DE10056880A1 - Stabilizer for halogen-containing thermoplastic resins, especially polyvinyl chloride, comprises cyanoacetyl urea, perchlorate and one or more inorganic compounds - Google Patents

Abstract

Stabilizer composition for halogen-containing thermoplastic resins is free of zinc soaps and comprises: (a) cyanoacetyl urea (I); (b) perchlorate; and (c) one or more compounds selected from zeolites, cationic layer lattice compounds, calcium hydroxy aluminum hydrogen phosphites and katoites. Stabilizer composition for halogen-containing thermoplastic resins is free of zinc soaps and comprises, (in parts by weight per 100 parts resin (phr)): (a) cyanoacetyl urea (0.01-0.5 phr) of formula (I); (b) perchlorate (0.001-0.5 phr); and (c) one or more compounds selected from zeolites, cationic layer lattice compounds, calcium hydroxy aluminum hydrogen phosphites and katoites (0.1-3 phr). R<1>, R<2> = 1-18C linear, branched or cyclic alkyl, or 6-18C aryl optionally substituted by 1-6C alkyl.

Description

Field of the Invention

The invention relates to stabilizer compositions for halogen-containing organic Plastics. These compositions contain cyanoacetylurea, or several perchlorates and one or more compounds selected from the group Group of zeolites, cationic layered lattice compounds, calcium hydroxy Aluminum hydrogen phosphite and katoite.

State of the art

Halogen-containing plastics or molding compounds made from them tend known to degradation or decomposition reactions when they are exposed to thermal stress or high energy radiation, for example Ultraviolet light, come into contact.

To stabilize PVC during processing, metal-containing ones are mostly used Stabilizers based on Pb, Ba, Cd, Sn, Ca and Zn are used. As early as 1940 Urea derivatives such as B. Diphenylthiourea to stabilize PVC proposed (compare: Gächter / Müller, "Plastic Additives", Carl Hanser Verlag 1989, p. 312) These connections are mostly in combination with metal-containing stabilizers used, since they are usually not sufficient Long-term stabilization result.  

EP-A-768 336 describes stabilizer combinations for chlorine-containing polymers, especially for polyvinyl chloride (PVC) containing special heterocyclic compounds, namely substituted uracil derivatives. Furthermore these combinations necessarily contain at least one connection selected from is from the group of perchlorate compounds, glycidyl compounds, beta-diketones or esters, dihydropyridines and polyhydropyridines, sterically hindered amines, Zeolites, hydrotalcites, dawsonites, alkali and alkaline earth compounds, antioxidants and lubricant and organotin stabilizers.

EP-A-930 332 describes stabilizer combinations for chlorine-containing polymers, especially for polyvinyl chloride (PVC) containing special heterocyclic compounds, namely substituted uracil derivatives. Furthermore these combinations necessarily contain at least one connection selected is from the group of Katoite, Calcium-Hydroxy-Aluminum-hydrogenphosphite, Aluminum hydroxides, lithium layered grid connections.  

Description of the invention

The plastics processing industry has a constant need for new ones Stabilizers. This applies in particular to the area of halogen-containing organic Plastics, with polyvinyl chloride (PVC) probably the most profiled representative of these Plastic class is.

The object of the present invention was to provide new stabilizers for to provide halogen-containing plastics. These stabilizers should stand out good effect profile under thermal stress and / or stress through distinguish high-energy radiation such as UV radiation. In particular, should halogen-containing plastics equipped with these stabilizers for thermal Stress have excellent values in the area of the initial color. About that In addition, there should be good long-term stability against discoloration under thermal stress be given. The stabilizers should also have the following properties: Easy incorporation into halogen-containing plastics without their rheological Adversely affect properties; good long-term stability of it equipped halogen-containing plastics, in particular PVC (polyvinyl chloride).

The present invention relates to stabilizer compositions for halogen-containing organic plastics containing

• a) one or more cyanoacetylureas of the formula (A)
  NC-CH ₂ -CO-N (R ¹ ) -CO-NH-R ² (A)
  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 C atoms or an aryl radical having 6 to 18 C atoms, which may be one or more alkyl radicals each having 1 to 6 C atoms can be substituted, mean in an amount of 0.01 to 0.5 parts by weight,
• b) one or more perchlorates in an amount of 0.001 to 0.5 parts by weight and
• c) one or more compounds which are selected from the group of Zeolites, cationic layered lattice compounds, calcium hydroxy Aluminum hydrogen phosphites - henceforth also abbreviated as CHAP - and Katoite in an amount of 0.1 to 3.0 parts by weight,

where the proportions of components a), b) and c) are each 100 Parts by weight of chlorine-containing thermoplastic plastic to be stabilized relate and with the additional proviso that the compositions none Zinc soaps included. Zinc soaps are relevant to those skilled in the art known - to understand zinc salts of fatty acids.

The compositions according to the invention are particularly characterized by that they contain halogen-containing organic plastics, especially polyvinyl chloride (such as commonly abbreviated as PVC), are excellent at stabilizing, especially against thermal degradation.

