JPH1045983A - 4-acylamidopiperidione compound in stabilizer combination for chlorine-containing polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a stabilizer combination for stabilizing a halogen-contg. polymer by combining a specific organozcng compd. with a specific compd. SOLUTION: This stabilizer combination comprises at least one organozcng compd. having a Zn-O- bond and at least one compd. selected from among compds. represented by formula I to IV [wherein X is O or S; (a) is 0-8; (b) is 2-12; (c) is 1 or 2; (k) is 2-6; R1 is H, a 1-8C alkyl, a 3-8C alkenyl, etc.; R2 a is 1-8C alkyl, NH2 , R3 NG, R4 O, (R3 -NG-CX)c E, etc.; G is a group represented by formula V; R3 is H, a 1-8C alkyl, etc.; R4 is H, a 1-4C alkyl, etc.; E is a group represented by formula VI; A is =CO, (CH2 )m ; (m) is 0 or 1; (n) is 2-12; (p) is 0 or 1; (q) is 1 or 2; (r) is 2-50; R5 is H, a 1-8C alkyl, etc.; R6 is H, a 1-12C alkyl, etc.; and R7 is H or CH3 ].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a chlorine-containing polymer,
Organozinc compounds having Zn-O and / or Zn-S bonds, especially zinc carboxylate, which are particularly suitable for stabilizing PVC, and formulas I, II,
It relates to a stabilizer combination comprising at least one of the compounds of the formulas III and IV.

[0002]

BACKGROUND OF THE INVENTION PVC can be stabilized by a number of additives. The compounds of lead, barium and cadmium are particularly suitable for this purpose, but are presently problematic for environmental reasons (plastic additives (Kunststoffadditiv)
e), el. Gechter and Her. Edited by Müller, Carl Hanser Verlag, 3rd edition, 1989, 3rd
Pages 03-311 and Plastic Handbook PVC
(Kunststoff-Handbuch PVC), Second Edition, 1985, Volume 2/1, Game. Vee. Beckel, Day. Brown,
Carl Hanser Verlag, 1985, 53rd
1-538). Therefore, the search for effective and stabilizing combinations of stabilizers without problems continues. Sterically hindered amines have already been added to PVC as light stabilizers. Its thermal stability also favors (eg EP-A-366271 and EP-A-488).
951).

[0003]

SUMMARY OF THE INVENTION To stabilize a chlorine-containing polymer, an organozinc compound such as zinc carboxylate has the formula:

Embedded image It has now been found that it can be advantageously combined with a compound of the formula The meanings of these groups and symbols are as follows: X represents O or S; a represents 0 to 8; b represents 2 to 12; c represents 1 or 2
K represents 2 to 6; R ₁ represents H or an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 3 to 8 carbon atoms, a phenylalkyl group having 7 to 9 carbon atoms or a carbon atom having 7 to 9 carbon atoms; R ₂ represents a C 5-8 cycloalkyl group; R ₂ represents a C 1-8 alkyl group, —N
_{H 2, R 3 NG-, R} 4 -O -, [R 3 -NG-CX]
_c E-, (alkyl having 1 to 4 carbon atoms) ₂ N (C
H ₂ ) _k— CX—, a phenyl group or a phenyl group substituted by C 1 -C 4 alkoxy or C 1 -C 4 alkyl with OH;

Embedded image R ₃ is H, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 3 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, R ₂ -CX-NG-
(CH ₂ ) _b , (C 1-4 alkyl) ₂
N (CH _{2) k} - represents or G; R ₄ represents an alkyl group, a cyclohexyl group or a benzyl group of 1 to 4 carbon atoms; E is

Embedded image The expressed; A _{is> CO, - (CH 2)} m -, - (CH 2)
_d -CO- or -NH (CH ₂₎ represents _n -CO-;
m represents 0 or 1; n represents 2 to 12; p represents 0 or 1; d represents 1 to 8; q represents 1 or 2; when it is a 0, a _{is> CO, - (CH 2)} m -, - (CH 2) d -
When p is 1, A is - (CH _{2) m} - represents;; CO - -, NH ( CH 2) n -CO- a represents the group L is -CH ₂ -
CHR ₆ —, — (CH ₂ ) ₃ —, —CH ＝ CH—,

Embedded image R ₅ represents H, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 3 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms or G; R ₆ represents H, a carbon atom; number 1 to represent an 12 alkyl group; R ₇
Represents H or CH _3; Q represents -O- or>NH; Y is _{-CH 2 -CH (OH) -CH 2} - to represent; represents a and s 3 to 60.

In the above formula: C 1 -C 4 alkyl is methyl, ethyl, n-propyl,
Isopropyl, n-, i-, secondary or tertiary butyl. Alkyl groups having 1 to 8 carbon atoms are similar and include, for example, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, 2-
An ethylhexyl group, an n-octyl group or an isooctyl group. C5-C8cycloalkyl is, for example, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl. Cyclopentyl and especially cyclohexyl are preferred.
The alkenyl substituent having 3 to 8 carbon atoms may be an alkenyl group which may be branched or unbranched, for example, an allyl group, a crotonyl group, a 2-methylallyl group or a hexenyl group. An alkoxy group having 1 to 4 carbon atoms is, for example, a methoxy group, an ethoxy group, a propoxy group,
It is an isopropoxy group, a butoxy group or an isobutoxy group. A phenylalkyl group having 7 to 9 carbon atoms is
For example, a benzyl group, a 1- or 2-phenylethyl group, a 3-phenylpropyl group, an α, α-dimethylbenzyl group or a 2-phenylisopropyl group, preferably a benzyl group.

In the above formula, X represents O or S;
To represent 4; b to from 2 represents 6; c is 1 or 2; k represents 2 or 3; R ₁ represents an alkyl group having 1 to H or a carbon atom 8; R ₂ is carbon C 1 atom to 8 alkyl, -NH _2, R ₃ -NG-,
_{[R 3 -NG-CX] c} E- or (alkyl of 1 to 4 carbon atoms) ₂ N (CH ₂₎ represents a _k -CX-; R ₃
Is H, an alkyl group having 1 to 8 carbon atoms, R ₂ -CX
-NG- (CH _{2) b,} (C1 -C4 _{alkyl) 2 N (CH 2) k} - or represents G; E is

Embedded image The expressed; R ₅ is H, an alkyl group or G of 1 -C 8; A is _{-CO, - (CH 2) m} -, -
(CH ₂ ) _d —CO— or —NH (CH ₂ ) _n —CO
M represents 0 or 1; n represents 2 to 6; p represents 0 or 1; d represents 1 to 4;
Represents 1 or 2; r represents an 50 2 to; when p is 0, A is _{-CO -, - (CH 2)} m -, - (CH
₂ ) represents _d— CO— or —NH (CH ₂ ) _n —CO—; when p is 1, A represents — (CH ₂ ) _m —;
Is _{-CH 2 -CHR 6 -, - (} CH 2) 3 -,

Embedded image R ₆ represents H or an alkyl group having 1 to 12 carbon atoms; Y represents —CH ₂ —CH (OH) —CH ₂ —
The expressed; R ₇ represents H or CH _3; Q represents -O- or>NH; and s represents 3 to 60, the formula I
Combinations of stabilizers for the compounds of formulas IV to IV are preferred.

Particularly preferred compounds of the formulas I to IV are those in which X represents O; a represents 0 to 4;
b represents 2 to 6; c represents 1; R ₁ represents H or an alkyl group having 1 to 8 carbon atoms; R ₂ represents [R
_3- NG-CX] _c E-; R ₃ is H, an alkyl group having 1 to 8 carbon atoms, R ₂ -CX-NG- (C
H ₂ ) _b or G; E is (CH ₂ ) _a or -N
H- (CH ₂₎ represents _b NH-; R ₅ represents G; A is - (CH _{2) m} - and represents; m is 0 or 1; n is 2 to represent 6; p is 0 the expressed; q represents 1 or 2; r represents 50 2 to; group L -CH ₂ -CHR
_{6 -, - (CH 2)} 3 - or an -CH = CH-;
R ₆ represents H; Y is —CH ₂ —CH (OH) —CH ₂
- a represents; R ₇ represents H; Q is> represents NH; and s represents 3 to 60, a compound.

