DE102010008854A1 - Stabilizer system for foamable halogen-containing polymers - Google Patents

Abstract

The present invention relates to a stabilizer system for halogen-containing polymers comprising the components a) a blowing or foaming agent, b) a zinc compound, c) a melamine derivative, d) a tris-hydroxyalkyl-isocyanuric acid ester. The present invention further relates to its use and to polymer compositions containing the system and their production.

Description

The invention relates to a stabilizer system for foamable chlorine-containing polymer compositions, its use and polymer compositions containing the system and their preparation.

Chlorine-containing polymer compositions are known for their good foamability and find industrial use especially in the form of foams. Due to their versatility, foams have a high value in the construction and materials industry.

However, chlorine-containing polymers have the disadvantage that they tend to discoloration even under moderate thermal stress as is necessary in foaming process and therefore can be processed thermoplastically only with the addition of stabilizers. While basic additives such as organic amines generally enhance discoloration, melamine combinations have recently become known to act as thermal stabilizers, as described in US Pat WO-A 2006/013040 is described.

In the production of foams from chlorine-containing polymers, the risk of discoloration due to the high Verschäumungstemperaturen and the presence of basic foaming agents or catalysts (Kicker) is particularly high.

Stabilizer combinations for halogen-containing polymers containing at least one zinc compound, at least one tris-hydroxyalkyl-isocyanuric acid ester and at least one other non-melamine-containing compound are in JP54154441 . JP55023121 and JP6192521 described.

EP-A 0282912 discloses at least one zinc carboxylate, at least one tris-hydroxyalkyl isocyanuric acid ester and at least one polyalcohol as stabilizers for vinyl chloride polymers.

EP-B 1088032 discloses combinations of calcium oxide and / or calcium hydroxide and tris-hydroxyalkyl isocyanuric acid esters. All examples contain zinc stearate as zinc source.

WO-A 2005/054358 discloses a combination of magnesium oxide or magnesium hydroxide, zinc stearate as cocomponent and tris-hydroxyalkyl isocyanuric acid esters as stabilizers for halogen-containing polymers.

EP-A 1913067 claims a zinc-free stabilizer composition comprising melamine derivatives and tris-hydroxyalkyl isocyanuric acid esters.

However, the stabilizer combinations of the prior art are not fully satisfactory in their thermostabilizing effect and tend to discolor strongly during the foaming process.

It is an object to provide a stabilizer system for halogenated polymers that makes it possible to minimize the discoloration tendency of halogen-containing polymers during the high temperature foaming process.

• a) ein Treib- oder Schäumungsmittel,
• b) eine Zinkverbindung,
• c) ein Melaminderivat,
• d) einen Tris-hydroxyalkyl-isocyanursäureester.

The object is achieved by a stabilizer system for halogen-containing polymers containing the components

• a) a blowing or foaming agent,
• b) a zinc compound,
• c) a melamine derivative,
• d) a tris-hydroxyalkyl isocyanuric acid ester.

It has surprisingly been found that a stabilizer system according to the invention in the production of foams acts mainly as a long-term thermal stabilizer, with no discoloration occurring in the presence of blowing or foaming agents.

To obtain foam-like objects or foamed articles from the composition according to the invention, various processes which are known per se and which contain blowing or foaming agents as component a) are suitable.

The compositions can be foamed by finely divided gases, whereby different types of gassing can be used.

For example, permanent gases, usually nitrogen, z. B. under about 200 bar pressure in PVC melts are incorporated. For foaming z. B. heated in a two-stage process exposed under pressure in a mold under pressure moldings exposed.

For example, flexible foams are also from corresponding plastisols, ie mixtures of polymers and plasticizers, with surfactant foaming agent additives and compressed air or CO ₂ as propellant resp. Foaming agent, for example, produced by continuous extrusion.

Other methods use physical blowing agents, such as readily evaporating hydrocarbons, e.g. For example, pentane, hexane, heptane, chlorinated hydrocarbons, methyl chloride, methylene chloride, trichlorethylene or chloro-fluoroalkanes. For example, the physical blowing agents in the raw materials or precursors are dissolved or supplied under pressure during processing. The formation of closed pores can be promoted by crosslinking.

Also known per se are chemical blowing agents. These are substances that decompose at higher temperatures to form inert gases. These are inorganic blowing agents, such as NaHCO ₃ or organic blowing agents, such as. B. to azo compounds, N-nitroso compounds and sulfonyl hydrazides, for example, with light-off temperatures between 90 and 275 ° C, wherein 100 to 300 ml of nitrogen are split off per gram.

Examples of such blowing agents are azodicarbonamide; modified azodicarbonamide; 4,4'-oxibis (benzenesulfohydrazide), diphenylsulfone-3,3'-disulfohydrazide, diphenylene oxide-4,4'-disulfohydrazide;trihydrazinotriazine;p-Toluylensulfonylsemicarbazid; 5-phenyltetrazole and isatoic anhydride. Particularly preferred is azodicarbonamide as a blowing agent, for example with a light-off temperature of 200 to 235 ° C or a reduced light-off temperature of 155 to 200 ° C. To reduce the onset tempering so-called kicker, z. As the Zn stabilizers contained in the Polymerisatmischung serve. The kicker can also be used in the form of zinc oxide / stearic acid. Other kickers which can be used are the alkali metal compounds, for example sodium compounds or potassium compounds, such as the alkali bicarbonates, preferably NaHCO ₃ or the alkali metal compounds from the aliphatic saturated C ₁ -C ₂₂ -carboxylates, the aliphatic olefinic C ₂ -C ₂₂ -Carboxylates, the aliphatic C ₂ -C ₂₂ carboxylates substituted with at least one OH group, the cyclic and bicyclic carboxylates having 5 to 22 carbon atoms, the aromatic C ₆ -C ₂₂ carboxylates containing at least one OH-substituted aromatic C ₆ -C ₂₂ -carboxylates, C ₁ -C ₁₈ -alkyl-substituted phenylcarboxylates, phenyl-C ₁ -C ₁₆ -alkylcarboxylates, C ₆ -C ₁₈ -phenolates, dehydroacetic acid and derivatives thereof; Mercaptides based on mercaptocarboxylic esters and glycinates.

The alkali metal compounds from the series of carboxylates are preferably salts of carboxylic acids having 7 to 20 C atoms, for example benzoates, alkenoates or alkanoates, preferably stearates, oleates, laurates, palmitates, hydroxystearates or 2-ethylhexanoates. Particularly preferred are stearates, oleates and p-tert-butyl benzoates. The potassium compounds are particularly preferred and potassium 2-ethylhexanoate very particularly preferred.

The compositions according to the invention may also contain per se known nucleating agents and pore regulators. As nucleating agents and pore regulators the foaming mixtures z. B. small amounts of finely divided solids or CO ₂ releasing mixtures of NaHCO ₃ and solid organic acids added.

The compositions according to the present invention may be ready-to-use blowing agent-containing PVC molding compounds, for example for the extrusion of structured-foamed pipes and profiles or for thermoplastic foam casting. Or it may be plastisols for processing into foamed plasticized PVC articles.

Foamed articles are also available from the compositions of the present invention via the high pressure processes known per se for the production of rigid PVC and flexible PVC foams.

From the compositions according to the invention, PVC foams, for example soft PVC foams, can be prepared by the low-pressure process known per se.

Furthermore, the compositions according to the invention can be used, for example, in the pressureless process known per se.

The methods mentioned can be, for example, from Hansjürgen Saechtling, plastic paperback, 22nd edition, Carl Hanser Verlag Munich , remove.

In a particularly preferred embodiment of the invention, component a) contains azodicarbonamide.

Useful are compositions as described above, furthermore containing as component b) at least one organic zinc compound and / or an inorganic zinc compound of the series of carbonates, chlorides, sulfates, oxides, hydroxides, basic oxides and mixed oxides.

Examples of organic zinc compounds are those from the series of aliphatic saturated C ₁ -C ₂₂ -carboxylates, aliphatic olefinic C ₂ -C ₂₂ -carboxylates, aliphatic C ₂ -C ₂₂ -carboxylates substituted by at least one OH-group, cyclic and bicyclic carboxylates having 5 to 22 carbon atoms of the aromatic C ₆ -C ₂₂ carboxylates, with at least one OH group substsituierten aromatic C ₆ -C ₂₂ carboxylates, C ₁ -C ₁₆ alkyl-substituted phenyl carboxylates, the Phenyl C ₁ -C ₁₆ alkylcarboxylates, C ₆ -C ₁₈ phenates, C ₅ -C ₂₆ chelates of 1,3-diketones or β-ketocarboxylic esters, dehydroacetic acid and its derivatives, mercaptides based on Mercaptocarboxylic acid esters, glycinates, phosphates, phosphites, phosphonites, phosphonates, the partial esters of phosphonates, sulfonates and sulfinates.

Preferred are polymer compositions (containing as b)), an organic zinc compound, wherein the zinc compound is a salt of a carboxylic acid having 7 to 20 carbon atoms or a C ₇ -C ₂₀ alkylphenolate.

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

If the component b) is a Zn-phenolate or if component b) contains such, it is in particular C ₇ -C ₂₀ -alkylphenolates, for example nonylphenolate.

