DE10356670A1 - Polymer stabilizer comprises an amine, a glycidyl derivative, acrylate ester, a carbonyl compound, beta-keto ester, cyclic anhydride, lactone or carbonate ester and a perchlorate, perfluoroalkane sulfonate or sulfate ester salt - Google Patents

Abstract

Stabilizer system for polymers comprises an amine component A which is a monoamine (A-1) or diamine (A-2), a component B which is a glycidyl derivative (B-1), an acrylate ester (B-2), a carbonyl compound (B-3), a beta -keto ester (B-4), a cyclic anhydride or lactone (B-5) or a carbonate ester (B-6), and a component C which is a perchlorate (C-1), a perfluoroalkane sulfonate (C-2) or a sulfate ester salt (C-1). Stabilizer system for polymers comprises: (A) an amine that is a monoamine of formula (A1), or optionally hydrogenated, optionally substituted azole, azine or azepine with 0-4 oxo or thiono groups and 0-3 additional ring nitrogen atoms or 0-1 ring oxygen or sulfur atoms, optionally fused with 1-2 benzene rings, or a diamine of formula (A2); (B) a glycidyl derivative of formula (B11 to B14), an acrylate ester of formula (B-2), a carbonyl compound of formula (B3), preferably a glutaraldehyde, terephthalaldehyde, glyoxal, acetonylacetone, an acetal or ketal or an aldehyde sulfite or dithionite adduct, a b-keto ester of formula (B4), a cyclic anhydride or lactone (B5), preferably succinic, glutaric, maleic, phthalic, pyromellitic, trimellitic, isatic, N-methylisatic anhydride, itaconic, citraconic or aconitic anhydride, butyrolactone, valerolactone or phthalide, or a carbonate ester (B6) preferably dimethyl, diethyl, dipropyl, dibutyl, ethylene or propylene carbonate; and (C) a perchlorate of formula (C1), a perfluoroalkane sulfonate of formula (C2) or a sulfate ester salt of formula (C3). R1>2NH (A1) (R1>NH)2R2> (A2) (CH2=CR8>-COO)nR6> (B2) R9>2C=O (B3) (R4>COCH2COO)nR6> (B4) (ClO4)nM (C1) (RfSO3)nM' (C2) (ROSO3)nM' (C3) R1>H or a 1-24C radical; R2>a 2-12C diradical; R3>R1> but not acyl; R4>Me or Ph; R3>+R4>a mono- or bicyclic group optionally containing an oxirane group; R5>(CH2)2, (CH2)3, CH=CH, 1,2-phenylene or 1,3-diglycidylurea-1,3-diyl; X : O, S or N-glycidyl; R6>R1>, (CH2)2SR1>, R2>, CH3C(CH2-)3, CH3CH2C(CH2-)3 or C(CH2-)4; n : 1-4; R7>R1>, R2>, benzenetriyl, benzenetetrayl or glycidyloxycarbonyl; R8>H, Me or CH2COOR3>; R9>R3> or R9>+R9> forms a mono-, bi- or tricyclic ring system; R : 1-18C alkyl or 10-18C alkenyl; Rf : 1-6C perfluoroalkyl; M : Li, Na, K, Mg, Ca, Sr, Ba, Ln, Ce, Al, Sn, Zn or a hydrotalcite, hydrocalumite or katoite layer lattice cation; and M' : M or NH4. Independent claims are included for: (1) producing the stabilizer system by homogenizing components A, B and C in a mixer or extruder; (2) stabilized polymer composition comprising a chlorine-containing polymer and the stabilizer system; (3) commodities comprising a stabilized polymer composition as above where the polymer is PVC; (4) commodities comprising a stabilized polymer composition as above where the polymer is foamed hard or soft PVC and the commodities are produced using isatic or N-methylisatic anhydride as blowing agent. [Image].

Description

The The invention relates to a stabilizer system for halogen-containing polymers and a method for stabilizing halogen-containing polymers. The polymer is especially PVC.

halogenated Plastics or molding compositions prepared therefrom are known to decompose Decomposition reactions when exposed to thermal stress or with high-energy radiation, for example ultraviolet light, get in touch.

to Stabilization of e.g. PVC before processing are so far in the practice heavy metal-containing stabilizers based on Cd, Pb, Sn and Zn or toxicologically questionable metals, such as barium, used. In these cases will be harmful anyway Effect - im With regard to improved resorbability and compatibility in the warm-blooded organism - by an overpass in fatty acid-based organic metal compounds, e.g. Laurate, Stearate and oleates, or by transformation into organoderivatives (organometallic compounds or organometallic), in particular tin, additionally increased. specially in the latter case is due to the alkylation of the metal under training one, even under metabolic conditions, hydrolysis-stable metal carbon bond created an enteric system, which capabilities has to overcome the blood-brain barrier to any eventuality develop neurotoxic potential.

These The problem is not limited to the users of finished PVC products, but also their manufacturers, those heavy metal stabilizers incorporate the PVC substrate. Also affected are the producers these stabilizers themselves, the heavy metal-containing precursors into just these stabilizers convict.

In addition to the toxic effect on the warm-blooded organism, these metals and their (organic) compounds or organo compounds have an "ecotoxic effect", ie a harmful effect on fish, crabs and other marine and freshwater organisms, see "List of Priority Hazardous Substances", adopted on the third North Sea Conference (The Hague, 3/1990). This list includes zinc in addition to lead, cadmium, arsenic and mercury. See also in the publication of the Federal Environmental Agency "Measures Sustainable Water Management" (last update April / 2000), in which organic tin compounds, zinc, lead, copper and cadmium are defined as problem areas and measures are prioritized. I S. 1492, last update of 25.04.2002) for heavy metals, namely Pb, Cd, Cr, Cu, Ni, Hg and Zn, maximum amounts can also be inorganic heavy metal salts in the highly bio-toxic neurotoxic In the case of waste incineration, organic stabilizers based on the elements C, H, N, O are converted into CO ₂ , H ₂ O and aminonium compounds, all of which are biocompatible but not degraded, so they are persistent and bioak thus cumulate.

The Substitution of heavy metal-containing stabilizers by organic Links should therefore be an important contribution to achieving this goal be. In the UK and Denmark has been or will be the use of Pb stabilizers in PVC drinking water pipes banned at the end of 2002 or 2003. In Denmark, this ban is in addition to connected to the overlay, instead of Pb, no Sn stabilizers use. Other countries Sweden, Norway or Finland want to follow this ban. A PB ban is EU-wide currently with the responsible authorities in negotiation.

It So there is a need for organic (green) stabilizers that are free of heavy metals (compounds) or other toxicologically harmful substances Metal compounds, in particular completely free of lead, tin and Barium are.

As early as 1940, urea derivatives such as N, N'-diphenylthiourea and monophenylurea for the stabilization of PVC were described (cf: "Plastics Additives Handbook" H. Zweifel, Carl Hanser Verlag, 5th edition 2001, SS 427-483 and "Kunststoff-Handbuch PVC "Vol 2/1, W. Becker / D Brown, Carl Hanser Verlag, 2nd edition, 1985, SS 531-534 and Kirk-Othmer:...". Encyclopedia of Chemical Technology "4 ^th Ed, 1994, Vol 12, Heat Stabilizers, SS 1071-1091), but these additives have only a limited field of use, for example for the stabilization of emulsion PVC (Luvitherm process) .Suspension PVC proves its thermal stabilizer effect, which improves by adding Zn soaps The lack of light stability also limits outdoor use.

Also substituted indoles such as 2-phenylindole are used. But Here, too, the application is limited due to the lack of light stability. In practice, need to improve thermal stability combinations with zinc soaps be used.

Farther come aminocrotonic, in particular bis-esters of 1,4-butanediol and thiodiethylene glycol, for use. Again, in practice, Zn soaps are in addition to use the insert quality to improve. Of disadvantage is however in the finished article and during processing a latent ammonia cleavage.

The WO 02/072 684 A1 describes the combination of the above classes of compounds with perchlorate salts. this leads to although to an improvement of the primary properties (improved Thermostabilisatorwirkung), the insufficient secondary functions, such as poor light stability and ammonia cleavage, but are not eliminated.

WHERE 02/048 249 A2 mentions alkanolamine-perchlorate salt combinations, the have improved light stability, but in terms of technical availability a reduced bandwidth exhibit. This lower bandwidth also complicates the use for tailor made solutions in view of processability of the polymer substrate and the properties of the finished article.

The pamphlets EP 0 736 569 A1 . EP 0 768 336 A2 . DE 197 41 778 A1 , EP 0 967 245 A1 . EP 0 967 209 A1 . EP 0 967 208 B1 . EP 0 930 332 A2 and EP 1 044 968 A1 describe N-heterocyclic compounds such as pyrrolodiazines, 4-aminopyrimidinones, pyrrolouracils and 6-aminouracils. These classes of compounds are typical intermediates for pharmaceuticals and natural product syntheses and therefore relatively expensive. Also, these substances tend due to their high melting points to incompatibility in the polymer, resulting in processing of rigid PVC, especially in the extrusion, in a "plate-out" phenomenon and in soft PVC, especially in storage, in an exudation - (sweating) behavior manifested.

task Therefore, the present invention is substance combinations to disposal which are characterized by good properties in terms of thermal and Photo stabilization of halogen-containing polymers, in particular PVC, minimizing plate-out and sweating behavior especially in rigid PVC. There is still a need To process soft PVC as a plastisol, whereby especially "Crash Pad "(" Slush Mold ") - Techniques be used. Likewise, it is necessary in many cases, the finished article to give antistatic properties and recyclability. In addition, should the new systems are inexpensive, in big Bandwidth in the large-scale scale (bulk chemicals) available be and tailor made solutions allow for applications in the polymer. Another requirement is to develop substance combinations that allow it, in particular PVC during the polymerization, and the subsequent cleaning and drying process to stabilize (so-called pre-stabilization).

• (A) eine NH-Verbindung der Formeln (A-1) oder/und (A-2) R¹ ₂NH (A-1) (R¹NH-)₂R² (A-2)und
• (B) ein Glycidylderivat (B-1), einen Acrylsäureester (B-2), eine Carbonylverbindung (B-3) (CH₂=CR⁸-CO₂-)_nR⁶ (B-2) R⁹ ₂C=O (B-3)einen β-Ketoester (B-4), ein zyklisches Anhydrid bzw. Lacton (B-5) oder/und einen Kohlensäureester (B-6) und
• (C) ein Perchlorat-(C-1), Perfluoralkansulfonat-(C-2) oder/und Sulfatester-Salz (C-3)

wobei die Kurzformeln, Substituenten und Indices folgende Bedeutung haben
R¹ = H oder ein C₁-C₂₄-Radikal, insbesondere C₁-C₂₄-Alkyl oder -Alkanoyl, das zusätzlich durch 1 bis 3 nichtbenachbarte O-Atome unterbrochen sein kann, 2-Hydroxy-C₂-C₂₄-Alkyl oder -Alkanoyl, Trishydroxymethyl-methyl, 1,1-Bishydroxymethyl-C₁-C₄-alkyl, C₃-C₂₀- Alkenyl oder -Alkenoyl, Cyclohexyl, Phenyl oder Benzoyl, 2-Hydroxyphenyl oder 2-Hydroxybenzoyl, C₇-C₁₂-Alkylphenyl oder -benzoyl, C₇-C₁₂-Phenylalkyl oder -alkanoyl und 2-Hydroxy-2-phenylethyl oder Cyanacetylcarbamoyl;
R² = ein C₂-C₁₂-Diradikal insbesondere C₂-C₁₂-Alkylen oder -Alkanoylen, das zusätzlich durch 1 bis 3 nichtbenachbarte O- oder S-Atome unterbrochen sein kann oder Neopentylen, Isophorondiylen, Bis-methylen-phenylen, Phenylen, Cyclohexylen, Bis-methylencyclohexylen, Bisphenylen(A) und Bis-phenylen(F);
(A-1) = außerdem 5- bis 7-ringgliedriger-NH-Heterozyklus (Azol, Azin oder Azepin), der teil- oder perhydriert, bis zu 4 Oxo- oder Thionogruppen tragen und/oder ein- oder mehrfach C- bzw. N- substituiert und/oder zusätzlich bis zu 3 N- oder 1 O- bzw. S-Atom(e) enthalten und weiter 1- bis 2-fach benzanneliert sein kann;
(B-1) = C-Glycidyl-, N-Glycidyl-, (Thio)Ether-Glycidyl- und/oder Ester-Glycidylverbindung der Formeln (B-1/1), (B-1/2), (B-1/3) und (B-1/4)

mit
R³ = R¹ (wobei R¹ = Acyl ausgenommen),
R⁴ = Methyl oder Phenyl oder R³ + R⁴ = Mono- oder Bizyklus, der ferner eine Oxirangruppe enthalten kann und
R⁵ = -(CH₂)₂-, -(CH₂)₃-, -CH=CH-, 1,2-Phenylen oder

X = O, S oder N-Glycidyl,
R⁶ = von n abhängig R¹, (CH₂)₂-SR¹, R², CH₃C(CH₂-)₃, CH₃CH₂C(CH₂-)₃-C(CH₂-)₄,
n = 1 bis 4,
R⁷ = von n abhängig R¹, R², Benzoltriyl, Benzol-tetra-yl oder

