WO2008071534A1 - Stabiliser combinations for halogenated polymers - Google Patents

Abstract

The invention relates to a stabiliser system for halogenated polymers, containing at least one inner-complex selected from the group comprising coordination polymer catena-µ-2,2',2"-nitrilotriethanol perchlorate metal inner complex and coordination polymer catena-µ-2,2',2"-nitrilotriethanol trifluoromethansulfonate metal inner complex and at least one heavy metal containing stabiliser, different from the at least one inner complex and which is a lead-containing or organozinc stabiliser. The invention further relates to compositions and objects comprising the stabiliser system and the use thereof.

Description

 Stabilizer combinations for halogen-containing polymers

The present invention relates to stabilizer systems for halogen-containing polymers and to compositions and articles containing the stabilizer systems and the use of the systems and compositions.

As is known, halogen-containing plastics tend to undergo undesired decomposition and degradation reactions during thermal stress during processing or in long-term use. This problem can be solved by the use of stabilizers added to the halogen-containing polymer before or during processing. The known stabilizers include, for example, the lead, organotin, calcium-zinc and barium-zinc stabilizers and organic stabilizers.

Therefore, stabilizers have been added for a long time in the processing of halogen-containing polymers, which should prevent degradation of the halogen-containing polymer during processing. It is known to improve the performance of lead stabilizers with perchlorate salts.

Thus, JP-A 58173159 describes the combination of tribasic lead sulfate and potassium perchlorate. The latter compound is used only in very small quantities and can be due to their poor dissolving power in water or organic solvents in PVC only poorly incorporated and distributed homogeneously.

WO-A 2005/059027 (EP 1694768) also describes stabilizer compositions containing lead compounds and perchlorates. Furthermore, JP-A 02182741 describes only the use in PVC copolymers.

Coordination Polymers Catena μ-2,2 ', 2 "-nitrilotrisethanol perchlorato or trifluoromethanesulfonato (triflato) metal-inner complexes are described and characterized in JG VERKADE et al., Inorg. Chem. 33, 2137 (1994) ,

The suitability of these inner complexes as stabilizers for halogen-containing polymers is described in WO-A 2006/136191.

The stabilizer combinations known from the prior art are usually combinations containing heavy metal-containing stabilizers. In principle, good stabilization results can be achieved with these stabilizers. However, the amount used is high in relation to the performance.

However, there is a need to reduce the heavy metal content in the environment. Therefore, it was urgently necessary to reduce the lead or tin content in stabilizer systems. In addition, good stabilizing properties should be made possible by special combinations.

It is therefore an object of the present invention to provide stabilizer systems for halogen-containing polymers which meet the above-mentioned needs.

The object is achieved by a stabilizer system for halogen-containing polymers containing at least one inner complex selected from the group consisting of co-ordination polymeric catena μ-2,2 ', 2 "nitrilotrisethanol perchlorato metal inner complex and coordination polymer catena μ 2,2', 2" nitrilotrisethanol trifluoromethanesulfonato metal inner complex ; and

at least one heavy metal-containing stabilizer which is different from the at least one inner complex and is a lead-containing or an organotin stabilizer.

It has been found that a combination of at least one of the above-mentioned inner complexes with a lead-containing stabilizer (lead stabilizer) or an organotin stabilizer in a stabilizer system have good stabilizer properties, whereby the lead or tin content can be lowered.

A stabilizer system according to the invention has at least two different components which can develop a stabilizing effect.

One component is a lead or organotin stabilizer. Preference is given to a lead stabilizer.

The inventive stabilizer system may contain a lead or organotin stabilizer or more lead or organotin stabilizers.

The stabilizer system according to the invention preferably contains one lead stabilizer or several lead stabilizers.

In addition, further metal-containing stabilizers may be contained in the stabilizer system according to the invention. This is preferably at least one calcium-zinc or barium-zinc stabilizer, these preferably containing the corresponding metal carboxylates, in particular fatty metal carboxylates.

As lead-containing stabilizers (lead stabilizers) are in the context of the present invention, in principle, all organic or inorganic lead compounds. Particularly suitable are, for example, basic lead salts of inorganic acids such as tribasic lead sulphate, tetrabasic lead sulphate, dibasic lead phosphide or dibasic lead phosphite sulphite or lead carbonate (lead white), lead salts of linear or branched, saturated or unsaturated, aliphatic or araliphatic or aromatic organic monocarboxylic acids such as acetic acid, Propionic, butyric, valeric, hexanoic, enanthic, octanoic, neodecanoic, 2-ethylhexanoic, pelargonic, decanoic, undecanoic, dodecanoic (lauric), tridecanoic, myristic, palmitic, 3,6-dioxaheptanoic, 3,6,9-trioxadic, behenic , Benzoic acid, p-tert-isostearic acid, stearic acid, 12-hydroxystearic acid, 9,10-dihydroxystearic acid, oleic acid, butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-di-tert-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, n-propylbenzoic acid acid, salicylic acid, p-tert-octylsalicylic acid, sorbic acid, cinnamic acid, acrylic acid, methacrylic acid, rosin acid (abietic acid); Dicarboxylic acids or their monoesters or hydroxy carboxylic acids, such as oxalic acid, malonic acid, maleic acid, fumaric acid, tartaric acid, mandelic acid, malic acid, glycolic acid, polyglycol dicarboxylic acids having a degree of polymerization of from about 10 to about 12, phthalic acid, isophthalic acid, terephthalic acid or hydroxyphthalic acid; Tri- or tetracarboxylic acids or their mono-, di- or triesters such as hemimellitic acid, trimellitic acid, pyromellitic acid or

Citric acid, or dimerized or trimerized linoleic acid. Likewise suitable are cycloaliphatic carboxylic acids, such as cyclohexane carboxylic acid, tetrahydrophthalic acid, A-methyltetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid or 4-methylhexahydrophthalic acid. Particularly suitable are neutral or basic lead stearate, lead white, 3- or 4-basic lead sulfate, 2-basic lead phosphite, 2- basic lead phthalate or 4-basic lead fumarate. Very particular preference is given to 2-basic lead phosphite and 3-basic lead sulphate.

Also suitable as lead compounds for stabilization are products such as those obtained by reacting lead oxide with hydroxy carboxylic acids, for example

Dimethylolpropionic acid are available. Such compounds and their preparation are described in EP 0 313 113.

Preference is given to lead phosphite or sulphate or their mixtures with at least one organic lead compound, in particular with a lead carboxylate

Lead stearate or lead oleate. Very particular preference is given to 2-basic lead phosphite and 3-basic lead sulfate and their mixtures with lead or calcium stearate or their combination with calcium-zinc-fatty acid carboxylates.