The zinc salts of the monovalent carboxylic acids, such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, neodecanoic acid, 2-ethylhexanoic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristylic acid, palmitic acid, isostearic acid, stearic acid are to be mentioned as examples , 12-hydroxystearic acid, behenic acid, montanic acid, benzoic acid, monochlorobenzoic acid, p-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-di-tert-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, cumic acid, n-propylbenzoic acid, aminobenzoic acid, N , N-dimethylbenzoic acid, acetoxybenzoic acid, salicylic acid, p-tert-octylsalicylic acid, oleic acid, elaidic acid, sorbic acid, linoleic acid, linolenic acid, thioglycolic acid, mercaptopropionic acid and octylmercaptopropionic acid; Monoesters and monoamides of divalent carboxylic acids, such as oxalic, malonic, succinic, glutamic, adipic, pimelic, suberic, azelaic, sebacic, phthalic, isophthalic, terephthalic, hydroxyphthalic, chlorophthalic, aminophthalic, maleic, fumaric, citraconic, mesaconic, itaconic, haconic, and thiodipropionic acid; and the di- or triesters of tri- or tetravalent carboxylic acids, such as aconitic acid, hemimellitic acid, trimellitic acid, mellophanic acid, pyromellitic acid and mellitic acid.

zu nennen, wobei in Formel (I) R, R', R'' und R''' Alkyl mit 1 bis 18 C-Atomen, Alkenyl mit 2 bis 18 C-Atomen, Cycloalkyl mit 5 bis 12 Ring-C-Atomen, mit 1 bis 3 C₁-C₄-Alkyl substituiertes Cycloalkyl mit 5 bis 12 C-Atomen, Alkyl mit 1 bis 18 C-Atomen, das mit Cycloalkyl mit 5 bis 12 Ring-C-Atomen substituiert ist, Phenyl-C₁-C₁₈-alkyl, C₁-C₁₈-Alkylphenyl, Phenyl, Alkoxyalkyl oder Alkylendioxyalkyl oder -phenyl darstellen.Examples of suitable chelates of 1,3-diketones and β-ketocarboxylic esters are compounds of the formula (I)

in formula (I) R, R ', R "and R'" are alkyl having 1 to 18 C atoms, alkenyl having 2 to 18 C atoms, cycloalkyl having 5 to 12 ring C atoms , cycloalkyl having 5 to 12 C atoms substituted with 1 to 3 C ₁ -C ₄ alkyl, alkyl having 1 to 18 C atoms, which is substituted by cycloalkyl having 5 to 12 ring carbon atoms, phenyl-C ₁ C ₁₈ alkyl, C ₁ -C ₁₈ alkyl phenyl, phenyl, alkoxyalkyl or alkylenedioxyalkyl or phenyl.

Examples of R, R ', R "and R'" are methyl, ethyl, propyl, isopropyl, isobutyl, n-butyl, sec-butyl, tert-butyl, 1-pentyl, 3-pentyl, 1 -Hexyl, 1-heptyl, 3-heptyl, 1-octyl, 2,4,4-trimethylphenyl, tert-octyl, nonyl, decyl, tridecyl, pentadecyl, heptadec-8-en-1-yl, n-octadecyl, allyl , Methallyl, 2-hexenyl, 1-methylcyclopentyl, cyclohexyl, cyclohexanepropyl, phenyl, m-tolyl, p-ethylphenyl, t-butylphenyl, benzyl, phenylpropyl and nonylbenzyl.

Alkoxyalkyl may be ethoxymethyl, n-butoxymethyl, 2-methoxyethyl, 2-methoxyphenyl and 4-n-octoxyphenylbenzyl. For example, alkylenedioxyalkyl or -phenyl may be 3- (ethylenedioxypropyl) or 3,4-methylenedioxyphenyl.

Component b) of the composition according to the invention is particularly preferably a Zn carboxylate. The carboxylates are preferably salts of carboxylic acids having 7 to 20 carbon atoms, for. As benzoates, alkanoates or alkenoates, preferably stearates, oleates, laurates, palmitates, hydroxystearates or 2-ethylhexanoates. Particularly preferred are octoates, stearates, caprylates, oleates or p-tert-butylbenzoates.

Mixtures of Ba / Zn or Ca / Zn carboxylates are particularly preferred as component b), with the Ca / Zn carboxylates being very particularly preferred.

Zinc octoate or zinc caprylate is also particularly preferred as component b).

If component b) denotes a Zn phenolate, these are, in particular, C ₇ -C ₂₀ -alkylphenates, for example nonylphenolate.

Component b) particularly preferably contains a zinc carboxylate in the stabilizer system according to the invention for halogen-containing polymers.

wobei in Formel (II) R¹ bis R³ Wasserstoff, C₁-C₂₀-alkyl oder Oleyl darstellen.According to the invention, in particular component c) melamine derivatives of the formula (II) are to be understood:

where in formula (II) R ¹ to R ^{3 represent} hydrogen, C ₁ -C ₂₀ -alkyl or oleyl.

In a particularly preferred embodiment of the invention, component c) contains melamine. This corresponds to a substitution of R ¹ , R ² and R ³ is hydrogen.

wobei in Formel (III) R⁴ bis R⁶ lineares oder verzweigtes C₁–C₄-alkylen darstellt, wobei C₂-alkylen (Tris-hydroxyethyl-isocyanursäureester) ganz besonders bevorzugt ist.According to the invention, component d) preferably denotes a tris-hydroxyalkyl isocyanuric acid ester of the following formula (III)

wherein in formula (III) R ⁴ to R ^{6 is} linear or branched C ₁ -C ₄ -alkylene, with C ₂ -alkylene (tris-hydroxyethyl-isocyanuric acid ester) being very particularly preferred.

In the stabilizer system according to the invention, component d) preferably contains tris-hydroxyethyl isocyanuric acid ester (THEIC). This corresponds to a substitution of R ⁴ , R ⁵ and R ⁶ equal to C ₂ .

In a particularly preferred embodiment, the stabilizer system according to the invention additionally contains catena-μ-2,2 ', 2 "-nitrilotrisethanol-perchlorato-sodium or sodium perchlorate in dissolved or supported form.

Another object of the present invention are also polymer compositions containing at least one stabilizer system as described above and a halogen-containing polymer (s).

The polymer compositions according to the invention can contain as halogen-containing polymer e), for example:
Polymers of vinyl chloride, vinyl resins containing vinyl chloride units in their structure, such as copolymers of vinyl chloride and vinyl esters of aliphatic acids, especially vinyl acetate, copolymers of vinyl chloride with esters of acrylic and methacrylic acid and with acrylonitrile, copolymers of vinyl chloride with diene compounds and unsaturated dicarboxylic acids or their anhydrides such as copolymers of vinyl chloride with diethyl maleate, diethyl fumarate or maleic anhydride, post-chlorinated polymers and copolymers of vinyl chloride, copolymers of vinyl chloride and vinylidene chloride with unsaturated aldehydes, ketones and others such as acrolein, crotonaldehyde, vinyl methyl ketone, vinyl methyl ether, vinyl isobutyl ether and the like; Vinylidene chloride polymers and copolymers thereof with vinyl chloride and other polymerizable compounds; Polymers of vinyl chloroacetate and dichlorodivinyl ether; chlorinated polymers of vinyl acetate, chlorinated polyacrylic esters and alpha-substituted polyacrylic esters, polymers of chlorinated styrenes, for example dichlorostyrene; chlorinated rubbers; chlorinated polymers of ethylene; Polymers and postchlorinated polymers of chlorobutadiene and their copolymers with vinyl chloride, rubber hydrochloride and chlorinated rubber hydrochloride; and mixtures of said polymers or mixtures with other polymerizable compounds.

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

In a particularly preferred embodiment of the invention, the halogen-containing polymer is polyvinyl chloride.

Particularly preferred are polymer compositions which are in the form of a foam.

Another object of the present invention is a process for producing a stabilized halogen-containing polymer composition according to the above-mentioned embodiment comprising the step of adding the stabilizer system of the present invention to a halogen-containing polymer.

Another object of the present invention is the use of stabilizer systems according to the invention for the stabilization of halogen-containing polymers.

Present compositions may also contain other stabilizers or stabilizer mixtures which improve the processing and use properties of such compositions and articles made therefrom. Such stabilizers include the Mg, Al, Mg, Al, and Mg / Zn compounds, with the individual compounds mentioned for inorganic and organic zinc compounds being suitable. In each case, instead of the zinc, the meaning of Mg, Al, Mg / Al or Mg / Zn be read.

It is expedient to use compositions as described above, based on 100 parts by weight of composition,
0.0001 to 8 parts by weight of blowing agent or foaming agent,
0.01 to 3.0 parts by weight of melamine derivative and
0.01 to 3.0 parts by weight of tris-hydroxyalkyl isocyanuric acid ester
0.01 to 8 parts by weight of zinc compound.

Preferred amounts ranges for the blowing agents or foaming agents are 0.01 to 5 parts by weight, more preferably 0.1 to 3 parts by weight and most preferably 0.1 to 2 parts by weight, based in each case on 100 parts by weight. Parts composition.

Preferred amount ranges for the melamine derivatives in the composition are 0.05 to 1.0 parts by weight based on 100 parts by weight of the composition. Particularly preferred are 0.1 to 0.5 parts by weight. The same applies to tris-hydroxyalkyl isocyanuric acid esters.

Preferred amounts ranges for the zinc compounds in the composition are 0.05 to 3 parts by weight, more preferably 0.1 to 1.5 parts by weight and especially 0.5 to 1.0 parts by weight, based in each case on 100 parts by weight of composition.

Preferred amount ranges for the so-called kicker in the composition are 0.01 to 5 parts by weight, particularly preferably 0.05 to 3 parts by weight, based on 100 parts by weight of composition. Other stabilizers which may be used are per se known compounds such as calcined dolomites, calcium monocarbonato-hydroxodialuminates (CAHC), hydrotalcites and zeolites.

Calcined dolomites

Calcined Dolomite correspond to the general formula: MtX ₁ · CaX ₂ with Mt = Mg or / and Zn and X ₁ or X ₂ = O or (OH) ₂ and X ₂ also CO ₃

The double salt MgO · CaO corresponds to the normal calcined magnesium dolomite. ZnO · CaO corresponds to calcined zinc dolomite (minrecordite). MgO · CaO is also referred to as fully calcined dolomite, MgO · CaCO ₃ as partially calcined dolomite. Mg (OH) _2. Ca (OH) ₂ is the hydration product of fully calcined magnesium dolomite MgO. CaO.

Calcined magnesium dolomites are preferred, with MgO · CaO being most preferred.