Cyanoacetylureas a) are substances known to the person skilled in the art and are characterized by the formula (A)

NC-CH ₂ -CO-N (R ¹ ) -CO-NH-R ² (A)

wherein 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 is optionally by one or more alkyl radicals each having 1 to 6 C atoms can be substituted. Particularly preferred in the context of the present invention in N, N'-dimethyl-N-cyanoacetylurea; in this compound, the radicals R ¹ and R ² in the formula (A) each represent a methyl group.

Cyanoacetylureas are in the compositions according to the invention in one Quantity from 0.01 to 0.5 parts by weight - based on 100 parts by weight halogenated organic plastic - used. Amounts from 0.1 to 0.4 parts by weight us in particular of about 0.3 part by weight are particularly preferred.

Perchlorates b) for the purposes of the invention are 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.

The perchlorate salts can with alcohols, such as polyols, cyclodextrins, or Ether alcohols or ester alcohols can be complexed or dissolved therein. To the Ester alcohols also include the polyol partial esters. With multi-value Alcohols or polyols also include their dimers, trimers, oligomers and Polymers in question, such as di-, tri-, tetra- and polyglycols, as well as di-, tri- and Tetrapentaerythritol or polyvinyl alcohol in various degrees of polymerization. in the With regard to perchlorate-alcohol complexes, those skilled in the art are expressly excluded EP-B-394 547, page 3, lines 37 to 56 of known types.

The perchlorate salts can be used in various common dosage forms be, for example as a salt or solution in water or an organic solvent as such, or mounted on a carrier material such as PVC, calcium silicate, zeolites or hydrotalcite, or incorporated into a hydrotalcite by chemical reaction or another layered grid connection. Are as polyol partial ethers Glycerol monoether and glycerol monothioether preferred.

The perchlorates can be used both individually and in a mixture with one another become.

The perchlorates are present in an amount in the compositions according to the invention from 0.001 to 0.5, and in particular 0.01 to 0.1 parts by weight, based on 100 parts by weight  halogen-containing organic plastic. Amounts of approximately 0.05 parts by weight are very particularly preferred.

The compounds c) are selected from the group of the following substance classes:

• 1. Zeolites
• 2. cationic layer lattice connections,
• 3. Calcium Hydroxy Aluminum (hydrogen) phosphites (CHAP compounds)
• 4. catoites.

The zeolites c1) - as is known to the person skilled in the art - are alkali or Alkaline earth metals.

You can use the general formula (II)

M _{x / n} [(AlO ₂ ) _x (SiO ₂ ) _y ] .wH ₂ O (II)

be described in which

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

Examples of zeolites are sodium aluminosilicates of the formulas
Na ₁₂ Al ₁₂ Si ₁₂ O ₄₈ .27 H ₂ O [zeolite A],
Na ₆ Al ₆ Si ₆ O ₂₄ .2 NaX.7.5 H ₂ O, X = OH, halogen, ClO ₄ [sodalite];
Na ₆ Al ₆ Si ₃₀ O ₇₂ .24 H ₂ O;
Na ₈ Al ₈ Si ₄₀ O ₉₆ .24 H ₂ O;
Na ₁₆ Al ₁₆ Si ₂₄ O ₈₀ .16 H ₂ O;
Na ₁₆ Al ₁₆ Si ₃₂ O ₉₆ .16 H ₂ O;
Na ₅₆ Al ₅₆ Si ₁₃₆ O ₃₈₄ .250 H ₂ O [zeolite Y],
Na ₈₆ Al ₈₆ Si ₁₀₆ O ₃₈₄ .264 H ₂ O (zeolite X];
or the zeolites which can be represented 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 .20 H ₂ O;
Ca _4.5 Na ₃ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] .30 H ₂ O;
K ₉ Na ₃ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] .27 H ₂ O.

Preferred zeolites correspond to the formulas
Na ₁₂ Al ₁₂ Si ₁₂ O ₄₈ .27 H ₂ O [zeolite A],
Na ₆ Al ₆ Si ₆ O ₂₄ .2 NaX.7.5 H ₂ O, X = OH, Cl, ClO ₄ , 1/2 CO ₃ [sodalite]
Na ₆ Al ₆ Si ₃₀ O ₇₂ .24 H ₂ O,
Na ₈ Al ₈ Si ₄₀ O ₉₆ .24 H ₂ O,
Na ₁₆ Al ₁₆ Si ₂₄ O ₈₀ .16 H ₂ O,
Na ₁₆ Al ₁₆ Si ₃₂ O ₉₆ .16 H ₂ O,
Na ₅₆ Al ₅₆ Si ₁₃₆ O ₃₈₄ .250 H ₂ O, [zeolite Y]
Na ₈₆ Al ₈₆ Si ₁₀₆ O ₃₈₄ .264 H ₂ O [zeolite X]
and such X and Y zeolites with an Al / Si ratio of approx. 1: 1 or which are obtained by partially or completely replacing the Na atoms with Li, K, Mg, Ca, Sr, Ba - or Zn atoms representable zeolites such as
(Na, K) ₁₀ Al ₁₀ Si ₂₂ O _64. 20 H ₂ O.
Ca _4.5 Na ₃ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] .30 H ₂ O
K ₉ Na ₃ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] .27 H ₂ O.