R⁸ = H, Methyl oder CH₂CO₂R¹ (wobei R¹ = Acyl ausgenommen)
R⁹ = R³ oder R⁹ ₂ in Formel (B-3) auch Mono-, Bi- oder Tricyklus
(B-3) = außerdem Glutar- oder Terephthalaldehyd, Glyoxal, Acetonylaceton, sowie Acetale oder Ketale bzw. Sulfit- oder Dithionit-Additionsverbindungen von Aldehyden
(B-4) = β-Ketoester der Formel (R⁴COCH₂CO₂)_nR⁶
(B-5) = zyklisches Anhydrid oder Lacton aus der Gruppe Bernsteinsäure-, Glutarsäure-, Maleinsäure-, Phthalsäure-, Pyromellitsäure-, Trimellitsäure-, Isatinsäure- und N-Methylisatinsäureanhydrid, Itacon-, Citracon- und Aconitsäureanhydrid, Butyro- und Valerolacton und Phthalid,
(B-6) = Kohlensäureester aus der Gruppe Dimethyl-, Diethyl-, Dipropyl- und Dibutylcarbonat sowie Ethylen- und Propylencarbonat,
(C-1), (C-2) und (C-3) Salze der Formeln (ClO₄)_nM (C-1) (C_mF_2m+1SO₃)_nM (C-2) (R¹OSO₃)_nM (C-3)mit R¹ = C₁-C₁₈-Alkyl oder C₁₀-C₁₈-Alkenyl, m = 1–6, n abhängig von der Ladung des M-Kations, M = Li, Na, K, Mg, Ca, Sr, Ba, Ln, Ce, Al, Sn, Zn oder ein Schichtgitterkation aus der Gruppe Hydrotalcit-, Hydrocalumit- oder ein Katoitschichtgitterkation und in Kategorie (C-2) und (C-3) auch Ammoniumsalze.These objects are achieved by a stabilizer system for halogen-containing polymers containing at least

• (A) an NH compound of the formulas (A-1) and / or (A-2) R ¹ ₂ NH (A-1) (R ¹ NH-) ₂ R ² (A-2) and
• (B) a glycidyl derivative (B-1), an acrylic acid ester (B-2), a carbonyl compound (B-3) (CH ₂ = CR ⁸ -CO ₂ -) _n R ⁶ (B-2) R ⁹ ₂ C = O (B-3) a β-ketoester (B-4), a cyclic anhydride or lactone (B-5) and / or a carbonic acid ester (B-6) and
• (C) perchlorate (C-1), perfluoroalkanesulfonate (C-2) or / and sulfate ester salt (C-3)

where the short formulas, substituents and indices have the following meaning
R ¹ = H or a C ₁ -C ₂₄ radical, in particular C ₁ -C ₂₄ -alkyl or -alkanoyl, which may additionally be interrupted by 1 to 3 nonadjacent O atoms, 2-hydroxy-C ₂ -C ₂₄ - Alkyl or alkanoyl, trishydroxymethylmethyl, 1,1-bis-hydroxymethyl-C ₁ -C ₄ -alkyl, C ₃ -C ₂₀ -alkenyl or alkenoyl, cyclohexyl, phenyl or benzoyl, 2-hydroxyphenyl or 2-hydroxybenzoyl, C ₇ -C ₁₂ alkylphenyl or benzoyl, C ₇ -C ₁₂ phenylalkyl or alkanoyl and 2-hydroxy-2-phenylethyl or cyanoacetylcarbamoyl;
R ² = a C ₂ -C ₁₂ -diradical, in particular C ₂ -C ₁₂ -alkylene or -alkanoylene, which may additionally be interrupted by 1 to 3 nonadjacent O or S atoms or neopentylene, isophoronediylene, bis-methylene-phenylene, Phenylene, cyclohexylene, bis-methylenecyclohexylene, bisphenylene (A) and bis-phenylene (F);
(A-1) = also 5- to 7-membered ring NH heterocycle (azole, azine or azepine), the partial or perhydrogenated, carry up to 4 oxo or thiono groups and / or one or more times C- or N-substituted and / or additionally up to 3 N or 1 O or S atom (s) and can be further 1 to 2-fold benzannelated;
(B-1) = C-glycidyl, N-glycidyl, (thio) ether glycidyl and / or ester glycidyl compound of the formulas (B-1/1), (B-1/2), (B-) 1/3) and (B-1/4)

With
R ³ = R ¹ (where R ¹ = acyl excluded),
R ⁴ = methyl or phenyl or R ³ + R ⁴ = mono- or bicyclic, which may further contain an oxirane group and
R ⁵ = - (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -, -CH = CH-, 1,2-phenylene or

X = O, S or N-glycidyl,
R ⁶ = n dependent on R ¹ , (CH ₂ ) ₂ -SR ¹ , R ² , CH ₃ C (CH ₂ -) ₃ , CH ₃ CH ₂ C (CH ₂ -) ₃ -C (CH ₂ -) ₄ .
n = 1 to 4,
R ⁷ = of n depends R ¹ , R ² , benzoltriyl, benzene-tetra-yl or

R ⁸ = H, methyl or CH ₂ CO ₂ R ¹ (where R ¹ = acyl excluded)
R ⁹ = R ³ or R ⁹ ₂ in formula (B-3) also mono-, bi- or tricyclic
(B-3) = also glutaric or terephthalaldehyde, glyoxal, acetonylacetone, as well as acetals or ketals or sulfite or dithionite addition compounds of aldehydes
(B-4) = β-ketoester of the formula (R ⁴ COCH ₂ CO ₂ ) _n R ⁶
(B-5) = cyclic anhydride or lactone from the group succinic, glutaric, maleic, phthalic acid, pyromellitic, trimellitic, isatic and N-methylisatric anhydride, itacon, citracon and aconitic anhydride, butyric and valerolactone and phthalide,
(B-6) = carbonic acid ester from the group consisting of dimethyl, diethyl, dipropyl and dibutyl carbonate and ethylene and propylene carbonate,
(C-1), (C-2) and (C-3) salts of the formulas (ClO ₄ ) _n M (C-1) (C _m F _{2m + 1} SO ₃ ) _n M (C-2) (R ¹ OSO ₃ ) _n M (C-3) with R ¹ = C ₁ -C ₁₈ -alkyl or C ₁₀ -C ₁₈ -alkenyl, m = 1-6, n depending on the charge of the M-cation, M = Li, Na, K, Mg, Ca, Sr, Ba, Ln, Ce, Al, Sn, Zn or a Schichtgitterkation from the group hydrotalcite, hydrocalumite or a Katoitschichtgitterkation and in category (C-2) and (C-3) also ammonium salts.

The Stabilizer systems are particularly well suited for stabilization of chlorine-containing polymers, in particular of PVC. The pre-stabilization allows the polymer, since it is now less damaged, add heat stabilizers in a reduced amount during processing to have to, be it in the form of conventional Stabilizers, such as organotin compounds or Ba / Zn or Ca / Zn fatty acid Carboxylates or general metal soaps, or even in the form of completely new and completely heavy metal-free stabilizer types on organic Base. This procedure guarantees savings in capital resources and conserves resources, is therefore under economic and environmentally friendly To classify aspects as particularly advantageous.

Preferred definitions of the substituents, short formulas and indices are the following:
The substituent R ¹ is C ₁ -C ₂₄ -alkyl or alkanoyl includes methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl or t-butyl, pentyl, hexyl, heptyl , Octyl, 2-ethylhexyl, isooctyl, trimethylpentyl, nonyl, neononyl, isononyl, decyl, neodecyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl and tetrakosyl, formyl, acetyl, propionyl, butyryl , Valeryl, i-butyryl, i-valeryl, pivaloyl, capronyl, caprylyl, caproyl, lauroyl, palmitoyl, stearoyl, (neo) decanoyl, fatty alkanoyl and cyanoacetyl. Very particular preference is given to methyl, ethyl, propyl, butyl and fatty alkyl.

C ₁ -C ₂₄ alkyl or alkanoyl interrupted by O means methoxyethyl ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, propoxyethyl, 4-methoxybutyl, 4-ethoxybutyl, i-propoxybutyl, propoxybutyl, n-butoxyethyl, n-butoxybutyl, n -Butoxyhexyl. CH ₃ OCH ₂ CH ₂ OCH ₂ CH ₂ -, CH ₃ OCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ -, CH ₃ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ -, C ₂ H ₅ OCH ₂ CH ₂ OCH ₂ CH ₂ -, C ₂ H ₅ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ -, methoxy- and ethoxyacetyl, 3-methoxy-propionyl and 4-ethoxy-butyryl. Particularly preferred are methoxy or ethoxypropyl and methoxyethyl and ethoxyethyl.

2-hydroxy-C ₂ -C ₂₄ -alkyl or -akanoyl includes hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl, 2-hydroxypentyl, 2-hydroxyhexyl, 2-hydroxyheptyl, 2-hydroxyoctyl, 2-hydroxynonyl, 2-hydroxydecyl, 2 -Hydroxyundecyl, 2-hydroxydodecyl, 2-hydroxytetradecyl, 2-hydroxyhexadecyl, 2-hydroxyoctadecyl, 2-hydroxyeicosyl, 2-hydroxydocosyl and 2-hydroxytetrakosyl, and trishydroxymethyl-methyl. 1,1-Bis-hydroxymethyl-C ₂ -C ₄ -alkyl includes 1,1-bis-hydroxymethyl-ethyl, 1,1-bis-hydroxymethyl-propyl and 1,1-bis-hydroxymethyl-butyl and hydracryl. Particularly preferred are hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl and trishydroxymethyl-methyl.

C ₃ -C ₂₀ alkenyl or alkenoyl means allyl, methallyl, 1-butenyl, 2-butenyl, 3-butenyl, isobutenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2 Hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl and also their isomers, as well as oleyl, acrylic, methacrylic and oleoyl. Particularly preferred is alkyl, methallyl or butenyl.

C ₇ -C ₁₂ alkylphenyl or benzoyl includes tolyl, o-, p-, m-xylyl, ethylphenyl, propylphenyl, butylphenyl, t-butylphenyl. Methylbenzoyl, ethylbenzoyl, propylbenzoyl and butylbenzoyl. Particularly preferred is tolyl, xylyl or butylphenyl.

C ₇ -C ₁₂ phenylalkyl or alkanoyl means benzyl, α-phenethyl, β-phenethyl, phenylpropyl and phenylbutyl. Phenylacetyl, 3-phenylpropionyl and 4-phenylbutyryl. Particularly preferred is benzyl or phenethyl.

R ¹ ₂ NH comprises as preferred component (A-1) as a secondary amine symmetrical amines such as di-n-butyl, di-n-hexyl and di-n-octylamine, diisobutyl, di-n-propyl, diisopropyl and bis-2-ethylhexylamine, bis-fatty alkylamines such as dilauryl, dimiristyl, dipalmityl, distearyl and dioleylamine, diallyl, dibenzyl and dicyclohexylamine, bis (methoxyethyl) amine and bis (methoxypropyl) amine and bis (ethoxyethyl) amine; or non-symmetrical amines such as N-methyl, N-ethyl, N-propyl and N-butylaniline; N-methyl, N-ethyl, N-propyl and N-butyl-benzyl-amine; N-methyl, N-ethyl, N-propyl and N-butyl-allyl-amine; N-methyl, N-ethyl, N-propyl and N-butylcyclohexylamine; N-methyl- and N-ethyl-butyl-amine, diacetamide, as well as N-methyl- and N-ethyl-N'-cyanoacetylcarbamide, as well as N-propyl, N-butyl, N-hexyl, N-octyl- , N-alkyl, N-phenyl, N-octyl, N-decyl, N-lauryl, N-tridecyl, N-miristyl, N-palmityl, N-stearyl, N-oleyl, N-eicosyl and N-docosyl-N'-cyanoacetylcarbamide; preferred are N-methyl and N-ethyl-aniline and diacetamide and N-methyl-N-cyanoacetylcarbamid.

(A-1) but also includes primary amines with comparable substituents R ¹ as the secondary amines, but one of the two substituents R ¹ = H is.