Examples of piperidine compounds of the formulas I to IV are: 01) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) ethylene-1,2-diacetamide 02) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) -ethylene-1,2-formamide 03) N, N'-bis (2,2,6,6- Tetramethylpiperidin-4-yl) adipamide 04) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) oxamide 05) 4-Hydroxybenzamide-2,2,6,6- Tetramethylpiperidine

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The compounds of the formulas I to IV are present in the chlorine-containing polymer in an amount of 0.005 to 5%, preferably 0.1 to 5%.
It can be present in a proportion of from 01 to 2%, in particular from 0.01 to 1%.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION

Zinc compound The organic zinc compound having a Zn-O bond is composed of zinc enolate, zinc phenolate and / or zinc carboxylate (zinc carboxylate). The latter are aliphatically saturated and unsaturated, carboxylates having 1 to 22 carbon atoms, substituted by at least one OH group, or whose chains are interrupted by one or more O atoms (oxa acids). Aliphatic saturated or unsaturated carbon atoms 2
To 22 carboxylates, 5 to 2 carbon atoms
Cyclic and bicyclic carboxylates, unsubstituted, mono- or poly-OH substituted and / or alkyl-substituted phenylcarboxylates having 1 to 16 carbon atoms, phenyl-carboxylates having 1 to 16 carbon atoms A system of an alkyl carboxylate or an unsubstituted or alkyl-substituted phenolate having 1 to 12 carbon atoms,
Or a compound from the system of abietic acid. Zn-S
Examples of compounds are Zn mercaptide, Zn mercapto carboxylate and Zn mercapto carboxylate.

Monovalent carboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, enanthic acid, octanoic acid, neodecanoic acid, 2-ethylhexanoic acid, pelargonic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecane Acid, myristic acid, palmitic acid, lauric acid, isostearic acid, stearic acid, 12-hydroxystearic acid, 9,10-dihydroxystearic acid, oleic acid, ricinoleic acid, 3,6-dioxaheptanoic acid, 3,
6,9-trioxadecanoic acid, behenic acid, benzoic acid, p
-Tert-butylbenzoic acid, dimethylhydroxybenzoic acid,
3,5-ditert-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, n-propylbenzoic acid, salicylic acid, p-tert-octylsalicylic acid and sorbic acid, cinnamic acid, mandelic acid And zinc esters of glycolic acid; divalent carboxylic acids and their monoesters, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, pentane-1,5-dicarboxylic acid, hexane-1,6 -Dicarboxylic acid, heptane-1,7-dicarboxylic acid, octane-1,8-dicarboxylic acid, 3,6,9-trioxadecane-1,10-dicarboxylic acid, lactic acid, malonic acid, maleic acid, tartaric acid, apple Acid, salicylic acid, polyglycol dicarboxylic acid (n =
10-12), zinc salts of phthalic acid, isophthalic acid, terephthalic acid and hydroxyphthalic acid; tri- or tetravalent carboxylic acids, such as di- or triesters of hemi-mellitic acid, trimellitic acid, pyromellitic acid, citric acid and So-called overbased zinc carboxylate, or zinc lauryl mercaptide, zinc thioglycolate, zinc thiosalicylate, zinc bis-i-octylthioglycolate, zinc mercaptopropionate, zinc thiolactate, zinc thiomalate, zinc bisoctyl mercaptopropio Names such as catenate, zinc bisisooctylthiolactate and zinc bislauryl thiomalate may be mentioned.

The zinc enolate preferably comprises enolates of acetylacetone, benzoylacetone, and dibenzoylmethane, and enolates of acetoacetate and benzoylacetate, and enolates of dehydroacetic acid. It is also possible to use inorganic zinc compounds, for example zinc oxide, zinc hydroxide, zinc carbonate, basic zinc carbonate or zinc sulfide.

Neutral or basic zinc carboxylate (zinc soap) having 2 to 22 carbon atoms, such as benzoate or alkanoate, preferably alkanoate, stearate having 8 carbon atoms;
Oleate, laurate, palmitate, behenate,
Versate, hydroxystearate and -oleate, dihydroxystearate, p-tert-butylbenzoate, or (iso) octanoate are preferred.
Particularly preferred are stearate, oleate, versatate, benzoate, p-tert-butylbenzoate and 2-ethylhexanoate.

In addition to the above zinc compounds, (inorganic) organoaluminum compounds having an Al--O bond are also suitable. Preferred aluminum compounds which can be used are preferably aluminum enolates and aluminum carboxylate. Examples of carboxylate and enolate groups can be found in the corresponding description above for zinc. Examples of the inorganic Al compound are aluminum hydroxide and aluminum phosphate.

The described organozinc compounds and their mixtures are, for example, from 0.001 to 10 parts by weight, advantageously from 0.01 to 5 parts by weight, preferably from 0.01 to 3 parts by weight, based on 100 parts by weight of the chlorine-containing polymer. It can be used in parts by weight. They can also be present in the form of mixed salts (coprecipitates).

The novel stabilizer combinations can be used together with other additives customary for the processing and stabilization of chlorine-containing polymers, examples of which are: 1. Stabilizers: epoxides and epoxidized fatty acid esters; phosphites; thiophosphites and thiophosphates; polyols; 1,3-dicarbonyl compounds; mercaptocarboxylic esters; dihydropyridines; antioxidants; light stabilizers and UV absorbers; Metal and alkaline earth metal compounds; perchlorates; zeolites;
Hydrotalcite; dawsonite. 2. Other common PVC additives such as lubricants; plasticizers; impact modifiers; processing aids; foaming agents; fillers; antistatic agents; biocides; Activators, flame retardants (in this regard, see the "Handbook of PVC For
mulating ", EJ Wickson, John Wiley & Sons, New Y
ork 1993).

Examples of such additives are known to those skilled in the art and can be found in the technical literature. Some of the known additives and processing aids are described below, but are not limited to: Phosphite: Organic phosphites are known co-stabilizers for chlorine-containing polymers. Examples are trioctyl, tridecyl, tridodecyl, tritridecyl, tripentadecyl, trioleyl, tristearyl, triphenyl, tricresyl, trisnonylphenyl, tris-2,4-
Tertiary butylphenyl or tricyclohexyl phosphite. Other suitable phosphites are variously mixed aryldialkyl and alkyldiaryl phosphites, such as phenyldioctyl, phenyldidecyl, phenyldidodecyl, phenylditridecyl, phenylditetradecyl, phenyldipentadecyl, octyldiphenyl, decyldiphenyl. , Undecyldiphenyl, dodecyldiphenyl, tridecyldiphenyl, tetradecyldiphenyl, pentadecyldiphenyl, oleyldiphenyl, stearyldiphenyl and dodecylbis-2,4-ditert-butylphenylphosphite.

In addition, phosphites of various diols and polyols may also be advantageously used, examples being tetraphenyldipropylene glycol diphosphite, polydipropylene glycol phenyl phosphite, tetramethylolcyclohexanol decyl diphosphite, Methylol cyclohexanol butoxyethoxyethyl diphosphite, tetramethylol cyclohexanol nonylphenyl diphosphite, bisnonylphenyl ditrimethylolpropane diphosphite, bis-2-butoxyethyl di-trimethylolpropane diphosphite, trishydroxyethyl isocyanurate Hexadecyl triphosphite, didecyl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite , Bis-2,4-di-tert-butylphenyl pentaerythritol diphosphite, and mixtures and statistical composition of these phosphites (H ₁₉
C ₉ -C ₆ H ₄ ) O _1.5 P (OC _12,13 H _25,27 ) _1.5
Or _{[C 8 H 17 -C 6 H 4} -O- ] ₂ P [i-C ₈ H
₁₇ O] or (H ₁₉ C ₉ -C ₆ H ₄ ) O _1.5 P (OC
_9,11 H _19,23 ) _1.5 aryl / alkyl phosphite mixture.

The organic phosphite can be used in an amount of, for example, 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, particularly preferably 0.1 to 3 parts by weight, based on 100 parts by weight of PVC.

Polyols: Examples of suitable compounds of this type are: pentaerythritol, dipentaerythritol, tripentaerythritol, bistrimethylolpropane, trimethylolethane, bistrimethylolethane, trimethylolpropane, sorbitol, mulitol Toll, isomaltitol, lactitol, lycacin, mannitol, lactose, leucrose, tris (hydroxyethyl) isocyanurate,
Palatinit, tetramethylolcyclohexanol (TMCH), tetramethylolcyclopentanol,
Tetramethylolcyclopyranol, glycerol, diglycerol, polyglycerol, thiodiglycerol, or 1-O-α-D-glycopyranosyl-D-mannitol dihydrate, and polyvinyl alcohol and cyclodextrin. Of these, TMCH and disaccharide alcohols are preferred.

