DE10238471A1 - Use of compositions containing 4-hydroxy-2-pyrones for stabilizing halogen-containing organic plastics - Google Patents

Abstract

Composition containing at least one 4-hydroxy-2-pyrone of the formula (I) DOLLAR F1 in which the radical R is hydrogen, an optionally substituted alkyl radical with a total of 1 to 18 carbon atoms or an optionally substituted aryl radical with a total of 6 to 24 carbon atoms means are suitable for stabilizing halogen-containing organic plastics, in particular PVC, against thermal and / or photochemical degradation.

Description

Field of the Invention

The invention relates to the use of compositions containing at least one 4-hydroxy-2-pyrone for stabilizing halogen-containing organic plastics.

Halogen-containing plastics or from them Molding compounds produced are known to tend to degradation or Decomposition reactions when exposed to thermal stress or with high-energy radiation, for example ultraviolet light, get in touch.

To stabilize PVC in the Processing is usually based on metal-containing stabilizers Pb, Ba, Cd, Sn, Ca and Zn used. Already in 1940 urea derivatives such as. Diphenylthiourea proposed to stabilize PVC (compare: Gächter / Müller, "Plastic Additives", Carl Hanser Verlag 1989, p 312) These connections are mostly used in combination with metal-containing stabilizers, because as a rule, they alone do not provide adequate long-term stabilization result.

In EP-A-768 336 it is proposed to use compositions for stabilizing PVC which contain aminouracile and perchlorates.

EP-A-0 059 052 describes a process for the preparation of 4-hydroxy-6-methyl-2-pyrone.

The disclosure JP-A-58 023 843 describes transparent, heat-stabilized PVC resins containing 2-alkyl-3-hydroxy-4-pyrones of the following formula:

A good odor characteristic is attributed to these resins in particular. It should be noted that the 2-alkyl-3-hydroxy-4-pyrones according to JP-A-58 023 843 represent a different class of substances than the 4-hydroxy-2-pyrones of the formula (I) according to the present invention described below.

Description of the invention

Object of the present invention was to provide compositions that are useful for stabilization of halogen-containing organic plastics, in particular PVC, against thermal and / or photochemical degradation.

Object of the present invention is the use of compositions containing at least one 4-Hydroxy-2-pyrone special structure for stabilizing halogen-containing organic plastics, in particular PVC, against thermal and / or photochemical degradation.

worin der Rest R Wasserstoff, einen gegebenenfalls substituierten Alkylrest mit insgesamt 1 bis 18 C-Atomen oder einen gegebenenfalls substituierten Arylrest mit insgesamt 6 bis 24 C-Atomen bedeutet. Unter der Bezeichnung "mit insgesamt" im Hinblick auf die angegebene Zahl an C-Atomen ist jeweils die Summe der C-Atome des Alkyl- bzw. des Arylrestes und – sofern dieser substituiert ist – der C-Atome der Substituenten zu verstehen.4-hydroxy-2-pyrones in the context of the present invention are understood to mean substances of the general formula (I)

wherein the radical R is hydrogen, an optionally substituted alkyl radical with a total of 1 to 18 carbon atoms or an optionally substituted aryl radical with a total of 6 to 24 carbon atoms. The term "with a total" with respect to the number of carbon atoms indicated is to be understood as the sum of the carbon atoms of the alkyl or aryl radical and - if this is substituted - the carbon atoms of the substituents.

The substances (I) are are 4-hydroxy-2-pyrones. Characteristic of this The following structural elements are substance classes:

• - it there is a lactone group,
• - in the α position to the oxygen atom in the 6-ring there is the substituent R,
• - in 4 position is an OH function.

It should be noted that there can be tautomeric forms for formula (I):

This is the classic, the professional well-known keto-enol tautomerism. The radical R in the formula (I) can Mean hydrogen.

If the radical R in the formula (I) is an alkyl radical having 1 to 18 carbon atoms, this radical can be saturated or unsaturated, be linear or branched; it can optionally be a substituent such as halogens, carbonyl groups, carboxyl groups, etc. contain.

Examples of usable according to the invention Compounds (I) in which the radical R is a saturated, linear or branched Alkyl radical means 4-hydroxy-6-methyl-2-pyrone, 4-hydroxy-6-ethyl-2-pyrone, 4-hydroxy-6-n-propyl-2-pyrone, 4-hydroxy-6-iso-propyl-2-pyrone, 4-hydroxy-6-n-butyl-2-pyrone, 4-hydroxy-6-sec-butyl-2-pyrone, 4-hydroxy-6-iso-butyl-2-pyrone, 4-hydroxy-6-pentyl-2-pyrone, 4-hydroxy-6-hexyl-2-pyrone, 4-hydroxy-6-heptyl-2-pyrone, 4-hydroxy-6-octyl-2-pyrone, 4-hydroxy-6-nonyl-2-pyrone, 4-hydroxy-6-decyl-2-pyrone, 4-hydroxy-6-undecyl-2-pyrone, 4-hydroxy-6-dodecyl-2-pyrone, 4-hydroxy-6-tridecyl-2-pyrone, 4-hydroxy-6-tetradecyl-2-pyrone, 4-hydroxy-6-pentadecyl-2-pyrone, 4-hydroxy-6-hexadecyl-2-pyrone, 4-hydroxy-6-heptadecyl-2-pyrone, 4-hydroxy-6-octadecyl-2-pyrone.

Particularly preferred compounds (I) are 4-hydroxy-2-pyrone, 4-hydroxy-6-methyl-2-pyrone and 4-hydroxy-6-ethyl-2-pyrone

Very particularly preferred as a compound (I) is 4-hydroxy-6-methyl-2-pyrone.

The radical R in the formula (I) can also an optionally substituted aryl radical with a total 6 to 24 carbon atoms. Halogens are preferred as substituents, especially fluorine or chlorine, as well as carbonyl groups, carboxyl groups, Alkyl residues, etc; are very particularly preferred as substituents saturated Alkyl residues, which can be linear or branched.

Examples of usable according to the invention Compounds (I) in which the radical R is an optionally substituted one Aryl radical with a total of 6 to 24 carbon atoms are 4-hydroxy-6-phenyl-2-pyrone, 4-hydroxy-6- (4-tert-butyl-phen-1-yl) -2-pyrone, 4-hydroxy-6-benzyl-2-pyrone.

Another object of the invention are stabilizer compositions for stabilizing halogen-containing organic plastics, in particular PVC, against thermal and / or photochemical degradation, characterized in that this Compositions of at least one 4-hydroxy-2-pyrone of those specified above contain general formula (I). Regarding (I), refer to the above already executed.

In the stabilization of halogen-containing organic plastics, the 4-hydroxy-2-pyrones to be used according to the invention are used in an amount of 0.001 to 5 phr, preferably 0.01 to 2 phr and in particular 0.01 to 0.5 phr. The information just mentioned means that the stabilized halogen-containing organic plastic is the 4-hydroxy-2-pyrone - regardless of the percentage in which the stabilizer compositions used according to the invention contain the 4-hydroxy-2-pyrone contain - in an amount of 0.001 to 5 phr, preferably 0.01 to 2 phr and in particular 0.01 to 0.5 phr.

The expression familiar to the expert phr ("parts per hundred resin") is known to indicate how many parts by weight the component in plastic - related per 100 parts by weight of plastic - are present.

In one embodiment, the stabilizer compositions according to the invention contain continue one or more plastic additives that are selected from the group of

• (d1) perchlorates,
• (d2) fluoroalkanesulfonic acids,
• (d3) aminouracile,
• (d4) zeolites,
• (d5) cationic layer compounds,
• (d6) CHAP compounds,
• (d7) Katoite,
• (d8) glycidyl compounds,
• (d9) beta-diketones and beta-keto esters,
• (d10) dihydropyridines and polydihydropyridines,
• (d11) polyols and polyol derivatives,
• (d12) sterically hindered amines (tetraalkylpiperidine compounds),
• (d13) alkali alumocarbonates (Dawsonite),
• (d14) alkali and alkaline earth compounds,
• (d15) antioxidants,
• (d16) separation and / or Lubricant,
• (d17) plasticizers,
• (d18) pigments,
• (d19) fillers,
• (d20) phosphites,
• (d21) thiophosphites and thiophosphates,
• (d22) mercaptocarboxylic acid esters,
• (d23) epoxidized fatty acid esters,
• (d24) UV absorbers and light stabilizers,
• (d25) blowing agent,
• (d26) urea,
• (d27) metal soaps,
• (d28) antistatic agents,
• (d29) cyanoacetylureas.

The compounds of classes (d1) and classes (d3) to (d29) are well known to the person skilled in the art as additives for halogen-containing plastics, in particular PVC. For representative examples of substances from these classes, the example cited at the beginning is exemplary EP-A-768 336 directed.

In connection with the use of the term "additive" for the compounds of classes (d1) to (d29) should be pointed out that the Expert in the field of plastics processing additives both under classified structurally as well as from a functional point of view.

With functional classification are typical plastic additives: antistatic agents, antifoggants, Antioxidants, UV stabilizers, adhesives, calendering aids, Mold release agents, lubricants, release agents, lubricants, plasticizers, Fragrances, flame retardants, fillers, Pigments, blowing agents, agents to increase thermal stability (thermal stabilizers).

The additive classes mentioned above (d1) to (d29) largely follow the structural classification, i.e. the chemical structure classification. With some However, the functional definition was preferred to classes.

It should also be noted that connections a certain class of substances, hence compounds that are classified as structural Aspects of the same class can be assigned in in practice often not only perform one function, but two or more. So can For example, calcium soaps act as lubricants and / or release agents, but they can also - about when processing the plastic polyvinyl chloride (PVC) - as a means serve to improve thermal stability.

