~idecyl, octadecyl or eicosyl, Rb as alkyl of 1 to 18 C atoms can be, for exarnple, above as defimed without elcosyl.

Exarnples of Ra and Rc as Cs-ClOhydroxyalkyl are 5-hydroxypentyl, 6-hydroxyhexyl or `

:
.

2 ~

7-hydroxyheptyl.

Examples of R8 and Rc as alkenyl of 2 to 22 C atoms are vinyl, propenyl, allyl, butenyl, methallyl, hexenyl, decenyl or hep~adecenyl. The corresponding examples of Rb as aLt~enyl of 2 to 12 C atoms can be seen from the above list by analogy.

The phenyl groups which are preferably substituted by one to three groups from the series comprising -OH, Cl-C4allcyl, Cl-C4aLIcoxy or halogen, as mentioned for Ra and RC, can be 4-hydroxyphenyl, 4-hydroxy-3,5-di-Cl-C4aL~cylphenyl, where Cl-C4aLlcyl is, for example, methyl or t-butyl, methylphenyl, dimethylphenyl, ethylphenyl, n-butylphenyl9 tert-butylphenyl, methyl-tert-butylphenyl, di-tert-butylphenyl, methoxy or ethoxyphenyl or monochlorophenyl.

Rb as phenyl substituted by Cl-C4alkyl comprises, for example, methylphenyl, ethylphenyl or tert-butylphenyl.

R'l, Rb and Rc as phenyl-Cl-C4alkyl are, for example, benzyl or methylben7yl.

Ra and Rc can also be cycloalkyl of ~ to 12 ring C atoms or cycloallcyl of S tO 12 ring C
atoms substituted by 1 to 3 Cl-C4aLkyl groups. Examples of these are cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclododecyl etc., and methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, tert-butylcyclohexyl.

Examples of 1,3-diketones are:
dehydroacedc acid, propionyldehydroacedc acid, aceticbenzoyldehydro acid 1,3-cyclohexanedione, dimedone, 2,2'-methylenebis(1,3-cyclohexanedione), 2-benzyl-1,3-cyclohexanedione, acetyltetralone, palmitoyltetralone, stearoyltetralone, benzoyltetralone, 2-acetylcyclohexanone, 2-benzoylcyclohexanone, 2-acetyl- 1 ,3-cyclohexanedione, benzoyl-p-chlorobenzoylmethane, bis-(4-methylbenzoyl)methane, bis-(2-hydroxybenzoyl)methane, benzoylacetone, tribenzoylmethane, diacetylbenzoylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane, lauroylbenzoylmethane, dibenzoylmethane, 4-methoxybenzoylbenzoyLrnethane, 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, benzoylphenylacetylmethane, bis-(cyclohexanoyl)methane or dipivaloylmethane.

1,3-Diketo compounds which can be used as costabilizers are in particular those described in DE-B 2,600,516 and EP-A 35,268, for example those of the forrnula given in the patent claim of DE-B 2,600,516. Preferred 1,3-diketo compounds are benzoylstearoylmethane, alkyl(for exarnple ethyl) ~-benzoylacetoacetate and triacylmethanes.

Particular preference is given tO 1,3-diketones of the formula IIb Rl C CH2--1I R2 (IIb) o o in which Rl is Cl-ClOalkyl, C5-ClOhydroxyaLl~yl, phenyl, hydroxyphenyl, CTCl0phenylalkyl or C7-ClOphenylalkyl substituted on the phenyl ring by an OH group and R2 is C~-ClOhydroxyalkyl, hydroxyphenyl or C7-Cl0phenylaL~cyl subs~ituted on the phenyl ring by an OH group, under the condition that R2 is other than hydroxyphenyl, if Rl is phenyl or hydroxyphenyl.

Rl as Cl-CI0alkyl is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, or n-decyl. Cl-C4ALkyl, in paIticular methyl and tert-butyl, is preferred.

Examples of Rl and R2 as Cs-Cl0hydroxyalkyl are 5-hydroxypentyl, 1,l^dimethyl-3-hydroxypropyl, 6-hydroxyhexyl, 8-hydroxyoctyl and 10-hydroxydecyl.
5-Hydroxypentyl, ~hydroxyhexyl and 7-hydroxyheptyl are preferred, The hydroxylalkyl group is preferably not in the a-pOSitiOn. R2 is in particular a group of the ~onnula -(CH2)r,-OH, in which n is an integer from S to 7~ R2 as 5-hydroxypentyl is of particular interest.

In the case where Rl and R2 are hydroxyphenyl, the OH group can be in the ortho, meta or para position. o-Hydroxyphenyl is preferred.

Examples of Rl as C7-Cl0phenylalkyl are benzyl and 2-phenylethyl.

, ~ . . .

2~26~

Rl and R2 as C7-CI0phenylaLlcyl which is substituted on the phenyl ring by an OH group are, for example, (2-hydroxyphenyl)methyl, (3-hydroxyphenyl)methyl, (4-hydroxyphenyl)methyl, 2-(2-hydroxyphenyl)ethyl and 2-(4-hydroxyphenyl)ethyl.

Within this group of stabilizers, preference is given to compounds of the above formula Ilb in which Rl is Cl-CIOalkyl, C5-CIOhydroxyalkyl, phenyl, hydroxyphenyl, C7-ClOphenylalkyl or C7-CIOphenylaL~yl substituted on the phenyl ling by an OH group, and R2 is Cs-CIOhydroxyalkyl, hydroxyphenyl or C7-Cl0phenylaL~cyl substituted on the ph~nyl ring by an OH group, under ~he condition that R2 is other than hydroxyphenyl, if Rl is phenyl or hydroxyphenyl.

Particular preference is given to compounds of the above formula IIb in which R1 is Cl-C1Oalkyl, C5-ClOhydroxyaLIcyl or phenyl and R2 is Cs-CIOhydroxyalkyl or hydroxyphenyl, very particular preference is given to those compounds in which Rl is Cl-C4alkyl or phenyl and R2 is Cs-C7hydroxyaLtcyl or hydroxyphenyl, furtherrnore in which R2 is a group -(CH2)n-OH, in which n is an integer from 5 to 7.

Further examples of particularly preferred compounds of the above formula IIb are those in which R1 is methyl, butyl or phenyl and R2 is 5-hydroxypentyl, 6-hydroxyhexyl, 7-hydroxyheptyl or ortho-hydroxyphenyl.

The names of the preferred compounds of the forrnula IIb are stearoylbenzoylmethar~e, dibenzoylmethane, 1 -phenyl-8-hydroxy- 1 ,3-octanedione, 1 -t-butyl-8-hydroxy- 1,3-octanedione, l-methyl-8-hydroxy- 1 ,3-octanedione and l-to-hydroxyphenyl)-1 ,3-butanedione.

Particular preference is also given to 1,3-diketo compounds of the formula IIc R4~
Rl--C--CH - C--R2_ S--R3' (IIc) O O
in which R1 and R3, independently of one another, are Cl-CI2alkyl, phenyl, Phenyl substituted by one to three Cl-Cl2aLlcyl groups, C7-ClOphenylalkyl or C7-C10phenylaLlcyl substituted by one to three Cl-Cl2alkyl groups, and Rl is additionally R2 -S-R3, R2 is Cl-CIOalkylene and R4 is hydrogen, C2-Csalkoxycarbonyl or C2-CsaLlcanoyl. Further .
.

~2~

details, examples and preferences can be seen from EP 307,358.

Polymer compositions which, as described above, contain as e) at least one calcium soap of the general forrnula Ca~OOCR~) 2 ~ in which Rx is an alkyl group of 1 to 22 C atoms, an alkenyl group of 2 to 22 C atoms, phenyl, phenyl-Cl-C4alkyl or Cl-C8alkylphenyl, are advantageous.

Examples of RX, for exarnple, as an alkyl group of 1 to 22 C atoms are methyl, ethyl, propyl, isopropyl, n-butyl, i-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, 2-ethylbutyl, l-methylpentyl, 1,3-dimethylbutyl, 1,1,3,3-tetramethylbutyl, l-methylhexyl, isoheptyl, l-methylheptyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylhexyl, l-methylundecyl, 3,5,5-trimethylhexyl, eicosyl, henicosyl and docosyl.

Rx as alkenyl of 2 to 22 C atoms can be, for example, allyl, 2-methallyl, 2-butenyl, tr~ns-2-butenyl, 2-hexenyl, trans-2,4-hexadienyl, decenyl, undecenyl, heptadecenyl, oleyl, cis-9-octadecenyl, trans-9-octadecenyl, cis,cis-9,12-octadecadienyl or cis ,cis,cis-9, 12,1 5-octadecatrienyl .

Examples of Rx as phenyl-Cl-C4allcyl are benzyl or methylbenzyl. Examples Of Rx as Cl-C8alkylphenyl are methylphenyl, ethylphenyl, propylphenyl, n-butylphenyl, ~rt-butylphenyl, octylphenyl, dimethylphenyl, methyl-tert-butylphenyl and di-tert-butylphenyl.

Polymer compositions which, as described above, contain as derivative of polyalkylpiperidines a derivative of 2,2,6,6-tetramethylpipendine are particularly advantageous.

In particular the following classes of polyaL~cylpiperidines carrying at least one group of the formula m, as mentioned above, are of importance:

(a) compounds of the formula IV

:' '' ' ' '' ~ .
'' : : ' . ' ~ '' . .. . .

- 10- .

RCH~R

L R 1l Nk~O~R (IV) RCH2 CH3 n in which n is a number *om 1 to 4, preferably 1 or 2, R is hydrogen or methyl, Rll is hydrogen, oxyl, hydroxyl, Cl-Cl2alkyl, C3-Cgalkenyl, C3-C8alkynyl. C7-Cl2aralkYl-Cl-CI8alkoxy, C5-C8cycloaL~coxy, C7-CgphenylaLlcoxy, Cl-C8aLIcanoyl, C3-CsaLkenoyl, Cl-Cl8alkanoyloxy, benzyloxy, glycidyl or a group -CH2CH(OH)-Z, in which Z is hydrogen, methyl or phenyl, in which Rll is preferably H, Cl-C4aL~yl, allyl, benzyl, acetyl or acryloyl and Rl2, if n is 1, is hydrogen, Cl-Cl8aLtcyl which may be interrupted by one or more oxygen atoms, cyanoethyl, benzyl, glycidyl, a monovalent radical of an aliphatic, cycloaliphatic, araliphatic, unsaturated or aromatic carboxylic acid, carbamic acid or a phosphorus-containing acid or a monovalent silyl radical, preferably a radical of an aliphatic carboxylic acid of 2 to 18 C atoms, a cycloaliphatic carboxylic acid of 7 to 15 C
atoms, an a,~-unsaturated carboxylic acid of 3 to 5 C atoms, or an aromatic carboxylic acid of 7 to 15 C atoms, if n is 2, Cl-Cl2aLlcylene, C4-Cl2allcenylene, xylylene, a divalent radical of an aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid, dicarbamic acid or a phosphorus-containing acid or a divalent silyl radical, preferably a radical of an aliphatic dicarboxylic acid of 2 to 36 C atoms, a cycloaliphatic or aromatic dicarboxylic acid of 8-14 C atoms or an aliphatic, cycloaliphatic or aromatic dicarbarnic acid of 8-14 C atoms, if n is 3, a ~ivalent radical of an aliphatic, cyloaliphatic or aromatic dicarboxylic acid, an aromatic tricarbamic acid or a phosphorus-containing acid or a trivalent silyl radical and, if n is 4, a tetravalent radical of an aliphatic, cycloaliphatic or aromadc tetracarboxylic acid, CH2-COOR (CH3)2 CH-COOR
, where R is --C NH
CH COOR \_<
CH2-COOR (CH3)2 being excluded.
:
:

:

. ~ . , .
: . . ~ .. , 2~2~

Compounds of the forrnula IV are of interest, with the proviso tha~, if n îs 2, radicals of aliphatic dicarboxylic acids of the formula -OOC-(CH2)8-COO- as Rl2 are excluded.
Compounds of the formula IV are also of interest, with the proviso that, if n is 2, radicals of aliphatic dicarboxylic acids of 8 to 12 C atoms as Rl2 are excluded.