The polyol can be used in an amount of, for example, 0.01 to 20 parts by weight, preferably 0.1 to 20 parts by weight, particularly preferably 0.1 to 10 parts by weight, based on 100 parts by weight of PVC.

1,3-Dicarbonyl compounds: Examples of 1,3-dicarbonyl compounds include acetylacetone, butanoylacetone, heptanoylacetone, stearoylacetone, palmitoylacetone, lauroylacetone, 7-
Tertiary nonylthioheptane-2,4-dione, benzoylacetone, dibenzoylmethane, lauroylbenzoylmethane, palmitoylbenzoylmethane, stearoylbenzoylmethane, isooctylbenzoylmethane, 5
-Hydroxycapronylbenzoylmethane, tribenzoylmethane, bis (4-methylbenzoyl) methane, benzoyl-p-chlorobenzoylmethane, bis (2-hydroxybenzoyl) methane, 4-methoxybenzoylbenzoylmethane, bis (4-methoxy) Benzoyl) methane, 1-benzoyl-1-acetylnonane, benzoylacetylphenylmethane, stearoyl-4-methoxybenzoylmethane, bis (4-tert-butylbenzoyl) methane, benzoylformylmethane, benzoylphenylacetylmethane, bis (cyclohexa Noyl) methane, di (pivaloyl) methane, methyl acetoacetate, ethyl, hexyl, octyl, dodecyl or octadecyl ester, ethyl benzoylacetate, butyl, 2-ethylhexyl, dodecyl Or octadecyl esters, stearoyl ethyl acetate, propyl, butyl, hexyl or octyl ester and dehydroacetic acid, and their zinc, alkali metal, alkaline earth metal or aluminum salts.

The 1,3-dicarbonyl compound is PVC10
For example, 0.01 to 10 parts by weight, preferably 0.01 to 3 parts by weight, and especially 0.1 to 0 parts by weight, based on 0 parts by weight.
It can be used in an amount of from 01 to 2 parts by weight.

Thiophosphite and thiophosphate: Thiophosphite and thiophosphate have the general formula: (RS) ₃ P, (RS) ₃ P 3O and (RS) ₃
A compound represented by P = S, for example, a patent specification DE
2809492, EP090770 and EP5733
94. Examples are: trithiohexyl phosphite, trithiooctyl phosphite, trithiolauryl phosphite, trithiobenzyl phosphite, tris [carboxy-i-octyloxy] methyl trithiophosphate, S, S,
S-tris [carbo-i-octyloxy] methyltrithiophosphate, S, S, S-tris [carbo-2-
[Ethylhexyloxy] methyltrithiophosphate,
S, S, S-tris-1- [carbohexyloxy] ethyltrithiophosphate, S, S, S-tris-1-
[Carbo-2-ethylhexyloxy] ethyltrithiophosphate, S, S, S-tris-2- [carbo-2
-Ethylhexyloxy] ethyltrithiophosphate.

The thiophosphite and thiophosphate are advantageously present in the chlorine-containing polymer in an amount of from 0.01 to 20.
%, Preferably 0.1 to 5%, and especially 0.1 to 1%.

Mercaptocarboxylic acid esters: Examples of these compounds are esters of thioglycolic acid, thiomalic acid, mercaptopropionic acid, mercaptobenzoic acid and thiolactic acid, such as FR2459816, EP9074.
8, FR 2552440 and EP 365483. Mercaptocarboxylic esters also include the corresponding polyol esters and their partial esters. They are advantageously 0.01 to 10%, preferably 0.1 to 5%, in the chlorine-containing polymer,
And especially it may be present in a proportion of 0.1 to 1%.

Epoxides and epoxidized fatty acid esters: The novel stabilizer combination may further contain at least one epoxidized fatty acid ester. Particularly suitable for this are esters of fatty acids from natural sources such as soybean oil or rapeseed oil. The epoxy compound is used, for example, in an amount of up to 0.1 part by weight, advantageously 0.1 to 30 parts by weight, preferably 0.5 to 2 parts by weight, per 100 parts by weight of the composition.
Used in an amount of 5 parts by weight. Other examples are epoxidized polybutadiene, epoxidized linseed oil, epoxidized fish oil,
Epoxidized tallow, methylbutyl or 2-ethylhexyl epoxy stearate, tris (epoxypropyl)
Isocyanurate, epoxidized castor oil, epoxidized sunflower oil, 3-phenoxy-1,2-epoxypropane, bisphenol A diglycidyl ether, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide and 3,4-epoxycyclohexylmethyl 3, 4-epoxycyclohexanecarboxylate. Derivatives of bisphenol A and bisphenol F are also suitable as epoxides, such as, for example, those described in South African Patent Specification ZA-2600 / 94.

Dihydropyridines and polydihydropyridines: Suitable monomers dihydropyridines are the compounds mentioned above, such as FR2039496, EP2007, EP3
62012 and EP24754. The following formula:

Embedded image (Where Z is CO ₂ CH ₃ , CO ₂ C ₂ H ₅ , CO ₂ ⁿ
Compounds represented by represents a C ₁₂ H ₂₅ or ^{_{-CO 2 C 2 H 4 -S- n}} C 12 H 25) are preferred.

Particularly suitable polydihydropyridines are of the formula:

Embedded image (Wherein T represents an unsubstituted alkyl group having 1 to 12 carbon atoms, L represents the meaning defined for T,
And n represents a number from 0 to 20, k represents 0 or 1, R and R ′ independently of one another are an ethylene, propylene, butylene or alkylene group or the following formula:
_{- (- C p H 2p -X-} ) t C p H 2p - represents a cycloalkylene bis methylene group represented, p is 2 to represent 8, t represents 0 to 10, and X is an oxygen atom Or a sulfur atom).

Compounds of this kind are described in detail in EP 0 268 887. The (poly) dihydropyridine may be used in the chlorine-containing polymer in a proportion of from 0.001 to 5 parts by weight, in particular from 0.005 to 1 part by weight, based on the polymer. Thiodiethylenebis [5-methoxycarbonyl-2,6-dimethyl-1,4-dihydropyridine-3-carboxylate] is particularly preferred.

Alkali metal and alkaline earth metal compounds: These terms basically mean the carboxylate of the above-mentioned acids or the corresponding oxides and hydroxides, carbonates or basic carbonates. Mixtures of them with organic acids are also suitable. Examples are NaOH, KO
H, CaO, Ca (OH) ₂ , MgO, Mg (O
H) ₂ , CaCO ₃ , MgCO ₃ , dolomite, huntite, and Na, K, Ca or Mg salts of fatty acids. In the case of alkaline earth metals and carboxylate of Zn, MO and M (OH) ₂ (M
= Ca, Mg, Sr or Zn), so-called over-based compounds. In addition to the novel stabilizer combinations, preference is given to the use of alkali metals, alkaline earth metals and / or aluminum carboxylate, for example Na, K, Ca or aluminum stearate.

Perchlorates: These examples have the formula: M (Cl
O ₄ ) _n (where M is Li, Na, K, Mg, Ca, B
a, Zn, Al, Ce or La, and the index n represents 1, 2 or 3 according to the valency of M). The perchlorate may be present as a complex with an alcohol or ether alcohol. In the present invention, the respective perchlorate is obtained, for example, by applying it to a carrier material, such as PVC, Ca silicate, zeolite or hydrotalcite, or by chemical reaction of hydrotalcite with perchloric acid. It can be used in various common forms supplied as salts or aqueous solutions. The perchlorate can be used in an amount of, for example, 0.001 to 5 parts by weight, advantageously 0.01 to 3 parts by weight, particularly preferably 0.01 to 2 parts by weight, based on 100 parts by weight of PVC.

Hydrotalcites and zeolites: The chemical composition of these compounds is known to the person skilled in the art and is, for example, DE3844351, US 4000100, EP062.
No. 813, WO 93/20135 are known from the patent specification.