The zeolites mentioned can also be water-poor or water-free. Other suitable zeolites are:
Na ₂ O.Al ₂ O _3. (2 to 5) SiO _2. (3.5 to 10) H ₂ O [zeolite P]
Na ₂ O.Al ₂ O ₃ .2 SiO _2. (3.5-10) H ₂ O (zeolite MAP)
or the zeolites which can be represented by partial or complete replacement of the Na atoms by Li, K or H atoms, such as
(Li, Na, K, H) ₁₀ Al ₁₀ Si ₂₂ O ₆₄ .20 H ₂ O.
K ₉ Na ₃ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] .27 H ₂ O
K ₄ Al ₄ Si ₄ O ₁₆ .6 H ₂ O [zeolite KF]
Na ₈ Al ₈ Si ₄₀ O ₉₆ .24 H ₂ O zeolite D as described in Barrer et al. J. Chem. Soc. 1952, 1561-71, and in US 2,950,952.

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 .21 H 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 , 98 H ₂ O [zeolite ZK-5, zeolite Q]. With regard to these zeolite types, reference is expressly made to EP-A 768 336 and the literature cited therein (compare EP-A 768 336 page 26, lines 40 to 54).

Zeolite P types of the formula II are particularly preferred in which x is a Number in the range from 2 to 5 and y are a number in the range from 3.5 to 10. All Zeolite MAP of formula II are particularly suitable, wherein x is the number 2 and y is a number are in the range of 3.5 to 10. In particular, it is zeolite Na-P, i. H. M stands for Na. This zeolite generally occurs in the variants Na-P-1, NaP-2 and Na-P-3 is characterized by its cubic, tetragonal or orthorhombic structure distinguish (compare EP-A 768 336, bridging pages 26 and 27 Paragraph).

Such finely divided, water-insoluble ones can also be used within the scope of the invention Use sodium aluminosilicates in the presence of water-soluble inorganic or organic dispersants were precipitated and crystallized. These can be in any way before or during the precipitation or crystallization the reaction mixture can be introduced.  

In the context of the present invention, Na zeolite A and Na zeolite P are whole particularly preferred.

The cationic layer lattice connections c2) are known Compounds, their structure and production, for example by W. T. Reichle in Chemtec (January 1986), pages 58-63.

The prototype of cationic layer lattice compounds is the mineral hydrotalcite [Mg ₆ Al ₂ (OH) ₁₆ ] (CO ₃ ) .4 H ₂ O. Hydrotalcite is structurally 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.

Scheme 1

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 consists in treating aqueous solutions of the corresponding metal salts with lye, the hydrotalcite which forms being precipitated. 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.

As already mentioned, hydrotalcite is only the prototype of cationic layered compounds. However, the synthetic methods known from hydrotalcite are also generally used for the synthesis of any cationic layer compounds. As is known to the person skilled in the art, these synthesis methods can be generally classified as hydrothermal synthesis. Hydrothermal synthesis in the narrower sense means 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, since the temperatures used are far above the boiling point of the water, usually even above its critical temperature (see Römpps Chemie-Lexikon, ⁷ 1973, p. 1539)

Cationic layer lattice compounds c2) are understood in the context of the present invention to mean compounds of the general formula (III)

[E _e Z _z D _d V _v (OH ^- ) _x ] (A ^n- ) _a .q H ₂ O (III)

in which mean:

• E is a monovalent cation from the group of alkali metals,
• E is a number in the range from 0 to 2,
• - Z is a divalent metal cation,  
• Z is a number in the range from 0 to 6,
• - D is a trivalent metal cation,
• D is a number in the range from 0 to 3,
• V is a tetravalent metal cation,
• V is 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 is a number in the range from 1 to 10,
• - with the proviso that x <a and e + 2z + 3d + 4v = x + na.

In one embodiment, v in the general formula (III) is zero. These layer connections can therefore be described by the general formula (III *):

[E _e Z _z D _d (OH ^- ) _x ] (A ^n- ) _a .q H ₂ O (III *)

in which mean:

• E is a monovalent cation from the group of alkali metals,
• E is a number in the range from 0 to 2,
• - Z is a divalent metal cation,
• Z is a number in the range from 0 to 6,
• - D is a trivalent metal cation,
• D is 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 is a number in the range from 1 to 10,
• - with the proviso that x <a and e + 2z + 3d = x + na.