Cl-CI2alkyl substituents, if present, 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.

Rll or Rl2 as Cl-CI8aLlcyl can be the abovementioned groups and in addition, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

Rll as C3-C8aLlcenyl, can be, for example, l-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl, 4-tert-butyl-2-butenyl.

Rll as C3-C8alkynyl is preferably propargyl.

Rll as C7^CI2aralkyl is in particular phenethyl and especially benzyl.

Rll as Cl-C8alkanoyl is, for example, ~ormyl, propionyl, butyryl, octanoyl, but preferably acetyl and as C3-Csalkenoyl in particular acryloyl.

Rl2 as a monovalent radical of a carboxylic acid is, for exarnple, an acetic acid, caproic acid, stearic acid, acrylic acid, methacrylic acid, benzoic acid or ~-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid radical.

Rl2 as a divalent radical of a dicarboxylic acid is, for example, a malonic acid, succinic acid, glutaric acid, adipic acid, subaric acid, sebacic acid, maleic acid, itaconic acid, phthalic acid, dibutylmalonic acid, dibenzylmalonic acid, butyl-(3,5-di-tert-butyl-4-hydroxybenzyl)malonic acid or bicycloheptenedicarboxylic acid radical.

Rl2 as a trivalent radical of a tricarboxylic acid is, for exarnple, a trimellitic acid, citric acid or nitrilotriacetic acid radical.

Rl2 as a tetravalent radical of a tetracarboxylic acid is, for example, the tetravalent radical , ~
, '~

- 2 ~ 9 ~

of butane-1,2,3,4-tetracarboxylic acid or of pyromellitic acid.

Rl2 as a divalent radical of a dicarbamic acid is, for example, a hexamethylenedicarbarnic acid or a 2,4-toluylenedicarbamic acid radical.

Preference is given to compounds of the formula IV in which R is hydrogen, Rll is hydrogen or methyl, n is 2 and R12 is the diacyl radical of an aliphatic dicarboxylic acid of 4-12 C atoms.

Exarnples of polyaLIcylpiperidine compounds of this class are the following compounds:

1) 4-hydroxy-2,2,6,6-tetramethylpiperidine 2) 1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine 3) 1-benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine 4) 1-(4-tert-butyl-2-butenyl)~-hydroxy-2,2,6,6-tetramethylpiperidine S) 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-pentamethylpiperidine 8) 1,2,2,6,6-pentamethylpiperidin-4-yl-~-(3,5-di-terlrbutyl-4-hydroxyphenyl) propionate 9) di-(1-benzyl-2,2,6,6-tetramethylpiperidin-4-yl)maleate 10) di-(2,2,6,6-tetramethylpiperidin-4-yl) succinate 11) 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-(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate 15) di-(1,2,3,6-tetramethyl-2,6-diethylpiperidin~-yl) sebacate 16) di-(1-allyl-2,2,6,6-tetramethylpiperidin-4-yl) phthalate 17) 1-hydroxy-4-~-cyanoethyloxy-2,2,6,6-tetramethylpiperidine 18) 1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl ace~ate 19) tri-(2,2,6,6-tetramethylpiperidin-4-yl) trimellitate 20) 1-acryloyl~-benzyloxy-2,2,6,~tetramethylpiperidine 21) di-(2,2,6,~tetramethylpiperidin-4-yl) diethylmalonate 22) di-(1,2,2,6,6-pentamethylpiperidin-4-yl) dibutylmalonate 23) di-(1,2,2,6,6-pentamethylpiperidin-4-yl) butyl-(3,5-d;-tert-butyl-4-hydroxybenzyl) malonate 24) di-(1-octyloxy-2,2,6,6-tetramethylpiperidin 4-yl) sebacate .
- ' ' ~ ' ~

- ~ :

2~2~

25) di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate 26) hexane-1',6'-bis-(4-carbamoyloxy-1-n-butyl-2,2,6,6-te~ramethylpiperidine) 27) toluene-2' ,4'-bis-(4-carbamoyloxy- 1 -n-propyl-2,2,6,6-tetramethylpiperidine) 28) dimethyl-bis-(2,2,6,6-tetramethylpiperidin-4-oxy)-silane 29) phenyl-tris-(2,2,6,6-tetramethylpiperidin-4-oxy)-silane 30) tris-(1-propyl-2,2,6,6-tetramethylpiperidin-4-yl)-phosphite 31) tris-(1-propyl-2,2,6,6-tetramethylpiperidin-4-yl) phosphate 3~) 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-tetrarnethylpiperidine 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) ~ I
R 1 l Nk~ N-- R l4 (V) RCH2 CH3 n in which n is the number 1 or 2, R and Rl I are as defined in (a), R13 iS hydrogen, Cl-C12alkyl, C2-C5hydroxyalkyl, Cs-C7cycloaLkyl, C7-C8aralkyl, C2-CI8aL~anoyl, C3-Csalkenoyl, benzoyl or a group of the formula RCH~R

Rll N ~--and, if n is 1, Rl4 is hydrogen, Cl-CI8alkyl, C3-C8aL~cenyl, Cs-C7cycloalkyl, hydroxyl-, cyano-, alkoxycarbonyl- or carbamido-substituted C1-4alkyl, glycidyl, a group of the formula -CH2-CH(OH)-Z or of the forrnula -CONH-Z, in which ~ is hydrogen, methyl or phenyl; if n is 2, Rl4 is C2-CI2allcylene, C6-CI2arylene, xylylene, a -CH2-CH(OH)-CH2 , group or a group -CH2-CH(OH)-CH2-0-D-O-, in which D is C2-ClOalkylene, C6-Clsarylene, C6-Cl2cycloaL~cylene, or provided Rl3 is not alkanoyl, aL~cenoyl or benzoyl, Rl4 can also be a divalent radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid or also the group -CO-, or Rl3 and Rl4 together, if n is 1, can be the divalent radical of an aliphatic, cycloaliphatic or aromatic 1,2- or 1,3-dicarboxylic acid.

Cl-CI2- or Cl-Cl8alkyl substituents, if present, are as already defined in (a).

C5-C7cycloalkyl substituents, if present, are in particular cyclohexyl.
Rl3 as C7-C8araLlcyl is in particular phenylethyl or especially benzyl. Rl3 as C2-C~hydroxyalkyl is in pa~icular 2-hydroxyethyl or 2-hydroxypropyl.

Rl3 as C2-Cl8 alkanoyl is, for example, propionyl, butyryl, o tanoyl, dodecanoyl, hexadecanoyl, octadecanoyl, or preferably acetyl and as C3-CsaL~cenoyl in particular acryloyl.

Rl4 as C2-C8alkenyl is, for exarnple, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl or 2-octenyl.

Rl4 as Cl-C4alkyl substituted by a hydroxyl, cyano, alkoxycarbonyl or carbamido group can be, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl, methoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2-aminocarbonylpropyl or 2-(dimethylaminocarbonyl)ethyl.

C2-Cl2alkylene substituents, if present, are, for example, ethylene, propylene, 2,2-dimethylpropylene, te~amethylene, hexamethylene, octarnethylene, decarnethylene or dodecamethylene.

C6-Clsarylene substituents, if present, are, for example, o-, m- or p-phenylene,1,4-naphthylene or 4,4'-diphenylene.

A particularly suitable C6-Cl2cycloalkylene is cyclohexylene.

Preference is given to compounds of the formula V in which n is 1 or 2, R is hydrogen, 2 ~

Rll is hydrogen or methyl, R13 iS hydrogen, Cl-Cl2alkyl or a group of the formula RCH2 CH3 ~
>~
Rll N ~--k' and Rl4, in the case where n is 1, is hydrogen or Cl-Cl2aLlcyl and, in the case where n is 2, C2-C8aLkylene.

Examples of polyaL~cylpipeIidine compounds of this class are the ~ollowing compounds:

37) N,N'-bis-(2,2,6,~tetramethylpiperidin-4-yl)-hexamethylene-l,~diamine 38) N,N'-bis-(2,2,6,~tetramethylpiperidin-4-yl)-hexame~hylene-l,~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,~tetramethylpiperidin-4-yl)-N,N'-dibutyladipamide 42) N,N'-bis-(2,2,6,6-tetramethylpiperidin-4-yl)-N,N'-dicyclohexyl-2-hydroxypropylene- 1 ,3-diamine 43) N,N'-~is-(2,2,6,6-tetramethylpiperidin-4-yl)-p-xylylenediamine 44) N,N'-bis-(2,2,6,6-tetramethylpiperidin-4-yl)-succinamide 45) di-(2,2,6,6-tetramethylpiperidin-4-yl) N-(2,2,6,6-tetramethyl-piperidin~-yl)-~-aminodipropionate 46) the compound of the formula .

`

2 ~

>~ Cl4Hg CH3--Nk)--N--CH2--CH(OH3 ---CH2--CH3 CH3 ~1 H3C--Cl--CH3 CH3 ¢~
CH3--N~ N--CH2 OEl(OH~ C~2--A C4Hg 47) 4-(bis-2-hydroxyethyla[nino)-1,2,2,6,6-pentamethylpiperidine 48) 4-(3-methyl-4-hydroxy-5-tert-butylbenzamido)-2,2,6,6-tetramethylpiperidine 49) 4-methacrylamido-1,2,2,6,~pentamethylpiperidine (c) compounds of the formula (VI) RC~H~3~R ;l R ll Nk~< ~R15 (VI) RCH2 CH3 n in which n is the number 1 or 2, R and Rll are as defined in (a) and Rl5 is, if n is 1, C2-C8aL~cylene or -hydroxyalkylene or C4-C22acyloxyalkylene and, if n is 2, the group (-CH2)2C(CH2-)2 Rl5 as C2-C8alkylene or -hydroxyaL~cylene is, for example, ethylene, 1-methylethylene, propylene, 2-ethylpropylene or 2-ethyl-2-hydroxymethylpropylene.

.

.