The content of a stabilizer system according to the invention of lead stabilizers is at least 5% by weight, preferably from 10 to 95% by weight, particularly preferably from 20 to 90% by weight, and very particularly preferably from 30 to 75% by weight. For basic lead stabilizers, the base content preferably varies from 1: 1 to 10: 1.

Suitable calcium-zinc or barium-zinc stabilizers in the context of the present invention are certain inorganic calcium, barium and zinc compounds and in principle all calcium, barium and zinc carboxylates and the phenolates of these metals. For example, zinc oxide, calcium, barium or zinc hydroxide or sulfate, zinc or barium carbonate, barium nonylphenolate, zinc sulfide, barium or zinc oxide or hydroxide addition compounds, such as overbased ones, are particularly suitable

Calcium, barium or zinc carbonates or carboxylates. The carboxylates are derived from carboxylic acids as exemplified above for lead stabilizers. Preferred are combinations of calcium-zinc stabilizers with lead stabilizers. An alternative heavy metal component is an organotin stabilizer. The stabilizer system according to the invention may contain one or more organotin stabilizers. Preference is given to mixtures of mono- and diorganotin stabilizers.

Examples include compounds of the composition:

with n = 1 or 2,

R = methyl, butyl, octyl, lauryl or carbobutoxyethyl and X = (CH ₂ ) "CO ₂ -C ₂ -C ₂ alkyl or CH ₂ CH ₂ OC ₂ -C ₂₂ -Acyl.

In addition, further metal-containing stabilizers may be contained in the stabilizer system according to the invention.

This is preferably at least one calcium-zinc or barium-zinc stabilizer, these preferably containing the corresponding metal carboxylates.

Suitable calcium-zinc or barium-zinc stabilizers in the context of the present invention are certain inorganic calcium, barium and zinc compounds and in principle all calcium, barium and zinc carboxylates and the phenolates of these metals. For example, zinc oxide, calcium, barium or zinc hydroxide, zinc or barium carbonate or sulfate, barium nonylphenolate, zinc sulfide, addition compounds such as overbased calcium, barium or zinc carbonates or carboxylates are particularly suitable. The carboxylates are derived from carboxylic acids as mentioned above Lead stabilizers are described by way of example. Preferred are combinations of barium-zinc with organotin stabilizers.

In addition to the above-mentioned lead or organotin stabilizers, the stabilizer system according to the invention contains at least one inner complex selected from the group consisting of coordination-polymer catena μ-2,2 ', 2 "-nitrilotrisethanol-perchlorato-metal inner complex and coordination polymer catena μ-2,2'. , 2 "-nitrilotrisethanol- trifluoromethanesulfonato (triflato) -metal-inner complex.

The stabilizer system according to the invention can thus contain such a perchlorato inner complex, a plurality of such perchlorato inner complexes and no triflate inner complex, such a triflato inner complex, a plurality of such triflate inner complexes and no perchlorato inner complex or both perchlorato and triflato complexes.

In addition, the stabilizer system according to the invention may contain further stabilizers. In addition, the stabilizer system according to the invention preferably additionally contains only the abovementioned metal-containing stabilizers which are not lead or organotin stabilizers and none of the abovementioned internal complexes. Further preferably, the stabilizer system according to the invention contains only the abovementioned combination of lead or organotin stabilizer and inner complex.

The at least one coordination-polymer catena-μ-2,2 ', 2 "-nitrilotrisethanol perchlorato (triflato) -metal inner complex is preferably an inner complex with the monomer unit of the formula (I)

in which

Mt = Li, Na, K, Mg, Ca, Sr, Ba and Zn; An = OClO ₃ or OS (O ₂ ) CF ₃ ; q = 1 or 2.

An = OClO ₃ is preferred. A preferred embodiment is therefore a stabilizer system according to the invention in which the at least one inner complex is a coordination-polymer catena-μ-2,2 ', 2 "-nitrilotrisethanol perchlorato-metal inner complex.

Further preferred is Mt = Na. A preferred embodiment is therefore a stabilizer system according to the invention in which the metal of the inner complex is sodium.

The following inner complexes are listed, where perchlorato = Pc and trifiato = Tf are used as abbreviations:

[(TEA) NaPc], [(TEA) NaTfJ, [(TEA) LiPc], [(TEA) LiTfJ, [(TEA) KPc], [(TEA) KTfJ, [(TEA) ₂ Mg (Pc) ₂ ] , [(TEA) ₂ Mg (Tf) ₂ ], [(TEA) ₂ Ca (Pc) ₂ ], [(TEA) ₂ Ca (Tf) ₂ ], [(TEA) ₂ Sr (Pc) ₂ ], [ (TEA) ₂ Sr (Tf) ₂ ], [(TEA) ₂ Zn (Pc) ₂ ], [(TEA) ₂ Zn (Tf) ₂ ], [(TEA) ₂ Ba (Pc) ₂ ], [(TEA ) ₂ Ba (Tf) ₂ ]. Very particularly preferred is the use of the coordination polymer catena μ-2,2 ', 2 "nitrilotrisethanol perchlorato sodium inner complex.

The proportion of the at least one coordination-polymer catena-μ-2,2 ', 2 "-nitilotrisethanol perchlorato (triflato) -metal-inner complex is in the context of the present invention preferably 0.001-1.0% by weight, preferably 0.01%. 0.5 wt .-% and particularly preferably 0.05 to 0.1 wt .-% based on the total amount of the stabilizer system.

In addition to one or more lead-containing stabilizer (s) or organotin stabilizer (s) and one or more coordination polymer catena μ-2,2 ', 2 "nitrilotrisethanol perchlorato (triflato) -Metall-Innerkomplex (s) and optionally further stabilizers a stabilizer system according to the invention contain further additives, such as:

- inorganic and organic bases

Epoxides and glycidyl compounds β-diketones and β-ketoesters

Polyols and sugar alcohols - sterically hindered amines (HALS) and heterocyclic amino alcohols

Hydrotalcites, zeolites and dawsonites

Phosphorous acid ester (phosphites)

antioxidants

UV absorbers and light stabilizers - optical brighteners

pigments

propellant

Antistatic agents - Lubricants - Plasticizers Preferably, the stabilizer system according to the invention additionally contains at least one antioxidant and / or an alcohol selected from polyols and sugar alcohols or heterocyclic aminoalcohols.

Inorganic and organic bases

Suitable additives are inorganic bases such as oxides or hydroxides of magnesium, calcium, barium, aluminum and zinc or organic bases such as melamine, cyanoguanidine and guanamines such as aceto and benzoguanamine, triethanolamine, triisopropanolamine, tripropanolamine, triisobutanolamine, tributanolamine and reaction products of α-olefmoxides with primary and secondary amines. The amount used of these bases is 0.1 to 20 wt .-%.