The production of fully and partially calcined magnesium dolomites is in EP 2,072,567 described. In this patent also product properties are published.

Calcium monocarbonato-hydroxodialuminates (CAHC)

They have the following formula: Ca _m Al ₂ (OH) _{6 + 2 (m-1)} CO ₃ .nH ₂ O, where m = 3.8 to 4.2 and n = 0 to 3.

Their production is for example in DE 10.2006.055.214 described.

hydrotalcites

The chemical composition of these compounds is known in the art, for. B. from the publications DE-A 3843581 . US-A 4,000,100 . EP-A 0062813 and WO-A 93/20135 , These may be Al / Mg / carbonate, Al / Mg / Ti / carbonate, Li / Mg / carbonate or Li / Al / Mg / carbonate based as described in US Pat. DE-A 10217364 (Company StidChemie), - DE-A 4425266 (Metal Company), EP-A 0549340 (Mizusawa Ind. Chem.) And JP-A 0761756 (Fuji Chem. Ind.). Compounds of the hydrotalcite series may be represented by the following general formula: M ₂ ⁺ _1-x M ₃ ⁺ _x (OH) ₂ (A ⁿ ) _{x / b} · dH ₂ O be described, wherein
M ²⁺ = as cation one or more of the metals from the group Mg, Ca, Sr, Zn or Sn, M ³⁺ = as cation Al or B, A ^{n represents} an anion with the valency -n,
b = n is a number of 1-2, 0 <x <0.5, d is a number from 0-20. Preference is given to compounds with
A ⁿ = OH ^- , ClO 4 ^- , HCO ₃ ^- , CH ₃ COO ^- , C ₆ H ₅ COO ^- , CO ₃ ^2- , (CHOHCOO) ₂ ^2- , (CH ₂ COO) ₂ ^2- , CH ₃ CHOHCOO ^- , HPO ₃ ^- or HPO ₄ ^2- .

Examples of hydrotalcites are
Al2O ₃ .6MgO.CO .12H ₂ O, Mg _4.5 Al ₂ (OH) ₁₃ · CO ₃ · 3.5H ₂ O, 4MgO · Al ₂ O ₃ · CO ₂ · 9H ₂ O, 4MgO · Al ₂ O ₃ · CO ₂ · 6H ₂ O, ZnO · 3MgO · Al ₂ O ₃ · CO ₂ · 8-9H ₂ O and ZnO · 3MgO · Al ₂ O ₃ · CO ₂ · 5-6H ₂ O

Particular preference is given to the types Alkamizer 1 and 2, Alkamizer P 93-2 (manufacturer Kyowa Chemical Ind. Co., JP) and L-CAM (lithium-modified hydrotalcite = lithium / carbonate / aluminum / magnesium, manufacturer Fuji Chem. Ind. Co. Ltd., - EP-A0761756 or Mizusawa Industrial Chemicals, Ltd.,: - EP-A 0549340 A1 and Metallgesellschaft AG, - DE-C 4425266 ). Very particular preference is given to using dehydrated hydrotalcites.

Zeolites (alkali or alkaline earth metal aluminosilicates)

They can be described by the formula Mx / n [(AlO ₂ ) _x (SiO ₂ ) _y ] .wH ₂ O, where n is the charge of the cation M; M is an element of the first or second main group, such as Li, Na, K or NH _4, and Mg, Ca, Sr or Ba; y: x is a number from 0.8 to 15, preferably from 0.8 to 1.2; and w is a number from 0 to 300, preferably from 0.5 to 30.

Examples of zeolites are sodium aluminosilicates of the formulas
Na ₁₂ Al ₁₂ Si ₁₂ O ₄₈ · 27H ₂ O [zeolite A], Na ₆ A ₁₆ Si ₆ O ₂₄ · 2NaX · 7.5H ₂ O, X = OH, halogen, ClO ₄ [sodalite]; Na ₆ A ₁₆ Si ₃₀ O ₇₂ · 24H ₂ O; Na ₈ A ₁₈ Si ₄₀ O ₉₆ · 24H ₂ O; Na ₁₆ Al ₁₆ Si ₂₄ O ₈₀ · 16H ₂ O; Na ₁₆ Al ₁₆ Si ₃₂ O ₉₆ · 16H ₂ O; Na ₅₆ Al ₅₆ Si ₁₃₆ O ₃₈₄ · 250H ₂ O [zeolite Y], Na ₈₆ Al ₈₆ Si ₁₀₆ O ₃₈₄ · 264H ₂ O [zeolite X]; Na ₂ O, Al ₂ O ₃ , (2-5) SiO ₂ , (3,5-10) H ₂ O [zeolite P]; Na ₂ O, Al ₂ O _3, 2SiO ₂ , · (3,5-10) H ₂ O (zeolite MAP); or the zeolites which can be prepared by partial or complete replacement of the Na atoms by Li, K, Mg, Ca, Sr or Zn atoms, such as (Na, K) ₁₀ Al ₁₀ Si ₂₂ O ₆₄ .2OH ₂ O; Ca _4.5 Na ₃ [(ALO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] .30H ₂ O; K ₉ Na ₃ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ]. 27H ₂ O. Very particular preference is given to Na zeolite A and Na zeolite MAP (cf. US Pat. No. 6,531,533 ). Also preferred are zeolites with extremely small particle size, in particular of the Na-A and Na-P type, as they are also in US-A 6,096,820 are described.

The calcined dolomites and / or hydrotalcites and / or calcium monocarbonato-hydroxodialuminates (CAHC) and / or zeolites can be used in amounts of, for example, 0.1 to 20, suitably 0.1 to 10 and in particular 0.1 to 5 parts by weight , based on 100 parts by weight of halogen-containing polymer.

In addition, other costabilizers may be present, such as 1,3-diketones, polyols, glycidyl compounds and epoxidized fatty acid esters, sterically hindered amines and. Phosphites (phosphorous acid esters) and perchlorate booster.

1,3-diketones

aufweisen, wobei in Formel (IV)
R^a – Alkyl mit 1 bis 22 C-Atomen, C₅-C₁₀-Hydroxyalkyl, Alkenyl mit 2 bis 22 C-Atomen, Phenyl, mit 1 bis 3 Gruppen der Reihe -OH, C₁-C₄-Alkyl, C₁- bis C₄-Alkoxy oder Halogen substituiertes Phenyl, Phenyl-C₁-C₄-alkyl, eine Gruppe der Formel (IVa)

Cycloalkyl mit 5 bis 12 Ring-C-Atome oder mit
1 bis 34 C₁-C₄-Alkylgruppen substituiertes Cycloalkyl mit 5 bis 12 Ring-C-Atomen; R^c Alkyl mit 1 bis 22 C-Atomen, C₅-C₁₀-Hydroxyalkyl, Alkenyl mit 2 bis 22 C-Atomen, Phenyl, mit 1 bis 3 Gruppen der Reihe -OH, C₁-C₄-Alkyl, C₁- bis C₄-Alkoxy oder Halogen substituiertes Phenyl oder Phenyl-C₁-C₄-alkyl, eine Gruppe der Formel (IVb)

Cycloalkyl mit 5 bis 12 Ring-C-Atomen oder mit
1 bis 3 C₁- bis C₄-Alkylgruppen substituiertes Cycloalkyl mit 5 bis 12 Ring-C-Atomen und R^b-H, Alkyl mit 1 bis 18 C-Atomen, Alkenyl mit 2 bis 12 C-Atomen, Phenyl, C₁-C₄-Alkyl substituiertes Phenyl, Phenyl-C₁-C₄-alkyl, oder eine Gruppe der Formel (V)

wobei in Formel (V) R^d-CH₃, -C₂H₅ oder Phenyl bedeutet, darstellen, oder worin R^a und R zusammen die Bedeutung eines Tetramethylenrestes oder eines Tetramethylenrestes, der mit einem Benzoerest anelliert ist, aufweisen oder R^a und R^c zusammen die Bedeutung eines Trimethylenrestes oder eines mit 1 bis 3 C₁-C₄-Alkylgruppen substituierten Trimethylenrestes aufweisen oder R^a oder R^c zusammen die Bedeutung eines Trimethylenrestes aufweisen, und eine Verbindung der folgenden Formel (VI) bilden,

wobei in Formel (VI) R^b die genannte Bedeutung hat und X Alkylen mit 1 bis 4 C-Atomen bedeutet.The 1,3-diketones may have the general formula (IV)

in which formula (IV)
R ^a - alkyl of 1 to 22 C atoms, C ₅ -C ₁₀ hydroxyalkyl, alkenyl of 2 to 22 C atoms, phenyl, of 1 to 3 groups of the series -OH, C ₁ -C ₄ alkyl, C ₁ - to C ₄ -alkoxy or halogen-substituted phenyl, phenyl-C ₁ -C ₄ -alkyl, a group of formula (IVa)

Cycloalkyl having 5 to 12 ring carbon atoms or with
1 to 34 C ₁ -C ₄ -alkyl substituted cycloalkyl having 5 to 12 ring carbon atoms; R ^{c is} alkyl having 1 to 22 C atoms, C ₅ -C ₁₀ hydroxyalkyl, alkenyl having 2 to 22 C atoms, phenyl, having 1 to 3 groups of the series -OH, C ₁ -C ₄ alkyl, C ₁ C ₁ -C ₄ -alkoxy or halogen-substituted phenyl or phenyl-C ₁ -C ₄ -alkyl, a group of formula (IVb)

Cycloalkyl having 5 to 12 ring carbon atoms or with
Cycloalkyl substituted from 1 to 3 C ₁ to C ₄ alkyl groups with 5 to 12 ring C atoms and R ^b -H, alkyl having 1 to 18 C atoms, alkenyl having 2 to 12 C atoms, phenyl, C ₁ C ₄ alkyl substituted phenyl, phenyl C ₁ -C ₄ alkyl, or a group of formula (V)

wherein in formula (V) R ^{d represents} -CH ₃ , -C ₂ H ₅ or phenyl, or wherein R ^a and R together have the meaning of a tetramethylene radical or a tetramethylene radical fused to a benzo radical, or R ^a and R ^c together have the meaning of a trimethylene radical or ^a trimethylene radical substituted by 1 to 3 C ₁ -C ₄ -alkyl groups, or R ^a or R ^c together have the meaning of a trimethylene radical, and form a compound of the following formula (VI),

wherein in formula (VI) R ^{b has} the meaning given and X is alkylene having 1 to 4 carbon atoms.