Compounds from the system of hydrotalcite have the general formula VI:

Embedded image ( ^Wherein , M ²⁺ = one or more metal elements selected from the group consisting of Mg, Ca, Sr, Zn and Sn;
³⁺ = Al or B, A ^n-represents an anion having a valency n, n is 1 to a number from 2, Table with 0 <x ≦ 0.5, and m is a number from 0 to 20) Can be done. ^An- is preferably of the formula:

Embedded image Represents a group represented by Examples of hydrotalcite are as follows:

Embedded image

Compounds from the zeolite (alkali metal and / or alkaline earth metal aluminosilicate) system have the general formula VII:

Embedded image (Where n represents the charge of the cation M, where M is an element from the first or second main group, such as Li, Na, K, Mg, C
a, Sr or Ba, or Zn;
(Representing a number from 8 to 15, preferably 0.8 to 1.2 and w representing a number from 0 to 300, preferably 0.5 to 30). The structure is, for example, "Atlas
of Zeolite "WM Meier and DH Olson, Butterw
orth-Heinemann, 3rd ed. 1992.

An example of a zeolite is the following formula:

Embedded image Or a zeolite which can be produced by partial or complete exchange of Na atoms with Li, K, Mg, Ca, Sr or Zn, for example:

Embedded image It is represented by

Other suitable zeolites are: Na ₂ O.Al ₂ O _3. (2-5) SiO _2.
(3.5 to 10) H ₂ O [zeolite P] _{Na 2 O · Al 2 O 3} · 2SiO 2 · (3.5 to 1
0) Zeolites which can be produced by partial or complete exchange of H ₂ O [zeolite MAP] or Na atoms with Li, K or H, such as (L
i, Na, K, H) ₁₀ Al ₁₀ Si ₂₂ O ₆₄ · 20H ₂ O,
K ₉ Na ₃ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] · 27H
_{2 O, K 4 Al 4 Si} 4 O 16 · 6H 2 O [zeolite K
_{-F], Na 8 Al 8 Si 40 O} 96 · 24H 2 O [zeolite D], Barrer like, J. Chem. Soc. 1952 , those described in 1561-71 and US2950952. The following zeolites are also suitable: K offretite according to EP-A-400 961; GB84181
Zeolite R described in No. 2; Zeolite LZ-217 described in US4503023; Ca-free zeolite LZ-218 described in US43333859; Zeolite T described in US4503023, Zeolite LZ-220; Na ₃
K ₆ Al ₉ Si ₂₇ O ₇₂ · 21H ₂ O [zeolite L];
Zeolite LZ-211 described in US4503023;
Zeolite LZ-212 as described in US4503023;
5416 Zeolite O, Zeolite LZ-217 described in US4503023; Zeolite LZ-219 described in US4503023;
07 (1969) Zeolite ZK-19; Barrer et al.
Zeolite W described in J. Chem. Soc. 1956, 2882 (K-
M); and Na ₃₀ Al ₃₀ Si ₆₆ O ₁₉₂ · 98H ₂ O
[Zeolite ZK-5, Zeolite Q].

In the above formula VII, a zeolite P type in which x represents 2 to 5 and y represents 3.5 to 10,
It is particularly preferred to use zeolite MAP in which in formula VII x represents 2 and y represents 3.5 to 10. Relevant substances are in particular the zeolites Na-P, ie those in which M is Na. The zeolites generally give rise to variants Na-P-1, Na-P-2 and Na-P-3 which differ in their cubic, tetragonal or orthorhombic system (RM Barrer, BM Monday, J. Chem.
Soc. A 1971, 2909-14). The literature just described also describes the production of zeolites P-1 and P-2. Zeolite P-3 is very rare and therefore of low practical interest. The structure of zeolite P-1 is described in the above Atlas of Zeo
Gismondites known from lite Structures
te). A very recent document (EP-A-3840)
70), the cubic system of zeolite P (zeolite B or Pc) and the tetragonal system (zeolite P ₁ )
And the distinction is made. The document also states that 1.0
It is a very recent P-type zeolite having a Si: Al ratio of 7: 1 or less. These are zeolites which give the notation MAP or MA-P for maximum aluminum P. Depending on the method of production, zeolite P may include small fractions of other zeolites. High purity zeolite P is W
O94 / 26662.

In the present invention, it is also possible to use finely divided, water-insoluble sodium aluminosilicate precipitated and crystallized in the presence of a water-soluble inorganic or organic dispersant. These can be introduced into the reaction mixture in any desired way before or during precipitation or crystallization. Na-zeolite A and Na-zeolite P are preferred. The hydrotalcites and zeolites may be naturally occurring minerals or synthetically produced compounds.

The hydrotalcite and / or zeolite is based on 100 parts by weight of the halogen-containing polymer.
For example, it can be used in an amount of 0.1 to 50 parts by weight, advantageously 0.1 to 10 parts by weight, particularly preferably 0.1 to 5 parts by weight.

Alkali metal alumocarbonates (dawsonites): These compounds have the formula:

Embedded image (Where M is H, Li, Na, K, Mg _1/2 , C
a _1/2 , Sr _1/2 or Zn _1/2 ; Z is CO ₂ ,
SO ₂ , (Cl ₂ O ₇ ) _1/2 , B ₄ O ₆ , S ₂ O ₂ (thiosulfate) or C ₂ O ₂ (oxalate); m represents M Mg _1/2 or Ca _{1 / If 2} then 1 and 2
Represents a number between 1 and 3 in all other cases; n represents a number between 1 and 4; o represents 2 and 4
And p represents a number between 0 and 30)
Can be represented by

The alumo salt compounds of the formula V which can be used can be naturally occurring minerals or synthetically produced compounds. The metal may be partially replaced by another. The alumo salt compound may be crystalline, partially crystalline or amorphous and may exist in the form of a dry gel. Almo salt compounds may also be present in the more rare crystalline variants. A process for producing such compounds is described in EP39.
4670. Examples of naturally occurring alumo salt compounds are indigirite, tunicite
(tunisite), alumohydrocalci
te), para-alumohydroca
lcite), strontio dresser
ite) and hydrostrontiodresserite (hydrost
rontiodresserite). Another example of an alumo salt compound is potassium alumocarbonate {(K ₂ O) · (Al
₂ O ₃ ) ・ (CO ₂ ) ₂・ 2 H ₂ O｝, sodium aluminothiosulfate ｛(Na ₂ O) ・ (Al ₂ O ₃ ) ・
_{(S 2 O 2) 2 ·} 2H 2 O}, potassium Al Mosul Fit _{{(K 2 O) · (} Al 2 O 3) · (SO 2) 2 · 2
H ₂ O｝, calcium alumoxalate ｛(CaO)
・ (Al ₂ O ₃ ). (C ₂ O ₂ ) ₂ .5H ₂ O｝, magnesium alumotetraborate ｛(MgO) ・ (Al ₂ O ₃ )
_{O 3) · (B 4 O} 6) 2 · 5H 2 O}, {( [Mg _0.2
Na _{0.6] 2 O) · (Al 2 O} 3) · (CO 2) 2 ·
4.1H ₂ O}, {([Mg _0.2 Na _{0.6] 2} O) ·
_{(Al 2 O 3) · (} CO 2) 2 · 4.3H 2 O} and {([Mg _0.3 Na _{0.4] 2 O) · (Al 2 O} 3) ·
(CO ₂ ) _2.2 · 4.9H ₂ O｝.

The mixed alumo salt compounds can be obtained by cation exchange according to methods known per se, preferably from alkali metal alumo salt compounds or by combined precipitation (see, eg, US Pat. No. 5,055,284). Preferred alumo salt compounds are those wherein M represents Na or K;
Z represents CO ₂ , SO ₂ or (Cl ₂ O ₇ ) _1/2 ;
m represents 1-3; n represents 1-4; o represents 2-4, and p represents 0-20. Z is particularly preferably CO ₂ .

The following equation:

Embedded image (Where M is a metal atom such as Na, K, Mg _1/2 , C
a _1/2 , Sr _1/2 or Zn _1/2 , and p is 0
Are also preferred. Particularly preferred are sodium armodihydroxycarbonate (DASC) and homologous potassium compounds (DAPC).

Dawsonite is a halogen-containing polymer 10
It can be used, for example, in an amount of 0.01 to 50 parts by weight, advantageously 0.1 to 10 parts by weight, particularly preferably 0.1 to 5 parts by weight, based on 0 parts by weight.