Representatives of the secondary amines included as further preferred component (A-1) are NH-heterocycles such as pyrroles, pyrazoles, imidazoles, (amino) triazoles, (iso) indoles, carbazoles, tetrahydrocarbazoles, phenoxazines, phenothiazines, indazoles, benzimidazoles, benzotriazoles, Pyrrolidines, piperidines, tetrahydroquinolines, trimethyldihydroquinolines (diacetone anilines), morpholines, piperazines, pyrrolinones, pyrrolinediones (maleimides), imidazolinones, imidazolinediones (acetylene ureas), pyrazolinones, oxazolinones, thiazolinones, triazolinones, (iso) indolinones, indazolinones, benzimidazolinones, benzoxazolinones, benzthiazolinones, Pyrrolidinones (butyrolactams), imidazolidinones (ethylene ureas), pyrazolidinones, oxazolidinones, thiazolidinones, morpholinones, piperidinones (valerolactams and 2,2,6,6-tetraalkylpiperidinones), piperazinones, pyrrolidinediones (succinimides, tetramic acids), piperidinediones (glutarimides), morpholinediones, piperazinediones , Imidazolidinediones (hydantoins), pyrazolidinediones, oxazolines dione, thiazolidinediones, (amino) pyrimidinediones, (amino) uracils, triazolidinediones (urazoles), pyrimidine triones (barbituric acids), triazinetriones (isocyanuric acids), triazine triamines (melamines), imidazolidinethiones (ethylene thioureas), dihydropyrimidinediones (propylene ureas), dihydropyridines (2,6 Dimethyl 3,5-dicarboxylates), tetrahydroazepinones (caprolactams), tetrazoles, isoindolinediones (phthalimides), imidazolidinetriones (parabanic acids), pyridazinones, pyridazinediones, dihydropyridazinediones (maleic hydrazides), phthalazinones, phthalazinediones, dihydrophthalazinediones (phthalic acid hydrazides), pyrimidine trinones (alloxanes); or (A-1) is ammonia in the form of a concentrated aqueous solution of ammonium salts such as NH ₄ -formate, acetate and propionate or in the form of urotropin.

Preference is given here pyrrolidine, piperidine (on), piperazine and morpholine, also substituted in the 2,6-position such as 2-methyl, 2-ethyl and 2-phenylmorpholine, 2,6-dimethyl, 2,6-diethyl and 2,6-diphenylmorpholine and piperazine dione, and pyrrole, 2-phenylpyrrole, 2,4-diphenylpyrrole, indole, 2-phenylindole, carbazole, 2-methylindole, indazole, 3-phenyl-indazole, imidazole, benzimidazole, 4 or 5-methylimidazole, triazole, aminotriazole, urazole, N-methyl or phenyl urazole, benzotriazole, tolutriazole and 4,5-dimethylbenzotriazole; (Benz) Imidazole (id) in, also substituted in the 2-position by R ¹ or SH, comprises besides imidazoline, imidazolidine and benzimidazoline 2-methyl-, 2-ethyl-, 2-propyl- and 2-phenylimidazolidine or 2 Mercapto-imidazolidine, and 2-methyl, 2-ethyl, 2-propyl and 2-phenyl-benzimidazoline, and 2-mercapto-benzimidazoline; (Benz) oxazole (id) in, also substituted in the 2-position by R ¹ or SH, besides oxazoline, oxazolidine and benzoxazoline comprises 2-methyl-, 2-ethyl-, 2-propyl- and 2-phenyloxazolidine as well as 2-mercaptooxazolidine , further 2-methyl, 2-ethyl, 2-propyl and 2-phenylbenzoxazoline and 2-mercapto-benzoxazoline; (Benz) thiazole (id) in, also substituted in the 2-position by R ¹ or SH, in addition to thiazoline, thiazolidine and benzothiazoline, 2-methyl, 2-ethyl, 2-propyl and 2-phenyl-thiazolidine and 2-mercapto-thiazolidine, furthermore 2-methyl-, 2-ethyl-, 2-propyl- and 2-phenylbenzothiazoline as well as 2-mercaptobenzothiazoline; (Benz) imidazolin (id) in (on) (thione) includes imidazolinone, imidazolidinone, benzimidazolinone and imidazolidinethione; (Benz) oxazole (id) inone includes oxazolinone, oxazolidinone and benzoxazolinone; (Benz) thiazole (id) inone includes thiazolinone, thiazolidinone and benzthiazolinone; further includes imidazolidinedione (hydantoin), ohazolidinedione and thiazolidinedione, also substituted in the 5-position one or two times by R ¹ , is included in addition to hydantoin 5-methyl, 5-ethyl, 5-propyl-5-butyl and 5 Phenyl- and 5-ureido-imidazolidinedione (allantoin), besides oxazolidinedione and thiazolidinedione, also 5,5-dimethyl-, 5,5-diethyl-, 5,5-dipropyl-, 5,5-dibutyl- and 5,5- Diphenylimidazolidinedione, oxazolidinedione and thiazolidinedione; further included are 6-aminouracil, 6-amino-1-methyl-uracil, 6-amino-1-ethyl-uracil and 6-methyluracil; 3,6-dimethyluracil, 6-ethyluracil, 6-propyluracil, 6-phenyluracil, 6-methyluracil and 6-benzyluracil; also include pyrazolidinone, 1-methyl-pyrazolidinone, 1-phenyl-pyrazolidinone and 1-phenyl-4-methyl-pyrazolidinone and azauracil, parabane, barbituric, isocyanuric and valerolactam and caprolactam, cyanamide, cyanoguanidine, N, N'- Diphenylguanidine, melamine, acetoguanamine, butyro-guanamine and benzoguanamine; Particularly preferred are morpholine, pyrrolidinone, pyrrolidinedione, imidazole, imidazolidine, imidazolidinone and imidazolidinedione, or imidazolidinethione (ethylene thiourea) and triazinetrione (isocyanuric acid) and tetrahydropyrimidi non (propyleneurea).

For the substituent R ² , C ₂ -C ₁₂ -alkylene or -alkanoylene includes ethylene, propylene, isopropylene, butylene, i-butylene, pentylene, hexylene, heptylene, octylene, 2-ethylhexylene, decylene, undecylene and dodecylene, oxalyl, Malonyl, succinyl, glutaryl and suberyl; preferred are ethylene, propylene, i-propylene or butylene.

C ₂ -C ₁₂ -alkylene or -alkanoylene interrupted by O or S means 3-oxapentylene, 3-thiapentylene, 3,6-dioxo-octylene, 3,6-dithiaoctylene and 3,6,9-trioxaundecylene, oxadiacetyl and thiadiacetyl; preferred are 3-oxapentylene and 3-thiapentylene.

(R ¹ NH-) ₂ R ² means 1,2-bis (dimethylamino) and 1,2-bis (diethylamino) ethane, 1,2- and 1,3-bis (dimethylamino) - and bis (diethylamino) propane, 1,3- and 1,4-bis (dimethylamino) - and bis (diethylamino) butane, 1,3- and 1,4-bis (dimethylamino) - and bis (diethylamino ) benzene, 1,5- and 1,6-bis (dimethylamino) pentane and hexane; preferred is bis (dimethylamino) ethane.

Under that listed as component (A) In compound classes, the monoamines (A-1) are particularly preferred.

C-glycidyl and N-glycidyl compounds include propene, α-butene, α-hexene, α-octene, α-decene, α-dodecene, α-tetradecene, α-hexadecene, -α-octadecene and styrene oxide, cyclohexene and cyclooctene oxide; dicyclopentadiene and bis-bisoxide and vinylcyclohexene-bisoxide; N-Glycidylmaleinimid, N-glycidylphthalimide, N-glycidyl-dimethylhydantoin, N, N'-diglycidyl-dimethylhydantoin, N-glycidyl succinimide and N-glycidyl glutarimide and N, N, N "-trisglycidyl isocyanurate; preferred are decene, dodecene, tetradecene, hexadecene, octadecene and styrene oxide and glycidylphthalimide, diglycidyldimethylhydantoin and trisglycidyl isocyanurate.

Thio (ether) -glycidyl- and ester glycidyl compounds include glycidyl methyl, ethyl, propyl, butyl, i-propyl, i-utyl, sec-butyl, t-butyl, pentyl, i-pentyl, hexyl, octyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, allyl, benzyl and phenyl ethers; Glycidyl decyl, dodecyl, tetradecyl, hexadecyl and octadecyl thioether, N, N'-diglycidyl aniline and N, N ', N "-trisglycidyl-hydroxyaniline; glycidyl, propionate, butyrate, hexanoate, octanoate, nonanoate, decanoate, neodecanoate, versatate, dodecanoate, palmitate, stearate, oleate and benzoate; Diglycidyl oxalate, phthalate, isophthalate and terephthalate as well as triglycidyl trimellitate and tetraglycidyl pyromellitate as well Tetraglycidylglycoluril; the others include polymers and copolymers glycidyl acrylate and methacrylate; preferred are octyl glycidyl ethers, Cyclohexanedimethanol diglycidyl ether, allyl glycidyl ether, neopentanedioldiglycidyl ether, Glycerol diglycidyl ether, trimethylolethane and propane triglycidyl ether and pentaerythritol tetra-glycidyl ether. Glycidyl (neo) decanoate, glycidyl terephthalate, Butanediol diglycidyl ether, diglycol diglycidyl ether, thiodiethylene glycol diglycidyl ether and glycidyl butyl, isobutyl and sec-butyl ethers.

• a) flüssige Bisphenol-A-diglycidylether wie Araldit^®GY 240, Araldit^®GY 250, Araldit^®GY 260, Araldit^®GY 266 oder GY 280, Araldit^®GY 2600, Araldit^®MY 790;
• b) feste Bisphenol-A-diglycidylether 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;
• c) flüssige Bisphenol-F-diglycidylether wie Araldit^®GY 281, Araldit^®PY 302, Araldit^®PY 306;
• d) feste Polyglycidylether von Tetraphenylethan wie CG Epoxy Resin^®0163;
• e) feste und flüssige Polyglycidylether von Phenolformaldehyd-novolak wie EPN 1138, EPN 1139, GY 1180, PY 307;
• f) feste und flüssige Polyglycidylether von o-Cresolformaldehyd-novolak wie ECN 1235, ECN 1273, ECN 1280, ECN 1299;
• g) flüssige Glycidylether von Alkoholen wie Shell^®Glycidylether 162, Araldit^®DY 0390, Araldit^®DY 0391;
• h) flüssige oder feste Glycidylester von Carbonsäuren wie Shell^®Cardura E 10 oder Resolution^®Cardura E 10 sowie Terephthalsäureester, Isophthalsäureester und Trimellit-säureester wie Araldit^®PY 284 und Araldit^®PT 910 oder Diglycidyloxalat;
• i) feste heterocyclische Epoxidharze (Triglycidylisocyanurat) wie Araldit^®PT 810;
• j) flüssige cycloaliphatische Epoxidharze wie Araldit^®CY179;
• k) flüssige N,N,O-Triglycidylether von p-Aminophenol wie Araldit^®MY 0510;
• l) Tetraglycidyl-4-4'-methylenbenzamin oder N,N,N',N'-Tetraglycidyldiaminophenyl-methan wie Araldit^®MY 720, Araldit^®MY 721 (Araldit^® ist eine Marke der Ciba Specialties, Basel).

Further liquid and solid glycidyl compounds may be mentioned below:

• a) liquid bisphenol A diglycidyl ethers such as Araldit ^® GY 240, Araldit ^® GY 250, Araldit ^® GY 260, Araldit ^® GY 266 or GY 280, Araldite ^® GY 2600, Araldit ^® MY 790;
• b) solid bisphenol A diglycidyl ethers such as 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;
• c) liquid bisphenol F diglycidyl ethers such as Araldit ^® GY 281, Araldit ^® PY 302, Araldit ^® PY 306;
• d) solid polyglycidyl ethers of tetraphenylethane such as CG Epoxy ^Resin® 0163;
• e) solid and liquid polyglycidyl ethers of phenol formaldehyde novolak such as EPN 1138, EPN 1139, GY 1180, PY 307;
• f) solid and liquid polyglycidyl ethers of o-cresol formaldehyde novolac such as ECN 1235, ECN 1273, ECN 1280, ECN 1299;
• g) liquid glycidyl ethers of alcohols such as Shell ^® glycidyl ether 162, Araldit ^® DY 0390, Araldit ^® DY 0391;
• h) liquid or solid glycidyl esters of carboxylic acids, such as Shell ^® Cardura E 10 or resolution ^® Cardura E 10, as well as terephthalic acid, isophthalic acid and trimellitic säureester as Araldit ^® PY 284 and Araldit ^® PT 910 or Diglycidyloxalat;
• i) solid heterocyclic epoxy resins (triglycidyl isocyanurate) such as Araldit ^® PT 810;
• j) liquid cycloaliphatic epoxy resins such as Araldit ^® CY179;
• k) liquid N, N, O-triglycidyl ethers of p-aminophenol such as Araldit ^® MY 0510;
• l) tetraglycidyl-4-4'-methyl benzenamine or N, N, N ', N'-Tetraglycidyldiaminophenyl-methane such as Araldit ^® MY 720, Araldite ^® MY 721 (Araldite ^® is a trademark of Ciba Specialties, Basel).

The acrylate (B-2) include methyl, ethyl, propyl, butyl, hexyl, octyl, 2-ethylhexyl, decyl and dodecyl and hydroxyethyl esters of acrylic and methacrylic acid and Acrylic and methacrylamide; preferred is butyl acrylate or methacrylate; likewise are included Diesters of ethylene, propylene, butylene, pentylene and hexylene glycol as well as those of thiodiglycol, such as trimethylolethane and propane tri (meth) acrylate and Pentaerythritol tetra (meth) acrylate; preferred are butylene and 3-thiapentylene glycol bisacrylate and methacrylate; further include itaconic acid esters, wherein dimethyl, Diethyl, dipropyl and Dibutylitaconat are preferred.