Epoxides and glycidyl compounds

Examples of epoxy compounds are epoxidized soybean oil, epoxidized olive oil, epoxidized linseed oil, epoxidized castor oil, epoxidized peanut oil, epoxidized corn oil, and epoxidized cottonseed oil.

Examples of glycidyl compounds are compounds with the glycidyl group:

which is directly bonded to carbon, oxygen, nitrogen or sulfur atoms, and wherein 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 .beta.-methylglycidyl esters obtainable by reacting a compound having at least one carboxyl group in the molecule and epichlorohydrin or glycerol dichlorohydrin or .beta.-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, pelargonic, lauric, myristic, palmitic and stearic acid.

However, it is also possible to use cycloaliphatic carboxylic acids, for example cyclohexane carboxylic 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.

Also, carboxyl-terminated adducts, eg. Trimellitic acid and polyols such as glycerine or 2,2-bis (4-hydroxycyclohexyl) propane. Further epoxide compounds which can be used in the context of this invention can be found in EP 0 506 617. II) glycidyl or (.beta.-methyl glycidyl) ethers obtainable by reacting a compound having at least one free alcoholic hydroxyl 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-l, 2-diol, or poly (oxypropylene) glycols, propane-l, 3 -diol, butane-1,4-diol, poly (oxytetramethylene) glycols, pentane-l, 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 CyCcrAlkanol- and C9-Cn-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, L-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 they are based on polynuclear phenols, for example 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.

Further possible terminal epoxides are, for example: glycidyl 1-naphthyl ether, glycidyl 2-phenylphenyl ether, 2-biphenyl glycidyl 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 ₅ N ₅ O-triglycidyl-p-aminopheno 1.

The (N-glycidyl) compounds also include N, N'-di-, N, N ', N "-Tri- and N ₅ N', N", N "'-Tetraglyzidylderivate of cycloalkylene, 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-l, 2-dithiol or bis (4-mercaptomethylphenyl) ether.

V) Epoxide 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-epoxyzyklopentyloxy) 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.

Suitable terminal epoxides include: a) liquid bisphenol A diglycidyl ethers such as Araldit® GY 240, Araldit® GY 250, Araldit® GY 260, Araldit® GY 266, Araldit® GY 2600, Araldit® MY 790 and Epicote® 828 (BADGE ); b) solid bisphenol 1-A diglycidyl ethers such as Araldit® GT 6071, Araldit® GT 7071, Araldit® GT 7072, Araldit® GT 6063, Araldit® GT 7203, Araldit® GT 6064, Araldit® GS 7304, Araldit® GS 7004, Araldit® GT 6084, Araldit® GT 1999, Araldit® GT 7077, Araldit® GT 6097, Araldit® GT 7097, Araldit® GS 7008, Araldit® GT 6099, Araldit® GS 6608, Araldit® GS 6609, Araldite® GT 6610 and Epikote® 1002; c) liquid bisphenol 1-F diglycidyl ethers such as Araldit®GY 281, Araldit®PY 302, Araldit®PY 306 (BFDGE); d) solid polyglycidyl ethers 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 Ether® 162, Araldit® DY 0390, Araldit® DY 0391; h) liquid and solid glycidyl esters of carboxylic acids such as Shell Cardura® E

Terephthalic acid esters, trimellitic acid esters and their mixtures Araldit®PY 284 and Araldit® P811; i) solid heterocyclic epoxy resins (triglycidyl isocyanurate) such as Araldit® PT 810; j) liquid cycloaliphatic epoxy resins such as Araldit® CY 179; k) liquid N, N, O-triglycidyl ethers of p-aminophenol such as Araldit® MY 0510;

1) Tetraglycidyl 4-4'-methylenebenzamine or N, N, N ', N'-tetraglycidyldiaminophenylmethane such as Araldit® MY 720, Araldit® MY 721.

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.

β-diketones and β-ketoesters

Useful 1,3-dicarbonyl compounds are linear or cyclic dicarbonyl compounds. R'iCO of formula CHR ₂ are preferably dicarbonyl - COR ^{^} used ₃ wherein R'i Ci-C ₂₂ alkyl, C ₅ -C ₁₀ hydroxyalkyl, C ₂ -C ₁₈ alkenyl, phenyl, substituted by OH, C ₁ -C ₄ -alkyl, Ci-C ₄ -alkoxy or halogen substituted phenyl, C ₇ -C ₁₀ - phenylalkyl, C ₅ -C ₁₂ -Zykloalkyl, by Ci-C4-alkyl-substituted Cs-Ci ₂ -Zykloalkyl or a group -RYS -R ^Λ ₆ or -RYO-R ^Λ ₆ ; R ^Λ ₂ is hydrogen, C ₁ -C ₈ -alkyl, C ₂ -C ₂ - alkenyl, phenyl, C ₇ -C ₁₂ alkylphenyl, C ₇ -Cio-phenylalkyl or a group -CO-R _"4; R ₃ has one of the meanings given for R ^{^} ₁ or Ci-cis-alkoxy, R _'4 Ci-C ₄ alkyl or phenyl; R ₅ is Ci-Cio-alkylene and K ₆ Ci-Ci ₂ -alkyl, phenyl, C ₇ -C ₈ -alkylphenyl or C ₇ -C 10 -phenylalkyl.

These include the hydroxyl-containing diketones PS-EP 0 346 279 A1 and the oxa- and thiadiketones in PS-EP 0 307 358 A1 as well as the isocyanuric acid-based ketoesters in PS 4,339,383.

R'i and as alkyl may in particular be C ₁ -C ₁₈ -alkyl, for. For example, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl or octadecyl.

R 'i and R " ₃ as hydroxyalkyl are in particular a group - (CH ₂ ) _n -OH, where n is 5, 6 or 7. R'i and R "2 as alkenyl may be, for example, vinyl, allyl, methallyl, 1-butenyl, 1-hexenyl or oleyl, preferably allyl.

R'i and R " ₃ as phenyl substituted by OH, alkyl, alkoxy or halogen can be, for example, tolyl, xylyl, tert-butylphenyl, methoxyphenyl, ethoxyphenyl, hydroxyphenyl, chlorophenyl or dichlorophenyl.

R'i and R "3 as phenylalkyl are in particular benzyl, R" 2 and R "3 as cycloalkyl or alkylcycloalkyl are in particular cyclohexyl or methylcyclohexyl.

R "2 as alkyl may in particular be C 1 -C 4 -alkyl, and R" 2 as C 2 -C 12 -alkenyl may in particular be allyl. R "2 as alkylphenyl may in particular be tolyl. R" 2 as phenylalkyl may in particular be benzyl. Preferably, R 1 is hydrogen. R 3 as the alkoxy may be e.g. Methoxy, ethoxy, butoxy, hexyloxy, octyloxy, dodezyloxy, tridezyloxy, tetradezyloxy or octadezyloxy. R as Ci-Cio-alkylene is in particular C2-C4-alkylene. R "6 as alkyl is in particular C 4 -C 12 -alkyl, for example butyl, hexyl, octyl, decyl or dodezyl.

