CA2056565C - Stabilised chlorine-containing polymers - Google Patents

Abstract

Chlorine-containing polymers can be stabilised against thermal and actinic degradation by addition of a) a sterically hindered amine, b) a zinc compound, c) a calcium, magnesium and/or barium compound, and d) a 1,3-dicarbonyl compound. Other additives such as phosphites or epoxides can further improve the stabilisation.

Description

_ , _ ;~c~s:~sss Stabilised chlorine-containing polymers The invention relates to stabilised chlorine-containing polymer compositions which contain a sterically hindered amine in combination with other stabilisers.
It is known that sterically hindered amines, for example derivatives of 2,2,6,6-tetramethylpiperidine, are excellent stabilisers for polymers against damage by short-wave light. However, addition of sterically hindered amines of this type to polyvinyl chloride or other chlorine-containing polymers frequently results in discoloration during processing or on use. Only addition of costabilisers allows this discoloration to be prevented or reduced.
Thus, JP-A-82/168 933 describes films made from plasticised polyvinyl chloride which are protected against light by means of a sterically hindered amine and a UV
absorber and contain, as costabilisers, zinc stearate, barium stearate and epoxidised soya oil.
JP-A-86/163 965 describes the stabilisation of PVC by means of a sterically hindered amine, a calcium/zinc stabiliser and epoxidised Soya oil.
EP-A-237 485 recommends a combination of sterically hindered amines and organotin stabilisers for stabilising rigid PVC, with further possible additives being titanium dioxide and calcium stearate. EP-A-421 933 proposes a combination of sterically hindered amines and zinc compounds and a hydrotalcite for stabilising chlorine-containing polymers, where further possible additives are 1,3-diketones and calcium compounds.
EP-A-432 096 proposes a combination of sterically hindered amines and zinc compounds and a blowing agent or foaming agent, it also being possible to use calcium compounds and 1,3-diketones.
It has now been found that stabiliser combinations of this type give very satisfactory results, even without organotin stabilisers and without hydrotalcite and without blowing agents or foaming agents, if they contain a zinc compound, a calcium, magnesium or barium compound and a 1,3-dicarbonyl compound.

2 - ~C~~.~'.J~J
The invention therefore relates to a stabilised chlorine-containing polymer composition comprising a) at least one chlorine-containing polymer, b) at least one sterically hindered amine, c) at least one organic or inorganic zinc compound, d) at least one organic or inorganic calcium, magnesium and/or barium compound, and e) at least one 1,3-dicarbonyl compound, but no organotin compounds, no hydrotalcite compounds and no blowing agents or foaming agents.
The chlorine-containing polymer may be, for example, a polymer or copolymer of vinyl chloride or of vinylidene chloride or a post-chlorinated polymer or copolymer of vinyl chloride or of vinylidene chloride, a chlorinated polyolefin, for example a chlorinated polyethylene, a chlorinated polymer or copolymer of styrene or of butadiene or a chlorinated rubber or a rubber hydrochloride, or a mixture of a chlorine-containing polymer of this type and another chlorine-containing or chlorine-free polymer.
The chlorine-containing polymer is preferably a polyvinyl chloride or a copolymer containing at least 80 % of vinyl chloride or a mixture (polyblend) of a homopolymer or copolymer of this type with another chlorine-containing or chlorine-free polymer. The chlorine-containing polymer may be an emulsion, suspension or bulk polymer.
The sterically hindered amine is preferably a polyalkylpiperidine derivative and preferably contains at least one group of the formula I

-N
RCH2 ~CH3 in which R is hydrogen or methyl, and is in particular a derivative of 2,2,6,6-tetramethylpiperidine of the formula I in which R is hydrogen. These compounds are preferably substituted in the 4-position of the piperidine ring by one or two polar groups or by one spiro ring system. These compounds may be low-molecular-weight or oligomeric or polymeric compaunds.

~CI~ vSDJ

The following classes of polyalkylpiperidines are particularly important:
a) Compounds of the formula II

Rtt N O Rt2 II

n in which n is a number from 1 to 4, preferably 1 or 2, R is hydrogen or methyl, Rt l is hydrogen, oxyl, hydroxyl, Ct-Ct2alkyl, C3-Cgalkenyl, C3-Cgalkynyl, C~-Ct2aralkyl, Ct-Ct8alkoxy, CS-CBCycloalkoxy, C~-Cgphenylalkoxy, Ct-Cgalkanoyl, C3-Csalkenoyl, Ct-Cl8alkanoyloxy, benzyloxy, glycidyl or a -CH2CH(OH)-Z group in which Z is hydrogen, methyl or phenyl, Rtt preferably being H, Ct-C4alkyl, allyl, benzyl, acetyl or acryloyl, and Rt2, if n is 1, is hydrogen, Ct-Ctgalkyl, 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 phosphorus-containing acid, or a monovalent silyl radical, preferably a radical of an aliphatic carboxylic acid having 2 to 18 carbon atoms, of a cycloaliphatic carboxylic acid having 7 to 15 carbon atoms, of an a,(i-unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms; if n is 2, Rt2 is Ct-Ct2alkylene, C4-Ct2alkenylene, xylylene, a divalent radical of an aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxyli~ acid, dicarbamic acid or phosphorus-containing acid, or a divalent silyl radical, preferably a radical of an aliphatic dicarboxylic acid having 2 to 36 carbon atoms, of a cycloaliphatic or aromatic dicarboxylic acid having 8 to 14 carbon atoms or of an aliphatic, cycloaliphatic or aromatic dicarbamic acid having 8 to 14 carbon atoms; if n is 3, Rt2 is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, of an aromatic tricarbamic acid or of a phosphorus-containing acid, or a trivalent silyl radical; and if n is 4, R12 is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.
Any Ct-Ct2alkyl substituents are, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, ~~IUvi~~a~