Aldehydes or / and ketones of formula (B-3) include methanal (also referred to as formalin, trioxane or paraformaldehyde or in the form of Na-hydroxymethylsulfinate and Na-hydroxymethylsulfonate), ethanal (also called para- or metaldehyde), propanal, butanal, i Butanal, hexanal, heptanal, octanal, i-octanal, nonanal, i-nonanal; Decanal and glutaraldehyde and benzaldehyde or salicylaldehyde and glyoxal (also in aqueous solution or in trimeric form), propanal dimethyl, diethyl or diallyl acetal, propanal ethylene and propylene acetal. Glyoxalbisnatrium bisulfite; preferred are methanal, ethanal, propanal, heptanal and glutaraldehyde and benzaldehyde; further included (partially with R ⁹ ₂ as a cycle) are tetralone, decalone, acetophenone, benzylacetone, cyclohexanone-di-methyl, -ethyl or -allyl and -ethylene-acetal, respectively. Cyclohexylmethylketone, dicyclohexylketone, cyclopenta- and -hexanone, cyclohepta- and -octanone and camphor, 2- and 3-pentanone and diisobutyl ketone, diisopropyl ketone, 3,3-dimethyl-2-butanone, 2-, 3- and 4-heptanone, 3 Hexanone, isobutyl methyl ketone, isopropyl methyl ketone, 5-methyl-3-heptanone, 5-methyl-2-hexanone, 2-, 3-, 4- and 5-nonanone, 2- and 3-octanone and 2-undecanone; preferred are heptanone, octanone and nonanone, camphor, methyl isobutyl ketone, diisobutyl ketone and cyclohexanone. Also included are those compounds which split off one of the abovementioned aldehydes (aldehyde eliminator).

β-keto ester of the formula (B-4) include methyl acetoacetate, ethyl, propyl, butyl, hexyl, octyl and 2-ethylhexyl esters; Benzoyl-methyl acetate and ethyl, laurylthio-ethyl-acetoacetate and benzoylacetate; Ethylene, butylene and thiodiethylene glycol bisacetoacetate and benzoylacetate; preferred are methyl and ethyl acetoacetate and methyl and ethyl benzoylacetate and butanediol and thiodiglycol bisacetoacetate or benzoylacetate.

cyclic Anhydride or lactone of the formula (B-5) are preferably maleic and phthalic anhydride and isatin and N-methylisatic anhydride or butyrolactone; particularly preferred are maleic and isatric anhydride.

carbonate ester of the formula (B-6) is preferably diethyl, ethylene or propylene carbonate.

Under those listed as component (B) Classes of compounds are the glycidyl derivatives (B-1), the cyclic ones Anhydrides of (B-5) and the carbonic acid esters (B-6) are particularly preferred.

perchlorate of the formula (C-1) is preferably Na and K perchlorate or hydrotalcite perchlorate (Alkamizer 5) or Mg or Ca perchlorate.

Perfluoroalkanesulfonate salt of the formula (C-2) preferably denotes salts of the "Triflic", "Pentaflic", "Heptaflic" and "Nonaflic"acids; Very particular preference is given to Na and K triflate or Mg or Ca and Al triflate, as well as NH ₄ triflate.

Sulfate ester salt of the formula (C-3) means Li, Na, K, Mg, Ca, Sr, Ba, Ln, Ce, Al, Zn and NH ₄ sulfate esters. Sulfate ester means sulfuric acid half ester; preferred are methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl and octadecenylsulfuric acid monoesters; Very particular preference is given to Na-methyl, octyl, decyl and dodecyl sulfate esters as well as the analogous K or Mg, Ca and Al salts.

Under those listed as component (C) Classes of compounds are the perchlorates (C-1) and the triflates (C-2) is particularly preferred.

Particularly preferred are - in addition to and in addition to the combinations listed in the claims - subsequent combinations with one or more components of (A) and (B):
(A ₁ ) butyl, allyl, cyclohexyl, benzyl, octyl, nonyl, decyl, dodecyl, hexadecyl, octadecyl and octadecenylamine; Aniline and methoxy- or ethoxypropylamine; tris (hydroxymethyl) aminomethane and bis (hydro xymethyl) -aminoethan; Monoethanol and isopropanolamine; Monohydroxyethylstearyl, -palmityl and -oleyl-min and mono-hydroxypropylstearyl, -palmityl and -oleylamine; Phenethylamine, butylene, hexylene, phenylene, neopentylenediamine and bis (aminomethyl) cyclohexane; Dibutyl, diallyl, dicyclohexyl, dibenzyl, ditridecyl, diethanol and diisopropanolamine; N-methyl and N-ethylaniline and N-methyl, N-ethyl and N-allyl-N'-cyanoacetylcarbamide; Imidazole, aminotriazole, benz (toluene) triazole, 5,5-dimethyl-imidazolidinedione, imidazolidinedione, imidazolidinone, imidazolidinethione, pyrrolidine, piperidine, morpholine, pyrrolidinone, pyrrolidinedione and imidazoline; Piperidone and piperazine, and 6-aminouracil, 6-amino-1-methyluracil and 6-amino-1-ethyluracil, and 6-methyluracil, 1-phenyl-3-methyl-pyrazolinone and 1-phenyl-pyrazolidinone and malonylurea or 1-methyl-barbituric acid or isocyanuric acid, succinimide, phthalimide, caprolactam, 2-phenylindole and propylene urea and
(B ₁ ) propene, butene, hexene, octene, dodecene, tetradecene, hexadecene, octadecene, cyclohexene and styrene oxide; Glycidylphthalimide, triglycidyl isocyanurate, methyl, ethyl, propyl, butyl, octyl and 2-ethylhexylglycidyl ethers; Butanediol, hexanediol, neopentanediol, bisphenol A and bisphenol F diglycidyl ethers; Trimethylolethane tri- and propane tri-glycidyl ethers and pentaerythritol tetraglycidyl ether; Decane, dodecane and neodecanoic acid glycidyl esters and diglycidyl iso- and terephthalate,
(A ₂ ) diethanol and diisopropanolamine and
(B ₂ ) butyl, hydroxyethyl acrylate and methacrylate
(A ₃ ) monoethanol, monoisopropanol, diethanol and diisopropanolamine and
(B ₃ ) isatin and N-methylisatinic anhydride
(A ₄ ) + (B ₄ ) octyl or dioctylamine + propene or butene oxide
(A ₅ ) + (B ₅ ) isooctyl or diisooctylamine + propene or butene oxide
(A ₆ ) + (B ₆ ) nonyl or dinonylamine + propene or butene oxide
(A ₇ ) + (B ₇ ) isononyl or diisononylamine + propene or butene oxide
(A ₈ ) + (B ₈ ) decyl or didecylamine + propene or butene oxide
(A ₉ ) + (B ₉ ) isodecyl- or diisodecylamine + propene or butene oxide
(A ₁₀ ) + (B ₁₀ ) undecyl or diundecylamine + propene or butene oxide
(A ₁₁ ) + (B ₁₁ ) isoundecyl- or diisoundecylamine + propene or butene oxide
(A ₁₂ ) + (B ₁₂ ) dodecyl or didodecylamine + propene or butene oxide
(A ₁₃ ) + (B ₁₃ ) isododecyl- or diisododecylamine + propene or butene oxide
(A ₁₄ ) + (B ₁₄ ) tridecyl or ditridecylamine + propene or butene oxide
(A ₁₅ ) + (B ₁₅ ) isotridecyl- or diisotridecylamine + propene- or butene oxide
(A ₁₆ ) + (B ₁₆ ) tetradecyl or ditetradecylamine + propene or butene oxide
(A ₁₇ ) + (B ₁₇ ) hexadecyl or dihexadecylamine + propene or butene oxide
(A ₁₈ ) + (B ₁₈ ) octadecyl or dioctadecylamine + propene or butene oxide
(A ₁₉ ) + (B ₁₉ ) eicosyl or dieicosylamine + propene or butene oxide
(A ₂₀ ) + (B ₂₀ ) docosyl or didocosylamine + propene or butene oxide
(A ₂₁ ) + (B ₂₁ ) octadecenyl or dioctadecenylamine + propene or butene oxide
(A ₂₂ ) + (B ₂₂ ) butyl or dibutylamine + propene or butene oxide
(A ₂₃ ) + (B ₂₃ ) isobutyl or diisobutylamine + propene or butene oxide
(A ₂₄ ) + (B ₂₄ ) hexyl or dihexylamine + propene or butene oxide
(A ₂₅ ) + (B ₂₅ ) heptyl or diheptylamine + propene or butene oxide
(A ₂₆ ) + (B ₂₆ ) benzyl or dibenzylamine + propene or butene oxide
(A ₂₇ ) + (B ₂₇ ) cyclohexyl or dicyclohexylamine + propene or butene oxide
(A ₂₈ ) + (B ₂₈ ) N-methyl or N-ethylcyclohexylamine + propene or butene oxide
(A ₂₉ ) + (B ₂₉ ) N-methyl or N-ethylaniline + propene or butene oxide
(A ₃₀ ) + (B ₃₀ ) allyl or diallylamine + propene or butene oxide
(A ₃₁ ) + (B ₃₁ ) monoethanol (isopropanol) or diethanol (isopropanol) amine + 4-vinyl-1-cyclohexene diepoxide
(A ₃₂ ) + (B ₃₂ ) monoethanol (isopropanol) or diethanol (isopropanol) amine + dicyclopentadiene diepoxide
(A ₃₃ ) + (B ₃₃ ) monoethanol (isopropanol) or diethanol (isopropanol) amine + bisphenol A or bisphenol F diglycidyl ether
(A ₃₄ ) + (B ₃₄ ) monoethanol (isopropanol) or diethanol (isopropanol) amine + triglycidyl isocyanurate.
(A ₃₅ ) + (B ₃₅ ) 6-aminouracil + ethylene, propylene or butylene carbonate
( _A36 ) + ( _B36 ) 6-amino-1-methyl-uracil or 6-amino-1-ethyl-uracil + ethylene, propylene or butylene carbonate
(A ₃₇₎ + (B ₃₇₎ 6-aminouracil, 6-amino-1-methyl-uracil or 6-amino-1-ethyl-uracil + allyl
( _A38 ) + ( _B38 ) 6-aminouracil, 6-amino-1-methyl-uracil or 6-amino-1-ethyl-uracil + butene oxide
(A ₃₉ ) + (B ₃₉ ) benz (tolu) triazole / aminotriazole / 2-phenylindole + methanal / ethanal / benzaldehyde + diethanol / diisopropanolamine (where "/" in the examples "and / or")
(A ₄₀ ) + (B ₄₀ ) imidazole / morpholine / pyrrolidine / piperidine / piperazine + methanal / ethanal / benzaldehyde + diethanol / diisopropanolamine
(A ₄₁ ) + (B ₄₁ ) pyrrolidinone / pyrrolidinedione / imidazolidinone / imidazolidinethione / (dimethyl, diphenyl) imidazolidinedi on + methanal / ethanal / benzaldehyde + diethanol / diisopropanolamine
(A ₄₂ ) + (B ₄₂ ) 6-Aminouracil / 6-amino-1-methyl-uracil / 6-amino-1-ethyl-uracil / barbituric acid / 1-methyl-barbituric acid / isocyanuric acid + methanal / ethanal / benzaldehyde + diethanol - / diisopropanolamine
(A ₄₃ ) + (B ₄₃ ) acetamide / benzamide / caprolactam / succinimide / phthalimide + methanal + diethanol / diisopropanolamine
(A ₄₄ ) + (B ₄₄ ) 6-Methyluracil / propyleneurea / 1-phenyl-pyrazolidinone / 3-methyl-1-phenyl-pyrazolino / methanal / ethanal / benzaldehyde + diethanol / diisopropanolamine
(A ₄₅ ) + (B ₄₅ ) maleic / succinic / glutaric / phthalic anhydride + monoethanol / monoisopropanolamine
(A ₄₆ ) + (B ₄₆ ) ammonium acetate + thiodiglycol (1,4-butanediol) bisacetoacetate
(A ₄₇ ) + (B ₄₇ ) urotropin + methyl (ethyl) acetoacetate
(A ₄₈ ) + (B ₄₈ ) 6-Aminouracil / 6-amino-1-methyluracil / 6-amino-1-ethyluracil + hexanal / heptanal / octanal
(A ₄₉₎ + (B ₄₉₎ camphor / heptanal / 2 (4) -heptanon / glutaraldehyde + diethanol- / diisopropanolamine
(A ₅₀ ) + (B ₅₀ ) cyanoacetylcarbamide / monomethyl- / monoethyl- / monoallylcyanacetylcarbamide + hexanal / heptanal / octanal
(A ₅₁ ) + B ₅₁ ) Cyanoacetylcarbamide / monomethyl- / monoethyl- / monoallylcyanacetylcarbamide + butene oxide / allylglycidyl ether / bisphenol A (F) -diglycidyl ether
(A ₅₂ ) + (B ₅₂ ) camphor / hexanal / heptanal / 2- (4) heptanone / glutaraldehyde + diallyl / dibutyl / dicyclohexylamine / morpholine / piperidine / pyrrolidine / N-methyl (ethyl) aniline
(A ₅₃ ) + (B ₅₃ ) butyl (meth) acrylate / dibutyl itaconate + monoethanol / monoisopropanolamine / diethano- / diisopropanolamine

These (A) + (B) combinations are preferred with Na or K perchlorate, Na or K triflate and Na or K-sulphate half ester (in the form of monoocyl bis -mistristyl sulphate) or their analogous Mg, Ca and Al salts are combined as component (C).