The novel stabilizer combinations can be used with other additives which are customary for the processing and stabilization of chlorine-containing polymers, examples of which are: Antioxidants: suitable examples are: It is as: 1. Examples of alkylated monophenols 2,6-di-tert-butyl-4-methylphenol, 2-
Butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl- 4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2,6-
Dioctadecyl-4-methylphenol, 2,4,6-
Tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6
(1′-methylundec-1′-yl) phenol,
2,4-dimethyl-6- (1′-methylheptadecyl)
1'-yl) phenol, 2,4-dimethyl-6-
(1′-Methyltridec-1′-yl) phenol and mixtures thereof.

2. Examples of alkylthiomethylphenols 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-diphenol Dodecylthiomethyl-4-nonylphenol.

[0047] 3. Hydroquinone and alkylated hydro
Examples of quinones 2,6-di-tert-butyl-4-methoxyphenol, 2,
5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl- 4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, bis (3,5-di-tert-butyl-4-hydroxyphenyl) ) Adipate.

[0048] 4. Examples of tocopherols α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E).

[0049] 5. Hydroxylated thiodiphenyl ether
Examples of 2,2'-thiobis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thiobis (6-tert-butyl-3-methylphenol) Phenol), 4,4′-thiobis (6-tert-butyl-2-methylphenol), 4,4′-thiobis (3,
6-disecond amylphenol), 4,4′-bis (2,
6-dimethyl-4-hydroxyphenyl) disulfide.

6 Examples of alkylidene bisphenols 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2'-methylenebis [4 -Methyl-6- (α-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-tert-butylphenol), 2,2′-ethylidenebis (6-tert-butyl-4-isobutylphenol), 2,2′-methylenebis [6- (α -Methylbenzyl) -4-nonylphenol], 2,2'-methylenebis [6- (α, α-dimethylbenzyl) -4-nonylphenol], 4,4'-
Methylene bis (2,6-di-tert-butylphenol),
4,4'-methylenebis (6-tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3- Tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5
-Tert-butyl-4-hydroxy-2-methylphenyl)
Butane, 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecylmercaptobutane, ethylene glycol-bis [3,3-bis (3′-tert-butyl- 4'-hydroxyphenyl) butyrate], bis (3-tert-butyl-4-hydroxy-5)
-Methylphenyl) dicyclopentadiene, bis [2-
(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis (3,5-dimethyl-2-)
Hydroxyphenyl) butane, 2,2-bis (3,5-
Di-tert-butyl-4-hydroxyphenyl) propane,
2,2-bis (5-tert-butyl-4-hydroxy-2-
Methylphenyl) -4-n-dodecylmercaptobutane, 1,1,5,5-tetra (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane.

[0051] 7. O-, N- and S-benzyl compounds
Examples of 3,5,3 ', 5'-tetratert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tris (3,5-di Tributyl-4-hydroxybenzyl) amine, bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5-ditert-butyl-4-hydroxybenzyl) sulfide, Isooctyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

[0052] 8. Examples of hydroxybenzylated malonates dioctadecyl 2,2-bis (3,5-di-tert-butyl-
2-hydroxybenzyl) malonate, dioctadecyl 2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) malonate, didodecylmercaptoethyl-
2,2-bis (3,5-ditert-butyl-4-hydroxybenzyl) malonate, bis [4- (1,1,3,3-
Tetramethylbutyl) phenyl] 2,2-bis (3,5
-Di-tert-butyl-4-hydroxybenzyl) malonate.

9. Examples of aromatic hydroxybenzyl compounds 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene,
1,4-bis (3,5-ditert-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene,
2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenol.

10. Examples of triazine compounds 2,4-bis (octylmercapto) -6- (3,5-
Di-tert-butyl-4-hydroxyanilino) -1,3,5
-Triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyanilino)-
1,3,5-triazine, 2-octylmercapto-
4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,3,5-triazine, 2,4,6-
Tris (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,2,3-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenylethyl) ) -1,3,5-Triazine, 1,3,5-tris (3,5-ditert-butyl-4-hydroxyphenylpropionyl) hexahydro-1,3,5-triazine, 1,3,5-tris (3,
5-Dicyclohexyl-4-hydroxybenzyl) isocyanurate.

11. Examples of benzylphosphonates dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-
4-hydroxybenzyl phosphonate, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzyl phosphonate, dioctadecyl 5-tert-butyl-4-hydroxy-3-methylbenzyl phosphonate, 3,5-di-tert-butyl- Calcium salt of monoethyl ester of 4-hydroxybenzylphosphonic acid.

12. Examples of acylaminophenols 4-hydroxylauric-anilide, 4-hydroxystearic-anilide, octyl N- (3,5-di-
Tert-butyl-4-hydroxyphenyl) -carbamate.

13. β- (3,5-di-tert-butyl-4-
(Hydroxyphenyl) propionic acid and the following monovalent or
Examples of ester alcohols with polyhydric alcohols : methanol, ethanol, octanol, octadecanol, 1,6-hexanediol,
1,9-nonanediol, ethylene glycol, 1,2
-Propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxalamide, 3-thiaundecanol, 3-thia Pentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

14. β- (5-tert-butyl-4-hydro
(Xy-3-methylphenyl) propionic acid and the following monovalent
Or examples of ester alcohols with polyhydric alcohols : methanol, ethanol, octanol, octadecanol, 1,6-hexanediol,
1,9-nonanediol, ethylene glycol, 1,2
-Propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxalamide, 3-thiaundecanol, 3-thia Pentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

15. β- (3,5-dicyclocyclohexene
(Sil-4-hydroxyphenyl) propionic acid and the following
Examples of ester alcohols with monohydric or polyhydric alcohols : methanol, ethanol, octanol, octadecanol, 1,6-hexanediol,
1,9-nonanediol, ethylene glycol, 1,2
-Propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxalamide, 3-thiaundecanol, 3-thia Pentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

16.3,5-Di-tert-butyl-4-hydro
Xyphenylacetic acid and the following monohydric or polyhydric alcohol
Examples of ester alcohols: methanol, ethanol, octanol, octadecanol, 1,6-hexanediol,
1,9-nonanediol, ethylene glycol, 1,2
-Propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxalamide, 3-thiaundecanol, 3-thia Pentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

[0061] 17. β- (3,5-di-tert-butyl-4-
Examples of amides of ( hydroxyphenyl) propionic acid N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine,
N, N′-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamine,
N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine. If desired, it is also possible to use mixtures of antioxidants with different structures.

The antioxidants can be used in amounts of, for example, 0.01 to 10 parts by weight, preferably 0.05 to 10 parts by weight, and especially 0.05 to 5 parts by weight, per 100 parts by weight of PVC.

UV absorbers and light stabilizers: Examples of these are as follows: 1.2- (2'-hydroxyphenyl) benzotriazo
Examples of Lumpur 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl -
2′-hydroxyphenyl) benzotriazole, 2-
(5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-
(1,1,3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (3 ′, 5′-di-tert-butyl-
2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-
5'-methylphenyl) -5-chlorobenzotriazole, 2- (3'-sec-butyl-5'-tert-butyl-2 '
-Hydroxyphenyl) benzotriazole, 2-
(2′-hydroxy-4′-octyloxyphenyl)
Benzotriazole, 2- (3 ′, 5′-ditertiaryamyl-2′-hydroxyphenyl) benzotriazole,
-(3 ', 5'-bis (α, α-dimethylbenzyl)-
2′-hydroxyphenyl) benzotriazole, 2-
(3′-tert-butyl-2′-hydroxy-5 ′-(2-
Octyloxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-
5 '-[2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-(2- Methoxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3 ′
-Tert-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl) benzotriazole,
2- (3'-tert-butyl-2'-hydroxy-5'-
(2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5'-)
[2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-
Methylphenyl) benzotriazole and 2- (3 ′
-Tert-butyl-2'-hydroxy-5 '-(2-isooctyloxycarbonylethyl) phenylbenzotriazole mixture, 2,2'-methylenebis [4- (1,
1,3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol]; 2- [3'-tert-butyl-5 '-(2-methoxycarbonylethyl) -2'-
[Hydroxyphenyl] benzotriazole and a transesterified product of polyethylene glycol 300; the following formula: [RC
H ₂ CH ₂ COO (CH ₂ ) ₃ —] ₂ — (wherein R represents a 3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl group). Compound.