In a further embodiment, e in the general formula (III) has the value zero. These layer connections can therefore be described by the general formula (III **):

[Z _z D _d V _v (OH ^- ) _x ] (A ^n- ) _a .q H ₂ O (III **)

in which mean:

• - Z is a divalent metal cation,
• Z is a number in the range from 0 to 6,
• - D is a trivalent metal cation,
• D is a number in the range from 0 to 3,
• V is a tetravalent metal cation,
• V is 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 is a number in the range from 1 to 10,
• - with the proviso that x <a and 2z + 3d + 4v = x + na.

In a preferred embodiment, e and v in the general formula (III) each have the value zero. These layer connections can therefore be described by the general formula (III ***):

[Z _z D _d (OH ^- ) _x ] (A ^n- ) _a .q H ₂ O (III ***)

in which mean:

• - Z is a divalent metal cation,
• Z is a number in the range from 0 to 6,
• - D is a trivalent metal cation,
• D is 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 is a number in the range from 1 to 10,
• - with the proviso that x <a and 2z + 3d = x + na.

With regard to the composition, the layered compounds of the formula (III ***) therefore have the structure of the "classic" hydrotalcites known to the person skilled in the art. Of these, those in which D is aluminum, d is 1 and z is a number in the range from 1 to 5 are preferred. These special hydrotalcites are characterized by the general formula (III ****):

[Z _z Al (OH ^- ) _x ] (A ^n- ) _a .q H ₂ O (III ****)

in which mean:

• - Z is a divalent metal cation,
• Z is 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 is a number in the range from 1 to 10,
• - with the proviso that x <a and 2z + 3 = x + na.

For the purposes of the invention, preference is given to cationic layer compounds (III) 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 (III) in which Z is magnesium and A ^{n- are} carbonate are particularly advantageous.

The CHAP compounds c3) are calcium hydroxy aluminum (hydrogen) phosphites and / or their hydrates. These compounds have the general formula (IV-a)

Ca _x Al ₂ (OH) _{2 (x + 2)} HPO ₃ .mH ₂ O (IV-a),

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 (IV-b)

Ca _x Al ₂ (OH) _{2 (x + 3-y)} (HPO ₃ ) _y .mH ₂ O (IV-b),

wherein:

• - x = a number in the range from 2 to 12,
• - the condition applies 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, provided x = a number in the range of Is 2 to 8.

The CHAP connections can be established, for example, using a method in which mixtures of calcium hydroxide and / or calcium oxide, Aluminum hydroxide and sodium hydroxide or calcium hydroxide and / or Calcium oxide and sodium aluminate with phosphorous acid in for the production of corresponding calcium aluminum hydroxy hydrogen phosphites Reacts amounts in aqueous medium and the reaction product in known per se Cut off and win. That directly from the implementation described above  the reaction product obtained can be prepared from aqueous by known processes Reaction medium are separated, preferably by filtration. The workup the separated reaction product is also carried out 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.

Both fine-particle, active aluminum hydroxide in Combination with sodium hydroxide as well as a sodium aluminate can be used. Calcium can be in the form of finely divided calcium oxide or calcium hydroxide or Mixtures of these are used. The phosphorous acid can be in different concentrated form can be used. The implementation temperatures are preferably between 50 and 100 ° C, more preferably between about 60 and 85 ° C. Catalysts or accelerators are not required, but they also interfere Not. In the case of the compounds, all or part of the water of crystallization can pass through thermal treatment are removed.

When used as stabilizers, the dried calcium hydroxy Aluminum hydroxyphosphites in those customary for hard PVC, for example Processing temperatures of 160-200 ° C no water, so that in the molded parts no annoying blistering occurs.

To improve their dispersibility in halogen-containing thermoplastic resins can the CHAP compounds in a known manner with surfactants be coated.

Katoites c4) are compounds of structure (V)

Ca ₃ Al ₂ (OH) ₁₂ .mH ₂ O (V),

where m is a number in the range from 0 to 10. The Katoite can if necessary, be surface modified. You have a very specific one Crystal lattice (so-called hydrogranate structure), which makes them different from others Distinguish calcium-aluminum-hydroxy compounds. This crystal lattice velvet 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 by six oxy-octahedra still carry hydrogen. The calcium is surrounded by 8 oxygen, some of them form disturbed cube, which is also called triangular dodecahedron.

The Katoite of the general formula Ca ₃ Al ₂ (OH) ₁₂ can be prepared, for example, in accordance with German Patent DE 24 24 763 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 reaction times are preferred from 0.1 to 9 hours. The Katoite fall with medium particle diameters from 0.1 to 100 µm, preferably 0.5 to 30 µm. It can happen that as By-product small amounts of calcium-containing hydroxyaluminates (Hydrocalumite) occur, which have a layer structure and through the above described general formula can be reproduced.

In the manufacture of katoite, excess aluminum or aluminum can also be used Calcium hydroxide are used, mixtures of unreacted Calcium and / or aluminum hydroxide and Katoit arise. These blends can also be used in the sense of the invention.