R e as alkylphenyl is in particular tolyl. R e as phenylalkyl is in particular benzyl.

Examples of 1,3-dicarbonyl compounds of the above general formula and their alkali, alkaline earth and zinc chelates are acetylacetone, butanoylacetone, heptanoylacetone, stearoylacetone, palmitoylacetone, lauroylacetone, 7-tert-nonylthioheptanedione-2,4, benzoylacetone, dibenzoylmethane, Lauroylbenzoylmethane, palmitoylbenzoylmethane, stearoylbenzoylmethane, isooctylbenzoylmethane, 5-

Hydroxycapronylbenzoylmethane, tribenzoylmethane, bis (4-methylbenzoyl) methane, benzoyl-p-chlorobenzoylmethane, bis (2-hydroxybenzoyl) methane, 4-methoxybenzoylbenzoylmethane, bis (4-methoxybenzoyl) methane, 1-benzoyl-1-acetylnonane, benzoyl-acetylphenylmethane, Stearoyl-4-methoxybenzoylmethane, bis (4-tert-butyl) butylbenzoyl) methane, benzoylformylmethane, benzoylphenylacetylmethane, biscyclohexanoylmethane, di-pivaloylmethane, 2-acetyl-cyclopentanone, 2-benzoylcyclopentanone, diacetylacetic acid, methyl, ethyl and allyl esters, benzoyl, propionyl methyl and ethyl butyrylacetate, triazetylmethane, methyl, ethyl, hexyl, octyl, dodecyl or octadecyl, benzoylacetic, methyl, ethyl, butyl, -2- ethylhexyl, dodecyl or octadecyl esters, as well as propionyl and butyrylacetic acid C 1 -C 6 -alkyl esters. Stearoylessigsäureethyl-, propyl, -butyl-, -hexyl- or -oktylester and polynuclear ß-ketoester as described in PS - EP-A-0 433 230 and Dehydrazetsäure and their zinc, magnesium or alkali metal salts. Preference is given to Ca, Mg and Zn salts of acetylacetone and of dehydrazetic acid.

Particular preference is given to 1,3-diketo compounds of the above formula in which K is C ₁ -C ₁₈ -alkyl, phenyl, phenyl which is substituted by OH, methyl or methoxy, C ₁ -C 10 -phenylalkyl or cyclohexyl, R _{2 is} hydrogen and R 3 has one of the meanings given for R \. Also included are heterocyclic 2,4-diones such as N-phenyl-3-acetylpyrrolidine-2,4-dione. Further representatives of this category are described in PS EP 0,734,414 A1. The 1,3-diketo compounds may be used in an amount of, for example, 0.01 to 10, preferably 0.01 to 3 and especially 0.01 to 2 parts by weight, based on 100 parts by weight of PVC.

Polyols and sugar alcohols

Examples of compounds of this type are: pentaerythritol, dipentaerythritol, tripentaerythritol, trimethylolethane, bistrimethylolpropane, inositol, polyvinyl alcohol, bistrimethylolethane, trimethylolpropane, sorbitol, maltitol, isomaltitol, lycasin, mannitol, lactose, leucrose, tris (hydroxyethyl) isocyanurate, palatinit, Tetramethylcyclohexanol, tetramethylolcyclopentanol, tetramethylolpyranol, glycerin, diglycerin, polyglycerol, thiodiglycerine or 1-O-o-C-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 in an amount of, for example, 0.01 to 20, suitably from 0.1 to 20 and in particular from 0.1 to 10 parts by weight, based on 100 parts by weight of PVC applied. Preference is given to tris (hydroxyethyl) isocyanurate.

Sterically hindered amines (HALS) and heterocyclic amino alcohols The sterically hindered amines are generally compounds containing the group

A V

/

N

wherein A and V independently of one another are C ₈ alkyl, C _3-8 alkenyl, C _5-8 -Zykloalkyl-, or C7-9 phenylalkyl or, together optionally replaced by O, NH or CH ₃ -N interrupted Form C2-5 -alkylene, or a cyclic sterically hindered amine, in particular a compound from the series of alkyl or polyalkylpiperidines, especially the tetramethylpiperidines containing the group

Examples of such polyalkylpiperidine compounds are the following (in the case of the oligomeric or polymeric compounds, n and r are in the range from 2 to 200, preferably in the range from 2 to 10, in particular from 3 to 7). An extensive list of such compounds can be found in EP 0 796 888 B1. In a particularly preferred embodiment of the present invention, heterocyclic compounds are used as the amino alcohols. Examples of these are: EO, PO and BO reaction products of ethylene and propylene ureas, parabanic acid, hydantoins, barbituric acids, glycolurils and isocyanuric acids. Particularly preferred in the context of the present invention is the use of tris (hydroxyethyl) isocyanate (THEIC) or tris (hydroxypropyl) isocyanate as a constituent of the stabilizer system according to the invention.

The content of a stabilizer system of the invention to THEIC, for example, about 0.01 to about 10 wt .-%.

Hydrotalcites, zeolites, alkali metal aluminosilicates and dawsonites

Also suitable as additives in the stabilizer systems according to the invention are hydrotalcites, zeolites and alkali metal alkoxides (Dawsonite).

The hydrotalcites may be based on Al / Mg / carbonate, Al / Mg / Ti / carbonate, Li / Mg / carbonate or Li / Al / Mg / carbonate, compounds of the hydrotalcite series may be represented by the following general formula:

M ²⁺ _{L x} M ₃ ⁺ _X (OH) ₂ (A ⁿ ) _{x / b *} d H ₂ O, where

M ²⁺ = cation of one or more metals of the group Mg, Ca, Sr,

Zn or Sn, M ³⁺ = an Al or B cation, A ^{n represents} an anion of valence n, b = n is a number of 1-2, 0 <x <0.5, d is one Number is 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 Al ₂ O ₃ 6MgO * * CO * 12 H ₂ O, Mg4, _{5 Al2} (OH) i3 * CO ₃ * 3.5 H 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 * 8-9 H ₂ O and ZnO * 3MgO * Al ₂ O ₃ * CO ₂ * 5-6 H ₂ O

Very particular preference is given to using dehydrated hydrotalcites.