2.2 Examples of 2 -hydroxy- benzophenones 4-hydroxy-, 4-methoxy-, 4-octoxy-, 4-decyloxy-, 4-dodecyloxy-, 4-
Benzyloxy-, 4,2 ', 4'-trihydroxy-
And 2'-hydroxy-4,4'-dimethoxy derivatives.

[0065] 3. Of substituted and unsubstituted benzoic acids
Examples of steles 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis (4-tert-butylbenzoyl) resorcinol, benzoyl resorcinol, 2,4-di-tertiary Butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2 -Methyl-4,6-ditert-butylphenyl 3,5
-Di-tert-butyl-4-hydroxybenzoate.

[0066] 4. Examples of acrylates ethyl α-cyano-β, β-diphenyl acrylate,
Isooctyl α-cyano-β, β-diphenyl-acrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, butyl α-cyano-β-methyl-p-methoxycinnamate , Methyl α-carbomethoxy-p-methoxycinnamate and N- (β-carbomethoxy-β-cyanovinyl) -2-methylindoline.

5. Examples of nickel compounds Nickel complexes of 2,2'-thiobis- [4- (1,1,3,3-tetramethylbutyl) phenol], for example 1: 1 or 1: 2 complexes, optionally n- With other ligands such as butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, monoalkyl esters, for example methyl of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid Or nickel salts of ethyl esters, ketoximes such as 2-hydroxy-
Nickel complexes of 4-methyl-phenylundecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, optionally with other ligands.

[0068] 6. Examples of sterically hindered amines bis (2,2,6,6-tetramethylpiperidyl) sebacate, bis (2,2,6,6-tetramethylpiperidyl) succinate, bis (1,2,2,6,6- Pentamethylpiperidyl) sebacate, bis (1,2,2,
6,6-pentamethylpiperidyl) n-butyl-3,5
Di-tert-butyl-4-hydroxybenzylmalonate,
Condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, N, N′-bis (2,2,6,6-tetramethyl-
Condensation product of 4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine, tris (2,2,6,6-tetramethyl-4 -Piperidyl) nitrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4-
Piperidyl) -1,2,3,4-butanetetraoate, 1,1 ′-(1,2-ethanediyl) -bis (3
3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-
Stearyloxy-2,2,6,6-tetramethylpiperidine, bis (1,2,2,6,6-pentamethylpiperidyl) -2-n-butyl-2- (2-hydroxy-
3,5-di-tert-butylbenzyl) malonate, 3-n-
Octyl-7,7,9,9-tetramethyl-1,3,8
-Triazaspiro [4.5] decane-2,4-dione,
Bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, N, N′-bis (2 , 2,6,6-tetramethylpiperidyl-4-piperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-
Condensation product with triazine, 2-chloro-4,6-bis (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -1,3,5-triazine and 1,2-bis Condensation product with (3-aminopropylamino) ethane, 2-chloro-4,6-di (4-n-butylamino-
1,2,2,6,6-pentamethylpiperidyl) -1,
Condensation product of 3,5-triazine and 1,2-bis (3-aminopropylamino) ethane, 8-acetyl-3-
Dodecyl-7,7,9,9-tetramethyl-1,3,8
-Triazaspiro [4.5] decane-2,4-dione,
3-dodecyl-1- (2,2,6,6-tetramethyl-
4-Pyhelidyl) pyrrolidine-2,5-dione, 3-dodecyl-1- (1,2,2,6,6-pentamethyl-4
-Piperidyl) pyrrolidine-2,5-dione.

[0069] 7. Examples of oxalamides 4,4'- dioctyloxyoxanilide , 2,2'-
Diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-ditertbutoxanilide, 2,2′-didodecyloxy-5,5′-ditertbutyloxanilide, 2
-Ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxalamide, 2
-Ethoxy-5-tert-butyl-2'-ethyloxanilide and said compound with 2-ethoxy-2'-ethyl-5.
Mixture with 4'-di-tert-butyloxanilide, ortho-
And mixtures of para-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.

8.2- (2-hydroxyphenyl)-
Examples of 1,3,5-triazine 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-
(Hydroxy-4-octyloxyphenyl) -4,6-
Bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,
6-bis (2,4-dimethylphenyl) -1,3,5-
Triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl ) -4,6-bis (4-
Methylphenyl) -1,3,5-triazine, 2- (2
-Hydroxy-4-dodecyloxyphenyl) -4,6
-Bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxypropoxy) phenyl] -4,6
-Bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) phenyl]-
4,6-bis (2,4-dimethylphenyl) -1,3
5-triazine.

The novel stabilizer mixture contains alkali metal or alkaline earth metal carboxylate, especially calcium carboxylate, aluminum carboxylate, 1,3
With dicarbonyl compounds, dihydropyridines, phosphites or combinations of these substances.

Plasticizers: Examples of suitable organic plasticizers are from the following group: A) Phthalates: Examples of such plasticizers are dimethyl, diethyl, dibutyl, dihexyl, di-2-ethylhexyl. , Di-n-octyl, diisooctyl, diisononyl, diisodecyl, diisotridecyl, dicyclohexyl, dimethylcyclohexyl, dimethyl glycol, dibutyl glycol, benzyl butyl and mixtures of diphenyl phthalates and phthalates, e.g. And alkyl phthalates having 9 to 11 carbon atoms, n-alkyl phthalates having 6 to 10 carbon atoms and n-alkyl phthalates having 8 to 10 carbon atoms. Of these, dibutyl, dihexyl, di-2-ethylhexyl, di-n-octyl, diisooctyl, diisononyl, diisodecyl, diisotridecyl and the abovementioned mixtures of benzylbutyl phthalate and alkyl phthalate are preferred. Particularly preferred are di-2-ethylhexyl, diisononyl and diisodecyl phthalate, usually DOP (dioctyl phthalate, di-2
-Ethylhexyl phthalate), DINP (diisononyl phthalate) and DIDP (diisodecyl phthalate).

B) Esters of aliphatic dicarboxylic acids, especially esters of adipic acid, azelaic acid and sebacic acid. Examples of such plasticizers are di-2-ethylhexyl adipate, diisooctyl adipate (mixture), diisononyl adipate (mixture), diisodecyl adipate (mixture), benzylbutyl adipate, benzyloctyl adipate, di-2-ethylhexyl azelate. ,
Di-2-ethylhexyl sebacate and diisodecyl sebacate (mixture). Preferred are di-2-ethylhexyl adipate and diisooctyl adipate.

C) Trimellitic acid ester For example, tri-2-ethylhexyl trimellitate, triisodecyl trimellitate (mixture), triisotridecyl trimellitate, triisooctyl trimellitate (mixture) and the number of tricarbon atoms 6-8 alkyl, C6-10 alkyl, C7-9 alkyl and C9-11 alkyltrimellitate. The latter trimellitate is formed by esterification of trimellitic acid with a corresponding mixture of alkanols. A preferred trimellitate is the above trimellitate from a mixture of tri-2-ethylhexyl trimellitate and an alkanol. Common abbreviations are TOTM (trioctyl trimellitate, tri-2-ethylhexyl trimellitate), T
IDTM (triisodecyl trimellitate) and TI
TDTM (triisotridecyl trimellitate).

D) Epoxy plasticizers These are basically epoxidized unsaturated fatty acids, for example epoxidized soybean oil. E) Polymer plasticizers The most conventional starting materials for the preparation of polyester plasticizers are: dicarboxylic acids, such as adipic acid, phthalic acid, azelaic acid and sebacic acid; and diols such as 1,2-propane Diols, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and diethylene glycol.

F) Phosphate esters Examples of such phosphate esters are tributyl phosphate, tri-2-ethylbutyl phosphate, tri-2-phosphate.
Ethylhexyl phosphate, trichloroethyl phosphate, 2-ethylhexyl diphenyl phosphate,
Cresyl diphenyl phosphate, triphenyl phosphate, tricresyl phosphate and trixylenyl phosphate. Tri-2-ethylhexyl phosphate and Reofos (registered trademark, Reofos) 50 and 95 (manufactured by FMC) are preferred. G) Chlorinated hydrocarbons (paraffins) H) Hydrocarbons I) Monoesters such as butyl oleate, phenoxyethyl oleate, tetrahydrofurfuryl oleate and alkyl sulfonates. J) Glycol esters such as diglycol benzoate.