To the connections of the Groups d1) to d29)

The compounds of groups d1) to d29) are generally used in the context of the present invention, unless specifically stated otherwise, in each case in an amount of 0.001 to 2 phr and in particular 0.01 to 0.5 phr. The phrase phr ("parts per hundred resin") familiar to the expert has already been used explained (see above).

The compounds d1) are perchlorates. Perchlorates in the sense of the invention are understood to mean metal salts and ammonium salts of perchloric acid. Examples of perchlorates suitable according to the invention are those of the formula M (ClO ₄ ) _n , where M in particular represents ammonium, Li, Na, K, Mg, Ca, Sr, Zn, Al, La or Ce. The index n corresponds to the valence of the cation M 1, 2 or 3. Sodium perchlorate is particularly preferred.

The perchlorate salts can be complexed with alcohols, for example polyols, cyclodextrins, or ether alcohols or ester alcohols, or dissolved therein. The polyol partial esters are also to be counted among the ester alcohols. In the case of polyhydric alcohols or polyols, their dimers, trimers, oligomers and polymers, such as di-, tri-, tetra- and polyglycols, and also di-, tri- and tetrapentaerythritol or polyvinyl alcohol in various degrees of polymerization are also suitable. With regard to perchlorate-alcohol complexes, those skilled in the art are expressly excluded EP-B-394 547 , Page 3, lines 37 to 56 known types.

The perchlorate salts can be in different common Dosage forms are used, for example as salt or solution in water or an organic solvent as such, or raised on a carrier material such as PVC, calcium silicate, zeolites or hydrotalcites, or integrated by chemical reaction in a hydrotalcite or another layer lattice compound. Glycerol monoethers and glycerol monothioethers are the polyol partial ethers prefers.

The perchlorates can be used individually as well can be used in a mixture with each other.

Compounds d2) it is fluoroalkanesulfonic acids. Among fluoroalkanesulfonic acids understood in the context of the present invention organic sulfonic acids, which have at least one fluorine atom per molecule. Preferably have those to be used according to the invention fluoroalkanesulfonates a sulfonic acid group per molecule. Fluoroalkanesulfonic acids which are 1 to 18 are also preferred C atoms per molecule contain. Completely fluorinated alkanesulfonic acids are very particularly preferred 1 to 18 carbon atoms per molecule. The fluoroalkanesulfonic acids can used as such or in the form of their salts, the Alkali metal salts are preferred. The term "fluoroalkanesulfonic acids" accordingly includes both the fluoroalkanesulfonic acids in the context of the present application such as their salts.

Examples of suitable fluoroalkanesulfonic acids are trifluoromethanesulfonic, perfluoroethanesulfonic, Perfluorooctane sulfonic acid.

The fluoroalkanesulfonic acids and whose salts can used individually or in a mixture with one another. Most notably it is preferred to use trifluoromethanesulfonic acid or its salts. Preferably become the fluoroalkanesulfonic acids in the form of their salts, in particular their alkali metal salts, used. Here again are the lithium, sodium and potassium salts prefers.

gekennzeichnet, worin die Reste R¹ und R² unabhängig voneinander jeweils Wasserstoff oder einen unverzweigten oder verzweigten, linearen oder cyclischen Alkylrest mit 1 bis 18 C-Atomen oder einen Arylrest mit 6 bis 18 C-Atomen, der gegebenenfalls durch ein oder mehrere Alkylreste mit jeweils 1 bis 6 C-Atomen substituiert sein kann, bedeuten. Dimethylaminouracil (D-3*) ist dabei ganz besonders bevorzugt.The compounds d3) are aminouracils; these are by the formula (D-3)

characterized in which the radicals R ¹ and R ² are each independently hydrogen or an unbranched or branched, linear or cyclic alkyl radical having 1 to 18 carbon atoms or an aryl radical having 6 to 18 carbon atoms, optionally with one or more alkyl radicals can each be substituted by 1 to 6 carbon atoms. Dimethylaminouracil (D-3 *) is particularly preferred.

In a special embodiment contain the stabilizer compositions according to the invention no aminouracile d3).

Compounds d4) are zeolites. As is known to the person skilled in the art, zeolites are alkali or alkaline earth aluminum silicates. You can use the general formula (D-4) M _{x / n} [(AlO ₂ ) _x (SiO ₂ ) _y ] ⋅wH ₂ O (D-4) be described in which

• - n the charge of the cation M;
• - M an element of the first or second main group, such as Li, Na, K, Mg, Ca, Sr or Ba;
• - y: x a number from 0.8 to 15, preferably from 0.8 to 1.2; and
• - w is a number from 0 to 300, preferably from 0.5 to 30.

Examples of zeolites are sodium aluminosilicates of the formulas
N / A₁₂al₁₂Si₁₂O₄₈⋅27H₂O [zeolite A],
N / A₆al₆S₁₆O₂₄⋅2NaX⋅7,5H₂O, X = OH, halogen, ClO₄[Sodalite];
N / A₆al₆Si₃₀O₇₂⋅24H₂O;
N / A_8thal_8thSi₄₀O₉₆⋅24H₂O;
N / A₁₆al₁₆Si₂₄O₈₀⋅16H₂O;
N / A₁₆al₁₆Si₃₂O₉₆⋅16H₂O;
N / A₅₆al₅₆Si₁₃₆O₃₈₄⋅250H₂O [zeolite Y],
N / A₁₆al₈₆Si₁₀₆O₃₈₄⋅264H₂O [zeolite X];
or by partial or complete Exchange of the Na atoms by Li, K, Mg, Ca, Sr or Zn atoms representable zeolites like
(Na, K)₁₀al₁₀Si₂₂O₆₄⋅20H₂O;
Ca_4.5N / A₃[(AlO₂)₁₂(SiO₂)₁₂] ⋅30H₂O;
K₉N / A ₃[(AlO₂)₁₂(SiO₂)₁₂] ⋅27H₂O.

Preferred zeolites correspond to formulas
N / A₁₂al₁₂Si₁₂O₄₈⋅27H₂O [zeolite A],
N / A₆al₆Si₆O₂₄⋅2NaX⋅7,5H₂O, X = OH, Cl, ClO₄. 1 / 2CO₃[Sodalite]
N / A₆al₆Si₃₀O₇₂⋅24H₂O,
N / A_8thal_8thSi₄₀O₉₆⋅24H₂O,
N / A₁₆al₁₆Si₂₄O₈₀⋅16H₂O,
N / A₁₆al₁₆Si₃₂O₉₆⋅16H2O,
N / A₅₆al₅₆Si₁₃₆O₃₈₄⋅250H₂O, [zeolite Y]
N / A₈₆al₈₆Si₁₀₆O₃₈₄⋅264H₂O [zeolite X] and such X and Y zeolites with an Al / Si ratio of approx. 1: 1 or through partial or complete exchange of the Na atoms can be represented by Li, K, Mg, Ca, Sr, Ba or Zn atoms Zeolites like
(Na, K)₁₀al₁₀Si₂₂0₆₄⋅20H₂O
Ca_4.5N / A₃[(AlO₂)₁₂(SiO₂)₁₂) ⋅30H₂O
K₉N / A ₃[(AlO₂)₁₂(SiO₂)₁₂] ⋅27H₂O

The zeolites listed can also a lower water content or be anhydrous. Other suitable zeolites are:
N / A₂O⋅Al₂O₃⋅ (2 to 5) SiO₂⋅ (3,5 to 10) H₂O [zeolite P]
N / A₂O⋅Al₂O₃⋅2SiO₂⋅ (3.5-10) H₂O (zeolite MAP)
or by partial or complete Exchange of the Na atoms by Li, K or H atoms representable zeolites how
(Li, Na, K, H)₁₀al₁₀Si₂₂O₆₄⋅20H₂O
K₉N / A ₃[(AlO₂)₁₂(SiO₂)₁₂] ⋅27H₂O
KA₄1aSiaO₆⋅6H_ZO [zeolite K-F]
N / A_8thal_8thSi₄₀O₉₆⋅24H₂O zeolite D as described in Barren et al. J. Chem. Soc. 1952, 1561-71, and in US 2,950,952  described.

The following zeolites are also suitable:
K-offretite, zeolite R, zeolite LZ-217, Ca-free zeolite LZ-218, zeolite T, zeolite LZ-220, Na ₃ K ₆ Al ₉ Si ₂₇ O ₇₂ ⋅21H ₂ O [zeolite L]; Zeolite LZ-211, zeolite LZ-212, zeolite O , Zeolite LZ-217, zeolite LZ-219, zeolite Rho, zeolite LZ-214, zeolite ZK-19, zeolite W (KM), Na ₃₀ Al ₃₀ Si ₆₆ O ₁₉₂ ⋅98H ₂ O [zeolite ZK-5, zeolite Q ]. With regard to these types of zeolite, express reference is made to the EP-A 768 336 and the literature cited there (compare EP-A 768 336 Page 26, lines 40 to 54).

Zeolite P types of the formula II are particularly preferably used, where x is a number in the range from 2 to 5 and y is a number in the range from 3.5 to 10. Zeolite MAP of the formula are particularly suitable II, where x is the number 2 and y is a number in the range from 3.5 to 10. In particular, it is zeolite Na-P, ie M stands for Na. This zeolite generally occurs in the variants Na-P-1, NaP-2 and Na-P-3, which differ in their cubic, tetragonal or orthorhombic structure (cf. EP-A 768 336 , the paragraph bridging pages 26 and 27).

Within the scope of the invention also such finely divided, water-insoluble sodium aluminosilicates use that in the presence of water soluble inorganic or organic dispersants were precipitated and crystallized. these can in any way before or during the precipitation or crystallization can be introduced into the reaction mixture.

Within the scope of the present invention Na zeolite A and Na zeolite P are particularly preferred.