2~2~

Rls as C4-C22acyloxyalkylene is, for exarnple, 2-ethyl-2-acetoxymethylpropylene.
Examples of polyalkylpiperidine compounds of this class are the following compounds:

50) 9-aza-8,8,10,10-tetramethyl-1,5-dioxaspiro[5.5]undecane 51) 9-aza-8,8,10,10-te~amethyl-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-pen~nethyl-l,S-dioxaspiro[5.5]undecane Sd.) 9-aza-3-ethyl-3-acetoxymethyl-9-acetyl-8,8,10,10-tetramethyl-1 ,5-dioxaspiro[5.5]undecane 55) 2,2,6,6-tetramethylpiperidine-4-spiro-2'-(1',3'-dioxane)-S'-spiro-5"-(1",3"-dioxane)-2"-spiro 4"'-(2"',2"',6"',6"'-tetramethylpiperidine).

td) compounds of the formulae VIL~, VIIB and VIIC, compounds of the formula VIIAbeing preferred, RCH~ CH3 R R 16 ~
~4/ N C--O

kXI i (VIIA) RCH2 CH3 0 n \~4/ 0--C--T2 R 11 N/ )< ¦ (VIIB) k-- N C = O

.

.. ~ ' .

k~c _ 1 (VIIC) RCH2 CH3 o n in which n is the number 1 or 2, R and Rll are as defined in (a), Rl6 is hydrogen, Cl-CI2alkyl, allyl, benzyl, glycidyl or C2-C6alkoxyalkyl and Rl7 is, if n is 1, hydrogen, Cl-Cl2alkyl, C3-C5aL~enyl, C7-C9aralkyl, C5-C7cycloaL~yl, C2-C4hydroxyalkyl, C2-C6alkoxyalkyl, C6-CIOaryl, glycidyl or a group 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, C2-CI2alkylene, C4-CI2alkenylene, C6-CI2arylene, a group -CH2-CH(OH)-CH2-O-D-O-CH2-CH(OH)-CH2-, in which D is C2-CIOaL~cylene, C6-CIsarylene, C6-CI2cycloalkylene or a group -CH2CH(OZ')CH2-(OCH2-CH(OZ')CH2)2-, in which Z' is hydrogen, Cl-CI8alkyl, allyl,benzyl, C2-CI2alkanoyl or benzoyl, Tl and T2, independently of one another, are hydrogen, C~-CI8aLkyl or unsubstituted or halogen- or Cl-C4aLlsyl-substituted C6-CIOaryl or CTCgaralkyl, or Tl and T2 together with the C atom linking them form a C~-C12cycloalkane ring.

C~-Cl2alkyl substituents, if present, are, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl9 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.

Cl-Cl8alkyl substituents, if present, can be, for example, the groups mentioned above and in addition, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

CrC6alkoxyalkyl subsLituents, if present, are, for example, methoxymethyl9 ethoxymethyl, propoxymethyl, tert-butoxymethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl, tert-butoxyethyl, isopropoxyethyl or propoxypropyl.

.
Rl7 as C3-C5alkenyl is, ~or example, 1-propenyl, allyl, methallyl, 2-butenyl or 2-pentenyl.

: ~ -, .

Rl7, Tl and T2 as C7-Cgaralkyl are in particular phenethyl or especially benzyl. In the case where Tl and T2 together with the C atom form a cycloaLlcane ring, it can be, for example, a cyclopentane, cyclohexane, cyclooctane or cyclododecane nng.

Rl7 as C2-C4hydroxyaLlcyl is, for example9 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

Rl7, Tl and T2 as C6-ClOaryl are in particular phenyl, a- or ~-naphthyl which are unsubstituted or substituted by halogen or Cl-C4aLkyl.

Rl7 as C2-Cl2aL~cylene is, for example, ethylene, propylene, 2,2-dimethylpropylene, tetrarnethylene, hexarnethylene, octamethylene, decamethylene- or dodecamethylene.

Rl7 as C4-Cl2alkenylene is in particular 2-butenylene, 2-pentenylene or 3-hexenylene.

Rl7 as C6-Cl2arylene is, for example, o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.

Z' as C2-Cl2aL~canoyl is, for example, propionyl, butyryl3 octanoyl, dodecanoyl, but preferably acetyl.

as C2-ClOaLkylene, C6-Cl~arylene or C6-Cl2cycloalkylene is as defined in (b~.

Ex~nples of polyalkylpiperidine compoùnds of this class are the following compounds:

56) 3-benzyl-1,3,8-triaza-7,7,9,9-tetrarnethylspiro[4.5]decane-2,4-dione 57) 3-n-octyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.$]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-glycidyl-1,3,8-triaza-7,7,8,9,9-pentarnethylspiro~4.5]decane-2,4-dione ~0) 1,3,7,7,8,9,9-heptamethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione ~1) 2-isopropyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4~ox~spiro[4.5]decane .
. . . : ,. : . : . :

' 2~2~

62) 2,2-dibutyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spir~[4.5]decane 63) 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2]eJIeicosane 64) 2-butyl-7,7,9,9-tetramethyl-1-oxa-4,8-diaza-3-oxo-spiro[4.5]decane and preferably:
65) 8-acetyl-3-dodecyl-1,3,8-tri~a-7,7,9,9-tetramethylspiro[4.5]decane-2,4-dione or the compounds of the following formulae:

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

2 ~

\~Z~
o~ ~
=o ~ ~ oo o~

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

2~ 3~

(e) compounds of the formula VIII, which in turn are preferred, N~N
R ~N~ n R20 (VIII), in which n is the number 1 or 2 and Rl8 is a group of the formula R~<,CH2R

E (A) _< N--R

H3C C~2R

in which R and Rll are as defined in (a), E is -O- or -NRIl-, A is C2-C6aLIcylene or -(CH2)3-~ and x is the number O or 1, Rl9 is identical to Rl8 or one of the groups -NR21R22-, -oR23, -NHCH20R2 or -N(CH2oR23)2, R20 is, if n is 1, identical to Rl~ or R
and, if n is 2, a group -E-B-E-, in which B is C2-C6aLlcylene which may be interrupted by -N(R21)-, Rll is Cl-Cl2alkyl, cyclohexyl, benzyl OF Cl-C4hydroxyalkyl or a group of the formula ~<
~N--R22 is Cl-Cl2aL~cyl, cyclohexyl, benzyl, Cl-C4hydroxyaLkyl and R23 is hydrogen, Cl-Cl2alkyl or phenyl, or R21 and R22 together are ~4-CsaL~cylene or -oxaaL~cylene7 for example , :
- ~ .

. '~' ~ ' ' ,:
' 2 ~

--CH2CH2~ --CH2CH2~
/ or a group of the fonnula ~N--Rll or R2l and R22 are also each a group of the formula ~ C4Hg H3C CH3 N~,N

C4Hg N

H3C~CH3 H
Cl-CI2alkyl substituents, if present, 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-C4hydroxyalkyl substituents, if present, are, for example, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

A as C2-C6aL~cylene is, for exarnple, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene or hexamethylene.

R2l and R22 together as C4-C5aLtcylene or -oxaalkylene are, for example, tetramethylene, pentamethylene or 3-oxapentamethylene.

Examples of polyaLtcylpiperidine compounds of this class are the compounds of the following formulae:

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

. .

. . . :

2 ~

H3C~N~CH3 H3C//~ CH3 70) N--C4Hg NJ~N
Il I
(cH3cH2)2N N N(CH2CH3)2 N(C4H9)2 H3C~ N~N H,~CH3 71) C2H5--Nk~N_1~ J N~ N--C2H5 7'7) ~ whereRis --NU--CU2CU2CH2--O~u]U3 :' . ' ' ~ ' - , , , '' ': , . .

-: ' . . ' . ' :
.

2 ~

~<~ .
z~

V ~ r ~C

:

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

., 2 ~

R R
75) R--NH--(CH2)3--N--(CH2)2--N--(CH2)3--NH R
C4Hg ~<CH3 w~lereRis --~ ~N~
N ~N H~ACH3 C4Hg--N

H3C~<CH3 R R
76) R --NH--(CH2)3--N--(CH2)2--N--(CH2)3 NH R

whereRis ~ ~N~N--CU3 N~N CH3 ~\
H3C~ CH3 C~ H3 R R I H3 77) R--N--(CH2)3--N--tcH2~2--N--(CH2)3--N R

' . ' , : .

2~2$~

,N C4Hg /~<
whereRis ~ ~N--~ N--CH3 N~N H~\CH3 H3C~<CH3 ~,<CH3 C8H17--N 7~NH

78) C8HI N NH(CH2)3 - _ ::
/~ ~ .-:

<CH

2 ~:

- . . , :

H3C>[~)<CH3 79) N--C4Hg H3C~3 1 J~ H~<CH3 HO--CH2CH2--N ,~--N N_~ N--CH2CH2--OH
H3C CH3 C4H9 C4Hg H~7\CH3 80) CHz--CH= CH2 H3C~N~CH3 H3C ¦~J CH3 N--C4Hg ~ Nl H~<CH3 H20 HC--H2C--N ,~--N N--~ N--CH2--CH= CH2 H3C>~CH3 C4Hg H37<CH3 (f) oligomeric or polymeric compounds whose repeadng structural unit contains a 2,2,6,~tetraalkylpiperidine radical of the forrnula III, in particular polyesters, polyethers, : :
polyamides, polyamines, polyurethanes, polyureas, polyaminotriazines~
poly(meth)acrylates, poly(meth)acrylamides and their copolymers which con~un radicals :
of this type.

Examples of 2,2,6,6-polyalkylpiperidine light stabilizers of this class are the compounds of tho followin~ formulae, in which m is a nu~r b~ 2 ~o about 2~, ~ .

, .

~2~

O O ~
Il 11 / \
81) ~ C - CH2- CH2 ~ C - O - CH2 - CH2 N ~ ~m 8~) .
H3C ~ ~ CH3 O. O
CH2-CH2-N\ ~ ~ C - (CH2)4-C ~ N - CH2- CH2- 0 - C - (CH2)4 - C

~3) NU-(CU213 N ~ NH C ~ C -NU ~ N - (CU~3NU- C ~ C

84) CH3 CH3 NH + CH2 + CH3 N ~ ~ N
N ~ N - (CH2)6 N

H3C ~ CH3 H3C ~ ~CH3 85) [ -N - CHz - CU(OH~---CH

U3C > ~ CU3 , :: : : ~:

:

2 ~

~ ~ O C4Hg O
86) ~ O N N-CH2- CH ~ CH- CH2- N ~ O - C - C C
H3C CU3 H3 ~ C~3 C4H9 - - --N (CH2)6 - N ]m N ~ N H3C ~ CH3 H3C ~ CH3 N - C4Hg H3C N CH3 ~13C N CH3 ~ H H

H3C ~ ~ CH3 H3C ~ N ~ CH3 H

8g) . .

O ~--CH2~ CH2--N~ O g- (C112)4--o C2H5 >~
gg)~ c _ f _ c _ o ~H2--CH2--N ,~ ~ ~
C~Hs ~

, 90) I H3 [ C CH2--~m H3C~ /CH3 O=C /~
O--~ . N--CH3 91) [ C CH2 m H3C\ /CH3 O=C /~
C6H13 N_~ N _ CH3 7~

92) ~0~

N~N
N N _ (CH2)6 N ]m H3C~ CH3 H3C~ CH3 H3C N CH3 H3~ NH CU3 . .