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

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

Group v-a) includes both monofunctional alcohols and Polyols with 3 to 30 carbon atoms and 2 to 6 hydroxyl groups into consideration optionally alkoxylated, preferably ethoxylated. From the group of monofunctional alcohols are preferred fatty alcohols with 6 to 22 carbon atoms used like caprin, lauryl, palmityl, stearyl, oleyl, linolyl, arachidyl and Behenyl alcohol and its technical blends as they are made from natural oils and Fats are accessible. Of these, fatty alcohols are very particularly preferred the ethoxylated representatives thereof used with 2 to 15 moles of ethylene oxide. From the Group of polyols are diols with 3 to 30 carbon atoms, such as butanediols, Hexanediols, dodecanediols, and trimethylolpropane, pentaerythritol, glycerol and their technical oligomer mixtures with average degrees of condensation from 2 to 10. From the group of polyols, those with are particularly preferred 3 to 30 carbon atoms, at least one hydroxyl group or one per 3 carbon atoms Wear ether oxygen, preferably glycerin and / or the technical Oligoglycerol mixtures with average degrees of condensation from 2 to 10.

The additives in group v-b) are partial or complete epoxidized unsaturated fatty acids or fatty alcohols with 6 to 22 carbon atoms or Derivatives thereof. As derivatives of the epoxidized fatty acids or fatty alcohols the esters thereof are particularly suitable, the epoxidized fatty acids and epoxidized fatty alcohols can be esterified with one another or else with non-epoxidized ones  Carboxylic acids or with non-epoxidized mono- or polyvalent Alcohols. The epoxidized fatty acids are preferably derived from the unsaturated ones Palmitoleic, oleic, elaidic, petroselinic, ricinoleic, linolenic, gadoleic, or erucic acid from which are fully or partially epoxidized by known processes. The epoxidized fatty alcohols are preferably derived from unsaturated alcohols Oleyl, elaidyl, ricinol, linoleyl, linolenyl, gadoleyl, arachidone or Eruca alcohol, which is also wholly or partly by known methods be epoxidized. Suitable esters of epoxidized fatty acids are esters of mono-, di- and / or trihydric alcohols, completely epoxidized, unsaturated Carboxylic acids with 6 to 22 carbon atoms are esterified, such as methyl, 2-ethylhexyl, Ethylene glycol, butanediol, neopentyl glycol, glycerol and / or Trimethylolpropane ester of epoxidized lauroleic acid, palmitoleic acid, oleic acid, Ricinoleic acid, linoleic acid and / or linolenic acid. To be favoured

Esters of trihydric alcohols and practically completely epoxidized unsaturated Carboxylic acids with 12 to 22 carbon atoms, and in particular esters of glycerol with practically completely epoxidized unsaturated carboxylic acids with 12 to 22 carbon atoms. As usual in fat chemistry, the epoxidized Carboxylic acid glycerides also represent technical mixtures as you go through them Epoxidation of natural unsaturated fats and unsaturated oils. Epoxidized beet oil, epoxidized soybean oil and epoxidized are preferred New breed sunflower oil used.

The additives in group v-c) are full or partial esters that follow the relevant methods of preparative organic chemistry, for example can be obtained by acid-catalyzed reaction of polyols with carboxylic acids. Suitable polyol components are those which are already in In connection with group a) were discussed. As an acid component preferably aliphatic, saturated and / or unsaturated carboxylic acids having 6 to 22 carbon atoms such as caproic acid, caprylic acid, capric acid, lauric acid, myristic acid,  Palmitic acid, palmitoleic acid, stearic acid, oleic acid, ricinoleic acid, linoleic acid, Linolenic acid, behenic acid or erucic acid are used. As usual in fat chemistry, the carboxylic acid can also be a technical mixture, as is the case with Pressure splitting of natural fats and oils occurs. Partial esters are preferred of glycerin and in particular of their technical oligoglycerol mixtures average degrees of condensation from 2 to 10 with saturated and / or unsaturated aliphatic carboxylic acids with 6 to 22 carbon atoms.

Finally, according to group vd), alkyl and aryl phosphites can be used, preferably those of the general formula (V)

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. Diphenyldecylphosphite is preferred.

The additives from group v-e) are preferably polymers of Acrylic acid and methacrylic acid and their copolymers. The concept of Copolymers are understood in two senses: first as pure copolymers of Acrylic acid and methacrylic acid and on the other hand as copolymers of (Meth) acrylic acid with other vinylically unsaturated, capable of polymerization Monomers. Examples of other monomers capable of polymerization are sulfonic and unsaturated monomers containing phosphonic acid groups, 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 Alkyl. Examples of additives from group v-e) are polyacrylic acid,  Polymethacrylic Acid - The following are acrylic acid and methacrylic acid as well 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- methyl propanesulfonic acid, (meth) acrylamide, N-hydroxydimethyl (meth) acrylamide and / or their salts. Are very particularly preferred among the polymeric additives those which have a predominantly anionic character, that is, the mostly carry acid groups free or in the form of their salts. In particular polymers of (meth) acrylic acid and their copolymers with styrene are preferred, Acrolein, alkylstyrenes with 1 to 4 carbon atoms in the alkyl radical, styrene sulfonic acid, Maleic acid and / or its salts, especially its sodium salts and Maleic anhydride. The polymeric additives expediently have Group e) a molecular weight of 1000 to 10000. The preparation of the polymer Additives can be prepared using known methods such as substance or Solvent polymerization takes place (see Ullmann's Encyclopedia of technical chemistry, volume 19, 4th edition, pages 2-11, 1980).