Compounds d5) are cationic layer lattice compounds, compounds known to those skilled in the art, their structure and preparation, for example by WT Reichle in Chemtec (January 1986 ), Pages 58-63.

The prototype of cationic layered lattice compounds is the mineral hydrotalcite [Mg ₆ Al ₂ (OH) ₁₆ ] (CO ₃ ) ⋅4H ₂ O. Structurally, hydrotalcite is derived from brucite [Mg (OH) ₂ ]. Brucite crystallizes in a layer structure with the metal ions in octahedral gaps between two layers of hexagonally tightly packed (OH ^- ) ions. Only every second layer of the octahedral gaps is occupied by metal ions M, so that layer packets (OH) -M- (OH) are formed. The intermediate layers in the brucite are empty, in the hydrotalcite some - approximately every second to fifth - of the Mg (II) ions are statistically replaced by Al (III) ions. As a result, the layer package receives a positive charge overall. This charge is balanced by anions, which are located in the intermediate layers together with easily removable crystal water. scheme 1 shows - schematically - the layer structure of hydrotalcite.

Hydrotalcites form powdery, talc-like masses with BET surfaces of up to about 150 m ² / g. Two basic syntheses are known from the literature: One possibility of synthesis is to treat aqueous solutions of the corresponding metal salts with lye, the hydrotalcite which forms precipitating out. Another possibility is based on water-insoluble starting compounds such as metal oxides and hydroxides. These are heterogeneous reactions that are usually carried out in an autoclave.

Schema 1: Struktur von Hydrotalcit

Scheme 1: Structure of hydrotalcite

As already mentioned, hydrotalcite is only the prototype of cationic layer connections. The hydrotalcite However, known synthesis methods are also generally used for synthesis any cationic layer connections used. Like that These synthesis methods can be known to those skilled in the art in general classify as hydrothermal synthesis. Under hydrothermal synthesis in the narrower sense one understands the synthesis of minerals from highly heated - above a temperature of 100 ° C and a pressure of 1 atm aqueous suspensions; Hydrothermal syntheses are usually carried out in pressure vessels because of the temperatures used more than the boiling point of the water, usually even above it critical temperature.

Under cationic layer lattice connections d5) compounds of the invention general formula (D-5) understoode_eZ_zD_dV (OH^-)_x(A^n-)_a⋅qH₂O (D-5)  wherein mean:

• - E a monovalent cation from the group of alkali metals,
• - e a number in the range from 0 to 2,
• - Z a divalent metal cation,
• - e.g. a number in the range from 0 to 6,
• - D a trivalent metal cation,
• - d a number in the range from 0 to 3,
• - V a tetravalent metal cation,
• - v a number in the range from 0 to 1,
• - (A ^n- ) an acid anion of the charge n-, where n is an integer from 1 to 3, and
• - q a number in the range from 1 to 10,
• - With the proviso that x> a and e + 2z + 3d + 4v = x + na is.

In one embodiment, v in the general formula (D-5) is zero. These layer connections can therefore be described by the general formula (D-5 *): [E _e Z _z D _d (OH ^- ) _x ] (A ^n- ) _a ⋅qH ₂ O (D-5 *) in which mean:

• - E a monovalent cation from the group of alkali metals,
• - e a number in the range from 0 to 2,
• - Z a divalent metal cation,
• - e.g. a number in the range from 0 to 6,
• - D a trivalent metal cation,
• - d a number in the range from 0 to 3,
• - (A ^n- ) an acid anion of the charge n-, where n is an integer from 1 to 3, and
• - q a number in the range from 1 to 10,
• - With the proviso that x> a and e + 2z + 3d = x + na is.

In another embodiment, e in the general formula (D-5) has the value zero. These layer connections can therefore be described by the general formula (D-5 **): [Z _z D _d V _v (OH ^- ) _x ] (A ^n- ) _a ⋅qH ₂ O (D-5 **) in which mean:

• - Z a divalent metal cation,
• - e.g. a number in the range from 0 to 6,
• - D a trivalent metal cation,
• - d a number in the range from 0 to 3,
• - V a tetravalent metal cation,
• - v a number in the range from 0 to 1,
• - (A ⁿ ) an acid anion of the charge n-, where n is an integer from 1 to 3, and
• - q a number in the range from 1 to 10,
• - With the proviso that x> a and 2z + 3d + 4v = x + na is.

In a preferred embodiment, e and v in the general formula (D-5) each have the value zero. These layer connections can therefore be described by the general formula (D-5 ***): [Z _z D _d (OH ^- ) _x ] (A ^n- ) _a ⋅qH ₂ O (D-5 ***) in which mean:

• - Z a divalent metal cation,
• - e.g. a number in the range from 0 to 6,
• - D a trivalent metal cation,
• - d a number in the range from 0 to 3,
• - (A ⁿ ) an acid anion of the charge n-, where n is an integer from 1 to 3, and
• - q a number in the range from 1 to 10,
• - With the proviso that x> a and 2z + 3d = x + well.

The layered compounds of the formula (D-5 ***) therefore have the structure of the "classic" hydrotalcites known to the person skilled in the art. Of these, those in which D aluminum, d the number 1 and z a number in the range are preferred from 1 to 5. These special hydrotalcites are characterized by the general formula (D-5 ****): [Z _z Al (OH ^- ) _x ] (A ^n- ) _a ⋅qH ₂ O (D-5 ****) in which mean:

• - Z a divalent metal cation,
• - e.g. a number in the range from 1 to 5,
• - (A ⁿ ) an acid anion of the charge n-, where n is an integer from 1 to 3, and
• - q a number in the range from 1 to 10,
• - With the proviso that x> a and 2z + 3 = x + well.

For the purposes of the invention, preference is given to such cationic layer compounds (D-5) in which Z represents at least one divalent metal ion selected from the group consisting of magnesium, calcium and zinc. Z preferably represents exactly one divalent metal ion from the group mentioned and in particular magnesium. Cationic layer compounds of the general formula I are very particularly preferred in which A ^{n- is} an acid anion with the charge (n-) selected from the anion group carbonate, hydrogen carbonate, perchlorate, acetate, nitrate, tartrate, oxalate and iodide, preferably carbonate , If at least one divalent metal ion is mentioned in the explanation of formula I above, this means that different divalent metal ions can be present side by side in the cationic layer connection. The indices x, y and z and m can be whole or fractional numbers within the specified conditions. Cationic layer compounds of the general formula (D-5) in which Z is magnesium and A ^{n- are} carbonate are particularly advantageous.

• – x = eine Zah1 im Bereich von 2 bis 8 und
• – m = eine Zahl im Bereich von 0 bis 12,

bzw. die allgemeine Formel (D-6b) Ca_xAl₂(OH)_{2 (x+3-y)}(HPO₃)_y⋅mH₂O (D-6b), worin:Compounds d6) are so-called CHAP connections. These are calcium hydroxy aluminum (hydrogen) phosphites and / or their hydrates. These compounds have the general formula (D-6a) Ca _x Al ₂ (OH) _{2 (x + 2)} HPO ₃ ⋅mH ₂ O (D-6a),
wherein:

• - x = a number in the range from 2 to 8 and
• - m = a number in the range from 0 to 12,

or the general formula (D-6b) Ca _x Al ₂ (OH) _{2 (x + 3-y)} (HPO ₃ ) _y ⋅mH ₂ O (D-6b), wherein:

• - x = a number in the range from 2 to 12,
• - the The condition is that (2x + 5) / 2> y> 0 and
• - m = a number in the range from 0 to 12,
• - With the proviso that y = 1 is excluded if x = a number in the range from 2 to 8 is.

The CHAP compounds can be prepared, for example, by means of a process in which mixtures of calcium hydroxide and / or calcium oxide, aluminum hydroxide and sodium hydroxide or of calcium hydroxide and / or calcium oxide and sodium aluminate with phosphorous acid are used to produce the desired calcium aluminum hydroxy hydrogen phosphites corresponding amounts in aqueous medium and the reaction product is separated in a conventional manner and wins. The reaction product obtained directly from the above-described reaction can be separated from the aqueous reaction medium by known processes, preferably by filtration. The separated reaction product is also worked up in a manner known per se, for example by washing the filter cake with water and drying the washed residue at temperatures of, for example 60 - 130 ° C, preferably at 90 - 120 ° C.

For the reaction can be both finely divided, active aluminum hydroxide in combination with sodium hydroxide as well as a sodium aluminate be used. Calcium can be in the form of finely divided calcium oxide or Calcium hydroxide or mixtures thereof can be used. The phosphorous Acid can can be used in different concentrated forms. The Reaction temperatures are preferably between 50 and 100 ° C, further preferably between about 60 and 85 ° C. Catalysts or accelerators are not required to interfere But also not. With the connections, the water of crystallization can be completely or partially removed by thermal treatment.

When used as stabilizers split the dried calcium-hydroxy-aluminum-hydroxyphosphite in the example usual for rigid PVC Processing temperatures of 160 - 200 ° C no water, so that in the moldings no annoying Blistering occurs.

To improve their dispersibility in halogen-containing thermoplastic resins, the CHAP compounds in a known manner with surface-active Agents are coated.

Compounds d7) are katoites. These are compounds of structure (D-7) Ca ₃ Al ₂ (OH) ₁₂ ⋅mH ₂ O (D-7), where m is a number in the range from 0 to 10. The Katoite can optionally be surface modified. They have a very specific crystal lattice (so-called hydrogranate structure), which makes them different from other calcium-aluminum-hydroxy compounds. This crystal lattice with lattice spacing is described in the article by C. Cohen-Addad et P. Ducros in Acta Cryst. (1967), 23, pages 220 to 225. Accordingly, it is a cubic crystal lattice. The aluminum is surrounded octahedrally by six oxygens, each of which still carries hydrogen. The calcium is surrounded by 8 oxygens, which form a disturbed cube, which is also known as the triangular dodecahedron.