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

93) ~ N (CH2)6 N - CH2--CH2 ] m H3C ~CH3 H3C~CH3 [ N (CH2)6 N CH2 CH2 ] m H3C~CH3 H3C~CH3 H3C N CH3 ~3C N CH3 H H

(g) compounds of the formula IX
RCH~R

R 11_ N ~;= O (IX) ~/ :

in which R and Rll are as deflned in (a).

Compounds of the forrnula IX in which R is hydrogen or me~yl and Rll is hydrogen or methyl are preferred. : ~ :
-Examples of compounds of this type are~
9~) 2,2,6,6-tetramethyl-4-piperidone (triacetoneamine) :
96) 1,2,2,6,6-pentamethyl-4-piperidone~

97) 2,2,6,6-tetramethyl-4-piperidone-1-oxyl ~

:

2~2~

97) 2,2,6,6-tetramethyl-4-piperidone-1-oxyl 98) 2,3,6-trimethyl-2,6-diethyl-4-piperidone.

The use of cyclic sterically hindered amines containing no ester groups and preferably those containing at least one triazine ring in the molecule as component a) in the compositions according to the invention is particularly advantageous. These amines preferably contain at least one group of the formula III and particularly preferably belong tO one of the types (a) to (g) described above.

Preference is given to polymer compositions, as described, containing as b) an organic zinc compound, in which the zinc compound is a salt of a carboxylic acid of 7 to 20 C
atoms or a C7-C20alkyl phenolate.

The zinc compounds from the series of carboxylates are preferably salts of carboxylic acids of 7 to 20 C atoms, for example benzoates, alkenoates or alkanoates, preferably stearates, oleates, laurates, palmitates, hydroxystearates or 2-ethylhexanoates. Stearate9 oleate and p-tert-butylbenzoates are particularly preferred.

Examples which can be named are the zinc salts of monobasic carboxylic acids, such as acetic acid, propionic acid, butyric acid, valeric acid, capr~ic acid, enanthic acid, caprylic acid, neodecanoic acid, 2-ethylhexanoic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, isostearic acid, stearic acid, l~-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 acidj 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, laidic acid, sorbic acid, linolic acid, linolenic acid, thioglycolic acid, mercaptopropionic acid and octylmercaptopropionic acid; zinc salts of the monoesters and monoamides of dibasic carboxylic acids, such as oxalic acid, malonic acid, succinic acid, glutamic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, hydroxyphthalic acid, chlorophthalic acid, arninophthalic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, haconic acid, aconitrinic acid and thiodipropionic acid; and the di- or ~r;esters of tri- or tetrabasic carboxylic acids such as - . . ~

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

2 ~

hemimellitic acid, ~imellitic acid, mellophanic acid, pyromellitic acid and mellitic acid.

Examples of suitable chelates of 1,3-diketones and ~-ketonecarboxylic esters are the compounds of the formula Zn(R--C_CRR--C-R )2 ~

in which R, R', R" and R"', independently of one another, are aLkyl of 1 to 18 C atoms, alkenyl of 2 to 18 C atoms, cycloaLlcyl of S to 12 ~ing C atoms, cycloaLkyl of 5 to 12 C
atoms substituted by 1 to 3 Cl-C4alkyl, aLkyl of 1 to 18 C atoms substituted by cycloalkyl of 5-12 ring C atoms, phenyl-CI-C18alkyl, Cl-Cl8alkylphenyl, phenyl, halogenoalkyl, halogenophenyl, alkoxyalkyl or aLkylenedioxyalkyl or -phenyl.

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

Ex~mples of halogenoalkyl or halogenophenyl are dichloromethyl, heptafluoropropyl, p-bromophenyl and 3,4-dichlorobenzyl. Alkoxyaikyl can be ethoxymethyl, n^butoxymethyl, 2-methoxyethyl, 2-methoxyphenyl and 4-n-octoxyphenylbenzyl.
Alkylenedioxyalkyl or -phenyl can be, for example, 3-(ethylenedioxypropyl) or 3,4-methylenedioxyphenyl.

Analogously, all 1,3-diketones already mentioned and not included in the above list can also be used in the form of their zinc chelate form as organic zinc compounds.

Preference is given to polymer compositions, as described above, containing as c) at least one compound from the series of hydrotalcites of the general formula I

M2+ ~ (OH)2~(An )X 5mH20 (I), , ~ ' .

2 ~

in which M2+ is magnesium or a solid solution of magnesium and zinc, An- is co32-, x is a number from 0 to 0.5 and m is a number from 0 to 2.

Preference is given to polymer compositions, as described above, containing at least one of the compounds of the fonnulae 4MgO-A1203-c02-9H20 4MgO-AI203-C02~6H20~

ZnO.3MgO.AI203.CO2.~-9H20 or Zno-3Mgo-Al2o3 co2-s-6H2o The polymer compositions can also contain further organic or inorganic calcium compounds and furthermore barium compounds, magnesium compounds and lead compounds. Calcium compounds are preferred. Advantageously, at least one organic or inorganic calcium compound, barium compound, magnesium compound andlor lead compound from the series comprising aliphatic Cl-C22 carboxyla~es, olefinic C2-C22 carboxylates, aliphatic C2-(,'22 carboxylates substituted by at least one OH group, cyclic and bicyclic carboxylates of 5-22 C atoms, aromatic C6-C22 carboxylates, aromatic C6-C22 carboxylates substituted by at least one OH, Cl-Cl6alkyl-substituted phenyl carboxylates, phenyl Cl-Cl6alkyl carboxylates, C6-Cl8 phenolates, Cs-C26 chelates of 1,3-diketones or ~-ketocarboxylic esters, dehydroacetic acid and derivatives thereof, carbonates, sulfates, oxides, hydroxides, basic oxides and mixed oxides, mercaptides based on mercaptocarboxylic esters, glycinates, phosphates, phosphites, phosphonites, phosphonates, partial esters of phosphonates, sulfonates and sulfimates is used, it being possible for the carbonates, sulfates and phosphites also to be used in their overbasic forms.

Examples and preferences of the organic and inorganic calcium compounds, and furthermore barium compounds, magnesium compounds and lead compounds should be derived analogously from the examples and preferences mentioned for the zinc compounds. In each case, instead of zinc, one of the metals of the se~ies comprising calcium, barium, magnesium or lead should be read.

, ~, -2 ~

Examples of chlorine-containing polymers which can be listed are: polymers of vinyl chloride, vinyl resins containing vinyl chloride units in their structure, such as copolymers of vinyl chloride and vinyl esters of aliphatic acids, 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 dicarboxylic acids or anhydrides thereof, such as copolymers of vinyl chloride with diethyl maleate, diethyl fumarate or maleic anhydride, postchlorinated polymers and polymers of vinyl chloride, copolymers of vinyl chloride and vinylidene chloride with unsaturated aldehydes, ketones and the like, such as acrolein, croton aldehyde, vinyl nnethyl 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 acetate9 chlorinated polymeric esters of acrylic acid and alpha-substituted acrylic acids; polymers of chlorinated styrenes, for example dichlorostyrene; chlorinated rubbers; chlorinated polymers of ethylene;
polymers and postchlorinated polymers of chlorobutadiene and copolymers thereof with vinyl chloride, rubber hydrochloride and chlorinated rubber hydrochloride; and mixtures of the polymers mentioned with one another or with other polymerizable compounds.

Furthermore, graft polymers of PVC with EVA, ABS and MBS are included. PIeferredsubstrates are also mixtures of the abovementioned homo^ and copolymers, in particular vinyl chloride homopolymers, with other therrnoplastic andlor elastomeric polymers, in particular blends with ABS, MBS, NBR, SAN, EVA, CPE, MBAS, PMA, PMMA, EPDM
and polylactones.
Suspension and buL~c polymers and emulsion polymers are also preferred.

Polyvinyl chloride, in particular suspension polymer and buLk polymer, is particularly preferred as chlorine-containing polymer.

Polymer compositions, as described above, containing relative to 100 parts by weight of the composition, a) 0.01 to 1.5 parts by weight of cyclic and acyclic sterically hindered arnines, b) 0.01 to 2 parts by weight of organic or inorganic zinc compounds and ~. :

~ $ ~

c) 0.1 to 3 parts by weight of compounds from the series of hydrotalcites, are advantageous.

The preferred ranges of the amounts of the sterically hindered amines in the polymer composition are 0.05 to 1.0 part by weight, relative to 100 parts by weight of the composidon. Q. 1 to 0.5 part by weight is particularly preferred.

The preferred ranges of the amounts of the zinc compounds in the polymer composition are 0.05 to I part by weight, relative to 100 parts by weight of the composition.

The preferred ranges of the amounts of the hydrotalcites in the polymer composition are 0.3 to 2 parts by weight, relative to 100 parts by weight of the composition. 0.4 to 1 part by weight is particularly preferred.

The chlorine-containing polymer can contain a plasticizer, chlorine-containing polymers containing no plasdcizer being preferred.

Examples of suitable organic plasticizers are those from the following groups:

A) Phthalates (phthalic esters) 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, dimethylglcyol, dibutylglycol, benzylbutyl and diphenyl phthalate and mixtures of phshalates, such as C7-Cg- and Cg-CllaL~cyl phthalates of predominantly linear alcohols, C6-CI0-n-aLlcyl phthalates and Cg-Cl0-n-aLtcyl phthalates. Of these, dibutyl, dihexyl, di-2-ethylhexyl, di-n-oc~rl, di-isooctyl, di-isononyl, di-isodecyl, di-iso~idecyl and benzylbutyl phthalate and the mixtures mentioned of aLlcyl phthalates are prefered.
Di-2-e~hylhexyl phthalate (DOP) is particularly preferred.

B) Esters of aliPhatic dicarboxvlic acids, in particular esters of adipic, æelaic and sebacic acid Examples of plasticizers of this type are di-2-ethylhexyl adipate, di-isooctyl adipate (mixture), di-isononyl adipate (mixture), di-isodecyl adipate (mixture), benzylbutyl ndipate, benzyloctyl adipate, di-2-ethylhexyl azelate, di-2-ethylhexyl sebacate and di-isodecyl sebacate (mixture). Di-~-ethylhexyl~ adipate and di-isooctyl ~dipate are , , ~

2 ~

preferred.