R ^a and R ^c as alkyl having 1 to 22 carbon atoms, for example, methyl, ethyl, propyl, n-butyl, tert-butyl, pentyl, hexyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, octadecyl or eicosyl, R ^b as alkyl having 1 to 18 carbon atoms may, for example, have the above meaning without eicosyl.

Examples of C ₅ -C ₁₀ hydroxyalkyl for R ^a and R ^c are 5-hydroxypentyl, 6-hydroxyethyl or 7-hydroxyheptyl.

Examples of R ^a and R ^c as alkenyl having 2 to 22 carbon atoms are vinyl, propenyl, allyl, butenyl, methallyl, hexanyl, decenyl or heptadecenyl. Corresponding examples of R ^b as alkenyl having 2 to 12 carbon atoms can be taken from the above enumeration.

The phenyl groups substituted by preferably one to three of -OH, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or halogen as mentioned for R ^a and R ^c may be 4-hydroxyphenyl, 4-hydroxy-3,5-di-C ₁ -C ₄ alkylphenyl, wherein C ₁ -C ₄ alkyl is, for example, methyl or t-butyl, methylphenyl, dimethylphenyl, ethylphenyl, n-butylphenyl , tert-butylphenyl, methyl-tert-butylphenyl, di-tert-butylphenyl, methoxy or ethoxyphenyl or monochlorophenyl.

If R ^{b is} C ₁ -C ₄ -alkyl-substituted phenyl, then such are, for. Methylphenyl, ethylphenyl or tert-butylphenyl.

The meaning of phenyl-C ₁ -C ₄ -alkyl for R ^a , R ^b and R ^c is, for example, benzyl or methylbenzyl.

R ^a and R ^c may also be cycloalkyl having 5 to 12 ring carbon atoms or substituted by 1 to 3 C ₁ -C ₄ alkyl groups substituted cycloalkyl having 5 to 12 ring carbon atoms. Examples of these are cyclopentyl, cycloheptyl, cyclobutyl, clclononyl, cyclododecyl, etc., and also methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, tert-butylcyclohexyl.

Examples of 1,3-diketones are:
Dehydroacetic acid, dehydropropionylacetic acid, dehydrobenzoylacetic acid, cyclohexane-1,3-dione, dimedone, 2,2'-methylenebiscyclohexane-1,3-dione, 2-benzylcyclohexane-1,3-dione, acetyltetralon, palmitoyltetralone, Stearoyltetralon, benzoyltetralon, 2-acetylcyclohexanone, 2-benzoylcyclohexanone, 2-acetylcyclohexane-1,3-dione, benzoyl-p-chlorobenzoylmethane, bis (4-methylbenzoyl) methane, bis (2-hydroxybenzoyl) methane, benzoylacetone, Trbenzoylmethane, diacetylbenzoylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane, lauroylbenzoylmethane, dibenzoylmethane, 4-methoxybenzoylbenzoylmethane, bis (4-methoxybenzoyl) methane, bis (4-chlorobenzoyl) methane, bis (3,4-methylenedioxybenzoyl) methane, benzoylacetyloctylmethane, benzoylacetylphenylmethane, stearoyl 4-methoxybenzoylmethane, bis (4-t-butylbenzoyl) methane, butanoylacetone, heptanoylacetone, distearoylmethane, acetylacetone, stearoylacetone, palmitoylacetone, lauroylacetone, benzoylformylmethane, benzoylphenylacetylmethane, bis (cyclohexanoyl) methane or di-pivaloylmethane.

1,3-diketo compounds useful as costabilizers are also those described in U.S. Pat DE-B 2600516 and the EP-A 35268 are described, for. B. those of the formula given in the claim of DE-B 2600516. Other 1,3-diketo compounds are benzoylstearoylmethane, 2-benzoylacetacetic acid alkyl (eg ethyl) ester and triacylmethane.

wobei in Formel (VII) R₁ C₁-C₁₀-Alkyl, C₅-C₁₀-Hydroxyalkyl, Phenyl, Hydroxyphenyl, C₇-C₁₀-Phenylalkyl oder am Phenylring durch eine OH-Gruppe substutuiertes C₇-C₁₀-Phenylalkyl ist und R₂ C₅-C₁₀-Hydroxyalkyl, Hydroxyphenyl oder am Phenylring durch eine OH-Gruppe substituiertes C₇-C₁₀-Phenylalkyl darstellt, mit der Bedingung, dass R₂ verschieden von Hydroxyphenyl ist, wenn R₁ Phenyl oder Hydroxyphenyl bedeutet.Further applicable 1,3-diketo compounds have the formula (VII)

wherein in formula (VII) R _{1 is} C ₁ -C ₁₀ alkyl, C ₅ -C ₁₀ hydroxyalkyl, phenyl, hydroxyphenyl, C ₇ -C ₁₀ phenylalkyl or on the phenyl ring by an OH group substutuiertes C ₇ -C ₁₀ - Phenylalkyl and R _{2 is} C ₅ -C ₁₀ hydroxyalkyl, hydroxyphenyl or C ₇ -C ₁₀ phenylalkyl substituted on the phenyl ring by an OH group, with the proviso that R _{2 is} other than hydroxyphenyl when R _{1 is} phenyl or hydroxyphenyl means.

R ₁ as C ₁ -C ₁₀ -alkyl, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl or n- decyl. C ₁ -C ₄ alkyl, especially methyl and tert-butyl, is preferred.

Examples of R ₁ and R ₂ as C ₆ -C ₁₀ -hydroxyalkyl are 5-hydroxypentyl, 1,1-dimethyl-3-hydroxypropyl, 6-hydroxyhexyl, 8-hydroxyoctyl and 10-hydroxydecyl. 5-hydroxypentyl, 6-hydroxyhexyl and 7-hydroxyheptyl are preferred. Preferably, the hydroxyalkyl group is not in the α-position. In particular, R _{2 represents} a group of the formula - (CH ₂ ) _n -OH, wherein n represents an integer of 5 to 7. Of particular interest is R ₂ as 5-hydroxypentyl.

If R ₁ and R _{2 are} hydroxyphenyl, the OH group may be in ortho, meta or para position. o-hydroxyphenyl is preferred.

Examples of R ₁ as C 7 -C ₁₀ phenylalkyl are benzyl and 2-phenylethyl.

R ₁ and R _{2 are} as C ₇ -C ₁₀ phenylalkyl which is substituted on the phenyl ring by an OH group, for. For example, (2-hydroxyphenyl) methyl, (3-hydroxyphenyl) methyl, (4-hydroxyphenyl) methyl, 2- (2-hydroxyphenyl) ethyl and 2- (4-hydroxyphenyl) ethyl.

Within this stabilizer group compounds are preferred having the formula IIb above wherein R _{1 is} C ₁ -C ₁₀ alkyl, C ₅ -C ₁₀ hydroxyalkyl, phenyl, hydroxyphenyl, C ₇ -C ₁₀ phenylalkyl or substituted on the phenyl ring by an OH group C ₇ -C ₁₀ phenylalkyl and R _{2 is} C ₅ -C ₁₀ hydroxyalkyl, hydroxyphenyl or C ₇ -C ₁₀ phenylalkyl substituted on the phenyl ring by an OH group, with the proviso that R _{2 is} different from hydroxyphenyl, when R _{1 is} phenyl or hydroxyphenyl.

Particular preference is given to compounds of the above formula in which R _{1 is} C ₁ -C ₁₀ -alkyl, C ₅ -C ₁₀ -hydroxyalkyl or phenyl and R _{2 is} C ₅ -C ₁₀ -hydroxyalkyl or hydroxyphenyl, or very particularly preferably in which R ₁ C ₁ -C ₄ alkyl or phenyl and R _{2 is} C ₅ -C ₇ hydroxyalkyl or hydroxyphenyl, further wherein R _{2 is} a group - (CH ₂ ) _n -OH, where n is an integer from 5 to 7 ,

Further examples of particularly preferred compounds of the above formula IIb are those in which R _{1 is} methyl, butyl or phenyl and R _{2 is} 5-hydroxypentyl, 6-hydroxyhexyl, 7-hydroxyheptyl or ortho-hydroxyphenyl.

Specifically mention are the preferred compounds of the formula IIb stearoylbenzoylmethane, dibenzoylmethane, 1-phenyl-8-hydroxyoctane-1,3-dione, 1-t-butyl-8-hydroxyoctane-1,3-dione, 1-methyl-8- hydroxyoctane-1,3-dione or 1- (o-hydroxyphenyl) butane-1,3-dione.

wobei in Formel (VIII) R₁' und R₃' unabhängig voneinander C₁-C₁₂-Alkyl, Phenyl, durch ein bis drei C₁-C₁₂-Alkylgruppen substituiertes Phenyl, C₇-C₁₀-Phenylalkyl oder durch ein bis drei C₁-C₁₂-Alkylgruppen substituiertes C₇-C₁₀-Phenylalkyl und R₁' zusätzlich -R₂-S-R₃ bedeutet, R₂'C₁-C₁₀-Alkylen darstellt und R₄' Wasserstoff, C₂-C₅-Alkoxycarbonyl oder C₂-C₅-Alkanoyl ist. Weitere Ausführungen dazu, Beispiele und Bevorzugungen sind der EP 307 358 zu entnehmen.Further suitable compounds have the formula (VIII)

wherein in formula (VIII) R ₁ 'and R ₃ ' independently of one another C ₁ -C ₁₂ alkyl, phenyl, phenyl substituted by one to three C ₁ -C ₁₂ alkyl groups, C ₇ -C ₁₀ phenylalkyl or by a bis three C ₁ -C ₁₂ alkyl groups substituted C ₇ -C ₁₀ phenylalkyl and R ₁ 'additionally -R ₂ -SR ₃ , R ₂ ' is C ₁ -C ₁₀ alkylene and R ₄ 'is hydrogen, C ₂ -C ₅ alkoxycarbonyl or C ₂ -C ₅ alkanoyl. Further details, examples and preferences are the EP 307,358 refer to.

glycidyl compounds

wobei diese direkt an Kohlenstoff, Sauerstoff-, Stickstoff- oder Schwefelatome gebunden ist, und wobei in Formel (IX) entweder R₃ und R₅ beide Wasserstoff sind, R₄ Wasserstoff oder Methyl und n = 0 ist, oder worin R₃ und R₅ zusammen -CH₂-CH₂- oder -CH₂-CH₂-CH₂- bedeuten, R₄ dann Wasserstoff und n = 0 oder 1 ist.