The Components (A) and (B) as well as (C-1) and (C-3) are "bulk" chemicals, so-called "commodities". Component (C-2) is available in the chemicals trade. The salts as well as the underlying acids are described in Kirk Othmer, Encyclopedia of Chemical Technology, 4th Ed., John Wiley & Sons., NY, Vol. 11, SS 558-564 (1994) and Chem. Rev. 77, pp. 69-90 (1977).

The Components (C-1), (C-2) and (C-3) may vary depending on water solubility or water solubility in different common Dosage forms (formulations) can be used, e.g. when Salt or as a solution in water or in an organic solvent or reared on a carrier material such as PVC, ca silicate, zeolites or hydrotalcites. Examples of such Formulations are also corresponding salts with alcohols (Polyols, cyclodextrins) or ether alcohols, amino alcohols or Ester alcohols or crown ethers are complexed or dissolved therein. Preferred are complexes or solutions in glycol mono- and diglycol monobutyl ether.

A another embodiment the combination of the components of the stabilizer systems according to the invention is based on the use of complexes (so-called amine complexes) component (A) and component (C), e.g. Complexes of Na or K-perchlorate or triflate with diethanol or diisopropanolamine or ethylene or Propyleneurea or ethylene thiourea imidazolidinone or Imidazolidinedione. These (A) + (C) complexes are labeled with the (B) component combined. In another variant, ethylene or propylene carbonate as a solvent for this Salts or complexes are used.

One Another object of the invention are mixtures of at least a component (A) and at least one component (B), the stabilizer components comprising at least one salt of the general formulas (C1), (C2) and (C3) are added, with at least one other common Stabilizer or additive.

Prefers are the fourth component group phosphites, polyols and disaccharide alcohols, β-diketones, Thiophosphites and thiophosphates, mercaptocarboxylic acid esters, dihydropyridines, Hydrotalcites, zeolites (alkali or alkaline-earth aluminosilicates), metal soaps, Alkali and alkaline earth compounds, epoxidized fatty acid esters and other epoxide compounds, hydroxycarboxylate metal salts, fillers, Lubricants, plasticizers, pigments, antioxidants, UV absorbers, Light stabilizers, optical brighteners, propellants, antistatic agents, Biocides (antimicrobials), antifogging agents, impact modifiers, Processing aids, gelling agents, flame retardants, metal deactivators and compatibilizers.

There may be other additives such as adhesives, calendering aids, form (release agents), lubricants and fragrances and colorants. Examples of such additional components are further un (See "Handbook of PVC Formulating" by EJ Wickson, John Wiley & Sons, New York 1993).

Especially Preferred as the fourth component type are epoxidized fatty acid esters and other epoxy compounds as well as polyols, alkaline earth and aluminum soaps and Mg, Ca and Al hydroxides, zeolites, hydrotalcites and phosphites. Very particularly preferred are phosphites, disaccharide alcohols, dehydrated hydrotalcites and zeolites and calcium or magnesium hydroxide or calcium stearate or basic Mg, Ca or Al salts or "overbased" compounds of the Magnesium and calcium.

phosphites

Organic phosphites are known co-stabilizers for chlorine-containing polymers. Examples are trioctyl, tridecyl, tridodecyl, tritridecyl, tripentadecyl, trioleyl, tristearyl, triphenyl, trilauryl, tricresyl, tris-nonylphenyl, tris-2,4-t-butyl-phenyl or tricyclohexylphosphite , Other suitable phosphites are differently mixed aryl-dialkyl- or alkyl-diaryl phosphites, such as phenyldioctyl, phenyldidecyl, phenyldidodecyl, phenylditridecyl, phenylditetradecyl, phenyldipentadecyl, octyldiphenyl, decyldiphenyl, undecyldiphenyl, dodecyldiphenyl, tridecyldiphenyl, tetradecyldiphenyl , Pentadecyldiphenyl, oleyldiphenyl, stearyldiphenyl and dodecyl-bis-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) phenylphosphite, tetraisodecyldipropylene glycol diphosphite, tris-dipropylene glycol phosphite, tetramethylolcyclohexanol-decyldiphosphite, tetramethylolcyclohexanolbutoxyethoxyethyldiphosphite, tetramethylolcyclohexanol-nonylphenyl diphosphite, bis -nonylphenyl-di-trimethylolpropane diphosphite, bis-2-butoxyethyl-di-trimethylolpropane diphosphite, trishydroxyethylisocyanurate hexadecyltriphosphite, didecylpentaerythritol diphosphite, di-stearyl pentaerythritol diphosphite, bis-2,4-di-t-butylphenylpentaerythritol diphosphite, and mixtures of these phosphites and aryl / alkyl phosphite Mixtures of the statistical composition (H ₁₉ C ₉ -C ₆ H ₄ ) O _1.5 P (OC _12.13 H _25.27 ) _1.5 or [C ₈ H ₁₇ -C ₆ H ₄ -O-] ₂ P [iC ₈ H ₁₇ O], (H ₁₉ C ₉ C ₆ H ₄ ) O _1.5 P (OC _9.11 H, _19.23 ) _1.5 . 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.

Polyols and sugar alcohols

When 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, glycerol, diglycerin, 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 can be used in an amount of, for example, from 0.01 to 20, desirably from 0.1 to 20 and in particular from 0.1 to 10 parts by weight, based per 100 parts by weight of PVC.

β-diketones

Useful 1,3-dicarbonyl compounds are linear or cyclic dicarbonyl compounds. Preferably, dicarbonyl compounds of the formula R ' ₁ CO CHR ₂ ' -COR ' ₃ are used, wherein R' ₁ C ₁ -C ₂₂ alkyl, C ₅ -C ₁₀ hydroxyalkyl, C ₂ -C ₁₈ alkenyl, phenyl, by OH , C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or halogen substituted phenyl, C ₇ -C ₁₀ phenylalkyl, C ₅ -C ₁₂ cycloalkyl, C ₁ -C ₄ alkyl-substituted C ₅ -C ₁₂ -cycloalkyl or a group -R ' ₅ -S-R' ₆ or -R ' ₅ -O-R'₆; R ' _{2 is} hydrogen, C ₁ -C ₈ alkyl, C ₂ -C ₁₂ alkenyl, phenyl, C ₇ -C ₁₂ alkylphenyl, C ₇ -C ₁₀ phenylalkyl or a group -CO-R'₄; R _'3 is a for R' meanings given ₁ or is C ₁ -C ₁₈ alkoxy, R _{'4 is} C ₁ -C ₄ alkyl or phenyl; R ' _{5 is} C ₁ -C ₁₀ -alkylene and R' _{6 is} C ₁ -C ₁₂ -alkyl, phenyl, C ₇ -C ₁₈ -alkylphenyl or C ₇ -C ₁₀ -phenylalkyl.

These include the hydroxyl-containing diketones of EP-A 0 346 279 and the oxa and thia-diketones of EP-A 0 307 358 as well as the based on isocyanic keto ester of US 4,339,383 ,

R ' ₁ and R' ₃ as alkyl may in particular be C ₁ -C ₁₈ -alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl or octadecyl.

R ' ₁ and R' ₃ as hydroxyalkyl are in particular a group - (CH ₂ ) _n -OH, where n is 5, 6 or 7.

R ' ₁ and R' ₂ as alkenyl may be, for example, vinyl, allyl, methallyl, 1-butenyl, 1-hexenyl or oleyl, preferably allyl.

R ' ₁ and R' ₃ as phenyl substituted by OH, alkyl, alkoxy or halogen may, for example, be tolyl, xylyl, tert-butylphenyl, methoxyphenyl, ethoxyphenyl, hydroxyphenyl, chlorophenyl or dichlorophenyl.

R ' ₁ 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. 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 be in particular benzyl. Preferably, R ' _{2 is} hydrogen. R ' ₃ as the alkoxy may be, for example, methoxy, ethoxy, butoxy, hexyloxy, octyloxy, dodecyloxy, tridecyloxy, tetradecyloxy or octadecyloxy. R ' ₅ as C ₁ -C ₁₀ -alkylene is in particular C ₂ -C ₄ -alkylene. R ' ₆ as alkyl is in particular C ₄ -C ₁₂ -alkyl, for example butyl, hexyl, octyl, decyl or dodecyl.

R ' ₆ as alkylphenyl is in particular tolyl. R ' ₆ 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-nonylthio-heptanedione-2,4, benzoylacetone, dibenzoylmethane, Lauroylbenzoylmethane, palmitoylbenzoylmethane, stearoylbenzoylmethane, isooctylbenzoylmethane, 5-hydroxycapronylbenzoylmethane, tribenzoylmethane, bis (4-methylbenzoyl) methane, benzoyl-p-chlorobenzoylmethane, bis (2-hydroxybenzoyl) methane, 4-methoxybenzoyl- benzoylmethane, bis (4-methoxybenzoyl) methane, 1-benzoyl-1-acetylnonane, benzoyl-acetyl-phenylmethane, stearoyl-4-methoxybenzoylmethane, bis (4-tert-butylbenzoyl) methane, benzoyl-formylmethane, benzoyl-phenylacetylmethane, bis- cyclohexanoyl-methane, di-pivaloyl-methane, 2-acetyl-cyclo-pentanone, 2-benzoylcyclopentanone, methyl, ethyl and di-acetoacetate, methyl and ethyl benzoyl, propionyl and butyryl acetoacetate, triacetylmethane, Acetess methyl, ethyl, hexyl, octyl, dodecyl or octadecyl ester, benzoylacetic acid, methyl, ethyl, butyl, 2-ethylhexyl, dodecyl or octadecyl ester, and propionyl and Butyrylacetic acid C ₁ -C ₁₈ alkyl esters. Stearoylessigsäureethyl-, propyl, butyl, hexyl or -octylester and polynuclear β-ketoester as described in EP-A 0 433 230 and dehydroacetic acid and their zinc, magnesium or alkali metal salts. Preferred are Ca, Mg and Zn salts of acetylacetone and dehydroacetic acid.

1,3-diketo compounds of the above formula wherein R, particularly preferred are _{'1 is} C ₁ -C ₁₈ alkyl, phenyl, substituted by OH, methyl or methoxy, C ₇ -C ₁₀ phenylalkyl or cyclohexyl, R' ₂ is hydrogen and R ' _{3 has} one of the meanings given for R' ₁ . Also included are heterocyclic 2,4-diones such as N-phenyl-3-acetylpyrrolidine-2,4-dione. Further representatives of this category are described in EP-A 0 734 414. The 1,3-diketo compounds may be used in an amount of, for example, from 0.01 to 10, advantageously from 0.01 to 3 and in particular from 0.01 to 2, parts by weight, based on 100 parts by weight of PVC.

Thiophosphites and thiophosphates

Thiophosphites or thiophosphates are compounds of the general type (RS) ₃ P, (RS) ₃ P = O or (RS) ₃ P = S, as described in the publications DE-A 28 09 492, EP-A 0 090 770 and EP 0 573 394 to be discribed. Examples of these compounds are trithiohexyl phosphite, trithiooctyl phosphite, trithio-lauryl phosphite, trithiobenzyl phosphite, trithiophosphoric acid tris- (carbo-i-octyloxy) -methyl ester. Trithiophosphoric acid tris (carbo-trimethylcyclohexyloxy) methyl ester, trithiophosphoric acid S, S, S-tris- (carbo-i-octyloxy) -methyl ester, trithiophosphoric acid S, S, S-tris- (carbo-2-ethylhexyloxy) methyl ester, trithiophosphoric acid S, S, S-tris-1- (carbo-hexyloxy) ethyl ester, trithiophosphoric acid S, S, S-tris-q- (carbo-2-ethylhexyloxy) -ethalester, trithiophosphoric acid S, S , S-tris-2- (carbo-2-ethylhexyloxy) ethyl ester.

Mercaptocarboxylic ester

Examples for this Compounds are esters of thioglycolic acid, thiomalic acid, mercaptopropionic acid, mercaptobenzoic or thiolactic acid, Mercaptoethyl stearate and oleate, as described in the publications FR-A 2 459 816, EP-A 0 090 748, FR-A 2 552 440, EP-A 0 365 483 are. The mercaptocarboxylic acid esters also include polyol esters or their partial esters.

dihydropyridines

worin Z für CO₂CH₃, CO₂C₂H₅, CO₂ ⁿC₁₂H₂₅ oder CO₂C₂H₄-SⁿC₁₂H₂₅ steht.Suitable monomeric dihydropyridines include compounds as described in FR-A 2039496, EP-A 0 002 007, EP-A 0 362 012 and EP-A 0 240 754. Preferred are those of the formula

wherein Z is CO ₂ CH ₃ , CO ₂ C ₂ H ₅ , CO ₂ ⁿ C ₁₂ H ₂₅ or CO ₂ C ₂ H ₄ -S ⁿ C ₁₂ H ₂₅ .

worin T für unsubstituiertes C_1-12-Alkyl steht, L dieselben Bedeutungen wie T hat, m und n Zahlen von 0 bis 20 bedeuten, k 0 oder 1 ist, R und R' unabhängig voneinander Ethylen, Propylen, Butylen oder eine Alkylen- oder Cycloalkylenbismethylengruppe des Typ -(C_pH_2p-X-)_lC_pH_2p- sind, p 2 bis 8 ist, t 0 bis 10 ist und X für Sauerstoff oder Schwefel steht.As polydihydropyridines especially compounds of the following formula are suitable

where T is unsubstituted C _1-12 -alkyl, L has the same meanings as T, m and n are numbers from 0 to 20, k is 0 or 1, R and R 'independently of one another are ethylene, propylene, butylene or an alkylene or cycloalkylenebismethylene group of the type - (C _p H _2p -X-) ₁ C _p H _2p -, p is 2 to 8, t is 0 to 10, and X is oxygen or sulfur.