C) Trimellit;c esters, for example tri-2-ethylhexyl trimellitate, tri-isodecyl trimellitate (mixture), tli-isotridecyl trimellitate, tIi-isooctyl trimellitate (mixture) and tri-C6-C8aL~cyl, tri-C6-C~OaL'cyl, tri-C7-CgaL~cyl and tri-Cg-CllaL~cyl trimellitate. The last-mentioned trimellitates are formed by esteriflcation of trimellidc acid with the corresponding aL~canol mixtures. Preferred trimellitates are tri-2-ethylhexyl trimellitate and the trimellitates mentioned of aLIcanol mixtures~

D) Polvmer plasticizers A definition of these plasticizers and examples of these are given in "Plastics Additives Handbook", edited by H. Gachter and H. Muller, Hanser Publishers, 1985, page 284, Chapter 5.7.10 and in "PVC Technology", edited by W.V. Titow, 4th Ed., Elsevier Publ., 1984, pages 165-170. The most conventional starting materials for the preparation of the 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, neopentylglycol and diethylene glycol; monocarboxylic acids, such as acetic, caproic, caprylic, lauric, myristic, palmitic, stearic, pelar~onic and benzoic acids; monofunctional alcohols, such as isooctanol, 2-ethylhexanol, isodecanol and C7-CgaL~canol and C9-CIlalkanol mixtures. Polyester plasticizers of the dicarboxylic acids mentioned and monofuncdonal alcohols are particularly advantageous.

E) Phosphoric esters A definidon of these esters can be found in the abovementdoned "Plastics Additdves Handbook" on page 271, Chapter 5.7.2. Examples of phosphoric esters of this type are tributyl phosphate, tri-2-ethylbutyl phosphate, tri-2-eehylhexyl phosphate, trichloroethyl phosphate, 2-ethylhexyl diphenyl phosphate, cresyl diphenyl phosphate, ~iphenyl phosphate, tricresyl phosphatç and trixylenyl phosphate. Tri-2-ethylhexyl phosphate is preferred.

F) Chlorinated hydrocarbons (paraffins) G) Hydrocarbons H) Monoçsters, for example butyl oleate, phenoxyethyl oleate, tetrahydrofurfuryl oleate ., : ., :
, . . :, .. . .
. . " . ~ . . .
. .
.

. . .

$ ~ ~

and aLlcylsulfonic esters.

I) Glycol esters, for example diglycol benzoates.

I)efinitions and examples of plasticizer~ of groups F) to I) can be found in the following handbooks:

"Plastics Additives Handbook", edited by H. Gachter and H. Muller, Hanser Publishers, 198~, page 284, Chapter 5.7.11 (Group F)), and Chapter 5.7.13 (Group G)).

"PVC Technology", edited by W.V. Titow, 4th Ed., Elsevier Publishers, 1984, pages 171-173, Chapter 6.10.2 (Group F)), 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)).

Particular preference is given to plasticizers from groups A) tO E), in particular A) tO C), especially the plasticizers pointed out in these groups as preferred. Di-2-ethylhexyl phthalate (DOP) is particularly advantageous.

The plasticizers can be used in an arnount of, for example, 15 to 70, advantageously 15 to 60, and in particular 20 to 50, parts by weight, relative to 100 parts by weight of the polymer composition.

The polymer composidons according to the present invendon can also contain further stabilizers, for example the abovementioned component d) 1,3-diketones, which isadvantageously used in amounts of 0.05 to 5, preferably in amounts of 0.10 to 1, parts by weight and in particular in amounts of 0.5 to 1 part by weight, in each case relative to 100 parts by weight of the composition.

A different stabilizer which can also be used is the component e) described above - the organic or inorganic calcium compounds - which are advantageously used in amounts of 0.05 to 5 parts by weight, preferably in amounts of 0.1 to 1 part by weight and in particular in amounts of 0.5 to 1 part by weight, in each case relative to 100 parts by weight of the composition.

In the case where further stabilizers from the series of organic or inorganic calcium compounds, barium compounds, magnesium compounds or lead compounds ~e used, as .

, ,...,..,. .

2 ~

mentioned above, 0 to 5 parts by weight, relative tO the composition, can be used. 0.05 to S parts by weight, preferably 0.1 to 1 part by weight, are advantageous.

The compositions according to the invention can also contain further stabilizers which are customary for chlorine-containing thermoplastics. Thus, they contain, for example, û-3 parts, relative to the composition, in particular 0-1.5, especially 0-1, par~s of one or more phosphites. These phosphites can be present for example in an amount of 0.01-3, in particular 0.01-1.5, for example 0.01-1, preferably 0.1-0.6, for example 0.2-0.5, parts.
Examples of phosphites of this type are for example those of the formulae 1"
R2 O\p o~ rO 2 R3 o7 and Rl --P ~X~ P OR

in which Rl, R2 and R3 are identical or different and are C6-Cl8alkyl, C6-CI8alkenyl, a substituted or unsubstituted phenyl radical or Cs-C7cycloalkyl.

Rl, R2 and R3 as C6-Cl8alkyl are, for example, n-hexyl, n-octyl, n-nonyl, decyl,dodecyl, tetradecyl, hexadecyl or octadecyl. Alkyl groups of 8 to 18 C atoms are preferred.

Rl, R2 and R3 as substituted phenyl 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.

Particularly suitable phosphites are trioctyl, tridecyl, tTidodecyl, tritetradecyl, tristearyl, trioleyl, triphenyl, tricresyl, tris-p-nonylphenyl or tricyclohexyl phosphite and particular preference is given to aryl dialkyl and alkyl diaTyl phosphites, for example phenyl didecyl, (2,4-di-tert-butylphenyl) didodecyl phosphite, (2,b-di-tert-butylphenyl) didodecyl phosphite and diallcyl and diaryl pentaerythritol diphosphites, such as distearyl pentaerythritol diphosphite.

Preferred organic phosphites are distearyl pentaerythritvl diphosphite, ~;s-p-nonylphenyl phosphite and phenyl didecyl phosphite.

Moreover, further known costabilizers can be present in the compositions according to the - . .

:
.:

9 ~

invention, for example 0-2, in particular 0-1.5, parts, relative to the composition. They are then preferably present in an amount of 0.01-2, in particular 0.05-1.5, for example 0.1-1, especially 0.1-0.5, parts. Costabiliærs of this type are arnino~rotonic esters, dehydroacetic acid, 2,4-dihydroxybenzophenone, 2,4-dihydroxy-4'-tert-butylbenzophenone, dihydropyridine derivatives and pyrrole derivatives.

Suitable aminocrotonic esters are in particular the esters with monohydric straight-chain C8-C20 alcohols, in paTticular Cl2-CI8 alcohols, andlor with 1,3- or 1,4-butanediol and/or 1,2-dipropylene glycol and/or thiodiethylene glycol.

Suitable pyrrole costabilizers are in particular those described in EP-A 22,087 and GB-A
2,078,761, for example of the -formula I given there, preferably those pyrrole derivatives defined in claims 2-9 of EP-A 22,087. One example is 2-methyl-3-cyclohexyloxycarbonyl-4-phenyl-lH-pyrrole.

Furtherrnore, the compositions according to the invention can contain, in addition to the ~bovementioned optional costabilizers or in their place further optional components, for example organic antimony compounds, such as antimony tris[isooctylthioglycolate](isooc~yl = 2-ethylhexyl).

Other stabilizers which can be used in the compositions according to the invention are polyols. The amounts to be used are, for exarnple, up to 3 parts by weight, relative to 100 parts by weight of the composition, advantageously up to 2 parts by weight and preferably 0.01 to 1 part by weight. Typical examples of polyols are pentaerythritol, dipentaerythritol, trimethylolpropane, ditrimethylolpropane, tris(2-hydroxyethyl) isocyanurate (I~IC), the latter being preferred, sorbitol, malmitol and inositol.

Furthermore, the compositions according to the invention can contain customary antioxidants, 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-lert-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~-methylphenol, 2-(a-melhylcyclohexyl)-4,6-dimethylphenol, 2 ~ 9 ~

2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,~di-tert-butyl-4-methoxymethylphenol, 2,6-dinonyl-4-methylphenol.

1.2. Alkvlated hydroquinones, for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol.

1.3. HYdroxylated thiodiphenvl ethers, for example 2,2'-thio-bis(6-tert-butyl-4-methylphenol~, 2,2'-thio-bis(4-octylphenol), 4,4'-thio-bis(~tert-butyl-3-methylphenol), 4,4'-thio-bis(~tert-butyl-2-methylphenol).

1.4. Alkvlidene bisphenols, for example 2,2'-methylene-bis(6-tert-butyl-4-methylphenol), 2,2'-methylene-bis(~tert-butyl4-ethylphenol), 2,2'-methylene-bis[4-methyl-~(a-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-sert-butylphenol), 2,2'-ethylidene-bis(4,6-di-tert-butylphenol), 2,2 '-ethylidene-bis(6-tert-butyl4-isobutylphenol), 2,2'-methylene-bis[~(a-methylbenzyl)-4-nonylphenol], 2,2'-methylene-bis[6-(a,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(S-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(S-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-S-methylphenyl)dicyclopentadiene, bis[2-(3'-tert-butyl-2'-hydroxy-S'-methylbenzyl)-~tert-butyl-4-methylphenyl]
terephthalate.

l.S. Benzyl comPounds, for example 1,3,5-tris(3,5-di-ter~-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl 3,5~i-tert-buty1-4-hydroxybenzyl mercaptoacetate, bis(4-tert-butyl-3-hydroxy-2,6-dime~ylbenzyl) dithiolterephthalate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, .
. , . ~, `

2 ~

1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, calcium monoethyl 3,5~i-tert-butyl-4-hydroxybenzylphosphonate, 1,3,5-tris(3,5-dicyclohexyl4-hydroxybenzyl) isocyanurate.

1.6. Acvlaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide, ~,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-s-triazine, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

1.7. Esters of ~-(3~5-di-tert-butvl-4-hydroxYphenvl~propionic acid with mono- orpolyhydric alcohols, for exarnple with methanol, octadecanol, 1 ,~hexanediol, neopentylglycol, thiodiethylene glycol, diethylene glycol, trie~ylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxalamide.

1.8. Esters of s-(S-tert-butyl4-hYdroxY-3-methYlPhenyl)propionic acid with mono- or polyhydric alcohols, ~or example with methanol, octadecanol, 1,6-hexanediol, neopentylglycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxalamide.

1.9. Esters of ~-(3~5-dicyclohexyl-4-hvdroxYphenvl)propionic acid with mono- or polyhydric alcohols, for example with methanol9 octadecanol, 1,6-hexanediol, neopentylglycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxalamide.

1.10. Amides of ~-(3~5-di-tert-butyl-4-hvdroxvphenyl)propionic acid, for exampleN,N'-bis(3,5 di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine, N,N'-bis(3,5 di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediarnine, N,N'-bis(3,5~di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine.

2. W absorbers and li~ht stabilizers 2.1. 2-(2'-HydroxyphenYl)benzotriazoles, for exarnple the S'-methyl, 3',5'-di-tert-butyl, S'-tert-bu~yl, 5'-(1,1,3,3-tetramethylbutyl), 5-chloro-3',5'-di-tert-butyl, S-chloro-3'-tert-butyl-5'-methyl, 3'-sec-butyl-5'-tert-butyl, 4'-octoxy, 3',5'-di-~ert-amyl, 3',5'-bis(a,a-dimethylbenzyl) derivatives.

-; , , , ~ ~ 2 ~

2.2. 2-Hvdroxybenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy, 2'-hydroxy-4,4'-dimethoxy derivatives.

2~3. Esters of substituted or unsubstituted benzoic acids, for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, resorcinol dibenzoate, resorcinol bis(4-tert-butylbenzoate), resorcinol monobenzoate, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate.