tort-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.
Ct-Ctxalkyl Rtt or Rt~ is, for example, one of the abovementioned groups or, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
C3-CBalkenyl Rt t may be, for example, 1-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl or 4-tert-butyl-2-butenyl.
C3-CBalkynyl Rt t is preferably propargyl.
C~-Ct2aralkyl Rt t is, in particular, phenethyl or especially benzyl.
Ct-CBalkanoyl Rt t is, for example, formyl, propionyl, butyryl or octanoyl, preferably acetyl, and C3-Csalkenoyl Rt t is, in particular, acryloyl.
A monovalent carboxylic acid radical Rt2 is, for example, an acetic acid, caproic acid, stearic acid, acrylic acid, methacrylic acid, benzoic acid or (3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid radical.
A divalent dicarboxylic acid radical Rt2 is, for example, a malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, malefic acid, itaconic acid, phthalic acid, dibutylmalonic acid, dibenzylmalonic acid, butyl(3,5-di-tert-butyl-4-hydroxybenzyl)malonic acid or bicycloheptenedicarboxylic acid radical.
A trivalent tricarboxylic acid radical Rtz is, for example, a trimellitic acid, citric acid or nitrilotriacetic acid radical.
A tetravalent tetracarboxylic acid radical Rt2 is, for example, the tetravalent radical of butane-1,2,3,4-tetracarboxylic acid or of pyromellitic acid.
A divalent dicarbamic acid radical Rt2 is, for example, a hexamethylenedicarbamic acid or 2,4-toluylenedicarbamie acid radical.
Preference is given to compounds of the formula II in which R is hydrogen, Rtt is hydrogen or methyl, n is 2 and Rt2 is the diacyl radical of a dicarboxylic acid having 4 to ~C~..'~'.:~JE~J
_5_ 22 carbon atoms.
The following are examples of polyalkylpiperidine compounds of this class:
I ) 4-hydroxy-2,2,6,6-tetramethylpiperidine 2) 1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine 3) I-benzyl-4-hydroxy-2,2,6,6-tetramethylpipeiidine 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-pentamethylpiperidine 8) 1,2,2,6,6-pentamethylpiperidin-4-yl ~i-(3,5-di-tert-butyl-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 I1) di(2,2,6,6-tetramethylpiperidin-4-yl)glutarate 12) di(2,2,6,6-tetramethylpiperidin-4-yi)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-diethyl-piperidin-4-yl)sebacate 16) di(1-a:lyl-2,2,6,6-tetramethylpiperidin-4-yl)phthalate 17) 1-hydroxy-4-(3-cyanoethyloxy-2,2,6,6-tetramethylpiperidine 18) 1-acetyl-2,2,6,6-tetramethylpiperidin-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(1,2,2,6,6-pentamethylpiperidin-4-yl) dibutylmalonate 23) di(1,2,2,6,6-pentamethylpiperidin-4-yl) butyl(3,5-di-ten-butyl-4-hydroxybenzyl) malonate 24) di(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate 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-tetramethylpiperidine) 27) toluene-2',4'-bis(4-carbamoyloxy-1-n-propyl-2,2,6,6-tetramethylpiperidine) 28) tetra(2,2,6,6-tetramethylpiperidin-4-yl) butanetetracarboxylate 29) tetra(I,2,2,6,6-pentamethylpiperidin-4-yl) butanetetracarboxylate 30) tris(1-propyl-2,2,6,6-tetramethylpiperidin-4-yl) phosphite 31) tris(1-propyl-2,2,6,6-tetramethylpiperidin-4-yl) phosphate - 6 - 2~~ 3J~J
32) phenyl bis-(1,2,6,6-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) I-glycidyl-4-hydroxy-2,2,6,6-tetramethylpiperidine b) Compounds of the formula III, Rlt N N R14 III

n in which n is the number 1 or 2, R and R11 are as defined under a), R13 is hydrogen, Cl-Cl2alkyl, C2-Cshydroxyalkyl, CS-C~cycloalkyl, C~-C8aralkyl, C2-Clgalkanoyl, C3-Csalkenoyl, benzoyl or a group of the formula Ril N
RCH2 \CH3 and, if n is l, R14 is hydrogen, Cl-Clgalkyl, C3-Csalkenyl, CS-C~cycloalkyl, Cl-C4alkyl which is substituted by a hydroxyl, cyano, alkoxycarbonyl or carbamide group, glycidyl, a group of the formula -CHZ-CH(OH)-Z or of the formula -CONH-Z in which Z is hydrogen, methyl or phenyl; if n is 2, R14 is Gz-Cl2alkylene, C6-Cl2arrlene, xylylene, a -CH2-CH(OH)-CH2 group or a -CHZ-CH(OH)-CH2-O-D-O- group in which D is C2-Clpalkylene, C6-Clsarylene or C6-Clzcycloallylene, or, with the proviso that R13 is not alkanoyl, alkenoyl or benzoyl, R14 is alternatively a divalent radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid or may alternatively be the -CO- group, or, if n is I, R13 and R14 together may be the divalent radical of an aliphatic, cycloaliphatic or aromatic 1,2- or 1,3-dicarboxylic acid.

~

C; ~~ t-' r I4i~.~....1J~J
.Any C~-C~~alkyl or C~-C~~alkyl substituents are as defined above under a).
Any CS-C~cycloalkyl substituents are, in particular, eyclohexyl.
C~-CBaralkyl Rt3 is, in particular, phenylethyl or especially benzyl.
C2-Cshydroxyalkyl Rt3 is, in particular, 2-hydroxyethyl or 2-hydroxypropyl.
C2-CtBalkanoyl Rt3 is, for example, propionyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl or octadecanoyl, but preferably acetyl, and Cg-Csalkenoyl Rt3 is, in particular, acryloyl.
C2-Cgalkenyl Rt4 is, for example, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl or 2-octenyl.
Ct-C4alkyl Rt4 which is substituted by a hydroxyl, cyano, alkoxycarbonyl or carbamide group may be, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl, methoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2-aminocarbonylpropyl or 2-(dimethylaminocarbonyl)ethyi.
Any C2-Ct2alkylene substituents are, for example, ethylene, propylene, 2,2,-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.
Any C6-Ctsarylene substituents are, for example, o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.
C6-Ct2cycloalkylene D is, in particular, cyclohexylene.
Preference is given to compounds of the formula III in which n is 1 or 2, R is hydrogen, Rtt is hydrogen or methyl, Rt3 is hydrogen, Ct-Ct2alkyl or a group of the formula ~C~~~J~J
_g_ Rcn, ctt; R
Rtt N
RCH2 \CH3 and, if n is 1, Rt4 is hydrogen or Ct-Ct2alkyl and, if n is 2, Rt4 is C2-CBalkylene.
The following are examples of polyalkylpiperidine compounds of this class:
37) N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yi)hexamethylenel,6-diamine 38) N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenel,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-hydroxypropylene-1,3-diamine 43) N,N'-bis(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-tetramethylpiperidin-4-yl)-(3-aminodipropionate 46) The compound of the formula CH3 - N N - CH2- CH(OH}- CH2-O

CH3 -N N CH2-CH(OH~-CH2-O
i 2~'5~5~5 _g_ 47) 4-(bis-2-hydroxyethylamino)-1,2,2,6,6-pentamethylpiperidine 48) 4-(3-methyl-4-hydroxy-5-ten-butylbenzamido)-2,2,6,6-tetramethylpiperidine 49) 4-methacrylamido-1,2,2,6,6-pentamethylpiperidine c) Compounds of the formula IV

O
Rtt - N R15 IV

RcH2 cH3 n in which n is the number 1 or 2, R and Rt t are as defined under a), and, if n is 1, Rts is C2-C8alkylene, C2-Cghydroxyalkylene or C4-C22acyloxyalkylene, and, if n is 2, Rts is the (-Cl-i2)ZC(CH2-)2 i;TOUp.
C2-Csalkylene or C2-Cghydroxyalkylene Rt5 is, for example, ethylene, 1-methylethylene, propylene, 2-ethylpropylene or 2-ethyl-2-hydroxymethylpropylene.
C4-C22acyloxyalkylene Rts is, for example, 2-ethyl-2-acetoxymethylpropylene.
The following are examples of polyalkylpiperidine compounds of this class:
50) 9-aza-8,8,1U,10-tetramethyl-1,5-dioxaspiro[5.5]undecane 51) 9-aza-8,8,10,10-tetramethyl-3-ethyl-1,5-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-pentamethyll,5-dioxaspiro[5.5]undecane 54) 9-aza-3-ethyl-3-acetoxymethyl-9-acetyl-8,8,I0,10tetramethyl-1,5-dioxaspiro[5.5]undecane 55) 2,2,6,6-tetramethylpiperidine-4-spiro-2'-(I',3'-dioxane)-5'-spiro-5"-(1 ",3"-dioxane)-~2"-spiro-4"'-(2"',2"',6"',6"'tetramethylpiperidine).
d) Compounds of the formulae VA, VB and VC