Definitions and examples of plasticizers from groups A) to J) can be found in the following handbook: "Handbook of Plastic Additives (Tashenbuch der Kunststoff)
additive) ", El. Gechter and Her. Edited by Müller, Carl Hanser Verlag, 1989, Chapter 5, pp. 341-442. "PVC Technology (PVC
Technology) ". Vee. Chito editing, 4th edition
Edition, Elsevier Publishers, 1984,
Chapter 6, pages 147-180. It is also possible to use mixtures of different plasticizers. The plasticizer can be used, for example, in an amount of 5 to 120 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of PVC.

Examples of suitable lubricants are montan waxes, fatty acid esters, PE waxes, amide waxes, chlorinated paraffins, glycerol esters or alkaline earth metal soaps, and the silicone-based lubricants described in EP 225261. Lubricants that can be used are also described in the Handbook of Plastic Additives (Tashenbuch der Kunsts
toffadditive) ", El. Gechter and Her. Edited by Müller, Carl Hanser Verlag, Third Edition, 1
989, pp. 478-488.

Fillers: Examples of possible fillers ("Handbook of PVC-Formulating", e.
Jay. Edited by Vickson, John Wiley and Sons, New York, 1993, 393-44
9) and examples of toughening agents (Additives Handbook (Taschen)
buch der Kunststoffadditive) ", El. Gechter and Her. Edited by Müller, Carl Hanser Verlag, 3rd Edition, 1989, pp. 549-615) are calcium carbonate, dolomite, wollastonite,
Magnesium oxide, magnesium hydroxide, silicate,
Glass fiber, calc, kaolin, chalk (chalk), mica (mica), metal oxides and hydroxides, carbon black or graphite, with chalk (chalk) being preferred.

Pigments: Suitable pigments are known to those skilled in the art.
Examples of inorganic pigments are TiO ₂ , carbon black, Fe ₂ O
_{3, Sb 2 O 3, (} Ti, Ba, Sb) O 2, Cr 2 O
_3. Spinels such as cobalt blue and cobalt green, Cd (S, Se), ultramarine blue. TiO ₂ and its particulate form are preferred. Examples of organic pigments are azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, pyrrolopyrrole pigments and anthraquinone pigments. Other details can be found in the Handbook of PVC-Formulating, edited by E. J. Vickson, John Wiley and Sons, New York, 1993, pp. 449-474.

Examples of chlorine-containing polymers to be stabilized and their recycles are: polymers of vinyl chloride, vinyl resins whose structure contains vinyl chloride units, such as vinyl esters of vinyl chloride and fatty acids. ,
Particularly copolymers of vinyl acetate, copolymers of vinyl chloride with acrylic acid and methacrylic acid, and with acrylonitrile, copolymers of vinyl chloride with diene compounds and unsaturated dicarboxylic acids or their anhydrides, for example vinyl chloride and diethyl maleate, diethyl Copolymers with fumarate or maleic anhydride, post-chlorinated polymers and copolymers of vinyl chloride, vinyl chloride and vinylidene chloride with unsaturated aldehydes, ketones and others such as acrolein, crotonaldehyde, vinyl methyl ketone, vinyl methyl ether, Copolymer with vinyl isobutyl ether, etc .; Polymer of vinylidene chloride and its copolymer with vinyl chloride and other polymerizable compounds; Vinyl chloroacetate and dichlorodivinyl ether Chlorinated polymers of vinyl acetate, chlorinated polymer esters of acrylic acid and α-substituted acrylic acid; chlorinated styrenes, for example polymers of dichlorostyrene; chlorinated rubbers; chlorinated polymers of ethylene; polymers of chlorobutadiene And post-chlorinated polymers and copolymers thereof with vinyl chloride, chlorinated natural and synthetic rubbers; and mixtures of the above polymers with one another or with other polymerizable compounds.

In the present specification, the term PVC is defined as P
It includes copolymers of VC with a polymerizable compound, such as acrylonitrile, vinyl acetate or ABS, and may be suspension polymers, bulk polymers and emulsion polymers. PVC
Homopolymers alone or in combination with polyacrylates are preferred.

Also included are graft polymers of PVC with EVA, ABS and MBS. Other preferred materials are the above homo- and copolymers, especially mixtures of vinyl chloride homo-copolymers with other thermoplastic and / or elastomeric polymers, especially ABS, MBS, NB
R, SAN, EVA, CPE, MBAS, PMA, PM
It is a blend with MA, EPDM and polylactone. Suspension and bulk polymers and emulsion polymers are preferred. Particularly preferred chlorine-containing polymers are polyvinyl chloride, especially suspension polymers and bulk polymers.

For the stabilization according to the invention, other suitable polymers are, in particular, recycled chlorine-containing polymers, which have been damaged by processing, use or storage. Is a polymer described in detail above. PVC recycles are particularly preferred. Recycles can also include small amounts of foreign materials that are often difficult to remove, such as paper, pigments, adhesives. These extraneous materials may also result from contact with various materials during use or rework, such as fuel residues, some coating materials, trace metals and initiator residues.

The mixture of stabilizers is used in a manner well known to those skilled in the art. For example, it is also possible for the stabilizer mixture to be processed with conventional additives before practical use, for example by shaping it into granules or extrudates or pastes. The invention further provides
There is provided the use of a stabilizer mixture as described above, as granules, extrudates or pastes and / or in forms with lubricants (so-called one-pack formulations) to stabilize halogen-containing polymers or polymer recycles. For the individual stabilizers and for the halogen-containing polymer itself, the preferences given above apply, as can one of the other components mentioned above.

The stabilizer mixture can be added to the polymer in a known manner, and the stabilizers mentioned above and, if desired, other stabilizers can be combined with known equipment, such as mixers, compounders, extruders, etc. It is mixed with the halogen-containing polymer using a machine, a mill, or the like. According to the invention, the stabilizers can be added individually or as a mixture with one another or otherwise in the form of so-called masterbatches. The present invention ultimately stabilizes a halogen-containing polymer comprising mixing the stabilizer component and, if desired, other additives with PVC using equipment such as a calender, mixer, compounder, extruder, and the like. A method is also provided.

The present invention also relates to a polymer composition comprising the novel stabilizer mixture stabilized by such a method. They can be formed into a desired shape by a known method. Such methods are rolling (calendering), extrusion, injection molding, sintering or spinning, as well as extrusion blow molding or processing by the plastisol method. The polymer composition can also be processed into a foam. The invention also relates to the use of the stabilized polymer composition for producing shaped articles that can be produced from halogen-containing polymers. The novel polymer compositions are suitable for semi-rigid and flexible formulations, such as flexible formulations for wire sheathing and cable insulation. In the form of semi-rigid blends, the novel polymer compositions are especially suitable for decorative films, foams, agricultural films, hoses, sealing and office films, extruded profiles and sheets, flooring films. Suitable for and sheet materials, coated products and synthetic leather as well as crash pad sheets (for use in the automotive sector).

In the form of a rigid compound, the novel polymer composition comprises hollow articles (bottles), packaging films (thermoformed films), blown films, crash pad sheets (automobiles), pipes, foams, heavy materials ( Particularly suitable for window frames, transparent wall profiles, architectural profiles, sidings, furniture, fittings, and equipment frames (computers, household appliances) and other injection molded articles. . Examples of the use of the polymer compositions according to the invention as plastisols are artificial leather, floor coverings, woven coatings, wallpaper, coil coatings and underbody protection for motor vehicles. PVC stabilized according to the invention is a sintered PVC
Examples of applications are slush, slush mold and coil coating.

N-piperidinyl triazine is described in a known reference (Houben-Weyl "Methoden der organischen Chem").
ie ", Vol.VIII, 233-237 :, SAUERSTOFFVERBINDEUNGEN II
I, 3rd Ed. Thieme Verlag Stuttgart, 1952). Starting materials for the reaction with various N-piperidinylamines are cyanuric chloride, diamino-chloro-1,
3,5-Triazine or various substituted bisdialkylamino-chloro-1,3,5-triazines or dialkylamino- and / or alkylamino-dichloro-1,3,5-triazines can be used.