Such Compounds are described in more detail in EP-A 0 286 887. The (poly) dihydropyridines can in Chlorine-containing polymer useful to 0.001 to 5 and in particular 0.005 to 1 parts by weight, based on the Polymer, be applied. Especially preferred is thiodiethylene bis (5-methoxycarbonyl-2,6-dimethyl-1,4-dihydropyridine-3-carboxylate).

hydrotalcites

The chemical composition of these compounds is known to the person skilled in the art, for example from the publications DE-A 38 43 581, US 4,000,100 , EP-A 0 062 813 and WO 93/20135. Compounds of the hydrotalcite series can 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 valence -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 ^-, NCO 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 ₂ .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.

All particularly preferred are the types Alkamizer 2, Alkamizer P 93-2 (Manufactured by Kyowa Chemical Ind. Co., JP) and L-CAM (lithium modified Hydrotalcite, manufacturer Mizusawa Industrial Chemicals Ltd., JP and Metallgesellschaft AG-DE). Preferably, dehydrated hydrotalcites are used.

Zeolites (alkali or alkaline earth metals)

They can be described by the formula M _{x / 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 0.5 to 30, is.

Examples of zeolites are sodium aluminosilicates of the formulas
Na ₁₂ Al ₁₂ Si ₁₂ O ₄₈ 27H ₂ O [zeolite A], Na ₆ Al ₆ Si ₆ O ₂₄ • 2NaX • 7.5H ₂ O, X = OH, halogen, ClO ₄ [sodalite]; Na ₆ Al ₆ Si ₃₀ O ₇₂ 24H ₂ O; Na ₈ Al ₈ 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 x 264 H 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 .20H 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 (see also US Pat US 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 6,096,820 are described.

The Hydrotalcites and / or zeolites can 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 applied become.

Epoxidized fatty acid esters and other epoxide compounds

The Inventive Stablisatorkombination can additionally preferably contain at least one epoxidized fatty acid ester. It come for that all esters of fatty acids from natural Sources (fatty acid glycerides), like soybean oil or rapeseed oil, in question. It can but also synthetic products such as epoxidized butyl oleate for Use come. Also used can be epoxidized polybutadiene and polyisoprene, optionally also in partially hydroxylated Form, or glycidyl acrylate and glycidyl methacrylate as homo- or Copolymer. These epoxy compounds may also be based on an alumino salt compound be upset; see also DE-A-4 031 818.

metal soaps

metal soaps are mainly metal carboxylates, preferably longer chain Carboxylic acids. common Examples are stearates and laurates, also oleates and salts shorter-chain aliphatic or aromatic carboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, sorbic acid; Oxalic, malonic, succinic, glutaric, adipic, fumaric, citric, benzoic, salicylic, phthalic, hemimellitic, trimellitic, pyromellitic.

As metals may be mentioned: Li, Na, K, Mg, Ca, Sr, Ba, Zn, Al, La, Ce and rare earth metals. Often one uses so-called synergistic mixtures such as barium / zinc, magnesium / zinc, calcium / zinc or calcium / magnesium / zinc stabilizers. The metal soaps can be used individually or in mixtures. An overview of common metal soaps can be found in Ullmann's Encyclopedia of Industrial Chemistry, 5 ^th Ed., Vol. A16 (1985), p. 361 ff.). The metal soaps or mixtures thereof can be used in an amount of, for example, 0.001 to 10 parts by weight, advantageously 0.01 to 8 parts by weight, particularly preferably 0.05 to 5 parts by weight, based on 100 parts by weight PVC, are applied.

Alkali and alkaline earth compounds

This is understood to mean primarily the carboxylates of the acids described above, but also corresponding oxides or hydroxides or carbonates. They are also their mixtures with organic acids in question. Examples are LiOH, NaOH, KOH, CaO, Ca (OH ₂ ), MgO, Mg (OH) ₂ , Sr (OH) ₂ , Al (OH) ₃ , CaCO ₃ and MgCO ₃ (also basic carbonates, such as magnesia, Alba and Huntit), as well as fatty Na and K salts. For alkaline earth and Zn carboxylates and their adducts with MO or M (OH) ₂ (M = Ca, Mg, Sr or Zn), so-called "overbased" compounds are used. In addition to the stabilizers according to the invention, preference is given to using alkali metal, alkaline earth metal and / or aluminum carboxylates.

hydroxycarboxylate

Farther can Hydroxycarboxylatmetallsalze be present, the metal a Alkali or alkaline earth metal or aluminum may be. Prefers are sodium, potassium, magnesium or calcium. The hydroxycarboxylic acid can its glycol, milk, apples, Wine or citric acid or salicylic or 4-hydroxybenzoic acid or else glycerol, glucono and sugar acid (see, for example, GB 1,694,873 and EP-A 1 303 564).

Hydrocalumites and Katoites

These calcium aluminum hydroxo salts have the composition
Ca ₂ Al (OH) ₆ X ₁ / Ca ₃ Al (OH) ₈ X or Ca ₃ Al ₂ (OH) ₁₀ X ₂ with X preferably = OH, ClO ₄ , HPO ₃ and HCO ₃ . These layer lattice compounds are in hydrated form.

Furthermore, other layer lattice compounds such as Al (OH) ₃ and Li hydrotalcite can be used. Further details can be found in EP-A 0 930 332.

fillers

It are used e.g. Calcium carbonate, dolomite, wollastonite, magnesium oxide, Magnesium hydroxide, silicates, china clay, talc, glass fibers, glass beads, Wood flour, mica, metal oxides or metal hydroxides, carbon black, graphite, powdered rock, Barite, glass fibers, talc, kaolin and chalk. Prefers are chalk (HANDBOOK OF PVC FORMULATION E.J. Wickson, John Wiley & Sons, 1993, p. 393-449) and reinforcing agents (TASCHENBUCH the plastic additives, R. Gächter & H. Müller, Carl Hanser, 1990, p. 549-615).

The fillers can in an amount of preferably at least 1 part, for example 5 to 200, suitably 5 to 150 and in particular 5 to 100 parts by weight, based on 100 parts by weight PVC, are used.

lubricant

When Lubricants are for example: montan wax, fatty acid esters, PE waxes, amide waxes, Chloroparaffins, glycerol esters or alkaline earth metal soaps, also fatty ketones and combinations thereof, as listed in EP-A 0 259 783. Prefers is calcium stearate.

softener

• (i) Phthalsäureester wie bevorzugt Di-2-ethylhexyl-, Di-iso-nonyl- und Di-iso-decylphthalat, die auch unter den gebräuchlichen Abkürzungen DOP (Dioctylphthalat, Di-2-ethylhexyl-phthalat), DINP (Diisononylphthalat), DIDP (Diisodecylphthalat) bekannt sind
• (ii) Ester aliphatischer Dicarbonsäuren, insbesondere Ester von Adipin-, Azelain- und Sebazinsäure, bevorzugt Di-2-ethylhexyladipat und Di-iso-octyladipat
• (iii) Trimellitsäureester, beispielsweise Tri-2-ethylhexyltrimellitat, Tri-iso-decyltrimellitat (Gemisch), Tri-iso-tridecyltrimellitat, Tri-iso-octyltrimellitat (Gemisch) sowie Tri-C₆-C₈-alkyl, Tri-C₆-C₁₀-alkyl-, Tri-C₇-C₉-alkyl- und Tri-C₉-C₁₁-alkyl-trimellitate; gebräuchliche Abkürzungen sind TOTM (Trioctyltrimellitat, Tri-2-ethylhexyl-trimellitat), TIDTM (Triisodecyltrimellitat) und TITDTM (Triisotridecyltrimellitat)
• (iv) Epoxyweichmacher; in der Hauptsache sind das epoxidierte ungesättigte Fettsäuren z.B. epoxidiertes Sojabohnenöl
• (v) Polymerweichmacher: Die gebräuchlichsten Ausgangsmaterialien für ihre Herstellung sind Dicarbonsäuren wie Adipin-, Phthal-, Azelain- und Sebacinsäure; Diole wie 1,2-Propandiol, 1,3-Butandiol, l,4-Butandiol, 1,6-Hexandiol, Neopentylglycol und Diethylenglykol, (s. ADMEX^®-Typen der Velsicol Corp. und PX-811 der Asahi Denka)
• (vi) Phosphorsäureester: Eine Definition dieser Ester ist im weiter vorn genannten "Taschenbuch der Kunststoffadditive" Kapitel 5.9.5, SS. 408 – 412, zu finden. Beispiele für solche Phosphorsäureester sind Tributylphosphat, Tri-2-ethylbutylphosphat, Tri-2-ethylhexylphosphat, Trichlorethylphosphat, 2-Ethyl-hexyl-di-phenylphosphat, Kresyldiphenylphosphat, Triphenylphosphat, Trikresylphosphat und Trixylenylphosphat; bevorzugt sind Tri-2-ethylhexyl-phosphat sowie Reofos^® 50 und 95 (Ciba Spezialitätenchemie)
• (vii) Chlorierte Kohlenwasserstoffe (Paraffine)
• (viii) Kohlenwasserstoffe
• (ix) Monoester, z.B. Butyloleat, Phenoxyethyloleat, Tetrahydrofurfuryloleat und Alkylsulfonsäureester
• (x) Glykolester, z.B. Diglykolbenzoate
• (xi) Citronensäureester, z.B. Tributylcitrat und Acetyltributylcitrat wie in WO 02/05206 beschrieben
• (xii) Perhydrophthal-, -isophthal- und -terephthalester sowie Perhydroglycol- und diglycolbenzoatester; bevorzugt ist Perhydro-diisononylphthalat (Hexamoll^® DINCH – Hersteller BASF) wie in DE-A 197 56 913, DE-A 199 27 977, DE-A 199 27 978 und DE-A 199 27 979 beschrieben.

Suitable organic plasticizers are, for example, those from the following groups:

• (i) phthalic acid esters, such as preferably di-2-ethylhexyl, di-isononyl and di-iso-decyl phthalate, which are also known under the common abbreviations DOP (dioctyl phthalate, di-2-ethylhexyl phthalate), DINP (diisononyl phthalate), DIDP (diisodecyl phthalate) are known
• (Ii) esters of aliphatic dicarboxylic acids, especially esters of adipic, azelaic and sebacic acid, preferably di-2-ethylhexyl adipate and di-iso-octyl adipate
• (iii) Trimellitic acid esters, for example, tri-2-ethylhexyl trimellitate, tri-iso-decyl trimellitate (mixture), tri-iso-tridecyl trimellitate, tri-iso-octyl trimellitate (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; common abbreviations are TOTM (trioctyl trimellitate, tri-2-ethylhexyl trimellitate), TIDTM (triisodecyl trimellitate) and TITDTM (triisotridecyl 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, l, 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 earlier 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, 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, eg diglycol zoates
• (xi) Citric acid esters, for example tributyl citrate and acetyltributyl citrate as described in WO 02/05206
• (xii) perhydrophthalic, isophthalic and terephthalic esters, and perhydroglycol and diglycol benzoate esters; is preferred perhydro-diisononyl phthalate (DINCH ^® Hexamoll - manufactured by BASF) as described in DE-A 197 56 913 describes DE-A 199 27 977, DE-A 199 27 978 and DE-A 199 27 979th

A definition of these plasticizers and examples of such are in "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 be used in an amount of, for example, 5 to 50 parts by weight, suitably 10 to 45 parts by weight, based on 100 parts by weight of PVC. Hard or semi-hard PVC preferably contains up to 20%, more preferably up to 5% or no plasticizer.