The Katoite of the general formula Ca ₃ Al ₂ (OH) ₁₂ can for example be based on the German patent DE 2 424 763 be prepared from the hydroxides of calcium and aluminum in appropriate stoichiometric amounts in the aqueous system. Depending on the test temperatures and reaction times, they occur with different average particle diameters.

Temperatures in the Range from 50 to 150 ° C and response times from 0.1 to 9 hours. The Katoite fall with average particle diameters of 0.1 to 100 μm, preferably 0.5 to 30 μm on. It can happen that small amounts of calcium-containing as a by-product Hydroxyaluminates (Hydrocalumite) accumulate, which has a layered structure have and represented by the general formula described above become.

In the manufacture of the katoite, excesses of Aluminum or calcium hydroxide are used, with mixtures of unreacted calcium and / or aluminum hydroxide and katoite. These blends can can also be used in the sense of the invention.

If desired, the Katoite of the above Formula modified surface be selected from the groups with one or more additives

• v-a) optionally alkoxylated alcohols one or more hydroxyl groups,
• v-b) partially or completely epoxidized unsaturated fatty acids, Fatty alcohols and / or their derivatives,
• v-c) Full and partial esters of polyols with 3 to 30 carbon atoms and 2 to 6 hydroxyl groups with carboxylic acids with 6 to 22 carbon atoms,
• v-d) alkyl and aryl phosphites,
• v-e) homopolymers and copolymers of acrylic acid and methacrylic acid,
• v-f) lignin and naphthalene sulfonates and / or trimer fatty acids,
• v-g) salts of fatty acids.

Additives come in the group v-a) Both monofunctional alcohols and polyols with 3 to 30 C atoms and 2 to 6 hydroxyl groups, if appropriate can be alkoxylated, preferably ethoxylated. From the group of monofunctional Alcohols are preferably used fatty alcohols with 6 to 22 carbon atoms such as caprin, lauryl, palmityl, stearyl, oleyl, linolyl, arachidyl and behenyl alcohol and their technical mixtures as they are made from natural oils and Fat accessible are. Of these fatty alcohols, those are very particularly preferred ethoxylated representatives thereof used with 2 to 15 moles of ethylene oxide. From the group of polyols, diols with 3 to 30 carbon atoms are suitable, such as butanediols, hexanediols, dodecanediols and trimethylolpropane, Pentaerythritol, glycerol and their technical oligomer mixtures with average degrees of condensation from 2 to 10. Very special preferred from the group of polyols are those with 3 to 30 C atoms which have at least one hydroxyl group per 3 C atoms or carry an ether oxygen, preferably glycerin and / or the technical oligoglycerol mixtures with average degrees of condensation from 2 to 10.

The additives of group vb) are partially or completely epoxidized unsaturated saturated fatty acids or fatty alcohols with 6 to 22 carbon atoms or derivatives thereof. Particularly suitable as derivatives of the epoxidized fatty acids or fatty alcohols are the esters thereof, it being possible for the epoxidized fatty acids and epoxidized fatty alcohols to be esterified with one another or else with non-epoxidized carboxylic acids or with non-epoxidized mono- or polyhydric alcohols. The epoxidized fatty acids are preferably derived from the unsaturated palmitoleic, oleic, elaidic, petroselinic, ricinoleic, linolenic, gadoleic or erucic acids, which are epoxidized in whole or in part by known processes. The epoxidized fatty alcohols are preferably derived from the unsaturated alcohols oleyl, elaidyl, ricinol, linoleyl, linolenyl, gadoleyl, arachidone or eruca alcohol, which are also completely or partially epoxidized by known processes. Suitable esters of epoxidized fatty acids are esters of mono-, di- and / or trihydric alcohols which are completely esterified with epoxidized, unsaturated carboxylic acids having 6 to 22 carbon atoms, such as methyl, 2-ethylhexyl, ethylene glycol, butanediol, Neopentyl glycol, glycerol and / or trimethylol propane esters of epoxidized lauroleic acid, palmitoleic acid, oleic acid, ricinoleic acid, linoleic acid and / or linolenic acid. Esters of trihydric alcohols and practically completely epoxidized unsaturated carboxylic acids with 12 to 22 carbon atoms are preferred, and in particular esters of glycerol with practically completely epoxidized unsaturated carboxylic acids with 12 to 22 carbon atoms. As is customary in fat chemistry, the epoxidized carboxylic acid glycerides can also be technical mixtures obtained by epoxidation of natural unsaturated fats and unsaturated oils. Epoxidized beet oil, epoxidized soybean oil and epoxidized sunflower oil of new breed are preferably used.

For additives in group v-c) are full or partial esters according to the relevant methods the preparative organic chemistry, for example by acid-catalyzed reaction of polyols with carboxylic acids be preserved. Possible polyol components are that have already been discussed in connection with group a). As an acid component are preferably aliphatic, saturated and / or unsaturated carboxylic acids with 6 to 22 carbon atoms like caproic acid, caprylic, Capric acid, Lauric acid, Myrisitic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, ricinoleic acid, linoleic acid, linolenic acid, behenic acid or erucic used. As usual in fat chemistry, the carboxylic acid can also represent a technical mixture, as is the case with pressure splitting of natural fats and oils accrues. Partial esters of glycerol and in particular of their technical oligoglycerol mixtures with average Degrees of condensation from 2 to 10 with saturated and / or unsaturated aliphatic carboxylic acids with 6 to 22 carbon atoms.

in der R¹, R² und R³ unabhängig voneinander für einen Alkylrest mit 1 bis 18 Kohlenstoffatomen oder einen Phenylrest stehen. Typische Beispiele für Additive der Gruppe d) sind Tributylphosphit, Triphenylphosphit, Dimethylphenylphosphit und/oder Dimethylstearylphosphit. Bevorzugt wird Diphenyldecylphosphit.Finally, according to group vd), alkyl and aryl phosphites can be used, preferably those of the following general formula

in which R ¹ , R ² and R ³ independently of one another represent an alkyl radical having 1 to 18 carbon atoms or a phenyl radical. Typical examples of additives of group d) are tributyl phosphite, triphenyl phosphite, dimethylphenyl phosphite and / or dimethylstearyl phosphite. Diphenyldecyl phosphite is preferred.

Additives from the group v-e) are preferably polymers of acrylic acid and methacrylic acid and their copolymers. The concept of copolymers is twofold Meaning understood: once as pure copolymers of acrylic acid and methacrylic acid and on the other hand as copolymers of (meth) acrylic acid with other vinyl unsaturated, capable of polymerization Monomers. Examples of others capable of polymerization Monomers are sulfonic and phosphonic unsaturated Monomers, unsaturated aliphatic carboxylic acids with 3 to 5 carbon atoms, amides of unsaturated aliphatic carboxylic acids with 3 to 5 carbon atoms, unsaturated monomers containing amino groups and / or their Salts, vinyl acetate, acrolein, vinyl chloride, acrylonitrile, vinylidene chloride, 1,3-butadiene, styrene, alkylstyrenes with 1 to 4 carbon atoms in the alkyl radical. examples for Additives of group v-e) are polyacrylic acid, polymethacrylic acid - in the following become acrylic acid and methacrylic acid and their derivatives simplified as (meth) acrylic acid or Derivatives abbreviated - and / or their Salts such as polysodium (meth) acrylate, copolymers of (meth) acrylic acid with maleic acid, maleic anhydride, Styrene sulfonic acid, α-methylstyrene, 2-vinylpyridine, 1-vinylimidazole, dimethylaminopropyl (meth) acrylamide, 2- (meth) acrylamido-2-methylpropanesulfonic acid, (meth) acrylamide, N-hydroxydimethyl (meth) acrylamide and / or their salts. Most notably preferred among the polymeric additives are those which predominate have an anionic character, that is, the majority of acid groups wear freely or in the form of their salts. Are particularly preferred Polymers of (meth) acrylic acid as well as their copolymers with styrene, acrolein, alkylstyrenes 1 to 4 carbon atoms in the alkyl radical, styrene sulfonic acid, maleic acid and / or their salts, especially their sodium salts and maleic anhydride. Conveniently, the polymeric additives of group e) have a molecular weight from 1000 to 10000. The preparation of the polymeric additives can by known methods such as bulk or solvent polymerization.

The additives of group v-g) are salts of fatty acids. Suitable fatty acids have been found already listed in connection with additives from group v-c). Prefers become the alkali salts of saturated fatty acids.

One or more additives from one or more of the groups v-a) to v-g) can be used to modify the Katoite are used, the total amount of additives in is in the range of 0.1 to 10% by weight, based on katoite. In combinations of the polymeric additives v-e) with other additives from groups v-a) to v-d) and v-f) and v-g) it is preferred to have the additives in amounts of 50 to 90% by weight, based on the total additive amount. Of the surface modified Katoites are particularly preferred those containing one or more additives from groups v-b), v-e) and v-g) are modified.

The modification of the Katoite can either in situ or afterwards respectively.

In the subsequent modification the Katoite with organic or aqueous solutions of the additives ground, preferably with grinding media mills and in particular with a ball mill and then usually dried. If the additives are at room temperature liquid or low-melting products, of course you don't have to solutions use of it. Otherwise, the additives v-a) to v-g) preferably clear, watery solutions or solutions with polar organic solvents.

The term polar organic solvents encompasses at room temperature ( 15 up to 25 ° C) liquid hydrocarbon compounds that carry at least one electronegative substituent than carbon. These include chlorinated hydrocarbons, alcohols, ketones, esters, ethers and / or glycol ethers. Suitable polar organic solvents are methanol, ethanol, n-butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanol, isophorone, ethyl acetate, lactic acid ethyl ester, 2-methoxyethyl acetate, tetrahydrofuran, ethyl glycol monomethyl ether, diethylene glycol monoethyl ether.