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

2.5. Nickel compounds, for example nickel complexes of 2,2'-thiobis[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or the 1:2 complex, if appropriate with additional ligands, such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel monoaLcyl 4-hydroxy-3,5-di-tert-butylbenzylphosphonates, such as the methyl or ethyl ester, nickel complexes of ketoximes, such as those of 2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of l-phenyl-4-lauroyl-S-hydroxypyrazole, if appropriate with additional ligands.

2.6. Oxalamides, for example 4,4'-dioctyloxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyloxanilide, 2,2'-didodecyloxy-S,S'-di-tert-butyloxanilide7 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxalamide, 2-ethoxy-S-tert-butyl-2'-ethyloxanilide and the mixture thereof with 2-ethoxy-2'-ethyl-5,4'-di-tere-butyloxanilide, mixtures of ~ and p-methoxy- and o- and p-ethoxy-disubstituted oxanalides.

2.7. 2-~2-Hydroxyphenyl~-1.3,5-triazines, for example 2,4,~(tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-~iazine, 2-(2-hydroxy4-octyloxyphenyl)4,~bis(2,4-dimethylphenyl)-1,3,5-¢ia2ine, 2-(2,4-dihydroxyphenyl)-4,~bis(2,4-climethylphenyl)1,3,5-~iazine, 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy4-octyloxyphenyl)-4,~bis(4-methylphenyl)- 1 ,3,5-triazine, :
. .
.. : .. , ~ . . . .
: .
. .,. - ~:
--: -- . . ~

2~2~

2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)- 1 ,3,5-triazine.

Depending on the intended use, further customary additives can be additionally incorporated in the compositions according to the invention, for example 3. Phosphites and phosphonites, for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, ~ris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl~
pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylenediphosphonite, 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[S.S]undecane.

4. Per xide-destrovin~ compounds, for exarnple esters of ~-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl ester, mercaptobenzimidazole, the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(~-dodecylmercapto) propionate.

5. Basic costabilizers, for example urea derivatives, thiourea derivatives, aL~cali metal salts and alkaline earth metal salts of higher fatty acids, for example magnesium stearate, sodium ricinoleate, potassium palmitate, tris(hydroxyethyl) isocyanurate.

6. Fillers and reinforcing agents, for exarnple calcium carbonate, silicates, glass fibres, asbestos, talcum, kaolin, mica, barium sulfate, metal oxides and metal hydroxides, carbon black, graphite.

7. Other additives, for example plasticizers, lubricants, emulsi~lers, pigrnents, fluorescent whiteners, flame retardants, antistatics, blowing agents.

Examples of further pardcularly valuable costabilizers which can be used individually or several of them together - in addition to or in place of the abovemendoned optional costabilizers - the amount used, for exarnple, for each costabilizer being û to 2.0 parts by weight, advantageously 0.05-1.0 part by weight, and in par~cular 0.1 to 0.5 part by weight, in each case reladve to 100 parts by weight of the composition, are listed below by way of example.

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

2 ~

Stabilizer mixtures consisting of a salt of an organic acid and a polyol in which the polyol is a synergistic mixture of di(trimethylol)propane in combination with a different polyol of 5 to 15 carbon atoms and 2 to 10 hydroxyl groups and a melting point of not less than 100C. A comprehensiv~ survey, examples and preferences can be found in EuropeanPatent 0,058,447.

Stabilizer mixtures essentially consisting of nitrogen-free ketoacids having at least 8 C
atoms and a metal salt of an organie nitrogen~free monoearboxylie acid having 6 to ~4 C
atoms or the salts of the ketoaeetie aeid having 4 to 33 C atoms and a phenol substituted by a hydrocarbon. A detailed description of stabiliær mixtures of this type, exarnples and preferenees ean be found in GB 1,099,731.

Compounds of the forrnula /~\N/

5, H

in which Rl is Cl-CI8alkyl, C3-CI8alkenyl, phenyl, C7-CI2phenylaL~yl or C7-CI2phenylalkyl whieh is substituted on the phenyl ring by Cl-C4aLlcyl and/or chlorine, and R2 is Cl-Cl8alkyl, hydroxyl-substituted C2-C22aLkyl or C2-C22aLkyl whieh is substituted by hydroxyl and a group -XR3, where X is oxygen or sulfur and R3 is Cl-CI8alkyl, phenyl or C7-CI2phenylalkyl, or R2 is furthermore C3-CIgalkenyl, CTCI2phenylaL~cyl or C7-CI2phenylaLkyl which is substituted on the phenyl ring by Cl-C4aL~cyl and/or chlorine.

Stabilizer mixtures eontaining 0.7-2 parts of thiodiethylene glycol bisacetoacetate of the formula (H3CCOCH2COOCH2CH2)2S, 0-0.5 part of at least one ealcium salt, barium salt or/and magnesium salt of an aliphatic C8-C24 monoearboxylic acid or hydroxymonoearboxylic aeid or of benzoie aeid or tert-butylbenzoie aeid, 0.01-0.2 part of at least one zine salt of an aliphatie C8-C24 monoearboxylie acid or hydroxymonocarboxylie acid or of benzoie aeid or tert-butylbenzoie aeid, which is , .~ . . - . . .
.

- . .

`` 2~2~

furtherrnore mixed with 3-10 parts of epoxidized unsaturated fatty acid esters and 10-70 parts of at least one organic plasticizer. A detailed description, examples and preferences can be found in GB 2,212,808.

Stabilizer mixtures containing 0.7-2 parts of thiodiethylene glycol bisacetoacetate of the formula (H3CCOCH2COOCH2CH2)2S, 0-0.5 part of at least one calcium salt, barium salt or/and magnesium salt of an aliphatic C8-C24 monocarboxylic acid or hydroxymonocarboxylic acid or of benzoic acid or tert-butylbenzoic acid, 0.01-0.2 part of a zinc salt of an aliphatic C8-C24 monocarboxylic acid or hydroxymonocarboxylic acid or of benzoic acid or tert-butylbenzoic acid, and in addition 3-10 parts of epoxidized unsaturated fatty acid esters. Further explanations, exarnples and preferences can be found in GB 2,192,004.

Compounds of the formula a and b \e = e (a), / \ (b) Rl O--CO--O CO--R3 R 2 CO--R3 in which Rl is Cl-C22aLlcyl, phenyl, phenyl which is substituted by one or two Cl-Cgalkyl, Cs-C7cycloalkyl or a group of the formulae A or B

\C
CO--R3 (A), e = e (B) or Rl is a group of the formulae ca or cb ~e _ e\ (ca), ' . ~ , .

, c = c\ (cb), --R--O--CO--O--C H

R2 and R3, independently of one another, are Cl-C20alkyl, phenyl, phenyl which is substituted by one or two Cl-C9aLkyl, or is Cs-C7cycloaLkyl and R4 is C2-CI2alkylene.
Mor~ detailed explanations, examples and preferences can be found in EP 224,438.
Compounds of the formula r~X n (Hal) _ t m \:~
(Y-NHR) in which m is a number 0, 1 or 2, n is a number 0, 2 or 3 and p is a number 1 or 2, H~l is -P, -Cl, -Br or -I, X is -NH2, -NHCH3 and/or -OCH3 or OC2Hs, Y is -CO- or-S02- and R is -H, -OH, -NH2, Cl-CI8alkyl which is unsubstituted or, for example, mono- totrisubstituted by OH and/or Cl-C4aLkoxy or phenoxy groups, or is phenyl, benzyl or phenethyl, or R is furtherrnore a group of the formula Xn -oY~

(Hal) in which X, Y, m, n and Hal are as de~med above. Detailed descnptions, examples and preferences can be found in EP 122,228 and EP 174,412.

' ., Stabiliær mixtures obtainable by mixing at least one compound of the formula [ROOC-C"H~,S-]3PX, in which X is O or S, n is an integer ~rom 1 $o 5 and R is straight-chain or branched Cl-C18nlkyl or substituted or unsubstituted cyclohexyl, and at least one PVC stabilizer of the t~pe Me(lI) carboxylate andlor Me(II) phenolate, in which Me~II) is one or more metals from the series comprising Ba, Sr, Ca, Mg, Zn and Cd, and in which 0.01-2 % by weight of the compound of the forrnula I and 0.1-4 % by weight of the Me(II) carboxylate andlor Me(II) phenolate are used, relatiYe to the PVC. Stabilizer mixtures of this type are described in more detail in EP 90,770, where examples and preferences can also be found.

2-Thio-~aminouracils of the formula /~N --R 1 3 J~N~
R~ O

in which Rl nnd R2, independently of one another, are a hydrocarbon radical of 1 to 24 carbon ntoms, which may be substituted by -OH, -CooR4, -o(C=o)R4, -~C~)R4, halogen or amino, and R3 is H, acyl of 2 to 24 carbon atoms or -~C=o)N~4, in which R4 is a hydrocarbon radical of 1 to 24 carbon atoms. Further embodiments, examples and preferences can be found in EP 41,479.

Aminouracils of the formula ' .

~'~

` 2~$~

o ~N/

RIHN I ~0 . x.3 in which Rl is Cl-C8alkyl, C5-C8cycloaLkyl, phenyl, benzyl, Cl-C4hydroxyalkyl, hydroxyphenyl, C2-C8alkoxyaL~cyl, C2-C8aLIcylthioaLtcyl, C6-CI0cycloaL~coxyalkyl, C6-ClOcycloalkylthioalkyl, C8-Cl4aralkoxyaLkyl C8-Cl4aralkylthioalkyl, C7-CI4aryloxyalkyl, C7-CI4arylthioaLlcyl, C2-C24alkylcarbonyl, C4-C26alkylcarbonylacetyl or a group -(C=X)NHR4, in which X is oxygen or sulfur and R4 is Cl-C8alkyl, R2 and R3, independently of one another, are C2-C2lalkyl, C6-CI2aryl or C7-Cgaralkyl, in which one of the two radicals R2 and R3 can also be hydrogen, and, if Rl is hydroxyphenyl or allcylcarbonylacetyl, R2 and R3 can also be methyl. These stabilizers are described in more detail in EP 65,934 and exarnples and preferences are available from the same reference.

Further stabili~ers are triazoles of the formula ' :
N -N
- N--N 1 or the formula R3~N~\R4 Rl N X--(CH2~ -~ R2 H
D

in which Rl is hydrogen, hydroxyl, Cl-C6alkoxyj carboxyl, C2-C6aL~coxycarbonyl, mercapto, Cl-C6alkylthio or a group -S-CH2-COOH or -S-CH2-COO-aL~cyl(CI-C6), X is thio, methylene or the group -COO- or -S-CH2-COO-, in each case bound to the aL~cyl via the ester oxygen atom, m is an integer ~om 1 to 20, n is 1 or 2, R2 is, if monovalent, hydrogen, hydroxyl or mercapeo and, if divalent, a direct bond, imino, Cl-C6aL~tylimino, oxy, thio or methylene, R3 is hydrogen, amino, mercapto or Cl-CI2aL~cylthio and, if R3 is hydrogen, R4 is hydrogen, -COOR5, in which Rs is hydrogen, Cl-C8alkyl or -CH2-COO-aL~cyl(CI-C8), or -S-R6, in which R6 iS hydrogen, Cl-CI2alkyl, N N
-CH2-CO~aLtcyl(Cl-C8) or C1-Cl2aL'sylthio or -NH-X'-NH- I~NJI, in which X' Is ihe H
group -CO-NH-alkylene-NH-(::O, -CO-aLkylene-S-alkylone-CO of, in each case,~ 1-12 C:

.