Zeolites can be described by the formula M _x / _n [(A10 ₂ ) _x (Si0 ₂ ) _y ] * w H 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

NaI ₂ Al ₂ SiI ₂ O ₄₈ * 27 H ₂ O [zeolite A], Na ₆ Al ₆ Si ₆ O ₂₄ * 2 NaX * 7.5 H ₂ O, X = OH, halogen, ClO ₄ [sodalite]; Na ₆ Al ₆ Si ₃₀ O _{72 *} 24 H ₂ O; Na ₈ Al ₈ Si ₄₀ O _{96 *} 24 H ₂ O; NaI ₆ Ali ₆ Si ₂₄ O ₈₀ * 16 H ₂ O; NaI ₆ Ali ₆ Si ₃₂ O ₉₆ * 16 H ₂ O; Na ₅₆ Al ₅₆ SiI ₃₆ O ₃₈₄ * 250 H ₂ O [zeolite Y], Na ₈₆ Al ₈₆ SiI ₀₆ O ₃₈₄ * 264 H ₂ O [zeolite X]; Na ₂ O, Al ₂ O ₃ , (2-5) SiO ₂ , (3,5-1O) 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 exchange of the Na atoms by Li, K, Mg, Ca, Sr or Zn atoms, such as (Na, K) i ₀ Ali ₀ Si ₂₂ O ₆₄ * 20 H ₂ O; Ca ₄ , ₅ Na ₃ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] * 30 H ₂ O; K ₉ Na ₃ [(AlO ₂ ) I ₂ (SiO ₂ ) i ₂ ] * 27 H ₂ O. Very particular preference is given to Na zeolite A and Na zeolite MAP (see also PS - 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 described in PS - US 6,096,820.

Dawsonite are by the general formula

M [Al (OH) ₂ CO ₃ ] (M = Na, K)

described. The preparation of Na-Dawsonite (DASC or SAC) and K-Dawsonite (DAPC) is published in PS-US 3.501.264 and US 4.221.771 as well as in PS-EP 0394.670 A1. The synthesis can be carried out hydrothermally or non-hydrothermally. The products may be crystalline or amorphous. Also included in the substance class are sodium magnesium alumino carbonates (SMAC); their preparation is described in PS - US 455.055.284.

The hydrotalcites, zeolites and alkali metal alkoxides which are suitable as additives may be present in a stabilizer system according to the invention in an amount of up to about 50% by weight, for example up to about 30% by weight.

These additives may be used in amounts of, for example, 0.1 to 20, suitably 0.1 to 10 and especially 0.1 to 5 parts by weight, based on 100 parts by weight of halogen-containing polymer.

Phosphorous acid ester (phosphites)

Examples of these are trioctyl, tridecyl, tridodezyl, tritridezyl, tripentadezyl, trioleyl, tristearyl, triphenyl, trilauryl, tricresyl, tris-nonylphenyl, tris-2,4-t-butylphenyl or Trizyklohexylphosphit. Further suitable phosphites are differently mixed aryl-dialkyl- or alkyl-diaryl phosphites, such as phenyldioctyl, phenyldidezyl, phenyldidodezyl, phenylditridezyl, phenylditetradezyl, phenyldipentadezyl, octyldiphenyl, decyldi-phenyl, undecyldiphenyl, dodecyldiphenyl, tridecyldiphenyl , Tetradecyldiphenyl, pentadezyldiphenyl, oleyldiphenyl, stearyldiphenyl and dodecylbis-2,4-di-t-butyl-phenylphosphite. Furthermore, it is also possible to use phosphites of various diols or polyols, for example tetraphenyldipropylene glycol diphosphite, poly (dipropylene glycol) phenyl phosphite, tetraisodicyl dipropylene glycol diphosphite, tris-dipropylene glycol 1-phosphite, tetramethyloxyclohexanol-decyldiphosphite, tetramethyloxycyclohexanol-butoxy-ethoxy ethyldiphosphite, tetramethyloxyclohexanol nonylphenyl diphosphite, bis-nonylphenyl-di-trimethylolpropane diphosphite, bis-2-butoxyethyldimethylolpropane diphosphite, trishydroxyethylisocyanurate hexadecyltriphosphite, didecylpentaerythritol diphosphite, distearylpentaerythritol diphosphite, bis-2,4-di-t-butylphenylpentaerythritol diphosphite , and mixtures of these phosphites and aryl / alkyl phosphite mixtures of statistical composition (H19C9- C ₆ H ₄₎ Oi ₁₅ P (OCi ₂₁ I ₃ H _(25127) I ₁ S or (C _{8 Hi7-C6} H4 -O-) 2 P (i-C8Hi7O), (Hi9C9- _C6 H4) Oi, 5P OC9, iiHi9,23) i; 5. Technical examples are Naugard P, Mark CH300, Mark CH301, Mark CH302 and Mark CH55 (manufacturer Crompton Corp. USA). The organic phosphites may be used in an amount of, for example, 0.01 to 10, preferably 0.05 to 5, and especially 0.1 to 3, parts by weight, based on 100 parts by weight of PVC.

A stabilizer system according to the invention may contain the described phosphite compounds in an amount of up to about 30% by weight, in particular up to about 10% by weight.

antioxidants

These include sterically hindered phenols, such as alkylated monophenols, e.g. For example, 2,6-di-tert-butyl-4-methylphenol, alkylthiomethylphenols, eg, 2,4-dioctylthiomethyl-6-tert-butylphenol, alkylated hydroquinones, e.g. As 2,6-di-tert-butyl-4-methoxyphenol, hydroxylated thiodiphenyl ethers, eg. B. 2,2'-thio-bis (6-tert-butyl-4-methylphenol), alkylidene-bisphenol Ie, z .B. 2,2'-methylene-bis- (6-tert-butyl-4-methylpheno-1), benzyl compounds, eg 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, hydroxybenzylated malonates, eg dioctadezyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, hydroxybenzyl-aromatics, eg 1,3,5-tris (3,5-) di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, triazine compounds, eg 2,4-bis-octyl-mercapto-6- (3,5-di-tert-butyl-4-hydroxyanilino) -l , 3,5-triazine, phosphonates and phosphonites, for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, azylaminophenols, for example 4-hydroxylauric anilide, esters of beta- (3,5-di-tert-butyl) 4-hydroxyphenyl) propionic acid, beta- (5-tert-butyl-4-hydroxy-3-methylphenyl) -propionic acid, beta- (3,5-dicyclohexyl-4-hydroxyphenyl) -propionic acid, esters of 3 , 5-di-tert-butyl-4-hydroxyphenylacetic acid with monohydric or polyhydric alcohols, amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid, eg. N, N'-bis (3, 5 -di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine, vitamin E (tocopherol) and derivatives, and D, L-ascorbic acid. The antioxidants may be used in an amount of, for example, 0.01 to 10 parts by weight, preferably 0.1 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of PVC become. UV absorber and light stabilizer

Examples are 2- (2'-hydroxyphenyl) -benzotriazoles, e.g. 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2-hydroxybenzophenones, esters of optionally substituted benzoic acids, e.g. 4-tert-butylphenyl salicylate, phenyl salicylate, acrylates, nickel compounds, oxalic acid diamides, e.g. 4,4'-di-octyloxy-oxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyl-oxanilide, 2- (2-hydroxyphenyl) -l, 3,5-triazine, e.g. 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethyl) phenyl) -l, 3,5-triazine, sterically hindered amines based on tetramethylpiperidine or tetramethylpiperazinone or tetramethylmorpholinone, eg Bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (2,2,6,6-tetramethylpiperidin-4-yl) succinate and benzoxazinones such as 1,4-bis benzoxazinonyl-benzene.