- l~ - 2~~::5s~

RCH2 CH3~R
I
N-C=O
R'~ - N ( VA
~C-N R 1~
Ii n RCH2 CH3 R Tt R N
\N-C=O VB
I

RCH2 CH3~R T1 RyN ~ VC
~C -N R 1~

n in which n is the number 1 or 2, R and Rtt are as defined under a), R16 is hydrogen, Ct-Cl2alkyl, allyl, benzyl, glycidyl or C2-C6alkoxyalkyl, and, if n is l, R1~
is hydrogen, C1-Cl2alkyl, C3-Csalkenyl, C~-Cgaralkyl, Cs-C~cycloalkyl, C2-C4hydroxyalkyl, C2-C6alkoxyalkyl, C6-Cloaryl, 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 Ct-C4alkyl or phenyl, and, if n is 2, Rl~ is C2-Ct2alkylene, C4-Cl2alkenylene, C6-Cl2arylene, a -CH2-CH(OH)-CH2-O-D-O-CHI,-CH(OH)-CHZ- group in which D is C2-Ctoalkylene, C6-Clsarylene or C6-Cl2cycloalkylene, or Rl~ is a -CH2CH(OZ')CH2-(OCH2-CH(OZ')CH2)2- group in which Z' is hydrogen, C~-Clgalkyl, allyl, benzyl, C2-Cl2alkanoyl or benzoyl, Tl and T2, independently of one another, are hydrogen, Cl-Cl8alkyl or unsubstituted or halogen- or Ct-C4alkyl-substituted C6-Cloaryl or C~-Cyaralkyl, or Tl and T2, together with the carbon atom connecting them, form a Cs-Ct2cycloalkane ring.
Any Cl-Cl2alkyl substituents are, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tent-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.

2(~5~5f~5 Any Ct-CtHalkyl substituents may be, for example, the abovementioned groups or, for example, n-tr-idecyl, n-tctradecyl, n-hexadecyl or n-octadecyl.
Any C2-C6alkoxyalkyl substituents are, for example, methoxymethyl, ethoxymethyl, propoxymethyl, tert-butoxymethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl, tert-butoxyethyl, isopropoxyethyl or propoxypropyl.
C3-Csalkenyl R~~ is, for example, 1-propenyl, allyl, methallyl, 2-butenyl or 2-pentenyl.
C?-C9aralkyl R~~, Tl and T2 are, in particular, phenethyl or especially benzyl. If Tt and T2, together with the carbon atom, form a cycloalkane ring, this may be, for example, a cyclopentane, cyclohexane, cyclooctane or cyclododeeane ring.
C2-C4hydroxyalkyl R~~ is, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.
C6-Ctparyl Rl~, Tt and T2 are, in particular, phenyl, a- or ~i-naphthyl, unsubstituted or substituted by halogen or Ct-C4alkyl.
C2-Ct2alkylene Rl' is, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.
C4-Ct2alkenylene R~~ is, in particular, 2-butenylene, 2-pentenylene or 3-hexenylene.
C6-CtZarylene R17 is, for example, o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.
C2-Ct2alkanoyl Z' is, for example, propionyl, butyryl, octanoyl or dodecanoyl, but preferably acetyl.
C2-Ctoalkylene, C6-Ctsarylene or C6-Ct2cycloalkylene D is as defined under b).
Preferred compounds of class d) are the compounds of the formula VA in which n is 1, R
is hydrogen, Rtt is hydrogen or methyl, Rt6 is hydrogen or Ct-Ct2alkyl, and R~~ is Ct-Ct2alkyl.

- 12 _ i4:C~~.~1J~J
The following are examples of polyalkylpiperidine compounds from class d):
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-glycidyl-1,3,8-triaza-7,7,8,9,9-pentamethylspiro(4.5]decane-2,4-dione 60) 1,3,7,7,8,9,9-heptamethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione 61) 2-isopropyl-7,7,9,9-tetramethyl-1-oxa-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[5.1.11.2]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 formulae below:

2C'~~S~o M
x U
U ~ U
J
M
x ~M
z U=o x ~ v U .i.
z U=O
U-z V x z U U -_ z O
M ~ O
N U U
N
x U
O_ x Z U
x U
U-z N
U O N
x U
I N
x x x U x n O ~ U x U
v o x N
II I U j ~~-z U z ~Z U=o ~ ~ z U=O
x O U=O
z UFO
M M
U ~ U U x r, U U
U U z en x ~ U
x x x ~ M
U U U U x x z U I U U
M
x U
0o O~

~~,~'. iJ~

e) Compounds of the formula VI, N N VI
~ ~ R20 R19/ \N
n in which n is the number 1 or 2, and Rlg is a group of the formula R CHg CH2R
- E - (A x ~N - Rll CH3 ~CH2R
in which R and Rl1 are as defined under a), E is -O- or -NR21-, A is C2-C6alkylene or -(CH2)3-O-, and x is the number 0 or 1, Rl9 is identical to Rlg or one of the groups -NR21R22, -ORS, -NHCH20R~ or -N(CH2OR23)2, R2~, if n is 1, is identical to Rl8 or R19 and, if n is 2, is an -E-B-E- group in which B is C2-C6alkylene which may be interrupted by -N(R21)-, R21 is C1-Cl2alkyl, cyclohexyl, benzyl, Cl-C4hydroxyalkyl or a group of the formula ~N-Ril CH3 ~CH2R
R22 is Cl-Cl2alkyl, cyclohexyl, benzyl or Cl-C4hydroxyalkyl, and R23 is hydrogen, C1-Cl2alkyl or phenyl, or R21 and R22 together are C4-Csalkylene or C4-Csoxaalkylene, for example ~C~~~J~J

-CH2CHy~ -CH2CH2 \
o , or a group of the formula /N _ R1 t - co.~cH~~ - CH2CH2J
or R2t and R~ are alternatively each a group of the fornlula N\
~NH-A-_ 'N
CH3 CH ~T'%3 H
Any C1-Ct2alkyl 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-C6alkylene A is, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene or hexamethylene.
If R2t and R22 together are C4-Csalkylene or C4-CSOxaalkylene, this is, for example, tetramethylene, pentamethylene or 3-oxapentamethylene.
Preference is given to compounds of the formula VI in which n is 4, Rt8 and Rt9 are a CHg CH3 N \N-Rtl CH~CHg HN N
N

~C~~:5f~5 ~~roup in which Rtt is hydrogen or methyl and R2t is hydrogen or Ct-C6alkyl, and R2~ is a tetravalent radical of an aliphatic tetramine.
The following are examples of polyalkylpiperidine compounds from class e):