~; : : ` :

:

2~2~9 atoms in the aLlcylene chain or is (Cl-CI2)alkylene, and if R3 is NH~, R4 is Cl-C4alkyl, N N
l! !l mercapto, Cl-C4aL~cylthio or -S-alkylene-S- ~N~ ~NH2 having 1-12 C atoms in the H

alkylene chain, and if R3 is mercapto, R4 is substituted or unsubstituted phenyl, and, if R3 is Cl-Cl2alkylthio, R4 is Cl-C4alkyl, Cl-Cl2alkylthio or substituted or unsubstituted phenyl.

Stabiliærs of this type, further embodiments, examples and preferences can be found ln DE 3,048,659.

Stabilizer mixtures consisting of a thioether of the formula f R--CO--CH--CO--O--Y--CH--J --S(--Z--S~

in which n is the number zero or 1, R is Cl-Cl8alkyl, Cs-C8cycloalkyl, C6-ClOaryl which is unsubstituted or substituted by Cl-C4alkyl and R is hydrogen or Cl-C4alkyl, X~ as a repeatedly occurring symbol, identical or different, is hydrogen or a group of the formu1a R--C(~CH--CO--O--Y---Y as a repeatedly occurring symbol, identical or different, is Cl-C6aLkylene or a group of the formula ~ CH2~ CH~ CH23 : .

2$2~

in which the . ( CH~ 3 group is bound to the oxygen atom and in which R2 is hydrogen or a group of the formula R--CO--fH--c~
~1 n can be the numbers 1 to 4 and p the numbers zero to 3, Z is Cl-C6alkylene or a group of the forrnula --CH2--Cl H--CH2 and b) a stabilizer containing a metal from the group comprising zinc, calcium, cadmium, barium, magnesium or andmony or furthermore also zinc combined with at least one of the abovementdoned metals.
Further explanadons, examples and preferences can be found in EP 19,576.
Compounds of the formula A ( x--~ c 1l~ ~ A) n in which n is the numbers 1 to 3, R is Cl-Cl2alkyl or phenyl, R1 and R2, independently of one another, are hydrogen, or R and X are Cl-C6alkylene which may be interrupted by -~, and if n is 1, A is one of the groups of the formulae ' 2 ~

N- O ~
Q~ ¦ ~ R 3 _ C--N\ , R S
C-O N N
Rsl~N~N R

~NJ~N~ or - ~ 3p - /CH~ CH----O~N ~ \N/
R4 I _ m in which p is zero or 1 and m is the numbers 1 ~o 250, Zl is ethylene which is unsubstituted or substituted by Cl-C24alkyl or aLI~oxy, C2-C24aL~cenyl, phenyl, C2-C24carbalkoxy, carbophenoxy, C2-C24alkanoyloxy, benzoyloxy, halogen or cyano, R3 is Cl-C24alkyl, R4 is hydrogen, Cl-C24aLkyl, a group -X-OH or -X-OCO-CH2-CO-R and Rs is hydrogen, -OH, -oR3, -SR3, -R3, -NHR3 or -X-OH, Q is a group Z-CO-, in which the carbonyl group is bound to the nitrogen of the formula II and Z is ethylene, which may have formed an adduct with a 1,3-homo- or (oxa-, aza-) heterodiene~ which in turn can partially or completely be part of a homo- or (oxa-, aza-) heterocycle of S to 40 ring members and 1 to 10 rings or furthenr.ore 2; is vinylene, o-phenylene which is unsubstituted or substituted by a group -CoN(R6)R7, COOR8 or -COSR8, or is the group -CH2-S-CH2-, R6 and R7, identical or different, are hydrogen or Cl-C12aLI~yl, and R8 iS
C~-Cl2alkyl or a group -CH2-COOR9 in which R9 is Cl-Cl2aLIcyl, or Q is a ring-rlosing group leading to a 5-10-membered heterocycle containing at least 2 heteroatoms, and, if n is 2, A is one of the groups of the fo~mulae --N/ )~C--O--B--O--C~ C~l--C--N~
il O O O O

-:

2 ~

o O O O
Il 11 11 11 C~ ,C~ }~ C~ \ /C~N/

\C~ ~`N , I ~ 2\ ,CH2 Il 11 ll ll O O O
o RS

\c)~cJ~(c> R\ )\\ 1 R4 o o o o \ ~C~ / 4 ~c~

c~ ~C or HC CH
o~ N ~O ~C

o in which B is Cl-C6alkylene, p-phenylene or one of the groups 1 (CHz~O ] r (CHz~ or ~(CH2~ S 3 r (CHz~
in which q is the numbers 1 to 4 and r the numbers 1 to 3, and Bl is a direct bond, B is C1O-C14arylene or Cs-C8cycloalkylene, and furtherrnore, if n is 3, A is a group of the formula N~N

~N/~N~I\N~R

in which R4 is as de~med above. Fur~er details, examples and preferences are available from EP 22,749.

In addition to the stabiliærs and costabilizers mentioned according to this invention, it is : . - .
, ~: .
, ~, .~

2 ~

- ss -also possible to use epoxy compounds, such as 1,2-epoxides and oxiranes, in amounts of, for example, up to 10 parts by weight, relatdve to 100 parts by weight of the composidon, advantageously up to S parts by weight, and preferably 0.01 up to 2 parts by wcight.
Examples of these are epoxidized polybutadiene, epoxidiæd soya flower oil, epoxidized linseed oil, epoxidized fish oil, epoxidized ~llow, methylbutyl or 2-ethylhexyl epoxystearate, tris(epoxypropyl) isocyanurate, epoxidized castor oil, epoxidized sunflower oil, 3-(2-xenoxy)-1,2-epoxypropane, bisphenol A polyglycidyl ether, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate.

The composidons according to the invention can be prepared in a manner known per se.
As a rule, the stabilizer system is incorporated in the polymer, for which apparatuses known per se, such as calenders, mixers, kneaders and the like, are the logical choice.

The composidons stabilized according to the present invention can be converted into the desired shape in a known manner. Examples of processes of this type are milling,calendering, extruding, injectdon moulding, sintering or spinning, furthermore extrusion blow moulding or processing by the plastdsol pr~cess. The compositdons can also be processed to give foams.

Preferred stabilized chlorine-containing polymer compositions are unplasticized or plusticiær-free or essentially plasticiær-free compositions.

The compositdons according to the inventdon are suitable in particular in the folm of unplasticiæd recipes for slush moulds (bottles), packaging sheets (thermoforming sheets), blown films, crash pad sheets (automobiles), pipes, foarns, heavy profiles (window frames), transp~rent wall profiles, structure profiles, sidings, fittings, of fice films and apparatus casings (computers, household appliances).

Other compositions in the form of plasticized recipes are suitable for cable sheathings, cable insuladons, decoradve sheets, roof sheets, foams, agricultural films, tubings, sealing profiles, office films and films for air-inflatable structures.

Applicadon examples of the compositions according to the invention in the form of plasdsols are ardficial leather, floors, textile coatings, wallpapers, coil coadngs and underbody protecdon for automobiles.

' . .
.: . -.. ..

. :
' ~ ~

2 ~

Exarnples of sintered PVC applications of the compositions according to the invention a~e slush, slush mould and coil coatings.

The use of the polymer composidons described above as unplasticized pro~lles for outdoor applications and as unplasticized films is preferred. Further preferred applications of the polymer composidons described above are slush mould or crash pads.

The examples which follow illustrate the invendon in more detail. All parts and percentages given are by weight, unless stated otherwise.

Examples 1-6: Various PVC compositions are prepared by mixing the individual components as shown in the table below (amounts given in parts by weight).

These are recipes for unplasticized PVC profiles for outdoor applicadons. The compositions 1-6 are subjected to a heat test in order to test the effect of the stabilizer in the PVC.

The heat test is carried out by rolling the PVC composidon on mixed rolls at 190C for S
minutes. The 0.3 mm thick rolled sheet formed is used to produce film specimens which are subjected to heat in a test furnace ((E~Mathis Thermotakter Type LTF-ST) at 190C.
After the intervals shown in the table below, the yellowness index (YI) according to ASTM D 1925-70 is determined on each of the test specimens (high YI values mean strong discoloradon and thus low stability).

. . ~ ~ . .

2~8~

xample _ _ Recipe 1 2 3 4 5 6 Acrylate-modiFled S-PVC, 100 100 100 100 100 100 K value 67 .
Titanium dioxide pigment 4 4 4 4 4 4 Chalk 6 6 6 6 6 6 Processing aid containing polymethyl methacrylate Distearyl phthalate 0.5 0.5 0.5 0.5 0.5 0.5 (internal lubricant) 12-Hydroxystearic acid 0.2 0.2 0.2 0.2 0.2 0.2 (external lubricant) BisphenolA 0.2 0.2 0.2 0.2 0.2 0.2 Calcium stearate 0.8 û.8 0.8 0.8 0.8 0.8 Zincstearate 1.0 1.0 1.0 1.0 1.0 1.0 Hydrotalcite 10 10 10 10 10 10 (ZnO:3MgO:Al203:CO2:8-9H20) . . . . . .
Dibenzoylmethane - 0.5 - 0.5 - 0.5 Stericallyhinderedamine 6)* 0.3 0.3 - -Stericallyhinderedamine ~)* 0.3 0.3 - -Stericallyhinderedamine ~)* - 0.3 0.3 .
- . :

.
,:

2 ~

5~
Mathis Therrnotakter test at 190C: YI

\~xample Min. \ 1 2 3 4 5 6 . .
0 23.4 7.5 21.7 6.9 21.6 6.8 43.3 20.2 44.9 18.2 37.~ 10.3 45.3 24.1 47.8 23.9 39.8 11.8 48.5 30.3 55.9 35.6 42.4 14.6 57.2 44.9 36.9 51.9 ~6.6 19.5 54.6 57.3 50.8 55.0 55.2 28.5 50.2 57.3 52.3 49.7 54.6 45.4 52.1 54.0 54.3 53.2 50.1 56.1 55.7 54.5 55.8 52.3 53.0 - 57.0 - SS.3 53.1 54.7 Examples 7-9: PVC compositions are prepared by mixing the individual components according to the table below (amounts given in parts by ,veight). These are recipes for unplasticized PVC ~llms. The mixtures according to Examples 7 to 9 are rolled on mixed rolls at 180C for S minutes. The 0.3 mm thick rolled sheet formed is used to produce filrn specimens which are subjected to heat in a test furnace (~Mathis Therrnotakter;Type LTF-ST) at 190C. After the intervals shown in the table below, the Yellowness Index (YI) according to ASTM D 1925-70 is deterrnined on each of the test specimens (high YI
values mean strong discoloration and thus low stabillty).