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, Se), ultramarine blue. Organic pigments include, for example, azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, diketo-pyrrolopyrrole 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, EJ Wickson, John Wiley & Sons, New York, 1993.

antioxidants

To counting alkylated monophenols, e.g. 2,6-di-tert-butyl-4-methylphenol, alkylthiomethylphenols, e.g. 2,4-dioctylthiomethyl-6-tert-butylphenol, alkylated hydroquinones, z. B. 2,6-di-tert-butyl-4-methoxyphenol, hydroxylated thiodiphenyl ethers, e.g. 2,2'-thio-bis- (6-tert-butyl-4-methylphenol), Alkylidene bisphenols, e.g. 2,2'-methylene-bis- (6-tert-butyl-4-methylphenol), Benzyl compounds, e.g. 3,5,3 ', 5'-tetra-tert-butyl-4,4'-di-hydroxydibenzylether, hydroxybenzylated malonates, e.g. Dioctadecyl-2,2-bis- (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, Hydroxybenzyl aromatics, e.g. 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, Triazine compounds, e.g. 2,4-bis-octylmercapto-6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, Phosphonates and phosphonites, e.g. Dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, Acylamino-phenols, e.g. 4-hydroxy-lauric acid anilide, esters of beta- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid, beta (5-tert-butyl-4-hydroxy-3-methylphenyl) -propionic acid, the Beta (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid, ester of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with mono- or polyvalent ones Alcohols, amides of beta- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid, e.g. N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine, Vitamin E (tocopherol) and offspring. The antioxidants can in an amount of, for example, 0.01 to 10 parts by weight, suitably 0.1 to 10 parts by weight and in particular 0.1 to 5 parts by weight, based to 100 parts by weight PVC, are applied.

UV absorber and light stabilizer

Examples for that 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'-dioctyloxy-oxanilide, 2,2'-di-octyloxy-5,5'-di-tert-butyl-oxanilide, 2- (2-hydroxyphenyl) -1,3,5-triazines, e.g. 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, hindered Amines based on tetramethylpiperidine or tetramethylpiperazinone or tetramethylmorpholinone, e.g. 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-benzoxazinonylbenzene.

Optical brighteners

Examples therefor are bis-benzene (1,4) -oxazoles, phenylcoumarins and bis-styryl-biphenyls such as 4-methyl-7-diethylaminocoumarin, 3-phenyl-7- (4-methyl-6-butoxybenzoxazole) coumarin, 4,4'-bis (benzoxazol-2-yl) stilbene and 1,4-bis (benzoxazol-2-yl) -naphthalene. Preferably, solutions are more optical Brightener in a plasticizer, for example DOP.

propellant

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

antistatic agents

antistatic agents are divided 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 alkanesulfonates and phosphoric acid bis-fatty alcohol ester alkali salts. Belong to (c) quaternary Fatty alkylammonium salts and to (d) include fatty alkyl betaines and fatty alkyl imidazoline betaines. Particular preferred compounds are lauric diethanolamide, myristyl diethanolamine, Naoctadecylsulfonate and Na-bis-octadecyl phosphate. The presence of component (A) allows in many cases due to the inherent properties a reduction in the amount of expensive antistatic agents used.

definitions and examples of further additives like impact modifiers and processing aids, gelling agents, biocides, metal deactivators, Flame retardants, antifogging agents and compatibilizers are described in "Kunststoffadditive", R. Gächter / H. Miller, Carl Hanser Verlag, 3rd ed., 1989, and 4th ed. 2001 and in the "Handbook of Polyvinyl Chloride Formulating "E. J. Wickson, J. Wiley & Sons, 1993, as well as in "Plastics Additives "G. Pritchard, Chapman & Hall, London, 1st Ed., 1998. Impact Modifiers are also detailed described in "Impact Modifiers for PVC ", J.T. Lutz / D. L. Dunkelberger, John Wiley & Sons, 1992.

Further Stabilizers can its phenylurea 2-phenylindole, 3-hydroxyaniline and its N-phenyl derivative, Bisaminoacrylates of butanediol and thiodiglycol, 2-pyrrolecarboxylic acid (see EP-A 1 299 466), 2,4-diphenylpyrrole and 2-alkyl-4-phenylpyrrole-3-carboxylic acid ester, 3-amino-4-alkyl / phenyl-pyrrole-3-carbon ester and Cahydroxy-aluminum-hydrogen phosphite (CHAP compounds see EP-A 0 506 831).

Prefers are also stabilizer systems which additionally disubstituted Cyanacetylcarbamide, such as N, N'-dimethyl-cyanacetylcarbamid or a 1,3-disubstituted 6-aminouracil, an enaminone, a substituted Indole or a urea or a tert. Ethanol or propanolamine contain. examples for suitable compounds are 1,3-dimethyl-6-aminouracil, 1,3-diallyl-6-aminouracil, 1,4-butanediol bis (β-aminocrotonate), thiodiethylene glycol bis (β-aminocrotonate), 2-phenyllaurylindole, N, N'-diphenylthiourea and triethanol, triisopropanolamine and stearyl or oleyldiethanol or diisopropanolamine. Further examples are in DE-A 101 07 329 described. See also EP-A 0 768 336, EP-A 0 967 245, EP-A 0 967 209, EP-A 0 967 208, EP-A 0 962 491, EP-A 1 044 968, WO 02/072 684 and WO 02/048 249.

A particular preference lies in the combination of blends (A) + (B) + (C) with phosphite esters, wherein the additional phosphite distearylpentaerythritol diphosphite, triphenyl phosphite, tris-nonylphenyl phosphite, phenyldidecyl phosphite, poly (dipropylene glycol) phenyl phosphite, tetraphenyl dipropylene glycol diphosphite, tetraisodecyl diproylenykoldiphosphit , Tris-dipropylene glycol phosphite, decyl diphenyl phosphite, trioctyl phosphite, trilauryl phosphite or (nonylphenyl _1,5 -C ₁₂ / C ₁₃ alkyl) _1,5- phosphite.

One Another object of the invention are compositions comprising a chlorine-containing polymer and a stabilizer system according to the invention. In these compositions, the compounds are the general ones Formulas (A) and (B) to achieve stabilization in chlorine-containing Polymer useful to 0.01 to 10, preferably to 0.05 to 5, based on 100 parts by weight of polymer, to use. The salts (C-1), (C-2) and (C-3) can in an amount of, for example, 0.001 to 10, suitably 0.01 to 5, particularly preferably 0.01 to 3 parts by weight, based on 100 Parts by weight of polymer. Preferred are compositions, where the ratio from the compound of general formulas (A) and (B) to the salt (C-1), (C-2) and (C-3) by weight, in the range of 1.5: 1.5: 1 to 10: 10: 1.

Examples of the chlorine-containing polymers to be stabilized are polymers of vinyl chloride, vinylidene 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 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, postchlorinated 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 alpha-substituted acrylic acid; Polymers of chlorinated styrenes, for example dichlorostyrene; Chlorinated rubbers; chlorinated polymers of ethylene; Polymers and postchlorinated poly mers 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.

Prefers is a PVC homopolymer, also in combination with polyacrylates.

Further Also suitable are 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 and / or 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 relatives 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, styrene-acrylonitrile copolymers based on acrylate (ASA) are also used. into consideration. Preferred as a component in this context Polymer compositions containing as components (i) and (ii) a Mixture of 25-75% by weight PVC and 75-25 Wt .-% of said copolymers. Really important are as component compositions of (i) 100 parts by weight PVC and (ii) 0-300 Parts by weight ABS and / or SAN modified ABS and 0-80 parts by weight the copolymers NBR, NAR and / or EVA, but especially EVA.

Farther also come in particular for stabilization in the context of this invention Recyclates of chlorine-containing polymers in question, which are here closer to the above described polymers, which by processing, use or storage damage have experienced. Particularly preferred is PVC recyclate. Another Use of the stabilizer combinations according to the invention is due to the fact that the Made of hard or soft PVC antistatic properties can be awarded. In this way it is possible reduce the use of expensive antistatic agents. Preferred for this Application is soft PVC or semi-rigid PVC.

Prefers is also the use of commodities, which are characterized by a distinguish special fine foam structure. This applies to hard, Soft and semi-hard PVC. This aspect is especially important Wallpapers and floors Soft PVC. Usually, heavy metal compounds such as Zn or Sn stabilizers as a kicker to achieve a fine foam required. Surprised it was found that compounds the composition (A-1) or (A-2) a kicker effect on isatric acid or N-methylisatin-anhydride exercise, which ensures the achievement of a fine foam structure.

Not It was also foreseeable that the Resistance properties of a commodity used as a component (C-1), (C-2) or (C-3) a Mg, Ca or Al salt instead of a Contains alkali salt, drastically improved, which is especially true for the cable and insulator manufacturing and semiconductor applications as cheap proves.

The According to the invention co-usable Compounds and the chlorine-containing polymers are those skilled in the art generally known and are described in detail in "Kunstoffadditive", R. Gächter / H. Müller, Carl Hanser Verlag, 3rd ed., 1989 and 4th ed. 2001, in DE-A 197 41 778 and EP-A 0 967 245, which are incorporated herein by reference is taken.

The stabilization according to the invention is suitable for both Chlorinated polymer compositions that are not plasticized or plasticizer-free or substantially plasticizer-free compositions pose as well as for plasticized compositions. Particular preference is given to applications in soft PVC or Semirigid PVC.

The Compositions of the invention are particularly suitable, in the form of hard formulations, for hollow bodies (bottles), packaging films (Thermoforming foils), blown film, "Crash Pad "films (automobiles), Pipes, foams, heavy profiles (window frames), light-wall profiles, Construction profiles, films (also produced by the Luvitherm process), Profiles, sidings, fittings, office films and equipment housing, Insulators, computers and components of household appliances as well for electronic applications especially in the semiconductor field.

Preferred other compositions in the form of semi-hard and soft formulations are for Drah sheathings, cable insulation, decorative foils, roof foils, foams, agricultural foils, hoses, sealing profiles, floors, wallpaper, automotive parts, soft foils, injection-molded parts, office foils and films for air-inflated halls. Examples of the use of the compositions according to the invention as plastisols are artificial leather, floors, 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 Luvitherm method. For details see "PVC Plastics Handbook", Volume 2/2, W. Becker / H. Braun, 2nd ed., 1985, Carl Hanser Verlag, SS. 1236-1277.

The Components (A) and (B) and (C) may be used together with other stabilizers or additives or PVC substrate are premixed, wherein preferred as further stabilizers alkaline earth hydroxides, zeolites, hydrotalcites, Calumite or Katoite can be present. Very special preferred are called so-called hot mixers, working in a temperature range from 80 ° C up to 120 ° C. Here is a optimal homogenization achieved. Diffuse in the presence of PVC powder in this case stabilizers and other additives in the PVC grain. presence Smaller amounts of water are not disturbing. A variant is that one the mixing process in a lubricant melt, the Ca-stearate or Mg-laurate or stearate, in the presence of a Ca- Mg hydroxide, a basic Mg, Ca or Al salt or of "overbased" compounds of the Magnesium and calcium or a polyol or a zeolite, wherein Maltitol, lactitol, palatinit or zeolite A, Ca-hydroxide, a basic Ca or Mg salt or an "overbased" compound of magnesium or calcium is preferred.

special preferred is the embodiment in which presented in this melt the components (A) and (C) and the component (B) are metered.

Appropriately the incorporation of the stabilizers in another variant according to following methods: as an emulsion or dispersion (a possibility is e.g. the shape of a pasty one Mixture, an advantage of the system according to the invention consists in this Dosage form in stability the paste); as a dry mixture during the mixing of additional components or polymer blends; by direct addition to the processing apparatus (e.g., calenders, mixers, kneaders, extruders and the like) or as a solution or melt or as flakes or pellets in dust-free form as One Pack. special Pre-mixtures of components (A), (B) and (C) are preferred in compact form in garnishing equipment, with a non-dusting, non-adhesive, free-flowing Granules are obtained, which are mixed with e.g. PVC and while the processing process very easy to unlock. Of great advantage is it during the Packaging (compacting or spraying) to add binders, which preferably consists of cellulose ethers or esters (mainly hydroxyethyl, Hydroxypropyl- and hydroxypropyl-methylcellulose or carboxymethylcellulose) consist. Alternatively, polyvinyl alcohol or polyvinylpyrrolidone may also be added become.

The stabilized according to the invention Polymer, can be prepared in a conventional manner, including using devices known per se, such as those mentioned above Processing equipment, the stabilizer mixture according to the invention and optionally further additives mixed with the polymer. Here, the stabilizers can individually or in mixture or in the form of so-called masterbatches.

The stabilized polymer according to the present invention can be known Assign to the desired shape to be brought. Such processes include, for example, grinding, calendering, Extrusion, injection molding or Spinning, further extrusion blisters. The stabilized polymer can also be processed into foams. Subject of the invention Thus, a method for stabilizing chlorine-containing polymers by Addition of the stabilizer mixture according to the invention to a chlorine-containing polymer, as well as articles containing PVC, the by the stabilizer mixtures according to the invention is stabilized.

One Another component of the invention is the combinations from (A), (B) and (C) to pre-stabilization of particular use of PVC. The PVC polymerization is known to be in aqueous medium carried out, why it is necessary is, the polymer prior to further processing into a finished article to a To dry powder, which is associated with thermal stress is that leading to injury of the "virgin" polymer has now been found that one Addition of the systems according to the invention during the Polymerization process leads to a reduction of the damage described. This Effect allows it, in the Nachstabilisierung (actual thermostabilization) the amount of thermal stabilizers, even those conventional The way in which money is saved - and from the environmental point of view - to one Conservation of resources leads.