Examples of these are bis-benzene (1,4) -oxazoles, phenylcoumarins and bis-styrylbiphenyls such as 4-methyl-7-diethylaminocoumarin, 3-phenyl-7- (4-methyl-6-butoxybenzoxazo-1) -coumarin , 4,4'-Bis (benzoxazol-2-yl) stilbene and 1,4-bis (-benzoxazol-2-yl) -naphthalene. Preference is given to solutions of optical brighteners in a plasticizer, for example DOP.

pigments

Also suitable as part of the stabilizer system according to the invention are pigments. Suitable substances are known to the person skilled in the art. Examples of inorganic pigments are TiO ₂ , zirconia-based pigments, BaSO ₄ , zinc oxide (zinc white) and lithopone (zinc sulfide / barium sulfate), carbon black, carbon black-titanium dioxide mixtures, iron oxide pigments, Sb ₂ O ₃ , (Ti, Ba, Sb) O ₂ , Cr ₂ O ₃ , spinels such as cobalt blue and cobalt green, Cd (S ₅ Se), ultramarine blue. Organic pigments include azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, diketopyrrolopyrrole pigments and anthraquinone pigments. Preferably, TiO _{2 is} also in micronized form. A definition and other descriptions can be found in the Handbook of PVC Formulating, EJWickson, John Wiley & Sons, New York, 1993. propellant

Propellants are e.g. organic azo and hydrazo compounds, tetrazoles, oxazines, isatric anhydride, N-methylisatinic anhydride, as well as soda and sodium bicarbonate. Preference is given to azodicarbonamide and sodium bicarbonate and mixtures thereof. Very particular preference is given to isatric anhydride or N-methylisatinic anhydride, especially in soft PVC or semi-hard PVC.

Antistatic antistatic agents are classified into nonionic (a), anionic (b), cationic (c) and amphoteric (d) classes. To (a) include fatty acid ethoxylates, fatty acid esters, ethoxylated fatty alkylamines, fatty acid diethanolamides and ethoxylated phenols and alcohols, and polyglycol monofatty acid esters. To (b) include alkali fatty bisulfonates and phosphoric acid bis-fatty alcohol ester alkali salts. To (c) include quaternary fatty alkyl ammonium salts and to (d) include fatty alkyl betaines and fatty alkyl imidazoline betaines. Individual preferred compounds are lauric diethanolamide, myristyl diethanolamine, Na octadecyl sulfonate and Na bis-octadecyl phosphate.

Lubricant A stabilizer system of the invention may further contain lubricants.

Suitable lubricants are, for example: montan waxes, fatty acid esters, PE and PP waxes, amide waxes, chloroparaffins, glycerol esters or alkaline earth metal soaps, furthermore fatty ketones, and combinations thereof, as listed in PS EP 0259.783 A1.

A stabilizer system according to the invention may contain the lubricants described in an amount of up to about 70% by weight, in particular up to about 40% by weight.

softener Also useful as additives for the stabilizer system of the present invention are organic plasticizers. Suitable organic plasticizers are, for example, those from the following groups:

(i) phthalic acid esters, such as preferably di-2-ethylhexyl, di-isononyl and diisodecyl phthalate, which are also known under the common abbreviations DOP (dioctyl phthalate, di-2-ethylhexyl phthalate), DINP (diisononyl phthalate ), DIDP (diisodiacyl phthalate) are known

(ii) esters of aliphatic dicarboxylic acids, in particular esters of adipic, azelaic and sebacic acid, preferably di-2-ethylhexyl adipate and diisoctyl adipate (iii) trimellitic acid esters, for example tri-2-ethylhexyl trimellitate, triisodecyltrimellitate ( mixture), tri-iso-tridezyltrimellitat, tri-iso-oktyltrimellitat (mixture) and tri-Ce-Cg-alkyl, tri-alkyl C ₆ -C _0, tri-C ₇ -C ₉ alkyl and Tn C ₉ -Ci i -alkyl trimellitates; common abbreviations are TOTM (trioctyl trimellitate, tri-2-ethylhexyl trimellitate), TIDTM (tri-benzyl trimellitate), and TITDTM (tri-isotride-cyl trimellitate) (iv) epoxy plasticizer; in the main, the epoxidized unsaturated fatty acids are, for example, epoxidized soybean oil

(v) polymer plasticizer: The most common starting materials for their preparation 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, (s. AdmEx ^® grades of Velsicol Corp. and PX-811 of Asahi Denka)

(vi) Phosphoric acid esters: A definition of these esters can be found in the above-mentioned "TASCHENBUCH der Kunststoffadditive" chapter 5.9.5, SS. 408 - 412. Examples of such phosphoric acid esters are tributyl phosphate, tri-2-ethylbutyl phosphate, tri-2-ethylhexyl phosphate, trichloroethyl phosphate, 2-ethyl-hexyl-di-phenyl phosphate, cresyl diphenyl phosphate, resorcin-bis-diphenyl phosphate, triphenyl phosphate, tricresyl phosphate and trixylenyl phosphate; preferred are tri-2-ethylhexyl phosphate and Reofos ^® 50 and 95 (Ciba Specialty Chemicals)

(vii) chlorinated hydrocarbons (paraffins) (viii) hydrocarbons (ix) monoesters, eg butyl oleate, phenoxyethyl oleate, tetrahydrofurfuryl oleate and alkyl sulfonic acid esters

(x) glycol esters, e.g. Diglykolbenzoate

(xi) citric acid ester, e.g. Tributyl citrate and acetyltributyl citrate as described in PS - WO 02/05206

(xii) perhydrophthalic, isophthalic and terephthalic esters, and perhydroglycol and diglycol zoate esters; DE 197.56.913 Al, DE 199.27.977 Al, DE 199.27.978 Al and DE 199.27.979 Al described - is preferably perhydro-diisononyl phthalate (DINCH ^® Hexamoll - manufactured by BASF) as in PS.