• I) Glyzidyl- und β-Methylglyzidylester erhältlich durch Umsetzung einer Verbindung mit mindestens einer Carboxylgruppe im Molekül und Epichlorhydrin bzw. Glyzerindichlorhydrin bzw. β-Methyl-epichlorhydrin. Die Umsetzung erfolgt zweckmäßig in Gegenwart von Basen.

They contain the glycidyl group of the formula (IX):

wherein this is bonded directly to carbon, oxygen, nitrogen or sulfur atoms, and wherein in formula (IX) either R ₃ and R _{5 are} both hydrogen, R _{4 is} hydrogen or methyl and n = 0, or wherein R ₃ and R ₅ together are -CH ₂ -CH ₂ - or -CH ₂ -CH ₂ -CH ₂ -, then R ₄ is hydrogen and n = 0 or 1.

• I) Glycidyl and β-methyl glycidyl esters obtainable by reacting a compound having at least one carboxyl group in the molecule and epichlorohydrin or glycerol dichlorohydrin or β-methyl epichlorohydrin. The reaction is conveniently carried out in the presence of bases.

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

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

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

• II) Glyzidyl- oder (β-Methylglyzidyl)-ether erhältlich durch Umsetzung einer Verbindung mit mindestens einer freien alkoholischen Hydroxygruppe und/oder phenolischen Hydroxygruppe und einem geeignet substituierten Epichlorhydrin unter alkalischen Bedingungen, oder in Anwesenheit eines sauren. Katalysators und anschließender Alkalibehandlung.

Also, carboxyl-terminated adducts, for. Trimellitic acid and polyols such as glycerin or 2,2-bis- (4-hydroxycyclohexyl) -propane. Further epoxide compounds which can be used in the context of this invention are present in EP 0 506 617 ,

• II) glycidyl or (β-methylglycidyl) ethers obtainable by reacting a compound having at least one free alcoholic hydroxy group and / or phenolic hydroxy group and a suitably substituted epichlorohydrin under alkaline conditions, or in the presence of an acidic. Catalyst and subsequent alkali treatment.

Ethers of this type are derived, for example, from acyclic alcohols, such as ethylene glycol, diethylene glycol and higher poly (oxyethylene) glycols, propane-1,2-diol, or poly (oxypropylene) glycols, propane-1,3-diol, Butane-1,4-diol, poly (oxytetramethylene) -glycols, pentane-1,5-diol, hexane-1,6-diol, hexane-2,4,6-triol, Glycerol, 1,1,1-trimethylolpropane, bistrimethylolpropane, pentaerythritol, sorbitol, as well as polyepichlorohydrins, butanol, amyl alcohol, pentanol, and monofunctional alcohols such as isooctanol, 2-ethylhexanol, isodecanol and C ₇ -C ₉ alkanol and C ₉ C ₁₁ -alkanol mixtures.

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

The epoxy compounds may also be derived from mononuclear phenols, such as phenol, resorcinol or hydroquinone; or are based on polynuclear phenols such as bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) -propane, 4,4'-dihydroxydiphenylsulfone or condensation products of phenols with formaldehyde such as phenol novolacs obtained under acidic conditions.

• III) (N-Glyzidyl)-Verbindungen erhältlich durch Dehydrochlorierung der Reaktionsprodukte von Epichlorhydrin mit Aminen, die mindestens ein Aminowasserstoffatom enthalten. Bei diesen Aminen handelt es sich zum Beispiel um Anilin, N-Methylanilin, Toluidin, n-Butylamin, Bis-(4-aminophenyl)-methan, m-Xylylendiamin oder Bis-(4-methylaminophenyl)-methan, aber auch N,N,O-Triglyzidyl-m-aminophenol oder N,N,O-Triglyzidyl-p-aminophenol.

Further possible terminal epoxides are, for example: glycidyl 1-naphthyl ether, glycidyl 2-phenylphenyl ether, N- (2,3-epoxypropyl) -phthalimide and 2,3-epoxypropyl-4-methoxyphenyl ether.

• III) (N-glycidyl) compounds obtainable by dehydrochlorination of the reaction products of epichlorohydrin with amines containing at least one amino hydrogen atom. These amines are, for example, aniline, N-methylaniline, toluidine, n-butylamine, bis (4-aminophenyl) methane, m-xylylenediamine or bis (4-methylaminophenyl) methane, but also N, N , O-triglyzidyl-m-aminophenol or N, N, O-triglycidyl-p-aminophenol.

• IV) S-Glyzidyl-Verbindungen, wie beispielsweise Di-S-Glyzidylderivate, die sich von Dithiolen, wie beispielsweise Ethan-1,2-dithiol oder Bis-(4-merkaptomethylphenyl)-ether ableiten.
• V) Epoxidverbindungen mit einem Rest der obigen Formel, worin R₁ und R₃ zusammen -CH₂-CH₂- bedeuten und n 0 ist, sind Bis-(2,3-epoxycyclopentyl)-ether, 2,3-Epoxycyclopentyl-Glyzidylether oder 1,2-Bis-(2,3-epoxycyclopentyloxy)-ethan. Ein Epoxidharz mit einem Rest der obigen Formel, worin R₁ und R₃ zusammen -CH₂-CH₂- sind und n 1 bedeutet, ist beispielsweise 3,4-Epoxy-6-methyl-cyclohexancarbonsäure-(3',4'-epoxy-6'-methyl-cyclohexyl)-methylester.

The (N-glycidyl) compounds also include N, N'-di-, N, N ', N "-tri- and N, N', N", N '''- tetraglycidyl derivatives of cycloalkylene ureas, such as ethyleneurea or 1,3-propyleneurea, and N, N'-diglycidyl derivatives of hydantoins, such as of 5,5-dimethylhydantoin or glycoluril and triglycidyl isocyanurate.

• IV) S-glycidyl compounds such as di-S-glycidyl derivatives derived from dithiols such as ethane-1,2-dithiol or bis (4-mercaptomethylphenyl) ether.
• V) Epoxy compounds having a radical of the above formula in which R ₁ and R ₃ together are -CH ₂ -CH ₂ - and n is 0 are bis (2,3-epoxycyclopentyl) ethers, 2,3-epoxycyclopentyl glycidyl ethers or 1,2-bis- (2,3-epoxycyclopentyloxy) -ethane. An epoxy resin having a radical of the above formula in which R ₁ and R ₃ together are -CH ₂ -CH ₂ - and n is 1, is, for example, 3,4-epoxy-6-methylcyclohexanecarboxylic acid (3 ', 4'- epoxy-6'-methylcyclohexyl) methyl ester.

• a) flüssige Bisphenol-A-diglyzidylether wie Araldit^®GY 240, Araldit^®GY 250, Araldit^®GY 260, Araldit^®GY 266, Araldit^®GY 2600, Araldit^®MY 790 und Epicote^® 828 (BADGE);
• b) feste Bisphenol-A-diglyzidylether wie Araldit^®GT 6071, Araldit^®GT 7071, Araldit^®GT 7072, Araldit^®GT 6063, Araldit^®GT 7203, Araldit^®GT 6064, Araldit^®GT 7304, Araldit^®GT 7004, Araldit^®GT 6084, Araldit^®GT 1999, Araldit^®GT 7077, Araldit^®GT 6097, Araldit^®GT 7097, Araldit^®GT 7008, Araldit^®GT 6099, Araldit^®GT 6608, Araldit^®GT 6609, Araldit^®GT 6610 und Epikote^® 1002;
• c) flüssige Bisphenol-F-diglyzidylether wie Araldit^®GY 281, Araldit^®PY 302, Araldit^®PY 306 (BFDGE);
• d) feste Polyglyzidylether von Tetraphenylethan wie CG Epoxy Resin^® 0163;
• e) feste und flüssige Polyglyzidylether von Phenolformaldehyd Novolak wie EPN 1138, EPN 1139, GY 1180, PY 307 (NODGE);
• f) feste und flüssige Polyglyzidylether von o-Cresolformaldehyd Novolak wie ECN 1235, ECN 1273, ECN 1280, ECN 1299 (NODGE);
• g) flüssige Glyzidylether von Alkoholen wie Shell Glyzidylether^® 162, Araldit^®DY 0390, Araldit^®DY 0391;
• h) flüssige und feste Glyzidylester von Carbonsäuren wie Shell Cardura^®E Terephthalsäureester, Trimellithsäureester sowie deren Mischungen Araldit^®PY 284 und Araldit^®P811;
• i) feste heterocyclische Epoxidharze (Triglyzidylisozyanurat) wie Araldit^®PT 810;
• j) flüssige cycloaliphatische Epoxidharze wie Araldit^®CY 179;
• k) flüssige N,N,O-Triglyzidylether von p-Aminophenol wie Araldit^®MY 0510;
• l) Tetraglyzidyl-4-4'-methylenbenzamin oder N,N,N',N'-Tetraglyzidyldiaminophenylmethan wie Araldit^®MY 720, Araldit^®MY 721.