- ~

~ample Recipe ~ 7 8 9 S-PVC, K value 57 100 100 100 Impact modifier based on methyl 2.5 2.5 2.5 butadienestyrene Processing aid containing polymethyl 1.5 1.5 1.5 methacrylate Glyceryl hydroxystearate 0.5 0.5 0.5 Calcium stearate .75 .75 .75 Zinc stearate .75 .75 .75 Stearoylbenzoylmethane 0.3 0.3 0.3 Hydrotalcite (ZnO:3MgO:AI2O3:CO2:8-9H2O) 0.6 . 0.6 0.6 Sterically hindered amine (~)* 0.3 Stericallyhinderedamine ~* 0.3 Stericallyhinderedamine (~)* 0.3 Mathis Thermotakter test at 190C: YI

\~xample Mi~ 7 8 9 0 10.410.8 10.3 35.027.7 24.1 12.~ 44.138.2 26.3 20.0 68.071.9 38.4 27.5 90.~117 77.3 35.0 125 - 98.2 42.S 115 ., '.

,- ' , .

-` 2~2~

*) Sterically hindered amines mentioned in Examples 1 to 9, depending on the reference number, have the following meaning:

NH + CH2 + CH3 N ~ CH3 CH3 N (CH2)6 N ]m ~ ~ m = 2-200 H3C > ~ CH3 H3C ~ ~ CH3 (~ .
R R
R - NH- (CH2)3 - N - (CH2)z - N - (CH2)3 - NH R

Bu~l ~ CH3 R =~ ~ N : ~ N - CH3 N ~ N ~ CH3 H ~ CH
Bu~l - N ~ N - CH3 H3C C~13 ~3 ~
R R
R - NU - (CU2)3 - N - ~ U22 - N - (CU213 - NU - R

2~3~9 Butyl ~
R = ~N~l_N < NH
N~N ~<CH3 H~7<CH
Butyl--N--~7<NH

The sterically hindered amines of the formulae O to (O are at the same time alsopreferred compounds.

. . . . . . .

::: ;.. - .. ;- .:~ - : . -

Claims (25)

What is claimed is:

1. A stabilized chlorine-containing polymer composition, containing a chlorine-containing polymer and a stabilizer mixture, containing:
a) at least one cyclic or acyclic sterically hindered amine, with the exception of the compound of the formula , where R is in plasticizer-containing polymer compositions, b) at least one organic zinc compound and/or inorganic zinc compound from the series comprising carbonates, chlorides, sulfates, oxides, hydroxides, basic oxides and mixed oxides, and c) at least one compound from the series of hydrotalcites.

d) A polymer composition according to claim 1, containing d) at least one 1,3-diketone.

3. A polymer composition according to claim 1, containing e) at least one organic or inorganic calcium compound.

4. A polymer composition according to claim 1, containing as a) at least one cyclic sterically hindered amine, in particular a compound from the series of derivatives of polyalkylpiperidines containing at least one group of the formula III

(III) in which R is hydrogen or methyl.

5. A polymer composition according to claim 4, in which the polyalkylpiperidine radical of the formula III is substituted in the 4-position by one or 2 polar substituents or a polar spiro ring system.

6. A polymer composition according to claim 1, containing as b) at least one organic zinc compound from the series comprising aliphatic saturated C2-C22 carboxylates, aliphatic olefinic C3-C22 carboxylates, aliphatic C2-C22 carboxylates which are substituted by at least one OH group, cyclic and bicyclic carboxylates having 5-22 C atoms, aromatic C7-C22 carboxylates, aromatic C7-22 carboxylates which are substituted by at least one OH group, Cl-Cl6alkyl-substituted phenylcarboxylates, phenyl-C1-C16alkylcarboxylates, C6-C18 phenolates, C5-C26 chelates of 1,3-diketones or .beta.-ketocarboxylic esters or dehydroacetic acid derivatives and mercaptides based on mercaptocarboxylic esters and glycinates.

7. A polymer composition according to claim 1, containing as c) at least one compound from the series of hydrotalcites of the general formula (I) (I) in which 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 1-4, x is a number from 0-0.5, m is a number from 0-2, and A is OH-, Cl-,Br-, CIO4-, HCO3-, CH3COO-, CO32-, SO42-, , (CHOHCOO)22-, (CHOH)4CH2OHCOO-, C2H4(COO)22-, (CH2COO)22-, CH3CHOHCOO-, SiO32-, SiO44-, Fe(CN)63-, Fe(CN)64- or HPO42.

8. A polymer composition according to claim 1, containing as c) at least one compound of the general formula Ia M?A12(OH)2x+6nz(An-)2?mH2O (Ia) in which in the present formula Ia M2+ is at least one metal from the series comprising Mg and Zn, An- is an anion, in which n is the valence of the anion, m is a positive number and x and z are positive numbers.

9. A polymer composition according to claim 2, containing as d) at least one 1,3-diketone of the general formula II or IIa (II) (IIa) in which Ra is alkyl of 1 to 22 C atoms, C5-C10hydroxyalkyl, alkenyl of 2 to 22 C atoms, phenyl, phenyl substituted by -OH, C1-C4alkyl, C1- to C4alkoxy or halogen, phenyl-C1-C4alkyl, a group of the formula , cycloalkyl of 5 to 12 ring C atoms, or cycloalkyl of 5 to 12 ring C atoms substituted by 1 to 3 C1-C4alkyl groups, Rc is alkyl of 1 to 22 C atoms, C5-C10hydroxyalkyl, alkenyl of 2 to 22 C atoms, phenyl, phenyl substituted by -OH, C1-C4alkyl, C1- to C4alkoxy or halogen, or phenyl-C1-C4alkyl, a group of the formula , cycloalkyl of 5 to 12 ring C atoms, or cycloalkyl of 5 to 12 ring C atoms substituted by 1 to 3 C1- to C4alkyl groups, Rb is -H, alkyl of 1 to 18 C atoms, alkenyl of 2 to 12 C atoms, phenyl, phenyl substituted by C1-C4alkyl, phenyl-C1-C4alkyl, or a group of the formula in which Rd is -CH3, -C2H5 or phenyl, or in which Ra and Rb together are a tetramethylene radical or a tetramethylene radical fused with a benzo radical, and X is alkylene of 1 to 4 atoms..

10. A polymer composition according to claim 2, containing as d) at least one 1,3-diketone of the general formula IIb (IIb) in which R1 is C1-C10alkyl, C5-C10hydroxyalkyl, phenyl, hydroxyphenyl, C7-C10phenylalkyl or C7-C10phenylalkyl substituted on the phenyl ring by an OH group and R2 is C5-C10hydroxyalkyl, hydroxyphenyl or C7-C10phenylalkyl substiluted on the phenyl ring by an OH group, under the condition that R2 is other than hydroxyphenyl, if R1 is phenyl or hydroxyphenyl.

11. A polymer composition according to claim 3, containing as e) at least one calcium soap of the general formula in which Rx is an alkyl group of 1 to 22 C

atoms or an alkenyl group of 2 to 22 C atoms, phenyl, phenyl-C1-C4alkyl or C1-C8alkylphenyl.

12. A polymer composition according to claim 4, containing as derivative of polyalkylpiperidines a derivative of 2,2,6,6-tetramethylpiperidine.

13. A polymer composition according to claim 4, containing as derivative of polyallkylpiperidines a compound of the formula VIII

(VIII), in which n is the number 1 or 2 and R18 is a group of the formula in which R is hydrogen or methyl and R11 is hydrogen, oxyl, hydroxyl, C1-C12alkyl, C3-C8alkenyl, C3-C8alkynyl, C7-C12aralkyl, C1-C18alkoxy, C5-C8cycloalkoxy, C7-C9phenylalkoxy, C3-C8alkanoyl, C3-C5alkenoyl, C1-C18alkanoyloxy, benzyloxy, glycidyl or a group -CH2CH(OH)-Z, in which Z is hydrogen, methyl or phenyl, E is -O- or -NR11-, A is C2-C6alkylene ,or -(CH2)3-O- and x is the number 0 or 1, R19 is identical to R18 or one of the groups -NR21R22, -OR23, -NHCH2OR23 or -N(CH2OR23)2, R20 is, if n is 1, identical to R18 or R19, and, if n is 2, a group -E-B-E-, in which B is C2-C6alkylene which may be interrupted by -N(R21)-, R11 is C1-C12alkyl, cyclohexyl, benzyl or C1-C4hydroxyalkyl or a group of the formula R22 is C1-C12alkyl, cyclohexyl, benzyl, C1-C4hydroxyalkyl and R23 is hydrogen, C1-C12alkyl or phenyl or R21 and R22 together are C4-C5alkylene or -oxaalkylene, for example or a group of the formula or R21 and R22 are also each a group of the formula

14. A polymer composition according to claim 13, containing one of the compounds of the formula R-NH-(CH2)3-?-(CH2)2-?-(CH2)3-NH-R

where R is or R-NH-(CH2)3-?-(CH2)2-?-(CH2)3-NH-R

where R is

15. A polymer composition according to claim 4, containing as derivative of polyalkylpiperidines an oligomeric or polymeric compound from the series comprising polyesters, polyethers, polyamides, polyamines, polyurethanes, polyureas, polyaminotriazines, poly(meth)acrylates, poly(meth)acrylamides and copolymers thereof whose repeating structural unit contains a 2,2,6,6-tetramethylpiperidine radical of the formula III.

16. A polymer composition according to claim 15, containing a compound of the formula in which m is a number from 2 to 200.

17. A polymer composition according to claim 6, containing as b) an organic zinccompound in which the organic zinc compound is a salt of a carboxylic acid of 7 to 20 C
atoms or a C7-C20alkylphenolate.

18. A polymer composition according to claim 7, containing as c) at least one compound from the series of hydrotalcites of the general formula I
(I), in which M2+ is Mg or a solid solution of Mg and Zn, An- is CO32-, x is a number from 0 to 0.5 and m is a number from 0 to 2.

19. A polymer composition according to claim 18, containing at least one of the compounds of the formulae 4MgO?A12O3?CO2?9H2O, 4MgO-A12O3-CO2?6H2O.

ZnO?3MgO?A12O3?CO2?8-9H2O or ZnO?3MgO?A12O3?CO2?5-6H2O.

20. A polymer composition according to claim 1, containing, relative to the composition, a) 0.01 to 1.5 parts by weight of cyclic or acyclic sterically hindered amines, b) 0.01 to 2 parts by weight of an organic or inorganic zinc compound, and c) 0.1 to 3 parts by weight of compounds from the series of hydrotalcites.

21. A polymer composition according to claim 1, containing d) 0.05-5 parts by weight of a 1,3-diketone.

22. A polymer composition according to claim 1, containing e) 0.05-5 parts by weight of an organic or inorganic calcium compound.

23. A polymer composition according to claim 1, in which the polymer is polyvinyl chloride or contains polyvinyl chloride.

24. Use of a polymer composition according to claim 1 as unplasticized profile for outdoor application or as rigid films.

25. Use of a polymer composition according to claim 1 as slush mould or as crash pads.

FO 7.3/SA/ms*