So that the surface of the Katoite is evenly modified in the presence of additives from group v-e) expedient if this is soluble are in polar organic solvents of the type described and / or water with pH values from 8 to 12. The term soluble means in this context that the polymeric additives v-e) in the polar organic solvents and in an aqueous solution with pH 10, adjusted with alkali hydroxides at 20 ° C, at least 0.01% by weight, preferably 0.1 wt .-% - based to the solution - and in particular are completely clear under the specified conditions.

The modification can also be done in situ that is, you can already use the calcium and aluminum hydroxide solutions, from which the katoite is formed, the additives, if appropriate, in the form of their solutions enforce.

Ultimately, you can do both Modification types combine what can be modified with several Additives recommends, in particular, different solution behavior demonstrate.

wobei diese direkt an Kohlenstoff-, Sauerstoff-, Stickstoff- oder Schwefelatome gebunden ist, und worin entweder R¹ und R³ beide Wasserstoff sind, R² Wasserstoff oder Methyl und n = 0 ist, oder worin R¹ und R³ zusammen -CH₂-CH₂- oder -CH₂-CH₂-CH₂- bedeuten, R² dann Wasserstoff und n = 0 oder 1 ist.Compounds d8) are glycidyl compounds. They contain the glycidyl group

which is directly bonded to carbon, oxygen, nitrogen or sulfur atoms, and in which either R ¹ and R ^{3 are} both hydrogen, R ^{2 is} hydrogen or methyl and n = 0, or in which R ¹ and R ³ together are -CH ₂ -CH ₂ - or -CH ₂ -CH ₂ -CH ₂ - mean, R ^{2 is} then hydrogen and n = 0 or 1.

Examples of suitable glycidyl compounds are those of the groups d8-I) to d8-V) described below.

Group connections d8-I)

Glycidyl and β-methylglycidyl esters available from Implementation of a compound with at least one carboxyl group in the molecule and epichlorohydrin or glycerol dichlorohydrin or b-methyl-epichlorohydrin. The reaction is conveniently carried out in the presence of bases.

As connections with at least one Carboxyl group in the molecule can aliphatic carboxylic acids be used. examples for these carboxylic acids are glutaric acid, adipic acid, pimelic, suberic, azelaic acid, sebacic or dimerized or trimerized linoleic acid; Acrylic and methacrylic acid, capronic acid, Caprylic, lauric, myristic, palmitic, stearic and pelargonic acids.

But it can also be cycloaliphatic carboxylic acids are used, such as cyclohexane carboxylic acid, tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid or 4-methylhexahydrophthalic acid.

Aromatic carboxylic acids can also be used, for example benzoic acid, Phthalic acid, isophthalic acid, trimellitic acid or pyromellitic acid.

It can also be carboxyl-terminated Adducts, e.g. of trimellitic acid and polyols such as glycerin or 2,2-bis (4-hydroxycyclohexyl) propane be used.

Group connections d8-II)

Glycidyl or (β-methylglycidyl) ether available from Implementation of a compound with at least one free alcoholic Hydroxy group and / or phenolic hydroxyl group and a suitable substituted epichlorohydrin under alkaline conditions, or in the presence of an acid catalyst and subsequent alkali treatment.

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

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

The epoxy compounds can also derived from mononuclear phenols, such as phenol, Resorcinol or hydroquinone; or they are based on polynuclear phenols such as, for example, on bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 4,4'-dihydroxydiphenyl sulfone or on condensation products obtained under acidic conditions of phenols with formaldehyde such as phenol novolaks.

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

Group connections d8-III)

(N-Glycidyl) compounds available from Dehydrochlorination of the reaction products of epichlorohydrin with Amines containing at least one amino hydrogen atom. With these Amines are, for example, aniline, N-methylaniline, toluidine, n-butylamine, bis- (4-aminophenyl) methane, m-xylylenediamine or bis- (4-methylaminophenyl) methane, but also N, N, O-triglycidyl-m-aminophenol or N, N, O-triglycidyl-p-aminophenol.

About the (N-glycidyl) compounds counting but also N, N'-di, N, N ', N "tri and N, N', N", N "tetraglycidyl derivatives of cycloalkylene ureas, such as ethylene urea or 1,3-propylene urea, and N, N'-diglycidyl derivatives of hydantoins, such as 5,5-dimethylhydantoin or glycoluril and triglycidyl isocyanurate.

Group connections d8-IV)

S-glycidyl compounds such as Di-S-glycidyl derivatives derived from dithiols such as Derive ethane-1,2-dithiol or bis (4-mercaptomethylphenyl) ether.

Group connections d8-V)

Epoxy compounds with a radical of the formula I in which R ₁ and R ₃ together are -CH ₂ -CH ₂ - and n = 0 are bis- (2,3-epoxycyclopentyl) ether, 2,3-epoxycyclopentylglycidyl ether or 1, 2-bis (2,3-epoxycyclopentyloxy) ethane. An epoxy resin with a radical of the formula I in which R ₁ and R ₃ together are -CH ₂ -CH ₂ - and n = 1 is, for example, 3,4-epoxy-6-methyl-cyclohexanecarboxylic acid- (3 ', 4'-epoxy-6'-methyl-cyclohexyl) methyl ester.

Suitable terminal epoxides are, for example ( ^TM means ^® ):

• - liquid bisphenol A diglycidyl ether like araldite^TMGY 240, araldite^TMGY 250, araldite^TMGY 260, araldite^TMGY 266, Araldite^TM  GY 2600, Araldite^TMMY 790:
• - fixed Bisphenol A diglycidyl ether such as araldite^TMGT 6071, araldite^TMGT 7071, araldite^TMGT 7072, Araldite ^TMGT 6063, Araldite^TMGT 7203, araldite^TMGT 6064, araldite^TM GT 7304, araldite^TM GT 7004, araldite^TMGT 6084, araldite^TMGT 1999, Araldite^TMGT 7077, araldite ^TMGT 6097, araldite^TMGT 7097, araldite ^TMGT 7008, araldite^TM GT 6099, araldite^TMGT 6608, araldite^TMGT 6609, araldite^TMGT 6610;
• Liquid bisphenol F diglycidyl ethers such as Araldit ^TM GY 281, Araldit ^TM PY 302, Araldit ^TM PY 306:
• - fixed Polyglycidyl ether of tetraphenylethane such as CG epoxy resin^TM 0163:
• - fixed and fluid Polyglycidyl ether of phenol formaldehyde novolak such as EPN 1138, EPN 1139, GY 1180, PY 307;
• - fixed and fluid Polyglycidyl ether of o-cresol formaldehyde novolak such as ECN 1235, ECN 1273, ECN 1280, ECN 1299;
• - liquid glycidyl ether of alcohols like Shell^TM glycidyl 162, araldite ^TMDY 0390, araldite ^TMDY 0391;
• Liquid glycidyl ethers of carboxylic acids such as Shell ^™ Cardura E terephthalic acid ester, trimellitic acid ester, Araldit ^™ PY 284;
• - solid heterocyclic epoxy resins (triglycidyl isocyanurate) such as Araldit ^TM PT 810;
• - liquid cycloaliphatic epoxy resins such as Araldit ^TM CY 179;
• - liquid N, N, O-triglycidyl ethers of p-aminophenol such as Araldit ^™ MY 0510;
• - Tetraglycidyl-4-4'-methylenebenzamine or N, N, N ', N'-tetraglycidyldiaminophenylmethane such as Araldit ^™ MY 720, Araldit ^™ MY 721.

Epoxy compounds are preferred with two functional groups use. But it can also epoxy compounds can be used with one, three or more functional groups.

Mainly epoxy compounds, especially diglycidyl compounds, used with aromatic groups.

If necessary, a mixture different epoxy compounds are used.

Terminal epoxy compounds are particularly preferred Diglycidyl ethers based on bisphenols, such as of 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), bis (4-hydroxyphenyl) methane or mixtures of bis (ortho / parahydroxyphenyl) methane (bisphenol F).

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

Compounds d9) are beta-diketones and beta-keto esters. 1,3-Dicarbonyl compounds which can be used can be linear or cyclic dicarbonyl compounds. Dicarbonyl compounds of the following formula (D-9) are preferably used, R ¹ -CO-CHR ² -CO-R ³ (D-9) in which mean:

• - 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 -SR ⁶ or -R ⁵ -OR ⁶ ,
• R ² : 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 : one of the meanings given for R ¹ or C ₁ -C ₁₈ alkoxy,
• R ⁴ : C ₁ -C ₄ alkyl or phenyl,
• R ⁵ : C ₁ -C ₁₀ alkylene,
• - R ⁶ : C ₁ -C ₁₂ alkyl, phenyl, C ₇ -C ₁₈ alkylphenyl or C ₇ -C ₁₀ phenylalkyl.

These include the hydroxyl group-containing diketones EP 346 279 and the oxa and thia diketones of EP 307 358 as well as the isocyanic acid based keto esters of US 4,339,383 ,

R ¹ and R ³ as alkyl can in particular be C ₁ -C ₁₈ alkyl, such as, 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 represent in particular a group - (CH ₂ ) _n OH, where n is 5, 6 or 7.

R ¹ and R ³ as alkenyl can mean, 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 can be, for example, 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 alkyl-cycloalkyl are in particular cyclohexyl or methylcyclohexyl.

R ² as alkyl can in particular be C ₁ -C ₄ alkyl. R ² as C ₂ -C ₁₂ alkenyl can in particular be allyl. R ² as alkylphenyl can in particular be tolyl. R ² as phenylalkyl can in particular be benzyl. R ² is preferably hydrogen. R ³ as alkoxy can 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, such as butyl, hexyl, octyl, decyl or dodecyl. R ⁶ as alkylphenyl is especially tolyl. R ⁶ as phenylalkyl is in particular benzyl.