Suitable terminal epoxides are, for example:

• a) liquid bisphenol A-diglycidyl ether, such as Araldite ^® GY 240, Araldit ^® GY 250, Araldit ^® GY 260, Araldit ^® GY 266, Araldite ^® GY 2600, Araldit ^® MY 790 and Epikote ^® 828 (BADGE);
• b) solid bisphenol A diglycidyl ether, such as Araldite ^® GT 6071, Araldit ^® GT 7071, Araldit ^® GT 7072, Araldit ^® GT 6063, Araldit ^® GT 7203, Araldit ^® GT 6064, Araldit ^® GT 7304, Araldit ^® GT 7004, Araldit ^® GT 6084, Araldite ^® GT 1999, Araldite ^® GT 7077, Araldite ^® GT 6097, Araldite ^® GT 7097, Araldite ^® GT 7008, Araldite ^® GT 6099, Araldite ^® GT 6608, Araldite ^® GT 6609, Araldite ^® GT 6610 and Epikote ^® 1002;
• c) liquid bisphenol F-diglycidyl ether, such as Araldite ^® GY 281, Araldit ^® PY 302, Araldit ^® PY 306 (BFDGE);
• d) solid Polyglyzidylether of tetraphenylethane such as CG Epoxy Resin ^® 0163;
• e) solid and liquid polyglycidyl ethers of phenolformaldehyde novolaks such as EPN 1138, EPN 1139, GY 1180, PY 307 (NODGE);
• f) solid and liquid polyglycidyl ethers of o-cresol formaldehyde novolac such as ECN 1235, ECN 1273, ECN 1280, ECN 1299 (NODGE);
• g) liquid glycidyl ethers of alcohols such as Shell ^® glycidyl ethers 162, Araldite ^® DY 0390, Araldit ^® DY 0391;
• h) liquid and solid glycidyl esters of carboxylic acids such as Shell Cardura ^® E terephthalic ester, trimellitic and mixtures thereof Araldit ^® PY 284, and Araldite ^® P811;
• i) solid heterocyclic epoxy resins (Triglyzidylisozyanurat) such as Araldit ^® PT 810;
• j) liquid cycloaliphatic epoxy resins such as Araldit ^® CY 179;
• k) liquid N, N, O-Triglyzidylether of p-aminophenol such as Araldit ^® MY 0510;
• l) Tetraglyzidyl-4-4'-methyl benzenamine or N, N, N ', N'-Tetraglyzidyldiaminophenylmethan as Araldit ^® MY 720, Araldite ^® MY 721st

Epoxy compounds having two functional groups are preferably used. However, it is also possible in principle to use epoxide compounds having one, three or more functional groups.

Primarily epoxy compounds, especially diglycidyl compounds, are used with aromatic groups.

Optionally, a mixture of different epoxy compounds can be used.

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

wobei in Formel (X) m = 2, 3, 4, 5 oder 6 ist.Very particular preference is given to bisglycidyl alcohol ethers of the following formula (X)

where in formula (X) m = 2, 3, 4, 5 or 6.

The terminal epoxide compounds can be used in an amount of preferably at least 0.1 part, for example 0.1 to 50, advantageously 1 to 30 and in particular 1 to 25 parts by weight, based on 100 parts by weight of PVC.

Epoxidized fatty acid esters (and other epoxide compounds)

In addition, the inventive stabilizer combination may preferably contain at least one epoxidized fatty acid ester. In particular, esters of fatty acids from natural sources (fatty acid glycerides), such as soybean oil or rapeseed oil, are suitable for this purpose. But it can also be synthetic products such as epoxidized butyl oleate used. It is likewise possible to use epoxidized polybutadiene and polyisoprene, if appropriate also in partially hydroxylated form, or glycidyl acrylate and glycidyl methacrylate as homo- or copolymer. These epoxy compounds may also be applied to an alumino salt compound; see also DE-A 4031818 ,

Liquid or highly viscous glycidyl or epoxy compounds can also be applied to siliceous or silicate-containing carriers and used in a solid, non-adhesive form.

Sterically hindered amines (HALS)

wobei in Formel (XI) A und V unabhängig voneinander C_1-8-Alkyl-, C_3-8 Alkenyl-, C_5-8-Cycloalkyl-, oder C_7-9-Phenylalkyl- sind, oder zusammen gegebenenfalls durch O, NH oder CH₃-N unterbrochenes C_2-5-Alkylen bilden, oder um ein cyclisches sterisch gehindertes Amin, insbesondere eine Verbindung aus der Reihe der Alkyl- bzw. Polyalkylpiperidine, vor allem der Tetramethylpiperidine enthaltend die Gruppe der Formel (XII)

The sterically hindered amines are generally compounds containing the group of the formula (XI)

in formula (XI), A and V, independently of one another, are C _1-8 -alkyl-, C _3-8 -alkenyl-, C _5-8 -cycloalkyl- or C _7-9 -phenylalkyl- or together where appropriate O, NH or CH ₃ -N interrupted C _2-5 -alkylene form, or a cyclic sterically hindered amine, in particular a compound from the series of alkyl or polyalkylpiperidines, especially the tetramethylpiperidines containing the group of formula (XII)

Polyols and disaccharide alcohols, β-diketones, thiophosphites and thiophosphates as well as mercaptocarboxylic acid esters are preferred as further component groups.

Polyols (and sugar alcohols)

Suitable compounds of this type are, for example: pentaerythritol, dipentaerythritol, tripentaerythritol, trimethylolethane, bistrimethylolpropane, inositol, polyvinyl alcohol, bistrimethylolethane, trimethylolpropane, sorbitol, maltitol, isomaltitol, lycasin, mannitol, lactose, leucrose, palatinit, tetra-methylcyclohexanol, tetramethylolcyclopentanol, tetramethylolpyranol , Glycerin, di-glycerin, polyglycerol, thiodiglycerin or 1-O-α-D-glycopyranosyl-D-mannitol dihydrate. Preference is given to disaccharide alcohols. Also used are polyol syrups such as sorbitol, mannitol and maltitol syrups. The polyols may be used in an amount of, for example, from 0.01 to 20, suitably from 0.1 to 20, and especially from 0.1 to 10 parts by weight, based on 100 parts by weight of PVC.

phosphites

wobei in den Formeln (XIII) und (XIV) R₁'', R₂'' und R₃'' gleich oder verschieden sind und C₆-C₁₈-Alkyl, C₆-C₁₈-Alkenyl, einen substituierten oder unsubstituierten Phenylrest oder C₅-C₇-Cycloalkyl bedeuten.The compositions of the invention may also contain other organic phosphites. Such phosphites may be contained about in an amount of 0.01 to 3, especially 0.01 to 1.5, preferably 0.1 to 0.6 parts by weight. Examples of such phosphites are, for example, those of the formulas (XIII) and (XIV)

wherein in the formulas (XIII) and (XIV) R ₁ ", R ₂ " and R ₃ "are the same or different and are C ₆ -C ₁₈ alkyl, C ₆ -C ₁₈ alkenyl, a substituted or unsubstituted one Phenyl radical or C ₅ -C ₇ -cycloalkyl.

If R ₁ ", R ₂ " and R ₃ "are C ₆ -C ₁₈ -alkyl, then these are, for example, For example, n-hexyl, n-octyl, n-nonyl, decyl, dodecyl, tetradecyl, hexydecyl or octadecyl. Preference is given to alkyl groups having 8 to 18 carbon atoms.

As substituted phenyl, R ₁ ", R ₂ " and R ₃ "are, for example, tolyl, ethylphenyl, xylyl, cumyl, cymyl, cresyl, 4-methoxyphenyl, 2,4-dimethoxyphenyl, ethoxyphenyl, butoxyphenyl, pn-octylphenyl, pn Nonylphenyl or pn-dodecylphenyl.

Particularly suitable phosphites are trioctyl, tridecyl, tridodecyl, tritetradecyl, tristearyl, trioleyl, triphenyl, tricresyl, tris-p-nonylphenyl or tricyclohexyl phosphite, and particularly preferred are the aryl-dialkyl and the alkyl-diaryl Phosphites, such as. Phenyldidecyl-, (2,4-di-tert-butylphenyl) -di-dodecyl-phosphite, (2,6-di-tert-butylphenyl) -di-dodecyl-phosphite and the dialkyl- and diaryl-pentaerythritol-diphosphites, such as distearyl diphosphite.

Preferred organic phosphites are distearyl pentaerythritol diphosphite, trisnonylphenyl phosphite and phenyl didecyl phosphite.

Furthermore, further known costabilizers may be present in the compositions according to the invention. Aminocrotonic acid esters, 2,4-dihydroxybenzophenone, 2,4-dihydroxy-4'-tert-butylbenzophenone and pyrrole derivatives may be mentioned as such costabilizers. For example, the amounts of such costabilizers 0.01 to 1.5 and preferably 0.1 to 1 parts by weight, based on the composition amount.

Particularly suitable aminocrotonic esters are the esters with monohydric straight-chain C ₈ -C ₂₀ -, in particular C ₁₂ -C ₁₈ -alcohols and / or with 1,3- or 1,4-butanediol and / or 1,2-dipropylene glycol and / or Thiodiethylene glycol into consideration.

As Pyrrol Costabilisatoren those are particularly to be mentioned, which in the EP-A 22 087 and the GB-A 2 078 761 are described. As an example, 2-methyl-3-cyclohexyloxy-carbonyl-4-phenyl-1H-pyrrole mentioned.

Furthermore, the compositions of the invention may contain other optional ingredients, for. As organic antimony compounds, such as antimony tris [isooctylthioglycolate].

In addition, it is also possible to use perchlorato complexes and / or perchlorate salt formulations.