[0090]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. Unless indicated otherwise, parts and percentages are by weight as before. Example 1: N, N'-bis [2,2,6,6-tetramethylpiperidin-4-yl] oxamide 156.3 g of 4-amino-2,2,6,6-tetramethylpiperidine were added to diethyl oxalate. Rate 56.6g
(0.4 mol), aminolysis occurs with the generation of intense heat. The temperature rises to about 100 ° C. Following the addition of 150 ml of xylene, the ethanol is distilled off at 88-137 ° C. over 18.5 hours. The batch is then taken up in 1500 ml of xylene, filtered hot and cooled. The precipitated crystals are filtered off with suction and recrystallized from xylene. Yield 120 g (82% of theory), mp 225-23
1 ℃

The following products (Examples 2-8) were prepared by reacting 4-amino-2,2,6,6-tetramethylpiperidine with the corresponding acid chloride, or bis-2,2,6 , 6, -tetramethylpiperidinyl-1,
Produced by reacting 6-hexanediamine with acetic anhydride:

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Example 9: To prepare stabilizers I and II, a Zn / Ca stearate mixture was prepared using the commercial product beta-
The diketone and (stabilizer I) and also the piperidine compound (Example 5) in a ratio of 8: 2: 1.5 (stabilizer II) were intensively applied for 1.5 hours in a tumble mixer. Mix. Of the mixture of these stabilizers, 1.0 part (stabilizer I) or 1.15 parts (stabilizer II) was replaced by 100 parts of S-PVC (K value 70) and 100 parts of dioctyl phthalate / epoxide soybean oil. The mixture is mixed with 21 parts of the mixture as well as a commercially available liquid arylalkyl phosphite and the mixture is plasticized on a milling roller at 190 ° C. for 5 minutes. Specimens are cut from the resulting sheet (0.2 mm thick) and subjected to thermal stress in a Mathis Thermotakter for the period shown in the table below. The yellowness index (YI) is then measured according to ASTM-1925-70.

The lower YI found indicates more effective protection by the stabilizer system from yellowing and therefore damage to the material. The long term thermal stability of the stabilized polymer is evident from the sudden onset of extensive discoloration. All stabilizers are very effective and prolong this discoloration under thermal stress conditions for longer periods. Heating test: YI of test piece at 180 ° C

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Wolfgang Wehner, Germany, 64372 Ober-la-Mustadt, Rostocker Straße 11 (72) Inventor Karl Josef Kuhn, Germany, 64686 Rottertal, Nierbergenstrasse 774 ( 72) Inventor Valerio Bolzatta, Italy, 40127 Bologna, Via Noveli, 2 (72) Inventor Gerhard Lights, Switzerland, 3007 Bern, Beaumontberg 15

Claims (9)

[Claims] 1. A) At least one kind of an organozinc compound having a Zn—O— bond and B) a compound represented by the formula: Wherein the groups and symbols have the following meanings: X represents O or S; a represents 0 to 8; b represents 2 to 12
C represents 1 or 2; k represents 2 to 6; R ₁ is H or an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 3 to 8 carbon atoms, 7 to 9 carbon atoms. It represents a phenylalkyl group or a cycloalkyl group having a carbon number of 5 to 8; R ₂ is C 1 -C
To 8 alkyl groups, —NH ₂ , R ₃ NG—, R ₄ —
_{O -, [R 3 -NG-} CX] c E -, ( alkyl having 1 to 4 carbon _{atoms) 2 N (CH 2) k} -CX-, a phenyl group or OH, alkoxy of 1 to 4 carbon atoms Or a phenyl group substituted by alkyl having 1 to 4 carbon atoms; G is R ₃ is H, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 3 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, R ₂ -CX-NG-
(CH ₂ ) _b , (C 1-4 alkyl) ₂
N (CH _{2) k} - or represents G; R ₄ represents an alkyl group, a cyclohexyl group or a benzyl group of 1 to 4 carbon atoms; E is embedded image The expressed; A _{is> CO, - (CH 2)} m -, - (CH 2)
_d -CO- or -NH (CH ₂₎ represents _n -CO-;
m represents 0 or 1; n represents 2 to 12; p represents 0 or 1; d represents 1 to 8; q represents 1 or 2; when it is a 0, a _{is> CO, - (CH 2)} m -, - (CH 2) d -
When p is 1, A is - (CH _{2) m} - represents;; CO - -, NH ( CH 2) n -CO- a represents the group L is -CH ₂ -
CHR ₆ —, — (CH ₂ ) ₃ —, —CH ＝ CH—, R ₅ represents H, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 3 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms or G; R ₆ represents H, a carbon atom; number 1 to represent an 12 alkyl group; R ₇
Represents H or CH _3; Q represents -O- or>NH; Y is _{-CH 2 -CH (OH) -CH 2} - to represent; represents a and s 3 to 60. ] A stabilizer combination for a halogen-containing polymer, comprising at least one compound represented by the formula: 2. In the above formula, the groups and symbols have the following meanings: X represents O or S; a represents 0 to 4;
b represents 2 to 6; c represents 1 or 2; k represents 2
Or 3; R ₁ is H or C 1-8
It represents an alkyl group; R ₂ is an alkyl group of 1 to 8 carbon _{atoms, -NH 2, R 3 -NG -} , [R 3 -NG-C
X] _c E- or (alkyl having 1 to 4 carbon atoms)
₂ N (CH _{2) k} -CX- represents; R ₃ is H, alkyl of 1 to 8 carbon atoms, R ₂ -CX-NG- (C
H ₂ ) _b , (C 1 -C 4 alkyl) ₂ N
E represents (CH ₂ ) _k -or G; The expressed; R ₅ is H, an alkyl group or G of 1 -C 8; A is _{-CO, - (CH 2) m} -, -
(CH ₂ ) _d —CO— or —NH (CH ₂ ) _n —CO
M represents 0 or 1; n represents 2 to 6; p represents 0 or 1; d represents 1 to 4;
Represents 1 or 2; r represents an 50 2 to; when p is 0, A is _{-CO -, - (CH 2)} m -, - (CH
₂ ) represents _d— CO— or —NH (CH ₂ ) _n —CO—; when p is 1, A represents — (CH ₂ ) _m —;
Is —CH ₂ —CHR ₆ —, — (CH ₂ ) ₃ —, R ₆ represents H or an alkyl group having 1 to 12 carbon atoms; Y represents —CH ₂ —CH (OH) —CH ₂ —
R ₇ represents H or CH ₃ ; Q represents —O— or>NH; and s represents 3 to 60. In the above formula, the groups and symbols have the following meanings: X represents O; a represents 0 to 4; b represents 2 to 6; c represents ₁ ; H represents an alkyl group having 1 to 8 carbon atoms; R ₂ represents [R ₃ -NG
-CX] _c E-; R ₃ represents H, an alkyl group having 1 to 8 carbon atoms, R ₂ -CX-NG- (CH ₂ ) _b or G; E represents (CH ₂ ) _a or- NH- (C
H ₂₎ represents _b NH-; R ₅ represents G; A is - (CH
_{2) m} - and represents; m is 0 or 1; n to from 2 represents 6; p is 0; q is 1 or 2; r is 2 to 50; group L is -CH ₂ -CHR ₆ -,-
(CH ₂ ) ₃ — or —CH ＝ CH—; R ₆ is H
The expressed; Y is _{-CH 2 -CH (OH) -CH 2} - represents; R ₇ represents H; Q represents>NH; and s is 3
The combination of claim 1, wherein the combination represents from 1 to 60. 4. The stabilizer combination according to claim 1, further comprising an alkali metal compound and / or an alkaline earth metal compound and / or an aluminum compound. 5. The stabilizer combination according to claim 1, further comprising calcium carboxylate. 6. The stabilizer combination according to claim 1, further comprising aluminum carboxylate. 7. Epoxides and epoxidized fatty acid esters, phosphites, thiophosphites, thiophosphates, polyols, 1,3-dicarbonyl compounds, mercaptocarboxylic acid esters, dihydropyridines, antioxidants, light stabilizers and ultraviolet absorbers The stabilizer combination according to claim 1, further comprising at least one substance from the group consisting of, alkali metal and alkaline earth metal compounds, perchlorates, zeolites, hydrotalcite and dawsonite. 8. A composition comprising a combination of a halogen-containing polymer and a stabilizer according to claim 1. 9. A method for stabilizing a halogen-containing polymer, comprising adding a stabilizer combination according to claim 1 to the halogen-containing polymer.