Examples of 1,3-dicarbonyl compounds of the above formula are acetylacetone, butanoylacetone, Hep tanoylacetone, stearoylacetone, palmitoylacetone, lauroylacetone, benzoylacetone, dibenzoylmethane, lauroylbenzoylmethane, palmitoylbenzoylmethane, stearoyl-benzoylmethane, isooctylbenzoylmethane, 5-hydroxycapronyl-benzoylmethane, tribenzoylmethane, tribenzoylmethane, tribenzoylmethane, methane, 4-methoxybenzoyl-benzoylmethane, bis (4-methoxybenzoyl) methane, 1-benzoyl-1-acetylnonane, benzoyl-acetylphenylmethane, stearoyl-4-methoxybenzoylmethane, bis (4-tert-butylbenzoyl) methane, benzoylformylmethane phenylacetylmethane, bis-cyclohexanoyl-methane, dipivaloyl-methane, 2-acetylcyclopentanone, 2-benzoylcyclopentanone, methyl, ethyl and - allyl esters of methyl diacetoacetate, methyl and ethyl acetate, methyl and acetic acid, methyl and ethyl acetates, ethyl, hexyl, octyl, dodecyl or octadecyl ester, benzoylacetic acid methyl, ethyl, butyl, -2-ethylhexyl, dodecyl or octadecyl ester, as well as propionyl and butyryles C ₁ -C ₁₈ acetic acid alkyl ester. Stearoylacetic acid ethyl, propyl, butyl, hexyl or octyl esters as well as polynuclear β-keto esters as in EP 433.230 and dehydroacetic acid and its zinc, magnesium or alkali salts.

1,3-Diketo compounds of the above formula are preferred, in which R ^{1 is} C ₁ -C ₁₈ -alkyl, phenyl, 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 .

The 1,3-dicarbonyl compounds of the above formula alone, as mixtures and / or as their alkali, alkaline earth and Zinc chelates are used.

The 1,3-diketo compounds can be found in an amount of, for example, 0.01 to 10, advantageously 0.01 to 3 and in particular 0.01 to 2 parts by weight, based on 100 parts by weight PVC, can be used.

worin Z für CO₂CH₃, CO₂C₂H₅, CO₂ ⁿC₁₂H₂₅ oder -CO₂C₂H₄-S-ⁿC₁₂H₂₅ steht. Das hochgestellte n hat dabei die Bedeutung, daß der C₁₂H₂₅-Alkylrest unverzweit ist.Compounds d10) are dihydropyridines and polydihydropyridines. As monomeric dihydropyridines come compounds such. B. in FR 2 039 496 . EP 2 007 . EP 362 012 and EP 24 754 described, in question. Preferred are those of the formula (D-10)

where 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 . The superscript n has the meaning that the C ₁₂ H ₂₅ alkyl radical is not branched.

Particularly suitable polydihydropyridines are compounds of the following formula TXRX-R'-XL wherein

• - X the rest
  
  means
• T represents unsubstituted C _1-12 alkyl,
• - L has the same meanings as T.
• - m and n are numbers from 0 to 20,
• - k the number is 0 or 1,
• R and R 'are independently ethylene, propylene, butylene or an alkylene or cycloalkylene bismethylene group of the type - (- C _p H _2P -X-) _t C _p H _2p ,
• - p is a number in the range from 2 to 8,
• - t is a number ranging from 0 to 10
• - X for oxygen or sulfur.

Such connections are in EP 286 887 described in more detail.

The (poly) dihydropyridines can in chlorine-containing polymer expedient to 0.001 to 5 and in particular 0.005 to 1 part by weight, based on the Polymer.

Thiodiethylene bis- [5-methoxycarbonyl-2,6-dimethyl-1,4-dihydro pyridine-3-carboxylate] are particularly preferred. and thiodiethylene bis- [5-methoxycarbonyl-2,6-dimethyl-1,4-dihydropyridine-3-carboxylate].

Compounds d11) are polyols and polyol derivatives. Polyols are organic compounds which contain at least two OH groups in the molecule. It can are compounds that function exclusively as OH groups included it can however, other functional groups may also be included. As polyols are suitable, for example, pentaerythritol, dipentaerythritol, tripentaerythritol, Bistrimethylolpropane, inositol, polyvinyl alcohol, bistrimethylolethane, Trismethylolpropane, sorbitol, maltitol, isomaltitol, lactitol, lycasin, Mannitol, lactose, leucrose, tris (hydroxylethyl) isocyanurate (THEIC), Palatinite, tetramethylolcyclohexanol, tetramethylolcyclopentanol, Tetramethylolcyclopyranol, glycerin, diglycerin, polyglycerin or Thiodiglycerin and reaction products of these polyols with ethylene oxide and / or propylene oxide. The polyols can be used alone or as a mixture can be used with each other.

Differentiate the polyol derivatives differs from the polyols just described in that the polyols are esterified or etherified on one or more OH groups, taking the stipulation applies that the polyol derivatives may contain a maximum of one free OH group per molecule. Prefers are - taking into account the just mentioned requirement - such Polyol derivatives, which are esters of polyols with carboxylic acids, about glycerol partial esters of fatty acids, for example glycerol dioleate or glycerol distearate.

With regard to examples of suitable compounds d12), expressly on page 7, line 22 to page 25, line 21, the one cited above EP-A-768 336 directed. The sterically hindered amines mentioned there are expressly included in the disclosure of the present invention.

With regard to examples of suitable compounds d13), expressly on page 27, line 17 to page 28, line 9 who cited above EP-A-768 336 directed. The Dawsonites mentioned there are expressly included in the disclosure of the present invention.

Compounds d14) are alkali and alkaline earth compounds. These are primarily the carboxylates of the acids described under d27), but also corresponding oxides or hydroxides or (hydrogen) carbonates. Their mixtures with organic acids are also suitable. Examples of suitable alkali and alkaline earth compounds d14) are NaOH, sodium stearate, sodium bicarbonate, KOH, potassium stearate, potassium bicarbonate, LiOH, Li ₂ CO ₃ , lithium stearate, CaO, calcium hydroxide, MgO, Mg (OH) ₂ , magnesium stearate, CaCO ₃ , MgCO ₃ and dolomite, huntite, chalk, basic magnesium carbonate and other Na and K salts of fatty acids.

In the case of alkaline earth metal and Zn carboxylates, their adducts with MO or M (OH) ₂ (M = Ca, Mg, Sr or Zn), so-called “overbased” compounds, can also be used.

In addition to stabilizer combination according to the invention Alkali, alkaline earth and / or aluminum carboxylates used.

With regard to examples of suitable compounds d15), expressly on page 31, line 34 to page 33, line 4, of the above EP-A-768 336 directed. The antioxidants mentioned there are expressly included in the disclosure of the present invention.

Regarding the substances of the group (d16) be express found that both Lubricants as well as release agents, as well as mixtures of lubricants and Release agents can be used. After the usual Such products are referred to in the parlance of the expert as Release agent, the frictional resistance predominantly between polymer melt and steel surface reduce the machine used in the shaping process; the reduction of the frictional resistance has the consequence that the mass pressure the melt is reduced. In contrast, lubricants predominantly work in the polymer melt and reduce the internal frictional forces, making the melt good even at high filler contents plastic flow that keeps for the filling of the shaping tool is important.

In one embodiment of the present Invention as solid or release agent at 20 ° C or liquid Calcium salts and / or magnesium salts and / or aluminum salts used, that are selected out

• - calcium salts of saturated or unsaturated, straight-chain or branched monocarboxylic acids with 6 to 36 carbon atoms,
• Calcium salts of unsubstituted or substituted with C _{1 -4} -alkyl radicals,
• - magnesium salts of saturated or unsaturated, straight-chain or branched monocarboxylic acids with 6 to 36 carbon atoms,
• - magnesium salts of saturated or unsaturated dicarboxylic acids with 6 to 10 carbon atoms,
• - aluminum salts of saturated or unsaturated, straight-chain or branched monocarboxylic acids with 6 to 36 carbon atoms

For the aforementioned calcium, magnesium and aluminum salts applies that they could be used both alone and in a mixture.

Other lubricants or release agents that can be used alone or in combination with one another as component d 16) are the substances known for this from the prior art. The following types of compounds are preferably suitable: hydrocarbon waxes which melt in the temperature range from 70 to 130 ° C., oxidized polyethylene waxes, free fatty acids with 8 to 22 carbon atoms and their branched chain isomers, for example stearic acid or also hydroxystearic acid, α-olefins, wax esters, ie Esters of longer-chain monocarboxylic acids and monoalcohols, primary and secondary, saturated and unsaturated higher alcohols with preferably 16 to 44 carbon atoms in the molecule, ethylenediamine distearate, montanic acid esters of diols, for example ethanediol, 1,3-butanediol and glycerol, mixtures of such montanic acid esters with unesterified Montanic acids, partial esters of fatty acids with 8 to 22 C atoms and polyols with 2 to 6 C atoms and 2 to 6 hydroxyl groups, which contain on average at least one free polyol hydroxyl group per molecule. The can still be used in the DE-C-19 07 768 Mixed esters described with hydroxyl or acid numbers in the range from 0 to 6 from aliphatic, cycloaliphatic or aromatic dicarboxylic acids with 2 to 22 C atoms in the molecule, aliphatic polyols with 2 to 6 hydroxyl groups in the molecule and aliphatic monocarboxylic acids with 12 to 30 C atoms in the molecule. Examples include mixed esters of maleic acid-pentaerythritol-behenic acid, mixed esters of adipic acid-pentaerythritol-oleic acid and mixed esters of adipic acid-pentaerythritol-stearic acid. Such lubricants or release agents can be used in the context of the present invention both individually and in combination with one another, and also in combination with the calcium, magnesium or aluminum salts mentioned above.