Perchlorate Booster

Catena μ-2,2 ', 2' '' - nitrilotrisethanol perchlorate (triflato) sodium or lithium

wobei
Mt = Li oder Na
An = OClO₃ oder OS(O₂)CF₃ These four inner complexes are coordination polymers having the following monomer unit of the formula (XV)

in which
Mt = Li or Na
An = OClO ₃ or OS (O ₂ ) CF ₃

An = OClO ₃ is preferred, with Mt = Na (TEAP) being particularly preferred. Their use as stabilizers is described in WO 2006/136191 , Very particular preference is TEAP 50 This product is in DE 10 2007 050 428 described.

Sodium (lithium) perchlorate (triflate) in dissolved or supported form

These lithium or sodium salts can be used as solutions, with the following solvents being preferred: water, glycols, glycol ethers, (poly) glycerols and polyglycol ethers.

However, particular preference is given to supported formulations of the salts, wherein the salt is sorbed in dissolved form (usually aqueous) on a solid support in a homogeneous distribution from (ad). The following substances are to be mentioned:
Silica (diatomaceous earth), calcium silicate, calcium carbonate, calcium oxide, calcium hydroxide, Na zeolite A, hydrotalcite and calcined dolomite, the latter being preferred.

These sodium or lithium compounds have a booster effect in PVC. They are preferably used in the substrate advantageously from 0.001 to 5 phr, preferably from 0.01 to 3 phr and most preferably from 0.01 to 2 phr.

Furthermore, the compositions of the invention may contain conventional plasticizers, antioxidants, light stabilizers and UV adsorbers.

softener

Phthalates (phthalates), examples of such plasticizers are dimethyl, diethyl, dibutyl, dihexyl, di-2-ethylhexyl, di-n-octyl, di-iso-octyl, di-iso-nonyl, Di iso-decyl, di-iso-tridecyl, dicyclohexyl, dimethylcyclohexyl, dimethyl glycol, dibutyl glycol, benzyl butyl and diphenyl phthalate and mixtures of phthalates, such as C ₇ -C ₉ and C ₉ -C ₁₁ alkyl phthalates from predominantly linear alcohols, C ₆ -C ₁₀ -n-alkyl phthalates and C ₉ -C ₁₀ -n-alkyl phthalates. Preferred of these are dibutyl, dihexyl, di-2-ethyl-hexyl, di-n-octyl, di-iso-octyl, di-iso-nonyl, di-iso-decyl, di-iso-tridecyl - And benzyl butyl phthalate and the said mixtures of alkyl phthalates. Particularly preferred is di-2-ethylhexyl phthalate (DOP).

Esters of aliphatic dicarboxylic acids, in particular esters of adipic, azelaic and sebacic acid. Examples of such plasticizers are di-2-ethylhexyl adipate, diisooctyl adipate (mixture), di-iso-nonyl adipate (mixture), di-iso-decyl adipate (mixture), benzyl butyl adipate, benzyloctyl adipate. Di-2-ethylhexyl azelate, di-2-ethylhexyl sebacate and diisodecyl sebacate (mixture). Preference is given to di-2-ethylhexyl adipate and di-iso-octyl adipate.

Trimellithsäureester, for example, tri-2-ethylhexyltrimellithat, tri-iso-decyltrimellithat (mixture), tri-iso-tridecyltrimellithat, tri-iso-octyltrimellithat (mixture) and tri-C ₆ -C ₈ alkyl, tri-C ₆ -C ₁₀ alkyl, tri-C ₇ -C ₉ alkyl and tri-C ₉ -C ₁₁ alkyl trimellitate. The latter trimellitates are formed by esterification of Trimellithsäure with the corresponding alkanol mixtures. Preferred trimellitates are tri-2-ethylhexyl trimellitate and the mentioned trimellitates from alkanol mixtures.

Polymer softeners, a definition of these plasticizers and examples of such are in the "Plastics Additives Handbook", editors H. Gächter and H. Müller, Hanser Publishers, 1985, page 284, chapter 5.7.10 as in "PVC Technology", publisher WV, Titow, 4th. Ed., Elsevier Publ. 1984, 165-170 , stated. The most common starting materials for the preparation of polyester plasticizers are: dicarboxylic acids, such as adipic, phthalic, azelaic and sebacic acids; Diols such as 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and diethylene glycol; Monocarboxylic acids such as Essing, Capron, Capryl, Laurine, Myristin, Palmitin, Stearin, Pelargon and Benzoic Acid; monofunctional alcohols, such as isooctanol, 2-ethylhexanol, isodecanol and C ₇ -C ₉ -alkanol and C ₉ -C ₁₁ -alkanol mixtures. Particularly advantageous are polyester plasticizers from the mentioned dicarboxylic acids and monofunctional alcohols.

Phosphoric acid ester, a definition of these esters is mentioned above "Plastics Additives Handbook" on page 271, chapter 5.7.2 ., to find. Examples of such phosphoric acid esters are tributyl phosphate; Tri-2-ethylbutyl phosphate, tri-2-ethylhexyl phosphate, trichloroethyl phosphate, 2-ethylhexyl-di-phenyl phosphate, cresyl diphenyl phosphate, triphenyl phosphate, tricresyl phosphate and trixylenyl phosphate. Preference is given to tri-2-ethylhexyl phosphate.
Chlorinated hydrocarbons (paraffins),
hydrocarbons,
Monoester, z. B. butyl oleate, phenoxylethyl oleate, tetrahydrofurfuryl oleate and Alkylsulfonsäureester.
Glycol ester, e.g. B. diglycerate.

Definitions and examples of plasticizers of groups F) to I) can be found in the following manuals:
"Plastics Additives Handbook", Editors H. Gächter and H. Müller, Hanser Publishers, 1985, page 284, Chapter 5.7.11 (Group F)), and Chapter 5.7.13 (Group G)) , "PVC Technology", publisher WV Titow, 4th. Ed., Elsevier Publishers, 1984, pages 171 to 173, Chapter 6.10.2 (Group F)), page 174, Chapter 6.10.5 (Group G)), page 173, Chapter 6.10.3 (Group H)) and page 173 to 174, Chapter 6.10.4 (Group I)) ,

Plasticizers from groups A) to E), in particular A) to C), are especially preferred, especially the plasticizers found to be preferred in these groups. Particularly favorable is di-2-ethylhexyl phthalate (DOP).

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

antioxidants

Alkylated monophenols, e.g. For example, 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-etylphenol, 2,6-di tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-i-butylphenol, 2,6-di-cyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4 , 6-dimethylphenol, 2,6-di-octadecyl-4-methylphenol, 2,4,6-tri-cyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, 2,6-di-nonyl 4-methyl phenol.

Alkylated hydroquinones, e.g. As 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amyl-hydroquinone, 2,6-diphenyl-4 -octadecyloxyphenol.

Hydroxylated thiodiphenyl ethers, e.g. B. 2,2'-thio-bis (6-tert-butyl-4-methylphenol), 2,2'-thio-bis (4-octylphenol), 4,4'-thio-bis (6 tert-butyl-3-methylphenol), 4,4'-thio-bis (6-tert-butyl-2-methylphenol).

Alkylidene Bisphenols, e.g. B. 2,2'-methylene-bis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2 ' -Methylene bis [4-methyl-6- (α-methylcyclohexyl) phenol], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylene bis ( 6-nonyl-4-methylphenol), 2,2'-methylenebis (4,6-di-tert-butylphenol), 2,2'-ethylidene-bis (4,6-di-tert-butyl) butylphenol), 2,2'-ethylidene-bis (6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis [6- (α-methylbenzyl) -4-nonylphenol], 2 , 2'-Methylenebis [6- (α, α-dimethylbenzyl) -4-nonylphenol], 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,4 ' -Methylene-bis- (6-tert-butyl-2-methylphenol), 1,1-bis- (5-tert. butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3-tert-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.

Benzyl linkages, e.g. 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-tri-methylbenzene, bis (3,5-di-tert-butyl 4-hydroxybenzyl) sulfide, 3,5-di-tert-butyl-4-hydroxybenzyl-mercaptoacetic acid isooctyl ester, 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-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) isocyanurate, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, Ca salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester, 1 , 3,5-tris isocyanurate (3,5-dicyclohexyl-4-hydroxybenzyl).

Acylaminophenols, e.g. 4-hydroxy-lauric acid anilide, 4-hydroxy-stearic acid anilide, 2,4-bis (octylmercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino-s-triazine, N- (3 , 5-di-tert-butyl-4-hydroxyphenyl) -carbaminsäureoctylester.

Esters of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols, such as. With methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide.

Esters of β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with monohydric or polyhydric alcohols, such as. With methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxy) ethyl isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide.

Esters of β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols, such as. With methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxy) ethyl isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide.

Amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid, such as. 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.

UV absorber and light stabilizer

2- (2'-hydroxyphenyl) -benzotriazoles, such as. As the 5'-methyl, 3Ä ', 5'-di-tert-butyl, 5'tert.-butyl, 5' - (1,3,3-Terramethylbutyl) -, 5-chloro-3 ', 5'-di-tert-butyl, 5-chloro-3'-tert-butyl-5'-methyl, 3'-sec-butyl-5'-tert-butyl, 4'-octoxy , 3 ', 5'-di-tert-amyl, 3', 5'-bis (α, α-dimethylbenzyl) derivative.

2-hydroxybenzophenones, such as. As the 4-hydroxy, 4-methoxy, 4-octoxy, 4-decycloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy, 2'-hydroxy-4 , 4'-dimethoxy derivative.

Esters of optionally substituted benzoic acids, such as. As 4-tert-butyl-phenyl-salicylate, phenyl salicylate, octylphenyl-salicylate, dibenzoylresorcinol, bis (4-tert-butylbenzoyl) -resorcinol, benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di-tert-butylphenyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester.