The additives of group v-g) are salts of fatty acids. suitable Fatty acids have already been used in connection with additives from group v-c) enumerated. The alkali metal salts of the saturated fatty acids are preferred here.

One or more additives from one or more of groups v-a) to v-g) can used to modify the Katoite, the total amount of Additives in the range of 0.1 to 10 wt .-% - based on Katoit - is. at Combinations of the polymeric additives v-e) with other additives from the groups v-a) to v-d) and v-f) and v-g) it is preferred to add the additives in amounts of 50 to 90% by weight - based on the total additive quantity. Particularly preferred are modified by the surface modified Katoites with or several additives from groups v-b), v-e) and v-g) are modified.  

The Katoite can be modified either in situ or subsequently.

In the subsequent modification, the Katoite with organic or aqueous solutions of the additives are thoroughly ground, preferably with Grinding mill mills and in particular with a ball mill and then usually dried. If the additives are at room temperature liquid or low-melting products are of course not necessary Use solutions of it. Otherwise, the additives v-a) to v-g) are used preferably clear aqueous solutions or solutions with polar organic Solvents.

The term polar organic solvents encompasses at room temperature (15 up to 25 ° C) liquid hydrocarbon compounds containing at least one bear more electronegative substituents 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 can be modified evenly, it is at Presence of the additives of group v-e) is expedient if they are soluble in polar organic solvents of the type described and / or water with pH Values from 8 to 12. The term soluble in this context means that the polymeric additives v-e) in the polar organic solvents and in one aqueous solution with pH 10, adjusted with alkali hydroxides at 20 ° C, at least 0.01 wt .-%, preferably 0.1 wt .-% - based on the solution - and in particular are completely clear under the specified conditions.  

The modification can also be done in situ, which means that you can already do that Calcium and aluminum hydroxide solutions from which the katoite forms, the If necessary, add additives in the form of their solutions.

Ultimately, you can also combine both types of modification, which is the modification with several additives recommends that in particular show different solution behavior.

The compounds c) are in one in the compositions according to the invention Amount of 0.1 to 3.0 parts by weight, based on 100 parts by weight of halogen organic plastic. Quantities from 0.2 to 1.0 05 parts by weight are included prefers.

In one embodiment, the stabilizer compositions to be used according to the invention containing cyanoacetylureas a), perchlorates b) and compounds c) are used in combination with one or more additives which are selected from the group of

• 1. Glycidyl compounds,
• 2. beta-diketones and beta-keto esters,
• 3. dihydropyridines and polydihydropyridines,
• 4. polyols and disaccharide alcohols,
• 5. sterically hindered amines (tetraalkylpiperidine compounds),
• 6. alkali alumocarbonates (Dawsonite),
• 7. alkali and alkaline earth metal hydroxides, bicarbonates and carbonates,
• 8. antioxidants,
• 9. release agents and / or lubricants,  
• 10. plasticizers,
• 11. pigments,
• 12. Fillers,
• 13. phosphites,
• 14. thiophosphites and thiophosphates,
• 15. mercaptocarboxylic,
• 16. epoxidized fatty acid esters,
• 17. UV absorbers and light stabilizers,
• 18. propellant
• 19 urea.

The compounds of classes (d1) to (d19) are known to those skilled in the art as additives for halogen-containing plastics, especially PVC, are well known. For representative Examples of substances from these classes are exemplary of the one cited at the beginning EP-A-768 336.

In a preferred embodiment, the stabilizer according to the invention Compositions, each containing at least one of components a), b), c) and d) included, in solid form. The expression "solid" is different from "pasty" or to understand "fluid".

However, in connection with the use of the term "additive" noted that the specialist in the field of plastics processing the Additives from both a structural and functional point of view classified.

In the case of functional classification, typical plastic additives are: 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 the Thermostability (thermal stabilizers).

The above-mentioned additive classes (d1) to (d19) largely follow the structural ones Classification, d. H. the chemical structure classification. Both Classes (d8) to (d12) as well as (d17) and (d18) became the functional definition preferred.

It should also be noted that compounds of a certain class of substances, hence connections that are structurally the same class can be assigned, in practice often not only perform one function, but two or more. For example, calcium soaps can be used as and / or release agents, but they can also - for example when processing the Plastic polyvinyl chloride (PVC) - as a means of improving Serve thermostability.

To the substances in groups d1) to d19) Glycidyl compounds d1)

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 following described groups d1-I) to d1-V).