With regard to examples of suitable compounds d17), expressly on page 29, line 20 to page 30, line 26, the one cited above EP-A-768 336 directed. The plasticizers mentioned there are expressly included in the disclosure of the present invention.

With regard to examples of suitable compounds d18), expressly on page 30, line 28 to page 30, line 35, of the above EP-A-768 336 directed. The pigments mentioned there are expressly included in the disclosure of the present invention. Titanium dioxide is preferred as pigment d18).

With regard to examples of suitable compounds d19), expressly on page 30, line 37 to page 30, line 43, the one cited above EP-A-768 336 directed. The fillers mentioned there are expressly included in the disclosure of the present invention. For the fillers d19), calcium carbonate (chalk), talc, kaolin and the like are preferred. Chalk is particularly preferred.

With regard to examples of suitable compounds d20), expressly on page 30, line 45 to page 31, line 3, the one cited above EP-A-768 336 directed. The phosphites mentioned there are expressly included in the disclosure of the present invention.

With regard to examples of suitable compounds d21), expressly on page 31, line 5 to page 31, line 19, of the above EP-A-768 336 directed. The thiophosphites and thiophosphates mentioned there are expressly included in the disclosure of the present invention.

With regard to examples of suitable compounds d22), expressly on page 31, line 21 to page 31, line 25, the one cited above EP-A-768 336 directed. The mercaptocarboxylic acid esters mentioned there are expressly included in the disclosure of the present invention.

With regard to examples of suitable compounds d23), expressly on page 31, line 27 to page 31, line 32, the one cited above EP-A-768 336 directed. The epoxidized fatty acid esters mentioned there. expressly included in the disclosure of the present invention.

With regard to examples of suitable compounds d24.), Expressly on page 33, line 6 to page 34, line 7, of the above EP-A-768 336 directed. The UV absorbers and light stabilizers mentioned there are expressly included in the disclosure of the present invention.

With regard to examples of suitable compounds d25), expressly on page 35, line 9 to page 35, line 12, the one cited above EP-A-768 336 directed. The blowing agents mentioned there are expressly included in the disclosure of the present invention.

With regard to compound d26) noted that it is urea and is therefore known to the person skilled in the art Substance of defined structure.

Compounds d27) are metal soaps; in particular soaps of the metals zinc, magnesium, calcium, aluminum, lead, barium, tin and cadmium. The organic zinc compounds with a Zn-O bond are zinc enolates and / or zinc carboxylates. The latter are compounds from the series of aliphatic saturated C _2-22 carboxylates, aliphatic unsaturated C _3-22 carboxylates, aliphatic C _{2 -22} carboxylates which are substituted with at least one OH group or the chain of which at least by an O atom is interrupted (oxa acids), the cyclic and bicyclic carboxylates with 5-22 C atoms, the unsubstituted phenyl carboxylates substituted with at least one OH group and / or C _1-16 alkyl-substituted phenyl C _{1- 6-} alkyl carboxylates, or optionally with C _{1 -12} alkyl substituted phenolates, or abietic acid.

To be mentioned by name, as examples that Zinc salts of the monovalent carboxylic acids, such as acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, neodecanoic acid, 2-ethylhexanoic acid, pelargonic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, myristic acid, palmitic acid, lauric acid, isostearic acid, stearic acid, 12-hydroxystearic acid, 9,10-dihydroxystearic acid, oleic acid, 3,6-dioxaheptanoic acid, 3,6, 9-trioxadecanoic acid, behenic, benzoic acid, p-tert-butylbenzoic acid, Dimethylhydroxybenzoesäure, 3,5-di-tert-butyl-4-hydroxybenzoic acid, tolylic acid, dimethylbenzoic acid, ethylbenzoic acid, n-propylbenzoic acid, salicylic acid, p-tert-octylsalicylic acid, and sorbic acid; Zinc salts of the divalent carboxylic acids or their monoesters, such as oxalic acid, malonic, Succinic acid, glutaric, adipic acid, fumaric acid, Pentane-1,5-dicarboxylic acid, Hexane-1,6-dicarboxylic acid, Heptane-1,7-dicarboxylic acid, Octane-1,8-dicarboxylic acid, 3,6,9-Trioxadecan-1,10-dicarboxylic acid, Lactic acid, malonic, Male acid, Tartaric acid, cinnamic acid, Mandelic acid, malic acid, glycolic acid, oxalic acid, salicylic acid, polyglycol dicarboxylic acid (degree of oligomerization of the polyglycol, preferably in the range of 10-12), phthalic acid, isophthalic acid, terephthalic acid and hydroxyphthalic; and the di or Triester of tri- or tetravalent carboxylic acids, such as hemimellitic acid, trimellitic acid, pyromellitic acid, citric acid, and further so-called overbased (overbased) zinc carboxylates.

The zinc enolates are preferred enolates of acetylacetone, benzoylacetone, des Dibenzoylmethans and enolates of acetoacetic and benzoyl acetate and dehydroacetic acid. You can also inorganic zinc compounds, such as zinc oxide, zinc hydroxide, zinc sulfide or zinc carbonate are used.

Zinc carboxylates are preferred carboxylic acid with 7 to 25 carbon atoms (zinc soaps), such as benzoates or alkanoates, preferably C8 alkanoates, stearate, oleate, laurate, Palmitate, behenate, versatate, hydroxystearate, dihydroxystearate, p-tert-butyl benzoate, or (iso) octanoate. Are particularly preferred Stearate, oleate, versatate, benzoate, p-tert-butylbenzoate and 2-ethylhexanoate.

In addition to the zinc compounds mentioned organic aluminum, cerium or lanthanum compounds are also possible, which have a metal O bond. Among the usable and preferred Aluminum compounds belong Carboxylates and enolates.

Compounds d28) it is antistatic. As known to those skilled in the art, makes a difference one with the antistatics outer and internal antistatic. External antistatic agents are products that are applied to PVC molded parts as a thin layer on the surface become. The disadvantage of this surface application is the low resistance of the antistatic effect, so that the protective effect with the Time wears off and before especially after a rinse and washing after treatment is required. Internal antistatic agents are Part of the PVC compound and are used together with other additives mixed with the PVC. The decisive advantage of internal antistatic agents is the permanent effect that can be achieved.

Examples of suitable antistatic agents are quaternary Ammonium salts, amine derivatives such as ethoxylated amines and more specifically organophosphate, also hygroscopic substances such as glycerin, glycol and other polyols.

The compounds d29) are cyanoacetylureas. Cyanoacetylureas are substances known to the person skilled in the art and are characterized by the formula (D-29) NC-CH ₂ -CO-N (R ^l ) -CO-NH-R ² (D-29) in which the radicals R ¹ and R ² independently of one another each have an unbranched or branched, linear or cyclic alkyl radical having 1 to 18 carbon atoms or an aryl radical having 6 to 18 carbon atoms, which may be one or more alkyl radicals each having 1 to 6 C atoms can be substituted. In the context of the present invention, N, N'-dimethyl-N-cyanoacetylurea is particularly preferred; in this compound, the radicals R ¹ and R ² in the formula (D-29) each represent a methyl group.

In one embodiment, the stabilizer compositions according to the invention are free of cyanoacetylureas d29).

Preferred embodiments

In a preferred embodiment contain the stabilizer compositions according to the invention for stabilizing halogen-containing organic plastics against thermal and / or photochemical degradation,

• - at least a 4-hydroxy-2-pyrone the closer above designated general formula (I), in particular 4-hydroxy-6-methyl-2-pyrone, and
• - at least a perchlorate, preferably sodium perchlorate.

In a further preferred embodiment, the stabilizers according to the invention contain together mensetzungen

• - at least a 4-hydroxy-2-pyrone the closer above designated general formula (I), in particular 4-hydroxy-6-methyl-2-pyrone,
• - at least a perchlorate, preferably sodium perchlorate,
• - at least a compound from the group of zeolites (additives of the group d4).

In a further preferred embodiment contain the stabilizer compositions according to the invention

• - at least a 4-hydroxy-2-pyrone the closer above designated general formula (I), in particular 4-hydroxy-6-methyl-2-pyrone,
• - at least a perchlorate, preferably sodium perchlorate,
• - at least a compound from the group of the cationic layer compounds (Group d5 additives).

In a further preferred embodiment contain the stabilizer compositions according to the invention

• - at least a 4-hydroxy-2-pyrone the closer above designated general formula (I), in particular 4-hydroxy-6-methyl-2-pyrone,
• - at least a perchlorate, preferably sodium perchlorate,
• - at least a compound from the group of CHAP compounds (additives of Group d6).

In a further preferred embodiment contain the stabilizer compositions according to the invention

• - at least a 4-hydroxy-2-pyrone the closer above designated general formula (I), in particular 4-hydroxy-6-methyl-2-pyrone,
• - at least a perchlorate, preferably sodium perchlorate,
• - at least a compound from the group of Katoite (additives of the group d7).

In a further preferred embodiment contain the stabilizer compositions according to the invention

• - at least a 4-hydroxy-2-pyrone the closer above designated general formula (I), in particular 4-hydroxy-6-methyl-2-pyrone,
• - at least a perchlorate, preferably sodium perchlorate,
• - at least a compound from the group of polyols and polyol derivatives (additives of group d 11).

In a further preferred embodiment contain the stabilizer compositions according to the invention

• - at least a 4-hydroxy-2-pyrone the closer above designated general formula (I), in particular 4-hydroxy-6-methyl-2-pyrone,
• - at least a perchlorate, preferably sodium perchlorate,
• - at least a compound from the group of alkali and alkaline earth compounds (additives group d14), in particular calcium or magnesium hydroxide.