H3C ' CH3 7l)) N - C4H9 N' \ N
(CH CH ) N- _N_ 'N(CH CH ) N(C4H9)2 N N
71 ) C2H5 - N N ~ ~ N ~N - C2H5 CH3 CH3 CH3 ~CH3 N~N -NH-CH CH CH -O N-CH
72) ~ ~ where R = 2 2. 2 3 R \N R H3C CH3 2(~~~Sf~~
-m-M ,y.M
x ~ U
U
x x U U
a M
v z x v v ~z v z~~ ~ z z x - /z M
M x x U
V
M M
x x o. v U
x v z ~ z U
x z zx U
M ~ N
x x M U x U
M M
U Z V ~ U U
x z -( z \ M U (V M x U U x Vcv ~ - V U
U x ! U
N z z z zx x U ~~ , N
x U-z z U M x x U
U
z M M
x x ! U U
N
/ z z ~~ z z x U -z U
Ov ~~~ M
M M M
v-z v U U
x z x U U
U x V
U
x U
M

- 1$ - 2C'~~,~'.J~J
R K
75) R-NH- (Cli1)3N- (CH2)2-N- (CH2)3~NH-R
where R =

N ~~H9 ~N ~NH
N ' 'N
~/ CH3 CH3 CaH9 N
CH3 ' .CH3 H
R R
7 C~ R - NH- (CH2)3 N - (CH2)2- N - (CH2y3 NH- R
where R =

N t4H9 N ,N - CH3 N ' 'N

CH3 I .CH3 - ~9 - 2t~~~S~S
CFi3 R R CH3 i i I
~~ R - N (CH.'S N - (CH's-N - (CH2)3 N R
where R =