Acrylates, such as. B. α-cyano-β, β-diphenylacrylic acid ethyl ester or isooctyl ester, α-carbomethoxy-cinnamic acid methyl ester, α-cyano-β-methyl-p-methoxycinnamate or butyl ester, α-carbomethoxy-p-methoxycinnamic acid methyl ester, N- (β-carbomethoxy-β-cyanovinyl) -2-methyl-indoline.

Nickel compounds, such as. Example, nickel complexes of 2,2'-thio-bis [4- (1,1,3,3-tetramethylbutyl) phenol], such as the 1: 1 or the 1: 2 complex, optionally with additional ligands, such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, such as methyl or ethyl esters, nickel complexes of ketoximes, such as 2-hydroxy-4 -methylphenyl and -ecylketoxim, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxy-pyrazole, optionally with additional ligands.

Oxidesäurediamide, such as. 4,4'-dioctyloxy-oxanilide, 2,2'-di-octyloxy-5,5'-di-tert-butyl-oxanilide, 2,2'-di-dodecyloxy-5,5 ' di-tert-butyl-oxanilide, 2-ethoxy-2'-ethyl-oxanilide, N, N'-bis (3-dimethylaminopropyl) - oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyl-oxanilide, mixtures of o- and p Methoxy and o- and p-ethoxy-di-substituted oxanilides.

2- (2-hydroxyphenyl) -1,3,5-triazine, such as. 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-dihydroxyphenol) -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-dodecycloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine.

Depending on the intended use, further customary additives can also be incorporated into the compositions according to the invention, such as, for example, B.
Fillers and reinforcing agents, such as. Calcium carbonate, silicates, glass fibers, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite;
Lubricants, pigments, flame retardants, antistatic agents, processing aids, impact modifiers (polyacrylates) or biocides.

The present invention comprises foamed articles obtainable by foaming a composition according to the invention as described above.

The articles may, for example, include pipes or profiles, such as door frames, roller shutter boxes, window sills and furniture parts, weatherstripping, shoe soles, buffers, shock absorbers, mats, sheets, hides, blocks, carpets, foam artificial leather, wall and floor coverings, upholstery materials and the like, among many other uses be.

Examples of foamed articles obtainable according to the invention are a) a closed-cell soft PVC foam of density d of 0.05 to 1.0 g / cm ³ , usable as a highly elastic material in gymnastic mats, as a shock protection insert in helmets, for the damping of machine vibrations and as wall and floor coverings, b) an open-cell soft-PVC foam of density d 0.07 to 0.33 g / cm ³ , usable as a sound-absorbing material and for breathing upholstery, c) a hard PVC structural foam density d 0.5 to 1.0 g / cm ³ , usable as heat-moldable lightweight construction materials for interior and exterior construction or d) a closed-cell hard PVC foam of density d 0.04 to 0.13 g / cm ³ , usable as sandwich core material for mains floats and liferafts or for freezer tanks for liquefied gases.

The following examples illustrate the invention in more detail.

Experimental Section (Examples 1-13)

I. Preparation of the rolled skins:

The mixtures prepared according to Table 1 (Examples R1 to R8) and Table 2 (Examples R9 to R13) are tested on a Polymix 150P (Schwabenthan) testing mill for 4 minutes, 10 rpm, friction: -10%) at 180 ° C plasticized. The resulting films (thickness 1.0 mm) are fed to further measurements.

II. Color measurement on rolled skins

From the rolling skins R1 to R8, the CIE b * value is measured with a colorimeter Datacolor Check (illuminant 65/10) from DATACOLOR (see Table 1).

III. Performing the static heat test (SHT):

Test strips (22 mm × 422 mm) are cut out from the skin skins prepared according to I (R9 to R13). These are loaded in a Mathis Thermotester LTE-T (from MATHIS AG, Switzerland) at 190 ° C. until significant discoloration. Subsequently, the CIE-b * and CIE-a * value is measured with a Datacolor Check colorimeter (illuminant 65/10) from DATACOLOR in 5-minute intervals and compared with the corresponding value of the rolling coat (zero minutes -Value). The results are summarized in tabular form (see Table 3). The smaller the b * value (lower yellowing) at a given time, the better the color behavior with respect to yellowing.

Positive CIE a * values indicate red discoloration. The greater the positive CIE a * value, the stronger this red discoloration. Tab. 1: Formulations (quantities in phr) Without propellant With propellant R1 R2 R3 R4 R5 R6 R7 R8 S-PVC (K-value 57) EVIPOL SH5730 100 100 100 100 100 100 100 100 Flow aid (DEGALAN 10F) 1 1 1 1 1 1 1 1 Titanium dioxide (KRONOS CL2220) 3 3 3 3 3 3 3 3 Antioxidant (IRGANOX 1076) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 calcium stearate 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 zinc stearate 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Hydrotalcite, Zn-containing (Alkamizer P93) 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 THEIC (tris-hydroxyethyl-isocyanurate) - 0.2 0.5 0.35 - 0.2 0.5 0.35 melamine 0.7 0.5 0.2 0.35 0.7 0.5 0.2 0.35 Blowing agent (azodicarbonamide) - - - - 0.5 0.5 0.5 0.5 CIE b * value 9.2 7.6 5.9 6.4 4.5 4.0 3.8 4.0

As can be seen from the table, in the inventive examples (R6, R7 and R8), the performance (lower b * value) is significantly better than in the reference examples, (R1, R2, R3, R4 and R5). Since the total amount of melamine or melamine and THEIC is constant (0.7 phr) in all examples, there is synergism with respect to the effect of Examples R6 to R8. This finding is surprising, as not foreseeable. The comparison of R5 to R8 with R1 to R4 shows an increase in activity, which is caused by the addition of the propellant. Tab. 2 formulations (quantities in phr) R9 R10 R11 R12 R13 S-PVC (K-value 57) EVIPOL SH5730 100 100 100 100 100 Flow aid (DEGALAN 10F) 1 1 1 1 1 Titanium dioxide (KRONOS CL2220) 3 3 3 3 3 Antioxidant (IRGANOX 1076) 0.1 0.1 0.1 0.1 0.1 calcium stearate 0.2 0.2 0.2 0.2 0.2 zinc stearate 0.2 0.2 0.2 0.2 0.2 Hydrotalcite, Zn-containing (Alkamizer P93) 0.4 0.4 0.4 0.4 0.4 THEIC (tris-hydroxyethyl-isocyanurate) 0.7 - 0.35 0.2 0.5 melamine - 0.7 0.35 - - calcium hydroxide - - - - 0.2 magnesium hydroxide - - - 0.5 - Blowing agent (azodicarbonamide) 0.5 0.5 0.5 0.5 0.5 Tab. 3 Static heat test (190 ° C); CIE-b * and CIE-a * values R9 R10 R11 R12 * R13 * CIE b * CIE a * CIE b * CIE a * CIE b * CIE a * CIE b * CIE a * CIE b * CIE a * 0 min. 5.1 -1.1 5.6 -0.8 4.9 -0.9 7.6 -0.9 5.6 -1.1 5 min. 5.8 -1.3 7.2 -0.4 5.5 -1.1 9.6 -0.8 5.8 -1.2 10 mm. 9.9 -1.2 9.6 -0.6 7.1 -0.8 17.5 2.4 10.4 -1.2 15 minutes. 21.9 2.1 22.0 6.1 18.9 1.4 20.3 13.0 22.1 2.5 * R12 and R13 are state of the art but with additional propellant.

From Tab. 3 it can be clearly seen that the inventive example R11 i. Cf. the reference examples (R9, R10, R12 * and R13 *) both in initial color, color retention and long-term stability lower CIE b * values and thus a better efficacy (lower yellowing).

Again, clearly shows a synergistic mode of action, since in all examples (R9 to R13) the total amount (phr) of THEIC and / or melamine or to THEIC and alkaline earth hydroxide + propellant constant 1.2 phr.

The CIE a * values (red values) after 15 minutes of thermal loading are lowest in the inventive example R11 with 1.4 and highest in the reference examples R10 and R11 with values of 6.1 and 20.3.

Again, there is a synergism, which is surprising, since unpredictable.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

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Cited non-patent literature

• Hansjürgen Saechtling, Plastic Paperback, 22nd Edition, Carl Hanser Verlag Munich [0027]
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• "PVC Technology", publisher WV Titow, 4th. Ed., Elsevier Publishers, 1984, pages 171 to 173, Chapter 6.10.2 (Group F)), page 174, Chapter 6.10.5 (Group G)), page 173, Chapter 6.10.3 (Group H)) and page 173 to 174, Chapter 6.10.4 (Group I)) [0138]

Claims (11)

Stabilizer system for halogen-containing polymers containing the components a) a blowing or foaming agent, b) a zinc compound, c) a melamine derivative, d) a tris-hydroxyalkyl isocyanuric acid ester. Stabilizer system according to claim 1, characterized in that additionally catena-μ-2,2 ', 2' '- nitrilotrisethanol perchlorato sodium or sodium perchlorate is contained in dissolved or supported form. Stabilizer system according to claim 1 or 2, wherein component a) contains azodicarbonamide. Stabilizer system according to one of claims 1 to 3, wherein component b) contains zinc carboxylate. Stabilizer system according to one of claims 1 to 4, wherein component c) contains melamine. A stabilizer system according to any one of claims 1 to 5, wherein component d) contains tris-hydroxyethyl isocyanuric acid ester (THEIC). Polymer compositions containing a stabilizer system according to any one of claims 1 to 6 and a halogen-containing polymer (s). Polymer composition according to claim 7, characterized in that the polymer composition is in the form of a foam. A polymer composition according to claim 7 or 8, wherein the halogen-containing polymer is polyvinyl chloride. A process for producing a stabilized halogen-containing polymer composition according to any one of claims 7 to 9, comprising the step of adding a stabilizer system according to any one of claims 1 to 6 to a halogen-containing polymer. Use of stabilizer systems according to any one of claims 1 to 6 for the stabilization of halogen-containing polymers.