(xiii) castor oil-based plasticizer (Soft-N-Safe ^®, manufacturer. DANISCO)

(xiv) terpolymers ketone ethylene ester Elvaloy ^® KEE, (Elvaloy ^® 741, Elvaloy ^® 742, manufacturer Messrs. Du Pont)

A definition of these plasticizers and examples of such are in "TASCHENBUCH der Kunststoffadditive", R. Gächter / H. Müller, Carl Hanser Verlag, 3rd ed., 1989, chapter 5.9.6, pages 412-415, as well as in "PVC Technology", WV Titow, 4 ^th . Ed., Elsevier Publ, 1984, pp. 165-170. It can also be used mixtures of different plasticizers. The plasticizers may contain in an amount of, for example, up to about 99.5% by weight, more preferably up to about 30% by weight, up to about 20% by weight or up to about 10% by weight. In a preferred embodiment of the present invention, the lower limit for the described plasticizers as part of the inventive stabilizer systems is about 0.1 wt .-% or more, for example about 0.5 wt .-%, 1 wt .-%, 2 wt. -% or 5 wt .-%.

Definitions and examples of other additives such as impact modifiers and processing aids, gelling agents, biocides, metal deactivators, flame retardants, antifogging agents and compatibilizers are described in "Handbook of the Kunststoffadditive ", R. Gächter / H. Mueller, Carl Hanser publishing house, 3. Aufl., 1989, as well as 4. Aufl. 2001 and in the" Hand book of Polyvinyl Chloride Formulating "EJ Wickson, J. Wiley & Sons, 1993, as well as in "Plastics Additives" G. Pritchard, Chapman & Hall, London, Is Ed., 1998. Impact modifiers are also described in detail in "Impact Modifiers for PVC," JT Lutz / DL Dunkelberger, John Wiley & Sons, 1992.

Another object of the present invention is a composition comprising a halogen-containing polymer and a stabilizer system according to the invention.

Preferably, the amount of the stabilizer system according to the invention based on the halogen-containing polymer is 0.1 to 20 wt .-%.

The halogen-containing polymer is preferably a chlorine-containing polymer, such as polyvinyl chloride (PVC). Further preferably, the halogen-containing polymer is a hard, soft or paste PVC. Also preferably, the halogen-containing polymer is a recycled polymer.

Another object of the present invention is the use of the stabilizer system according to the invention for stabilizing a halogen-containing, in particular chlorine-containing, polymer.

Examples of the chlorine-containing polymers to be stabilized are polymers of vinyl chloride, vinylidene chloride, vinyl resins containing vinyl chloride units, 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 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 polymeric esters of acrylic acid and α-substituted acrylic acid; Polymers of chlorinated styrenes, for example dichlorostyrene; Chlorinated rubbers; chlorinated polymers of ethylene; Polymers and post-chlorinated polymers of chlorobutadiene and their copolymers with vinyl chloride, chlorinated natural and synthetic rubbers, and mixtures of said polymers with each other or with other polymerizable compounds. In the context of this invention, PVC also means copolymers of vinyl chloride with polymerizable compounds such as acrylonitrile, vinyl acetate or ABS, which may be suspension, bulk or emulsion polymers.

Preference is given to a PVC homopolymer, also in combination with polyacrylates or polymethacrylates.

Also suitable are graft polymers of PVC with EVA, ABS and MBS, as well as graft polymers of PVC with PMMA. 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 and polylactones, in particular from the group ABS, NBR, NAR, SAN and EVA. The related abbreviations for the copolymers are familiar to the person skilled in the art and mean the following: ABS acrylonitrile-butadiene-styrene; SAN styrene-acrylonitrile; NBR acrylonitrile-butadiene; NAR acrylonitrile acrylate; EVA ethylene vinyl acetate. In particular, acrylate-based styrene-acrylonitrile copolymers (ASA) are also suitable. Preferred as a component in this context are polymer compositions containing as components (i) and (ii) a mixture of 25-75 wt .-% PVC and 75-25 wt .-% of said copolymers. From Of particular importance as a component are compositions of (i) 100 parts by weight of PVC and (ii) 0-300 parts by weight of ABS and / or SAN-modified ABS and 0-80 parts by weight of the copolymers NBR, NAR and / or EVA, but especially EVA.

Also suitable for stabilization in the context of this invention are, in particular, recyclates of chlorine-containing polymers, which are the above-described polymers which have suffered damage as a result of processing, use or storage. Particularly preferred is PVC recyclate. Another use of the stabilizer system according to the invention is that antistatic properties can be imparted to the finished article made of hard or soft PVC. In this way it is possible to reduce the use of expensive antistatic agents. Preferred for this application is soft PVC or semi-rigid PVC.

Furthermore, the present invention relates to articles containing a composition of the invention. These are preferably commodities. Examples of these are wood composite plastics (WPC Wood Plastic Composites), foils, profiles, floor coverings, automotive parts, wall-mounted wallpaper, hoses, injection molded parts or wire sheathing.

Furthermore, the present invention relates to the use of a composition according to the invention for producing an article according to the invention.

Another object of the invention are utility (utensils), which in particular contain PVC and stabilizer systems according to the invention.

Preference is also the use of consumer goods, which are characterized by a special fine foam structure. This applies to hard, soft and semi-hard PVC. This aspect is particularly important for wallpapers and floors made of soft PVC. Normally, heavy metal compounds such as Zn or Sn stabilizers are required as kickers to obtain a fine foam. Surprisingly, it has been found that TEA metal inner complexes exert a kicker effect on isatinic acid or N-methylisatic anhydride, which ensures the achievement of a fine foam structure.

The compositions according to the invention are particularly suitable, in the form of hard formulations, for hollow bodies (bottles), packaging films (thermoforming films), blown films, "crash pad" films (automobiles), pipes, foams, heavy profiles (window frames), Lichtwandpro file, Baupro foils, blister packs (also produced by the Luvitherm method), profiles, sidings, fittings, office films, margarine mugs, praline packaging and apparatus housings, insulators, computer housings and components of household appliances as well as for electronic applications, in particular in the semiconductor field, which are particularly suitable for the production of window profiles with high whiteness and surface gloss.

Preferred other compositions in the form of semi-hard and soft formulations are for wire sheathing, cable insulation, decorative films, roofing foils, foams, agricultural films, hoses, sealing profiles, flooring, wallpaper, automotive parts, soft films, injection molded parts (blow molding), office films and Foils suitable for inflatable halls. Examples of the use of the compositions according to the invention as plastisols are toys (rotational molding), artificial leather, flooring, textile coatings, wallpaper, coil coatings and underbody protection for motor vehicles. Examples of sintered PVC applications of the compositions according to the invention are slush, slush mold and coil coatings and in E-PVC for films produced by the Luvithermverfahren. For further information, see "Kunststoffhandbuch PVC", Volume 2/2, W. Becker / H. Braun, 2nd ed., 1985, Carl Hanser Verlag, pp. 1236-1277. Application Testing: Examples 1 to 13

The composition of the formulations is shown in Table 1 below (all data in phr):

Table 1: Formulation compositions (Example 1 - 13)

1) = Vinnolit S 3268; 2) = Vinnolit K 707; 3) Kronos 2220; 4) HYDROCARB 95T, OMYA; 5) Stabilizer 704P (one-pack Fa. IKA-Wolfen) 6) Paraloid K120N ER, Fa. Rohm & Haas 7) NaClO ₄ dissolved in 0.5 ml BDG (same molar with TEAP); 8) Coordination polymer Catena μ 2,2 ', 2 "nitrilotrisethanol perchlorato sodium inner complex (same molar with NaClO ₄ ) Production of rolled skins:

100 g of the dry mixtures prepared according to Tab. 1 are applied to a Collin laboratory measuring mill (Model: W100E, BJ: 2005, COLLIN, D-85560 Ebersberg) in each case 5 minutes (roll diameter: 110 mm, 10 rpm, friction: -10%) at 200 ⁰ C plasticized. The resulting films (thickness 0.3 mm) are fed to further measurements.