N ~4H9 ~N ~N-CH3 N ~ ~ ~N

CH3 I.CH3 CHg CgHI~ N

N N
N~NH(CH2y3 CBHI~- N
CHg I'CH3 H

~~~u v~~a.~
_ 7~ _ CH3 ~ ~CHg 79) N - C4H9 CH3 CH3 N ~;V CH3 CH3 HO-CH CH -N N~N~N N-CH CH -OH

CH3 CH3 CH3 CHg CH2-CH=CH2 HgC N CH3 H3C ~ _CH3 g0) N - C4H9 H3C CH3 N~N CH
/ 'N' \ 3 H2C= HC-H2C- N N N N - CH2-CH= CH2 H3C CH3 CH3 CHg f) Oligomeric or polymeric compounds whose recurnng structural unit contains a polyalkylpiperid~ne radical of the formula (I), in particular polyesters, polyethers, , polyamides, polyamines, polyurethanes, polyureas, polyaminotriazines, poly(meth)acrylates, poly(meth)acrylamides, and copolymers thereof which contain these radicals. Of these, the polyesters and polyaminotriazines are preferred.
Examples of 2,2,6,6-polyalkylpiperidine light stabilisers from this class are compounds of the formulae below, in which rn is a number from 2 to about 200.

iW',r'.;~J~J

R1) O O
II II
~C-CH2-CH2-C-O-CH2-CH2-N O
m 82) CH3 CH3 O O CH3 CHg O O
II II II II
(~ v -j-CH2-CH2-N O-C- (CH2)4-C-O N-CH2-CH2-O-C- (CH2)4-C
~m CH3 CH3 CHg CHg 83) NH- (CH2~-N NH-- ~~ ~ ~~ -NH N-. (CH2y~_NH- ~~
m CH3 ~ ~ CH3 CH3 \C2H5 CH3 ~CoHc 84) NH- ~ - CH2- ~ - CH3 N% \NCH3 CH3 N (CHZ)6 N
-N m CH3 CH3 CHg CH3 CH3 ~ H CH3 CH3 H CH3 _ 7'? _ ~~1~~i5~.~
85) N CH2- CH(OH~- CH2 ~m CH3 I 'CH3 86) CHg CH3 CH3 CH3 O C H
~O N-CH2-CH=CH-CH2-N O-C-C C
L m 87) N
N - (CH2)6 N
N ' 'N
CH3 CH3 CH3 , _CH3 N /y\H

88) O N-CHZ ~ ~ CH2-N O-C- (CH2)4-C

m ~~WjS~J

gc)) O C2H~ O CH3 CHg II I ~
C -C C-O CH2-CH2-N O-f-m 90) C - CH2-f-~m O=C CH3 CH3 91) ~C-CH2 L ~m O=C CH3 CHI
C6H~3 -N N CH3 ~C'~ ::5~~

92) 93) N
N i 'N N- (CH2)6 N
N ~ H3 CH3 CH3 CH3 CH3 N _CH3 CH3 N- 'CH3 H H
N (CH2)6 N CH2~ CH2 ~m CH3 / IC' f'CH3 CH3 CH3 CH3 7 N//''~~CH3 CH3 N CH3 H H
94) II II
N (CH2)6 N C CH2 C
CH3 CH3 CH3 \?~~CH3 m CH3 N CH3 CHg N CH3 H H
Of these classes, a), d), e) and fj are particularly preferred, in particular the compounds 10, 13, 14, 23, 24, 28, 29, 63> 65, 75, 77, 81, 84 and 92.
These sterically hindered amines are known compounds and many are commercially available. It is also possible to use two different sterically hindered amines, for example one of low molecular weight and one of higher molecular weight, as described in US-A-4 692 486.
The zinc compound used as component c) may be an organozinc compound, for example the zinc salt of a carboxylic acid, sulfonic acid, phosphonic acid or phosphinic acid, or the zinc salt of a phenol or a zinc chelate, for example the enolate of a 1,3-diketo compound.

2C~~:~5~~
Component c) may alternatively be an inorganic zinc compound, for example an oxide, hydroxide, carbonate, phosphate, phosphite, sulfate, chloride, fluoride or hypophosphite.
c) is preferably the zinc salt of a Ct-C~carboxylic acid, of a C6-Ctgphenol or of a CS-C22-1,3-diketone. The carboxylic acid may be a saturated or unsaturated aliphatic or cycloaliphatic carboxylic acid or an aromatic or aromatic-aliphatic carboxylic acid.
Examples are formic acid, acetic acid, propionic acid, butyric acid, caproic acid, 2-ethylhexanoic acid, caprylic acid, lauric acid, myristic acid, enanthic acid, neodecanoic acid, palmitic acid, stearic acid, isostearic acid, 12-hydroxystearic acid, oleic acid, behenic acid, montanic acid, benzoic acid, chlorobenzoic acid, p-ten-butylbenzoic acid, p-dodecylbenzoic acid, salicylic acid, 3,4-di-tert-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, thioglycolic acid, lactic acid, abietic acid, ~3-mercaptopropionic acid, (3-dodecylmercaptopropionic acid, phenylacetic acid and monoesters and monoamides of dicarboxylic acids. Zinc salts of long-chain a-aminocarboxylic acids and of a-acylaminocarboxylic acids are also suitable for this purpose.
Examples of C6-CtBphenols are phenol, cresol, xylenol, 4-ten-butylphenol, 4-nonylphenol, 4-dodecylphenol, 4-chlorophenol and 2-hydroxybiphenyl.
Examples of CS-C22-1,3-diketones are acetylacetone, butanoylacetone, stearoylacetone, lauroylacetone, benzeylacetone, dibenzoylmethane, lauroylbenzoylmethane, stearoylbenzoylmethane and bis(4-methylbenzoyl)methane.
c) is preferably the zinc salt of an aliphatic C~-C2ocarboxylic acid. It is also possible to use mixtures of zinc compounds, for example zinc salts of technical grade carboxylic acid mixtures or technical grade alkylphenol mixtures. Particular preference is given to zinc stearate, zinc laurate, zinc 2-ethylhexanoate and zinc oleate.
The calcium, magnesium or barium compound used as component d) may be an organic compound, for example the calcium, magnesium or barium salt of a carboxylic acid, sulfonic acid, phosphonic acid, phosphinic acid, phenol or enol. Component d) may alternatively be an inorganic compound, for example an oxide, hydroxide, carbonate, phosphate, phosphite or hypophosphite of calcium, magnesium or barium.
d) is preferably the calcium, magnesium or barium salt of a Ct-CZZCarboxylic acid or of a ~C~~::J~J
_ 26 _ C~-C;sphenol, in particular the salt of an aliphatic C~-C~pcarboxylic acid.
Examples of such carboxylic acids and phenols are as described for the zinc salts. The stearates, laurates and oleates of calcium, magnesium and barium are particularly suitable.
1,3-Dicarbonyl compounds which can be used as component e) are linear or cyclic dicarbonyl compounds. Preference is given to dicarbonyl compounds of the formula VII

II II
Rt-C-CHR2-C R3 VII
in which R1 is Ct-C22alkyl, CS-Ctohydroxyalkyl, C2-Ctgalkenyl, phenyl, phenyl which is substituted by OH, Ct-C4alkyl, Ct-C4alkoxy or halogen, C~-Ctpphenylalkyl, CS-Ct2cycloalkyl, CS-Ct2cycloalkyl which is substituted by Ct-C4alkyl, or an -RS-S-R6 or -RS-O-R6 group, R2 is hydrogen, Ct-CBalkyl, C2-Ct2alkenyl, phenyl, C~-Ct2alkylphenyl, C~-Ctpphenylalkyl or a -CO-R4 group, R3 is as defined for Rt or is Ct-CiBalkoxy, R4 is Ct-C4alkyl or phenyl, RS is C1-Ctpalkylene, and R6 is Ct-Cl2alkyl, phenyl, C~-CtBalkylphenyl or C~-Ctophenylalkyl.
These include the hydroxyl-containing diketones of EP-A-346 279 and the oxa-and thiadiketones of EP-A-307 358.
Alkyl Rt and R3 may be, in particular, Ct-CtBalkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, ten-butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl or octadecyl.
Hydroxyalkyl R1 and R3 are, in particular, -(CHz)n OH groups in which n is 5, 6 or 7.
Alkenyl Rl and R3 may be, for example, vinyl, allyl, methallyl, 1-butenyl, 1-hexenyl or oleyl, preferably allyl.
OH-, alkyl-, alkoxy- or halogen-substituted phenyl Rt and R3 may be, for example, tolyl, xylyl, tert-butylphenyl, methoxyphenyl, ethoxyphenyl, hydroxyphenyl, chlorophenyl or dichlorophenyl.
Phenylalkyl Rt and R3 are, in particular, benzyl.
Cycloalkyl or alkylcycloalkyl RZ and R3 are, in particular, cyclohexyl or iG~''..~'.3J~J
mcthylcyclohexyl.
Alkyl RZ may be, in particular, Ct-C4alkyl.
C2-Ct2alkenyl R2 may be, in particular, allyl. Alkylphenyl R2 may be, in particular, tolyl.
Phenylalkyl R2 may be, in particular, benzyl. R2 is preferably hydrogen.
Alkoxy R3 may be, for example, methoxy, ethoxy, butoxy, hexyloxy, octyloxy, dodecyIoxy, tridecyloxy, tetradecyloxy or octadecyloxy.
Ct-Ctoalkylene RS is, in particular, CZ-C4alkylene.
Alkyl R6 is, in particular, C4-Ct2alkyl, for example, butyl, hexyl, octyl, decyl or dodecyl.
Alkylphenyl R6 is, in particular, tolyl. Phenylalkyl R6 is, in particular, benzyl.