Group d1-I compounds

Glycidyl and β-methylglycidyl esters can be obtained by reacting a compound with at least one carboxyl group in the molecule and epichlorohydrin or Glycerol dichlorohydrin or b-methyl-epichlorohydrin. The implementation takes place appropriate in the presence of bases.

As compounds with at least one carboxyl group in the molecule aliphatic carboxylic acids can be used. Examples of these carboxylic acids are Glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid or dimerized or trimerized linoleic acid, acrylic and methacrylic acid, capronic, Caprylic, lauric, myristic, palmitic, stearic and pelargonic acids.

However, cycloaliphatic carboxylic acids can also be used, such as for example 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.

Carboxyl-terminated adducts, e.g. B. of trimellitic acid and polyols, such as glycerin or 2,2-bis (4-hydroxycyclohexyl) propane become.

Group d1-II compounds

Glycidyl or (β-methylglycidyl) ether obtainable by reacting a compound with at least one free alcoholic hydroxy group and / or phenolic  Hydroxy group and a suitably substituted epichlorohydrin under alkaline Conditions, or in the presence of an 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 C ₇ -C ₉ alkanol and C ₉ -C ₁₁ alkanol mixtures.

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

The epoxy compounds can also be derived from mononuclear phenols, such as for example 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 obtained under acidic conditions Condensation products of phenols with formaldehyde such as phenol novolaks.

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

Group d1-III compounds)

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

However, the (N-glycidyl) compounds also include N, N'-Di-, N, N ', N "-Tri- and N, N ', N ", N" "tetraglycidyl derivatives of cycloalkylene ureas such as ethylene urea or 1,3-propyleneurea, and N, N'-diglycidyl derivatives of hydantoins, such as from 5,5-dimethylhydantoin or glycoluril and triglycidyl isocyanurate.

Group d1-IV compounds)

S-glycidyl compounds, such as di-S-glycidyl derivatives, which differ from Dithiols such as ethane-1,2-dithiol or bis (4-mercaptomethylphenyl) ether derived.

Group d1-V compounds)

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-methylcyclohexane carboxylic acid (3 ', 4'-epoxy-6'-methyl-cyclohexyl) methyl ester.

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

• Liquid bisphenol A diglycidyl ethers such as Araldit ™ GY 240, Araldit ™ GY 250, Araldit ™ GY 260, Araldit ™ GY 266, Araldit ™ GY 2600, Araldit ™ MY 790:  
• 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;
• Liquid bisphenol F diglycidyl ethers such as Araldit ™ GY 281, Araldit ™ Y 302, Araldit ™ PY 306:
• Solid polyglycidyl ethers of tetraphenylethane such as CG Epoxy Resin ™ 0163:
• - Solid and liquid polyglycidyl ethers of phenol formaldehyde novolak such as EPN 1138, EPN 1139, GY 1180, PY 307;
• - Solid and liquid polyglycidyl ethers of o-cresol formaldehyde novolak such as ECN 1235, ECN 1273, ECN 1280, ECN 1299;
• - Liquid glycidyl ethers of alcohols such as Shell ™ Glycidylether 162, Araldit ™ DY 0390, Araldit ™ DY 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 ™ PT 810;
• - liquid cycloaliphatic epoxy resins such as Araldit ™ 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 with two functional groups are preferably found Use. But it can also epoxy compounds with one, three or more functional groups are used.

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

If necessary, a mixture of different epoxy compounds can also be used become.

Particularly preferred terminal epoxy compounds are diglycidyl ethers on the Base of bisphenols, such as 2,2-bis (4-hydroxyphenyl) propane (Bisphenol A), bis (4-hydroxyphenyl) methane or mixtures of Bis (ortho / para-hydroxyphenyl) methane (bisphenol F).

The terminal epoxy compounds can be used 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 of PVC, are used.

beta-diketones and beta-keto esters d2)

1,3-Dicarbonyl compounds which can be used can be linear or cyclic dicarbonyl compounds. Dicarbonyl compounds of the following formula are preferably used

R ¹ -CO-CHR ² -CO-R ³ ,

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 of EP-346 279 and Oxa and thia-diketones of EP-307 358 as well as those based on isocyanic acid Ketoester of US 4,339,383.