In a further preferred embodiment contain the stabilizer compositions according to the invention

• - at least a 4-hydroxy-2-pyrone the closer above designated general formula (I), in particular 4-hydroxy-6-methyl-2-pyrone,
• - at least a perchlorate, preferably sodium perchlorate,
• - at least a compound from the group of metal soaps (additives of the group d27), in particular calcium / zinc metal soaps, barium / zinc metal soaps and Lead metal soaps.

Method according to the invention

Another object of the invention is a process for the stabilization of halogen-containing organic Plastics, especially PVC, against thermal and / or photochemical Degradation, taking the plastics, one or more 4-hydroxy-2-pyrones according to the above Formula (I) mentioned, in which the radical R is also the one specified above Has meaning, adds.

In this process, a stabilizer composition containing at least one 4-hydroxy-2-pyrone of the formula (I) specified in more detail is added to the plastics to be stabilized, in which the radical R is hydrogen, an alkyl radical having 1 to 18 carbon atoms. Atoms or an optionally substituted one Aryl residue with a total of 6 to 24 carbon atoms means, and intimately mixes the components in suitable equipment. The stabilizer compositions used in this process preferably contain one or more perchlorates in addition to one or more compounds (I).

The incorporation of the stabilizer compositions according to the invention using the following methods:

• - as Emulsion or dispersion (one possibility is e.g. the shape of a pasty Mixture. One advantage of the combination according to the invention is this dosage form in the stability of the paste.);
• - As Dry mix during the mixing of additional components or polymer mixtures;
• - by direct addition to the processing apparatus (e.g. calender, mixer, Kneader, extruder and the like) or
• - as solution or melt.

Stabilized PVC

Another object of the invention is PVC, containing at least one 4-hydroxy-2-pyrone according to the above formula (I), in which the radical R has the meaning also described above.

Such a stabilized PVC can be produced in a manner known per se, for which purpose one uses devices known per se, such as the processing apparatus mentioned above a stabilizer combination according to the invention as well as if desired more usual Plastic additives mixed with PVC.

The stabilized preferably contains halogen organic plastic - preferred is PVC - the 4-hydroxy-2-pyrone in an amount of 0.001 to 5 phr and in particular 0.01 to 0.5 phr, preferably 0.01 to 2 phr and in particular 0.01 to 0.5 phr used.

In a preferred embodiment contains the stabilized PVC in addition to at least one 4-hydroxy-2-pyrone or more perchlorates. With regard to the perchlorates be on the explanations above the additives d 1) referenced.

The stabilized according to the present invention PVC can be brought into the desired shape in known ways. Such processes are, for example, grinding, calendering, extruding, injection molding, Sintering or spinning, furthermore extrusion blowing or processing after the Plastisol process.

Extrusion and injection molding are included particularly as a method for processing the PVC stabilized according to the invention prefers.

The PVC stabilized according to the invention is suitable for Hard, semi-hard and soft formulations.

Halogenated organic plastics

With the halogen-containing organic Plastics that it with the stabilizer compositions according to the invention to stabilize, it is especially chlorine-containing Polymers or their recyclates. Examples of such to be stabilized chlorine-containing polymers or their recyclates are: polymers of vinyl chloride, Vinyl resins containing vinyl chloride units in their structure, such as copolymers of vinyl chloride and vinyl esters of aliphatic acids, especially vinyl acetate, copolymers of vinyl chloride with esters of acrylic and methacrylic acid and with acrylonitrile, copolymers of vinyl chloride with diene compounds and unsaturated dicarboxylic acids or their anhydrides, such as copolymers of vinyl chloride with diethyl maleate, diethyl fumarate or maleic anhydride, Post-chlorinated polymers and copolymers of vinyl chloride, copolymers of vinyl chloride and vinylidene chloride with unsaturated Aldehydes, ketones and others such as acrolein, crotonaldehyde, vinyl methyl ketone, Vinyl methyl ether, vinyl isobutyl ether and the like; Polymers of vinylidene chloride and copolymers thereof with vinyl chloride and other polymerizable Links; Polymers of vinyl chloroacetate and dichlorodivinyl ether; chlorinated polymers of vinyl acetate, chlorinated polymeric esters of acrylic acid and the alpha-substituted acrylic acid; Polymers of chlorinated Styrenes, for example dichlorostyrene; chlorinated polymers of ethylene; Polymers and post-chlorinated polymers of chlorobutadiene and their Copolymers with vinyl chloride; and mixtures of the polymers mentioned among themselves or with other polymerizable compounds.

The graft polymers are also comprised of PVC with EVA, ABS and MBS. Mixtures are also preferred substrates the above-mentioned homopolymers and copolymers, in particular Vinyl chloride homopolymers, with other thermoplastic or / and elastomeric polymers, especially blends with ABS, MBS, NBR, SAN, EVA, CPE, MBAS, PMA, PMMA, EPDM and polylactones.

Also preferred are suspension and bulk polymers, as well as emulsion polymers.

As a chlorine-containing polymer Polyvinyl chloride is particularly preferred, in particular suspension polymer and bulk polymer.

In the context of this invention, PVC is also understood to mean copolymers or graft polymers of PVC with polymerizable compounds such as acrylonitrile, vinyl acetate or ABS, these being Sus can act as pension, bulk or emulsion polymers. PVC homopolymer is also preferred in combination with polyacrylates.

Recyclates containing chlorine also come Polymers in question, these being those described in more detail above Polymers, which are processed, processed or stored an injury have experienced. PVC recyclate is particularly preferred. In the recyclates can it also contains small amounts of foreign substances, e.g. Paper, Pigments, adhesives that are often difficult to remove. This, Foreign substances can also from contact with various substances during use or Refurbishment, such as Fuel residues, paint components, traces of metal and initiator remnants.

About the substances used
Solvin 258 RB = PVC (Solvay)
Zeolite A = Sasil A 40 (Degussa)
Sodium perchlorate was used in the form of its monohydrate salt
4-Hydroxy-6-methyl-2-pyrone (prepared according to the EP-A-0 059 052 described methods)

Examples 1 to 4

In Table 1 below on the one hand the individual recipe components of the examined test recipes specified, on the other hand, the determined test results are shown. In The first line of the table shows the respective numbers of the examples specified. The proportions of the individual components are in phr specified; phr means "part per hundred resin" and gives how many parts by weight of the respective component after the addition the composition in PVC - related per 100 parts by weight of PVC - present are. Accordingly, the recipes contain 100 parts each PVC (Solvin 258 RB).

Examples 2 and 4 are according to the invention. The examples 1 and 3 are used for comparison.

The following were the test recipes Measurements carried out:

• - Stability test at thermal load: According to the recipes, rolled skins were manufactured and the static thermal stability at 180 ° C determined. The production The rolled skins were made by using the PVC powder mixture and the recipe components mentioned on a laboratory rolling mill 5 minutes long at 170 ° C homogenized and plasticized. From the so produced approximately 0.5 mm thick rolled skins became test pieces (test specimens) the size of 17 × 17 mm cut out. The test specimens were at 180 ° C in the oven placed on glass plates on rotating trays and again every 15 minutes taken until all samples were "burnt" (i.e. blackening reached had).
• - Stability test after the Congo red method: Furthermore, the rolled skins were used for further Characterization of the Congo red method known to the person skilled in the art according to the Euro standard EN 60811-3-2: 1995 section 9 used. For this purpose, from the rolled skins small samples (50 ± 5 mg) and taken in the corresponding glass tubes in a metal block to 200 ° C (± 0.5 ° C) heated. In the top of the glass tube a strip of universal indicator paper was introduced. The Time until the color of the indicator paper just changed to red, was measured in minutes.

Table 1:

Claims (11)

Use of compositions containing at least one 4-hydroxy-2-pyrone of the formula (I)

wherein the radical R is hydrogen, an optionally substituted alkyl radical with a total of 1 to 18 carbon atoms or an optionally substituted aryl radical with a total of 6 to 24 carbon atoms, for stabilizing halogen-containing organic plastics against thermal and / or photochemical degradation. Use according to claim 1, wherein the 4-hydroxy-2-pyrone uses compounds in which the radical R is a saturated, means linear or branched alkyl radical. Use according to claim 1 or 2, wherein the 4-hydroxy-2-pyrone the compound uses 4-hydroxy-6-methyl-2-pyrone. Use according to one of claims 1 to 3, wherein the compositions in addition to one or more compounds (I) and one or more perchlorates contain. Use according to claim 4, wherein the perchlorates are in the form of their salts. Stabilizer compositions for stabilizing halogen-containing organic plastics against thermal and / or photochemical degradation, characterized in that these compositions have at least one 4-hydroxy-2-pyrone of the formula (I)

in which the radical R is hydrogen, an optionally substituted alkyl radical with a total of 1 to 18 carbon atoms or an optionally substituted aryl radical with a total of 6 to 24 carbon atoms. Stabilizer compositions according to claim 6, wherein the compositions in addition to one or more compounds (I), one or more perchlorates contain. Process for stabilizing halogen-containing organic plastics, wherein these plastics have a stabilizer composition containing at least one 4-hydroxy-2-pyrone of the formula (I)

in which the radical R is hydrogen, an optionally substituted alkyl radical with a total of 1 to 18 carbon atoms or an optionally substituted aryl radical with a total of 6 to 24 carbon atoms, and the components are mixed intimately in suitable apparatus. Method according to claim 8, the stabilizer compositions used in addition to one or more Compounds (I) contain one or more perchlorates. PVC containing at least one 4-hydroxy-2-pyrone of the formula (I)

in which the radical R is hydrogen, an optionally substituted alkyl radical with a total of 1 to 18 carbon atoms or an optionally substituted aryl radical with a total of 6 to 24 carbon atoms. PVC according to claim 10, containing at least one 4-hydroxy-2-pyrone of the formula (I) and at least one perchlorate.