Examples of 1,3-dicarbonyl compounds of the formula VII are acetylacetone, butanoylacetone, heptanoylacetone, stearoylacetone, palmitoylacetone, lauroylacetone, 7-tert-nonylthioheptane-2,4-dione, benzoylacetone, dibenzoylmethane, Iauroylbenzoylmethane, palmitoylbenzoylmethane, stearoylbenzoylmethane, 5-hydroxycapronylbenzoylmethane, tribenzoylmethane, bis(4-methylbenzoyl)methane, benzoyl-p-chlorobenzoylmethane, bis(2-hydroxybenzoyl)methane, 4-methoxybenzoylbenzoylmethane, bis(4-methoxybenzoyl)methane, 1-benzoyl-i-acetylnonane, benzoylacetylphenylmethane, stearoyl-4-methoxybenzoylmethane, bis(4-tert-butylbenzoyl)methane, benzoylformylmethane, benzoylphenylacetylmethane, bis(cyclohexanoyl)methane, di(pivaloyl)methane, methyl, ethyl, hexyl, octyl, dodecyl and octadecyl acetoacetate, ethyl, butyl, 2-ethylhexyl, dodecyl and octadecyl benzoylacetate and ethyl, propyl, butyl, hexyl and octyl stearoylacetate.
Component e) is preferably a compound of the formula VII in which R1 is Ct-Ctgalkyl, phenyl, phenyl which is substituted by OH, methyl or methoxy, C7-Ctophenylalkyl or cyclohexyl, R2 is hydrogen, and R3 is as defined for R1.
The compositions according to the invention preferably comprise 100 parts by weight of componem (a), from 0.01 to 2 parts by weight of component (b), from 0.01 to 3 parts by weight of component (c), from 0.01 to 3 parts by weight of component (d) and from 0.05 2C'~~SL~~

to ? parts by weight of component (e), in particular 100 parts by weight of component (a), from 0.1 to 1 part by weight of component (b), from 0.1 to 2 parts by weight of component (c), from 0.1 to 2 parts by weight of component (d) and from 0.: to 1 part by weight of component (e).
In addition, the composition may contain further additives which are known and conventional for processing and stabilising chlorine-containing polymers, for example plasticisers, phosphates, lead compounds, cadmium compounds, metal-free PVC
stabilisers, impact modifiers, heat resistance improvers, epoxide compounds, antioxidants, UV absorbers, light stabilisers, pigments, dyes, fillers, lubricants and flameproofmg agents.
Examples of plasticisers are the esters of phthalic acid, adipic acid, azelaic acid, sebacic acid and trimellitic acid, polyesters made from aliphatic diols and dicarboxylic acids, phosphoric acid esters, chloroparaffins and epoxidised fatty acid esters.
Further examples are given in "Taschenbuch der Kunststoff-Additive" [Pocketbook of Plastics Additives], R. Gachter, H. Miiller, Hanser-Verlag 1983, pages 280-307. The plasticisers may be used in an amount of from 15 to 100 parts by weight, based on 100 parts by weight of the chlorine-containing polymer.
Organic phosphates are known costabilisers for chlorine-containing polymers stabilised by means of metal carboxylates, in particular in combination with stabilisers based on zinc, barium, magnesium or cadmium. Examples of phosphates of this type are trioctyl phosphate, tridecyl phosphate, tridodecyl phosphate, decyl Biphenyl phosphate, triphenyl phosphate, phenyl didecyl phosphate, tris(nonylphenyl) phosphate, trilauryl phosphate, trioctadecyl phosphate, distearyl pentaerythritol diphosphite, 2,4-di-ten-butylphenyl di(dodecyl) phosphate, tris(2,4-di-tert-butylphenyl) phosphate, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite and 3,9-bas(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane.
Compounds of lead and cadmium have a similar action to the calcium, magnesium and barium compounds, but are ecologically suspect. Examples of these are the metal salts of fatty acids, for example stearates, palmitates and oleates, and inorganic salts, for example basic sulfates and phosphates.

~

~ ,rr~r~~~-~.( .....J uJ
_~y_ Examples of metal-free stabilisers for chlorine-containing polymers are aliphatic polyols, such as pentaerythritol, dipentaerythritol, trimethylolpropane, tris(2-hydroxyethyl) isocyanurate, sorbitol, mannitol and furan; aminocrotonic acid esters;
mercaptobenzoic acid esters; dehydracetic acid; 2,4-dihydroxybenzophenone; enol carbonates, as described in EP-A-224 438; aromatic amides, as described in EP-A-122 228 and 174 412;
and nitrogen-containing heterocyclic compounds, as described in EP-A-2007, 22 087, 22 749, 41 479, 65 934, 260 226 and 354 179, DE-A-3 048 659 and 3 124 853, GB-A-2 170 and US-A-4 908 398.
Examples of impact modifiers are polyacrylates, ethylene-vinyl acetate copolymers and chlorinated polyethylene, and examples of heat resistance improvers are poly(meth)acrylates, acrylate-maleimide copolymers and acrylonitrile-methylstyrene copolymers.
Epoxide compounds are also known stabilisers for chlorine-containing polymers.
If they have a suitable structure, they may simultaneously function as plasticisers.
Examples of epoxide stabilisers are epoxidised polybutadiene, epoxidised Soya oil, epoxidised linseed oil, epoxidised fish oil, epoxidised tallow, methylbutyl and 2-ethylhexyl epoxystearate, tris(epoxypropyl) isocyanurate, epoxidised castor oil, epoxidised sunflower oil, 3-(2-phenoxy)-1,2-epoxypropane, bisphenol A polyglycidyl ether, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide and 3,4-epoxycyclohexylmethyl-3,4-epoxy-cyclohexane carboxylate.
Examples of antioxidants are:
1. Alkylated 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-diactadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol and 2,6-dinonyl-4-rnethylphenol.
2. Alkylated hydro uinones, for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-ten-amylhydroquinone and 2,6-diphenyl-4-octadecyloxyphenol.
3. Hydrox 1~ ated diphenyl thioethers, for example ~:C~5~5~5 2,2'-thiobis(6-ten-butyl-4-mcthylphenol), 2,2'-thiobis(4-octylphencl), 4,4'-thiobi::(6-tert-butyl-3-methylphenol) and 4,4'-thiobis(6-ten-butyl-2-methylphenol).
4. Alkvlidenebisphenols, for example 2,2'-methylenebis(6-tent-butyl-4-methylphenol), 2,2'-methylenebis(6-ten-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(«-methylcyclohexyl)phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4-methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4,6-di-ten-butylphenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-(«-methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-(«,«-dimethylbenzyl)-4-nonylphenol], 4,4'-methylenebis(2,6-di-ten-butylphenol), 4,4'-methylenebis(6-ten-butyl-2-methylphenol), I ,1-bis(5-ten-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, I,l-bis(5-ten-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3'-tent-butyl-4'-hydroxyphenyl) butyrate], bis(3-ten-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene and bis[2-(3'-tent-butyl-2'-hydroxy-5'-metltylbenzyl)-6-tert-butyl-4-methylphenyl]
terephthalate.
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)dithiol terephthalate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris(4-tent-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 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.
6. Acylaminophenois, for example 4-hydroxylauranilide, 4-hydroxystearanilide, 2,4-bis(octylmercapta)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-s-triazine and octyl ~~'W~~r r ...:J~J
_3I_ N-(3,S-di-tert-butyl-4-hydroxyphenyl)carbamate.
7. Esters of 3-(3,S-di-ten-bull-4-hydroxyphenyl)propionic acid with monohydric or polyhydric alcohols, for example with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate and N,N'-bis(hydroxyethyl)oxalamide.
8. Esters of Q-(S-tert-but~ydroxy-3-meth~phenyl)propionic acid with monohydric or polyhydric alcohols, for example with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate and N,N'-bis(hydroxyethyl)oxalamide.
9. Esters of (3-(3,5-dicyclohexyl-4-hydroxyphen~propionic acid with monohydric or polyhydric alcohols, for example with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate and N,N'-bis(hydroxyethyl)oxalamide.