Claims (48)

Stabilizer system for polymers comprising at least (A) an NH compound of the formulas (A-1) or / and (A-2) R ¹ ₂ NH (A-1) (R ¹ NH-) ₂ R ² (A-2) and (B) a glycidyl derivative (B-1), an acrylic acid ester (B-2), a carbonyl compound (B-3) (CH ₂ = CR ⁸ -CO ₂ -) _n R ⁶ (B-2) R ⁹ ₂ C = O (B-3) a β-ketoester (B-4), a cyclic anhydride or lactone (B-5) and / or a carbonic acid ester (B-6), and (C) a perchlorate (C-1), perfluoroalkanesulfonate (C-2 ) and / or sulfate ester salt (C-3) where the short formulas, substituents and indices have the following meaning R ¹ = H or a C ₁ -C ₂₄ radical, in particular C ₁ -C ₂₄ alkyl or alkanoyl, in addition may be interrupted by 1 to 3 nonadjacent O atoms, 2-hydroxy-C ₂ -C ₂₄ -alkyl or -alkanoyl, trishydroxymethyl-methyl, 1,1-bis-hydroxymethyl-C ₁ -C ₄ -alkyl, C ₃ - C ₂₀ alkenyl or alkenoyl, cyclohexyl, phenyl or benzoyl, 2-hydroxyphenyl or 2-hydroxybenzoyl, C ₇ -C ₁₂ alkylphenyl or benzoyl, C ₇ -C ₁₂ phenylalkyl or alkanoyl and 2-hydroxy-2- phenylethyl or cyanoacetylcarbamoyl; R ² = a C ₂ -C ₁₂ -diradical, in particular C ₂ -C ₁₂ -alkylene or -alkanoylene, which may additionally be interrupted by 1 to 3 nonadjacent O or S atoms or neopentylene, isophoronediylene, bis-methylene-phenylene, Phenylene, cyclohexylene, bis-methylene-cyclohexylene, bisphenylene (A) and bis-phenylene (F); (A-1) = also 5- to 7-membered ring NH heterocycle (azole, azine or azepine), the partial or perhydrogenated, carry up to 4 oxo or thiono groups and / or one or more times C- or N-substituted and / or additionally up to 3 N or 1 O or S atom (s) and can be further 1- to 2-fold benzannelated; (B-1) = C-glycidyl, N-glycidyl, (thio) ether glycidyl and / or ester glycidyl compound of the formulas (B-1/1), (B-1/2), (B-) 1/3) and (B-1/4)

with R ³ = R ¹ (where R ¹ = acyl excluded), R ⁴ = methyl or phenyl or R ³ + R ⁴ = mono- or bicyclic, which may also contain an oxirane group and R ⁵ = - (CH ₂ ) ₂ - , - (CH ₂ ) ₃ -, -CH = CH-, 1,2-phenylene or

X = O, S or N-glycidyl, R ⁶ = of n dependent R ¹ , (CH ₂ ) ₂ -SR ¹ , R ² , CH ₃ C (CH ₂ -) ₃ , CH ₃ CH ₂ C (CH ₂ - ) ₃ C (CH ₂ -) ₄ , n = 1 to 4, R ⁷ = of n depending R ¹ , R ² , benzoltriyl, benzene-tetra-yl or

R ⁸ = H, methyl or CH ₂ CO ₂ R ¹ (where R ¹ = acyl excluded) R ⁹ = R ³ or R ⁹ ₂ in formula (B-3) also mono-, bi- or tricyclic (B-3) = also glutaric or terephthalaldehyde, glyoxal, acetonylacetone, and acetals or ketals, or sulfite or dithionite addition compounds of aldehydes (B-4) = β-keto esters of the formula (R ⁴ COCH ₂ CO ₂ ) _n R ⁶ (B -5) = cyclic anhydride or lactone from the group succinic, glutaric, maleic, phthalic, pyromellitic, trimellitic, isatic and N-methylisatinic anhydride, itaconic, citraconic and aconitic anhydride, butyric and valerolactone and phthalide , (B-6) = carbonic acid ester from the group dimethyl, diethyl, dipropyl and dibutyl carbonate and ethylene and propylene carbonate, (C-1), (C-2) and (C-3) salts of the formulas (ClO ₄ ) _n M (C-1) (C _m F _{2m + 1} SO ₃ ) _n M (C-2) (R ¹ OSO ₃ ) _n M (C-3) with R ¹ = C ₁ -C ₁₈ -alkyl or C ₁₀ -C ₁₈ -alkenyl, m = 1-6, n depending on the charge of the M-cation, M = Li, Na, K, Mg, Ca, Sr, Ba, Ln, Ce, Al, Sn, Zn or a Schichtgitterkation from the group hydrotalcite, hydrocalumite or a Katoitschichtgitterkation and in category (C-2) and (C-3) also ammonium salts. Stabilizer system according to claim 1, characterized that (A) = (A-1), (B) = a glycidyl derivative, a cyclic anhydride or / and a carbonic acid ester and (C) a perchlorate or / and as perfluoroalkanesulfonate a triflate salt is. Stabilizer system according to claim 1 or 2, characterized in that the salt (C) is a Na, K, Ca, Mg or Al salt is. Stabilizer system according to one of claims 1 to 3, characterized in that (A) is an open-chain or cyclic secondary amine is. Stabilizer system according to claim 4, characterized in that the open-chain secondary amine is a di-C ₄ -C ₈ -alkylamine, diallylamine, cyanoacetylcarbamide, dialkanolamine, dicyclohexylamine, dibenzylamine and N-methyl- or N-ethylaniline and the cyclic secondary amine, Aminouracil, morpholine, pyrrolidine or piperidine. Stabilizer system according to claim 4, characterized in that that the cyclic secondary amine an azole, azoline, azolidine, azole (id) inone or thione, or azolidinedione is. Stabilizer system according to claim 6, characterized that the cyclic secondary amine (benz) imidazole, (Benzene, toluene) triazole, aminotriazole, carbazole, 2-phenylindole, pyrrolidinone, pyrrolidinedione, Imidazolidinone, imidazolidinethione or an unsubstituted or 5-mono- or 5,5-disubstituted imidazolidinedione. Stabilizer system according to claim 4, characterized in that that the cyclic secondary amine isocyanuric or phthalimide. Stabilizer system according to one of claims 2 to 8, characterized in that the glycidyl derivative (B-1) is a C ₄ -C ₁₈ alkenoxide, allyl glycidyl ether, bisphenol A or F diglycidyl ether or a glycidyl ester. Stabilizer system according to claim 2 or 3, characterized characterized in that (A-1) is an open-chain secondary amine and (B) is a glycidyl derivative (B-1). Stabilizer system according to claim 10, characterized that the open-chain secondary amine diethanolamine or diisopropanolamine. Stabilizer system according to one of claims 1 to 3 and 9, characterized in that (A-1) a primary amine and (B) is a glycidyl derivative (B1). Stabilizer system according to claim 12, characterized in that that the primary amine (A) is monoethanol or monoisopropanolamine. Stabilizer system according to claim 1, characterized that (A-1) mono- or Diethanol- or mono- or diisopropanolamine and (B-6) isatin or N-methylisatinic is. Stabilizer system according to claim 1, characterized that (A-1) is a mixture of azole and diethanol or diisopropanolamine and (B-4) is an aldehyde as a carbonyl moiety or an aldehyde releaser. Stabilizer system according to claim 15, characterized in that that (B-3) methanal, ethanal, propanal or their splitters, benzaldehyde or salicylaldehyde. Stabilizer system according to claim 1, characterized in that (A-1) is an unsubstituted or monosubstituted cyanoacetylcarbamide, 6-aminouracil, 6-amino-1-methyluracil, 6-amino-1-ethyluracil, monoethanol, monoisopropanolamine, diethanol or diisopropanolamine and (B-2) a (meth) acrylic or an itaconic acid ester is. Stabilizer system according to claim 1 or 2, characterized in that (A-1) 6-aminouracil, 6-amino-1-methyluracil or 6-amino-1-ethyluracil and (B-6) carbonate ester is. Stabilizer system according to claim 18, characterized that (B-6) is the carbonic acid ester Ethylene or propylene carbonate. Stabilizer system according to one of claims 1 to 3 and 9, characterized in that (A-1) 6-aminouracil, 6-amino-1-methyl or 6-amino-1-ethyluracil and (B-1) is a glycidyl derivative. Stabilizer system according to claim 1, 2 or 20, characterized in that the glycidyl derivative is a C-glycidyl compound, a glycidyl ether or a glycidyl ester. Stabilizer system according to claim 1 or 2, characterized in that (A-1) is an unsubstituted or monosubstituted Cyanacetylcarbamid and (B-6) is a carbonic acid ester. Stabilizer system according to claim 22, characterized in that that the monosubstituted cyanoacetylcarbamide monomethyl, monoethyl or monoallylcyanacetylcarbamide and the carbonic acid ester ethylene or propylene carbonate is. Stabilizer system according to one of claims 1 to 4, characterized in that (A-1) is an unsubstituted or a monosubstituted cyanoacetylcarbamide; and (B-1) a glycidyl derivative. Stabilizer system according to claim 24, characterized that the monosubstituted cyanoacetylcarbamide monomethyl, monoethyl or monoallylcyanacetylcarbamide and the glycidyl derivative a C-glycidyl compound, a glycidyl ether or a glycidyl ester. Stabilizer system according to one of claims 1 to 4, characterized in that (A-1) a unsub is substituted or monosubstituted cyanoacetylcarbamide, and as (B-3) is an aldehyde as the carbonyl component. Stabilizer system according to claim 26, characterized that the monosubstituted cyanoacetylcarbamide monomethyl, monoethyl or monoallylcyanacetylcarbamide and the aldehyde hexanal, heptanal or Octanal is. Stabilizer system according to claim 1, characterized that (A-1) 6-aminouracil, 6-amino-1-methyluracil or 6-amino-1-ethyluracil and (B-3) hexanal, Heptanal or octanal. Stabilizer system according to one of claims 1 to 28, containing as further components metal soaps and / or at least another substance from the group of polyols and disaccharide alcohols, Glycidyl compounds, hydrotalcites, alkali / alkaline earth metal aluminosilicates, Alkali / alkaline earth hydroxides, alkaline earth oxides (especially Ca oxide or / and hydroxide) or - (hydrogen) carbonates or alkali (alkaline earth) hydroxy-carboxylates or metal carboxylates, basic Mg, Ca or Al salts, overbased compounds of magnesium and calcium, Phosphites, plasticizers, antioxidants, fillers, pigments, light stabilizers, Lubricant and epoxidized fatty acid ester. Stabilizer system according to one of claims i to 28, containing as further component a phosphite. Stabilizer system according to claim 30, characterized in that the phosphite distearylpentaerythritol diphosphite, triphenyl phosphite, tris-nonylphenyl phosphite, phenyldidecyl phosphite, poly (dipropylene glycol) phenyl phosphite, tetraphenyl dipropylene glycol diphosphite, tetra-isodecyl-dipropylene glycol diphosphite, tris-dipropylene glycol phosphite , Decyldiphenyl phosphite, trioctyl phosphite, trilauryl phosphite or (nonylphenyl _1,5 -C ₁₂ / C ₁₃ alkyl) _1,5 phosphite. Process for the preparation of the stabilizer system according to one of the claims 1 to 31, characterized in that a homogenization of Components (A), (B) and (C) to the stabilizer system in a (hot) mixer or extruder performed becomes. Method according to claim 32, characterized in that that the homogenization in a lubricant melt at 80 ° C to 120 ° C performs. Containing stabilized polymer composition a chlorine-containing polymer and a stabilizer system according to one the claims 1 to 31. Method according to claim 32, characterized in that that the homogenization is carried out in the presence of PVC. Method according to claim 32, characterized in that that after homogenization, compaction by spray-drying, optionally in the presence of suitable binders. A polymer composition according to claim 34, characterized characterized in that based on 100 parts by weight of chlorine-containing polymer, (A) and (B) 0.01-10 Parts by weight of the components and 0.001-5 Parts by weight of component (C) are included. Process for the stabilization of chlorine-containing polymers by adding a stabilizer system according to one of claims 1 to 31 to the chlorine-containing polymer. Process for the stabilization of chlorine-containing polymers according to claim 38, characterized in that the chlorine-containing polymer is plasticized PVC is. Use of a method according to claim 39 stabilized soft PVC for the production of floors, motor vehicles Parts, soft films, hoses, injection molded parts or wire coating or as plastisol for the production of wallpaper, Floors or Synthetic leather (Crashpad or "Slush mold "). Process for the stabilization of chlorine-containing polymers according to claim 38, characterized in that the chlorine-containing polymer rigid PVC is. Use of a method according to claim 41 stabilized rigid PVC for the production of films (also Luvitherm), PVC pipes or profiles. Utensils, containing a stabilized polymer composition according to claim 34, wherein the polymer is PVC. Commodities of a stabilized polymer composition according to claim 34, wherein the polymer is foamed Hard or soft PVC, and being in the manufacture of the commodities as Propellant isatric anhydride or N-methylisatic anhydride was used. Use of the stabilizer system according to the claims l to 31 for the stabilization of recycled halogen-containing polymers. Use of stabilized polymer compositions according to claim 34 in electronics, insulators and semiconductors. Use of the stabilizer system according to one of claims 1 to 31 for pre-stabilization of polyvinyl chloride. Use of the stabilizer system according to one of claims 1 to 31 for antistatic equipment of polyvinyl chloride.