Performance of dehydrochlorination measurements (DHC):

The DHC is a measure of the HCl elimination of PVC, which takes place under thermal stress. The split-off hydrochloric acid is charged with nitrogen gas into a receiver with dist. Rinsed water and there measured the increase in conductivity in microsiemens per centimeter (μS / cm). The corresponding minute values [Min] are used as key figures. The longer the time interval to reach a certain conductivity, the more thermostable is the PVC sample. Device type: PVC Thermomat 763 (Metrohm)

The measurements are carried out according to DN 53381 Part 1, Method B: Conductivity measurement.

Parameter: Sample weight: 500 ± 0,5mg

Temperature: 200 ^° C

Flow: 7 l / h (nitrogen 5.0)

Absorption volume: 60ml (dem. Water)

Evaluation: t ₁₀ , tso and t ₂ oo (conductivity of 10, 50

and 200 μS / cm - in minutes)

The following values were obtained (see Table 2) Table 2: DHC values

Review of the results of Examples 1-13 shows the following:

1. Addition of TEAP with constant concentration of the lead stabilizer shows a significant improvement in the values (2 vs. 1)

2. TEAP addition to the lead stabilizer at reduced dosage shows a similar improvement to that of 1 (3 vs 2 and 1).

3. TEAP addition to the lead stabilizer at a greatly reduced dosage shows comparable or slightly improved values (10 vs. 1).

4. Molecular addition of TEAP or NaP gives a clear improvement in the values at transition to TEAP (5 vs. 7, 6 vs. 8, 10 vs. 12 and 11 vs. 13). 5. Equivalent addition of TEAP or NaP shows comparable or still improved values (6 vs. 7 and 11 vs. 12).

From 4 and 5 there is a technical superiority of TEAP in comparison to NaP and thus a technical advance

Performing the static heat test (SHT) - s. Table 3:

From the rolled skins prepared according to Examples 1 to 3, square test pieces (15 mm × 15 mm) are cut out. These are loaded in a Heraeus oven at 200 ⁰ C 70Minuten to significant discoloration. Subsequently, the YI value (yellowness index) is determined according to DIN 53381 and compared with the YI value of the unloaded rolled skin (zero minute value). The results are summarized in Tab. 3 and FIG.

Accordingly, Figure 1 shows the yellowness index (YI) as a function of time (t) in minutes, with the graph at 70 min. the upper measuring point of the curve for example 1, the mean measuring point of the curve for example 3 and the lower measuring point of the curve for example 2 are to be assigned.

The higher the YI value, the yellower (darker) the sample. The lower the YI value, the brighter the sample and the better the result.

Table 3: SHT (YI values)

Results can be interpreted as follows:

1. Low addition levels of TEAP result in an improvement, especially in long-term stability - LZ (2 vs. 1)

2. TEAP addition to equal amounts of lead stabilizer give an improvement in LZ (3 vs. 1).

3. The increase in the LC indicates both 2 and 3. This means that chain crosslinking of the degrading polymer (PVC) takes place to a lesser extent on TEAP addition.

Claims

claims 1. stabilizer system for halogen-containing polymers containing at least one inner complex selected from the group consisting of coordination-polymer catena-μ-2,2 ', 2 "-nitrilotrisethanol-perchlorato-metalloid In-complex and coordination polymer catena μ-2,2 ', 2 "-nitrilotrisethanol trifluoromethanesulfonato metal-inner complex; at least one heavy metal-containing stabilizer, which differs from the at least one inner complex and a lead-containing or a Organotin stabilizer is. 2. Stabilizer system according to claim 1, characterized in that the at least one heavy metal-containing stabilizer is a lead-containing stabilizer. 3. Stabilizer system according to claim 2, characterized in that the at least one lead-containing stabilizer is neutral or basic lead stearate, lead white, 3- or 4-basic lead sulfate, 2-basic lead phosphite, 2-basic lead phthalate or 4-basic lead fumarate. 4. stabilizer system according to one of claims 1 to 3, characterized in that it further contains at least one calcium-zinc or barium-zinc stabilizer or a fatty calcium carbonate. 5. Stabilizer system according to one of claims 1 to 4, characterized in that the at least one inner complex is a coordination Catena-μ-2,2 ', 2 "- nitrilotrisethanol perchlorato-metal inner complex. 6. stabilizer system according to one of claims 1 to 5, characterized in that the metal of the inner complex is sodium. 7. stabilizer system according to one of claims 1 to 6, characterized in that the proportion of at least one inner complex is 0.001 - 1.0% by weight based on the total amount of the stabilizer system. 8. stabilizer system according to one of claims 1 to 7, characterized in that additionally at least one additive selected from the group consisting of inorganic and organic bases, epoxides and glycidyl compounds, ß- Diketones and β-ketoesters, polyols and sugar alcohols, hindered amines (HALS) and heterocyclic amino alcohols, hydrotalcites, zeolites and dawsonites, phosphorous esters (phosphites), antioxidants, UV absorbers and light stabilizers, optical brighteners, pigments, propellants, antistatic agents, lubricants and Plasticizer is included. A composition containing a halogen-containing polymer and a stabilizer system according to any one of claims 1 to 8. 10. The composition according to claim 9, characterized in that the halogen-containing polymer is a chlorine-containing polymer, in particular PVC. 11. The composition according to claim 10, characterized in that the halogen-containing polymer is rigid PVC, plasticized PVC or paste PVC. 12. The composition according to any one of claims 9 to 11, characterized in that the halogen-containing polymer is a recycled polymer. 13. An article comprising a composition according to any one of claims 9 to 12. 14. An article according to claim 13, characterized in that this is a wood-plastic composite material (WPC = Wood Plastic Composite), a film, a profile, floor covering, a motor vehicle part, a wall wallpaper, a hose, an injection molded part or a wire sheath is. 15. Use of a stabilizer system according to any one of claims 1 to 8 for stabilizing a halogen-containing polymer. 16. Use of a composition according to any one of claims 9 to 12 for the manufacture of an article according to claim 13 or 14.