10. Amides o~3-(3,S-di-tert-but~ydroxyphenyl)propionic acid, for example N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine, N,N'-bis(3,S-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine and N,N'-bis(3,S-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine.
Examples of UV absorbers and light stabilisers are:
1. 2-(2'-Hydroxyphenyl)benzotriazoles, for example the 5'-methyl, 3',5'-di-ten-butyl, 5'-tent-butyl, 5'-(1,1,3,3-tetramethylbutyl), 5-chloa°o-3'>5'-di-tert-butyl, 5-chloro-3'-ten-butyl-S'-methyl, 3'-sec-butyl-5'-tent-butyl, 4'-octoxy, 3',5'-di-ten-amyl and 3',5'-bis(a,a-dimethylbenzyl) derivatives.
2. 2-HydroxybenzoQhenones, for example the 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.
3. Esters of substituted or unsubstituted benzoic acids, for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol, 2,4-di-ten-butylphenyl ~C'~~5~fi i 3,5-di-ten-butyl-4-hydroxybenzoate and hexadecyl 3,5-di-ten-butyl-4-hydroxybenzoate.
4-Acr-ylates, for example ethyl and isooctyl a-cyano-(3,[3-diphenylacrylate, methyl a-carbomethoxycinamate, methyl and butyl a-cyano-(3-methyl-p-methoxycinamate, methyl a-carbomethoxy-p-methoxycinnamate and N-((3-carbomethoxy-~3-cyanovinyl)-2-methylindoline.
5. Nickel compounds, for example nickel complexes of 2,2'-thiobis[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 and 1:2 complexes, if desired with additional ligands, such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of monoalkyl 4-hydroxy-3,5-di-ten-butylbenzylphosphonates, such as of the methyl or ethyl esters, nickel complexes of ketoximes, such as of 2-hydroxy-4-methylphenylundecyl ketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, if desired with additional ligands.
6. Oxalic acid diamide.s, 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-tent-butyl-2'-ethyloxanilide and the mixture thereof with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide, and mixtures of o- and p-methoxy- and of o-and p-ethoxy-disubstituted oxanilides.
The pigments used may be inorganic, organic or metallic. Examples of fillers are chalk, carbon black, graphite, talc, kaolin or silicate minerals. However, the compositions according to the invention do not contain any hydrotalcite compounds.
Lubricants are, in particular, fatty acids and the salts, esters and amides thereof, fatty alcohols, paraffins and polyethylene waxes. Flameproofing agents are, in particular, antimony oxide, aromatic bromine compounds and phosphoric acid esters.
A review on the use of impact modifiers, colorants, fillers, lubricants and flameproofing agents in chlorine-containing polymers, in particular in PVC, is given in "Taschenbuch der Kunststoff Additive" [Pocketbook of Plastics Additives], R. Gachter, H.
Miiller, Hanser-Verlag, 1983.

I~iC~.~n~S~J
3_ The compositions according to the invention can be prepared in a conventional manner. In general, the stabiliser system is incorporated into the polymer, for which purpose a range of known equipment, for example calenders, mixers, kneaders and the like, exists.
The compositions stabilised in accordance with the present invention can be shaped in a conventional manner. Examples of such processes are calendering, extrusion, injection moulding, sintering and spinning, furthermore extrusion blowing or processing by the plastisol process.
The compositions according to the invention are particularly suitable in the form of rigid formulations for hollow articles (bottles), packaging films (thermoformed films), blown films, crash-pad films (automobiles), tubes, heavy profiles (window frames), projection screen profiles, building profiles, sidings, fittings, office films and equipment casings (computers and domestic appliances).
Other compositions in the form of soft formulations are suitable for wire sheathing, cable insulation, decorative films, roof sheeting, agricultural sheeting, tubes, seal profiles, office films and sheeting for air halls.
Examples of the use of the compositions according to the invention as plastisols are artificial leather, flooring, textile coatings, curtains, coil coatings and underseal for motor vehicles.
Examples of sintered PVC applications of the compositions according to the invention are slush, slush mould and coil coatings.
The examples below illustrate the invention in greater detail. All parts and percentages relate to the weight, unless stated otherwise.
The hindered amines and 1,3-diketones below are used in the examples:
H- I 8-acetyl-3-dodecyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4,5]decane-2,4-dione 'c:~.~'~:3J~J

H-~ H O N - CH2CH20COCH2CH2C OCH3 CH3 CHg n Mn _ 2000 H-3 di-(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate NH-CgHt~-tert N- 'N
H-4 ( ~ N (CH2)6 N
H3C 1'CH3 H3C 1'CH3 n H H
Mn _ 2500 H-S di-(2,2,6,6-tetramethylpiperidin-4-yl) sebacate HzC rH., H-S O CH2- C -(- CH3)2 (CH~j3C
D-1 Dibenzoylmethane D-2 Benzoylstearoylmethane Example 1: A semi-rigid PVC composition is prepared in accordance with the following recipe:

2(~~~SSS
-35_ 100 p;uts by weight of suspension PVC having a K-value of 70 (Vinnol~ H 70 DF), 17 parts by weight of dioctylphthalate, 3 parts by weight of epoxidised Soya oil (Reoplast~ 39), 1 part by weight of didecyl phenyl phosphite, 0.5 part by weight of zinc oleate, 0.8 part by weight of barium p-tent-butylbenzoate, 0.6 part by weight of butyl glycol and 0.3 part by weight of sterically hindered amine.
One part of the samples is additionally mixed with 0.3 part of a diketone. The constituents are homogenised for 5 minutes at 180°C on mixing rolls, forming a 0.3 mm thick film.
Samples are cut from the film and warmed to 180°C in a test oven (Mathis Thermotester~
LTF-ST). The discoloration which occurs is measured in accordance with ASTM D
1925-70 as the yellowness index (YI). The higher this index, the greater the discoloration.
Table 1 shows the results.

°

l ur: /' f ' f-' ~.C ~.:.i~J
_ 36 _ Table 1 I-lindered Diketone*) Yellowness index after amine*) 0 6 12 1824 30 36 42 min 0.3 H-1 - 141519 2325 21 21 24 0.3H-1 0.3D-1 8 9 9 9 9 11 13 15 0.3 H-2 - 111317 1820 18 18 20 0.3 H-2 0.3 D-1 7 8 8 9 9 10 15 17 0.3 H-3 - 9 1216 1821 17 17 18 0.3 H-3 0.3 D-1 8 9 10 1110 1 12 9 U

0.3 H-4 - 141722 2430 35 37 42 0.3 H-4 0.3 D-1 121314 1514 17 18 20 0.3 H-5 - 9 1115 2117 I9 20 23 0.3 H-5 0. 3 D-1 8 9 10 1010 11 13 14 0.3 H-6 - 9 1316 2123 26 21 20 0.3 H-6 U.3 D-1 8 9 9 ~>'20 91 11 I 1 *) Parts per 100 parts of PVC
It can be seen that the samples containing the diketone (D-1) remain paler over the entire measured time than the samples without diketone.
Example 2: A rigid PVG formulation is mixed from the following components:

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_37_ 100 parts by weight of suspension PVC having a K-value of 60 (Corvic~ S 60/104), 3 parts by weight of epoxidised Soya oil (Reoplast~ 39), 1.2 parts by weight of zinc stearate and 0.6 pan by weight of calcium stearate The amounts of hindered amine and diketone indicated in Table 2 are added. The constituents are mixed for 5 minutes at 190°C on mixing rolls to give a 0.3 mm thick film.
The samples cut from the films are heated at 180°C as in Example 1, and the yellowness index is measured at intervals of 5 minutes.
Table 2 Hindered Diketone*) Yellowness index after amine*) 10 15 20 25 30 35 40 min 0.3 H-4 I - 149 56 63 64 66 68 69 69 0.3 H-4 I 0.1 D-2 I 11 13 16 22 33 48 55 58 0.3 H-4 I 0.3 D-2 I 10 12 15 17 20 29 44 50 *) Parts per 100 parts of PVC
The paling effect of the diketone, which is particularly pronounced in the first 25 minutes, can also be seen here.
Example 3: Samples of a rigid PVC formulation are prepared as described in Example 2 from the following components:
l0U parts by weight of a suspension PVC having a K-value of 67 (Vestolit~ P 1982 K), ~~'W i~~
6 parts by w~i~~ht of chalk (OmyaC~ 95 T), 4 parts by weight of titanium dioxide (Kronos~ CL 220), 1 part by weight of P1ZMA-based processing assistant (Irgamod~ F 138), 0.5 part by weight of didecyl phenyl phosphite 0.8 pan by weight of zinc stearate, 1.1 part by weight of barium laurate and 0.1 part by weight of bisphenol A
The amounts of hindered amine and 1,3-diketone indicated in Table 3 are added.
Table 3 shows the values for the yellowness index on heating at 190°C.
Table 3 Hindered Diketone*) Yellowness index after amine*) 10 I S 20 25 30 35 40 min 0.3 H-4 , - ~ 23 25 37 40 43 44 46 55 0.3 H-4 I 0.1 D-2 I 18 20 24 26 29 33 36 41 0.3 H-4 ~ 0.3 D-2 ~ 11 13 14 17 19 23 29 37 *) Parts per 100 parts of PVC
Example 4: Samples of a semi-rigid PVC composition are prepared as described in Example 2 from the following components:
100 parts by weight of a suspension PVC having a K-value of 71 (Corvic~ S 71/102), 20 parts by weight of dioctyl phthalate, 0.64 part by weight of didecyl phenyl phosphite 0.52 part by weight of zinc oleate, 0.59 part by weight of barium tert-butylbenzoate, 0.07 part by weight of 2,6-di(tert-butyl)-p-kresol and .~r,-r r ,:..3JE3._) _3y_ 0.1( part by wei~~ht of an arotr~atic solvent mixture (ShcllsolCO A).
The amounts of hindered amine and 1,3-diketone indicated in Table 4 are added.
Table 4 shows the yellowness index of the samples on heating at 190°C.
Table 4 Hindered Diketone*) Yellowness index after amine*) 10 IS 20 25 30 35 40 min 0.3 H-4 - ~ 8 14 18 23 26 30 39 59 0.3 H-4 ~ 0.1 D-2 ~ 5 5 7 9 12 17 25 43 0.3 H-4 I 0.3 D-2 I 4 5 5 6 7 10 13 22 *) Parts per 100 parts of PVC
The considerable paling action of the diketone over the entire test period can be seen here.
Example 5: Samples of the following semi-rigid composition are prepared as described in Example 2:
100 parts by weight of a suspension PVC hav_ng a K-value of 71 (Corvic~ S 71/102), 20 parts by weight of dioctyl phthalate, 0.6 part by weight of didecyl phenyl phosphite, 0.57 part by weight of zinc oleate, 0.27 part by weight of calcium p-tent-butylbenzoate, and 0.52 part by weight of an aromatic solvent mixture (Shellsol0 A).
The amounts of hindered amine and 1,3-diketone indicated in Table 5 are added.
Table 5 shows the yellowness index of the samples on heating at 190°C.

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Table 5 Hindered Diketone*) Yellowness index after amine*) S 10 15 20 25 30 min 0.3 H-4 ~ - ~ 6 7 9 13 17 23 0.3 H-4 I 0.1 D-2 I 4 5 6 8 12 19 0.3 H-4 ~ 0.3 D-2 ~ 4 4 5 7 9 17 *) Parts per 100 parts of PVC
A considerable positive effect of the diketone over the entire test period can be seen here.

Claims (18)

1. A stabilised chlorine-containing polymer composition comprising a) at least one chlorine-containing polymer, b) at least one sterically hindered amine, c) at least one organic or inorganic zinc compound, d) at least one organic or inorganic calcium, magnesium and/or barium compound, and e) at least one 1,3-dicarbonyl compound, but no organotin compounds, no hydrotalcite compounds and no blowing agents or foaming agents.

2. A polymer composition according to claim 1, wherein component a) is a polyvinyl chloride or a copolymer containing at least 80 % of vinyl chloride, or a mixture (polyblend) of a polymer of this type with another chlorine-containing or chlorine-free polymer.

3. A polymer composition according to claim 1, wherein component b) is a polyalkylpiperidine derivative containing at least one group of the formula I
in which R is hydrogen or methyl.

4. A polymer composition according to claim 3, in which R in the formula I is hydrogen.

5. A polymer composition according to claim 3, wherein component b) is a polyalkylpiperidine derivative of the formula II

in which R is hydrogen, R11 is hydrogen or methyl, n is 2 and R12 is the diacyl radical of a dicarboxylic acid having 4 to 22 carbon atoms.

6. A polymer composition according to claim 3, wherein component b) is a polyalkylpiperidine compound of the formula VA
in which n is 1, R is hydrogen, R11 is hydrogen or methyl, R16 is hydrogen or C1-C12alkyl and R17 is C1-C12alkyl, allyl or benzyl.

7. A polymer composition according to claim 3, wherein component b) is a polyalkylpiperidine compound of the formula VI
in which n is 4, R18 and R19 are a group in which R11 is hydrogen or methyl and R21 is hydrogen or C1-C6alkyl, and R20 is the tetravalent radical of an aliphatic tetramine.

8. A polymer composition according to claim 3, wherein component b) is an oligomeric or polymeric polyalkylpiperidine compound from the series comprising the polyesters and polyaminotriazines.

9. A polymer composition according to claim 1, wherein component c) is the zinc salt of a C1-C22carboxylic acid, of a C6-C18phenol or of a C5-C12-1,3-diketone.

10. A polymer composition according to claim 9, wherein c) is the zinc salt of an aliphatic C7-C20 carboxylic acid.

11. A polymer composition according to claim 1, wherein component d) is the calcium, magnesium or barium salt of a C1-C22carboxylic acid, of a C5-C12-1,3-diketone or of a C6-C18phenol.

12. A polymer composition according to claim 11, wherein d) is the calcium, magnesium or barium salt of an aliphatic C7-C20carboxylic acid.

13. A polymer composition according to claim 1, wherein component e) is a 1,3-dicarbonyl compound of the formula VII
in which R1 is C1-C22alkyl, C5-C10hydroxyalkyl, C2-C18alkenyl, phenyl, phenyl which is substituted by OH, C2-C4alkyl, C1-C4alkoxy or halogen, C7-C10phenylalkyl, C5-C12cycloalkyl, C5-C12cycloalkyl which is substituted by C1-C4alkyl, or an -R5-S-R6 or -R5-O-R6 group, R2 is hydrogen, C1-C8alkyl, C2-C12alkenyl, phenyl, C7-C12alkylphenyl, -44_ C7-C10phenylalkyl or a -CO-R4 group, R3 is as defined for R1 or is C1-C18alkoxy, R4 is C1-C4alkyl or phenyl, R5 is C1-C10alkylene, and R6 is C1-C12alkyl, phenyl, C7-C18alkylphenyl or C7-C10phenylalkyl.

14. A polymer composition according to claim 13, wherein component e) is a compound of the formula VII in which R1 is C1-C18alkyl, phenyl, phenyl which is substituted by OH, methyl or methoxy, C7-C10phenylalkyl or cycloalkyl, R2 is hydrogen, and R3 is as defined for R1.

15. A polymer composition as claimed in claim 1, comprising 100 parts by weight of (a), from 0.01 to 2 parts by weight of (b), from 0.01 to 3 parts by weight of (c), from 0.01 to 3 parts by weight of (d) and from 0.05 to 2 parts by weight of (e).

16. A polymer composition according to claim 15, comprising 100 parts by weight of (a), from 0.1 to 1 part by weight of (b), from 0.1 to 2 parts by weight of (c), from 0.1 to 2 parts by weight of (d) and from 0.1 to 1 part by weight of (e).

17. A polymer composition according to claim 1, containing, in addition to components (a) to (e), one or more additives from the series comprising plasticisers, phosphites, lead compounds, cadmium compounds, metal-free PVC stabilisers, impact modifiers, heat resistance improvers, epoxide compounds, antioxidants, UV absorbers, light stabilisers, pigments, dyes, fillers, lubricants and flameproofing agents.

18. A process for stabilising chlorine-containing polymers against damage by heat and light, by adding a) at least one sterically hindered amine, b) at least one organic or inorganic zinc compound, c) at least one organic or inorganic calcium, magnesium and/or barium compound, d) at least one 1,3-dicarbonyl compound, and, if desired, further additives, but no organotin compounds, hydrotalcite compounds, blowing agents or foaming agents.