R ¹ and R ³ as alkyl can in particular be C ₁ -C ₁₈ alkyl, such as. B. 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 z. B. 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 allryl is in particular C ₄ -C ₁₂ alkyl, such as. B. 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, heptanoylacetone, stearoylacetone, palmitoylacetone, lauroylacetone, benzoylacetone, dibenzoylmethane, lauroylbenzoylmethane, palmitoylbenzoylmethane, stearoyl-benzoylmethane-benzoylmethylbenzoyl methylbenzoyl methylbenzoyl methylbenzoyl methylbenzoyl methylbenzoyl methylbenzoyl methylbenzoyl methylbenzoyl methylbenzoyl benzoyl methylbenzyl benzoyl, benzoyl methoxyl benzyl ) methane, benzoyl-p-chlorobenzoylmethane, bis (2-hydroxybenzoyl) methane, 4-methoxybenzoyl-benzoylmethane, bis (4-methoxybenzoyl) methane, 1-benzoyl-1-acetylnonane, benzoyl-acetylphenylmethane, stearoyl-4-methanoxybenz , Bis (4-tert-butylbenzoyl) methane, benzoylformylmethane, benzoylphenylacetylmethane, biscyclohexanoylmethane, dipivaloylmethane, 2-acetylcyclopentanone, 2-benzoylcyclopentanone, 2-benzoylcyclopentanone, diacetoacetic acid methyl, ethyl, and allyl ester Propionyl and butyryl methyl and ethyl acetate, triacetyl methane, methyl acetoacetate, ethyl, hexyl, octyl, dodecyl or octadecyl ester, methyl benzoylacetic acid, ethyl yl, butyl, -2-ethylhexyl, dodecyl or octadecyl ester, and also C ₁ -C ₁₈ alkyl propionyl and butyrylacetic acid. Stearoylacetic acid ethyl, propyl, butyl, hexyl or octyl esters as well as polynuclear β-keto esters as described in EP 433.230 and dehydroacetic acid and its zinc, magnesium or alkali salts.

Preferred are 1,3-diketo compounds of the above formula, wherein 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 can be used alone, as mixtures and / or used as their alkali, alkaline earth and zinc chelates.  

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

Dihydropyridines and Polydihydropyridines d3)

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

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 means 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 meaning as T.
• M and n are numbers from 0 to 20,  
• - k is the number 0 or 1,
• R and R 'are independently of one another 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 in the range from 0 to 10
• - X stands for oxygen or sulfur.

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

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

Thiodiethylene-bis- [5-methoxycarbonyl-2,6-dimethyl-1,4- dihydropyridine-3-carboxylate] and thiodiethylene bis- [5-methoxycarbonyl-2,6- dimethyl-1,4-dihydropyridine-3-carboxylate].

Polyols and polyol derivatives d4)

Particularly suitable polyols are, 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 as well as reaction products these polyols with ethylene oxide and / or propylene oxide.

If desired, the polyols can be attached to one or more OH groups be esterified or etherified. Preferred polyol derivatives are the esters of Represent polyols with carboxylic acids, such as partial glycerol esters of fatty acids, for example glycerol monooleate, glycerol dioleate, glycerol monostearate, Glycerol distearate, pentaerytrite or TMP partial esters or esters of dicarboxylic acids  (e.g. adipic acid, maleic acid) with polyols such as pentaerythritol, glycerol or Trismethylolpropane.

The polyols or polyol derivatives can be used alone or as a mixture with one another be used.

The polyols or polyol derivatives can be used in an amount of, for example, 0.01 to 20, expediently 0.1 to 20 and in particular 0.1 to 10 parts by weight, based on 100 parts by weight halogenated organic plastic.

With regard to examples of suitable compounds d5), be explicit on page 7, line 22 to page 25, line 21, of EP-A-768 336 cited above. These Sterically hindered amines are mentioned in the disclosure of the present Invention expressly included.

With regard to examples of suitable compounds d6), be explicit on page 27, line 17 to page 28, line 9, of EP-A-768 336 cited above. These Dawsonite mentioned in the disclosure of the present invention expressly included.

With regard to examples of suitable compounds d7), be explicit on page 28, line 54 to page 29, line 6, of EP-A-768 336 cited above. These Alkali and alkaline earth compounds mentioned in the disclosure of the present invention expressly included.

With regard to examples of suitable compounds d8), be explicit on page 31, line 34 to page 33, line 4, of EP-A-768 336 cited above. These Antioxidants mentioned in the disclosure of the present invention expressly included.

Regarding the substances of group (d9) it is expressly stated that both Lubricants as well as release agents, as well as mixtures of lubricants and release agents  can be used. According to the usual usage of the specialist such products are called release agents, which have frictional resistance predominantly between the polymer melt and the steel surface of the reduce the molding process used; the reduction of The consequence of frictional resistance is that the melt melt pressure is reduced. In contrast, lubricants mainly act in the polymer melt and set them internal friction forces, which means that the melt can also be Filler content maintains a good plastic flow, which is necessary for filling the shaping tool is important.

In one embodiment of the present invention, solid or liquid calcium salts and / or magnesium salts and / or aluminum salts which are selected from are used as lubricants or release agents at 20 ° C.

• - 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 C-atoms,
• - Aluminum salts of saturated or unsaturated, straight chain or branched monocarboxylic acids with 6 to 36 carbon atoms

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

Other lubricants or release agents that are used alone or in combination with each other Component (d9) can be used, are relevant for this from the State of the art substances. The following preferably come Compound types in question: hydrocarbon waxes in the temperature range of  Melt at 70 to 130 ° C, oxidized polyethylene waxes, free fatty acids with 8 to 22 C atoms and their branched chain isomers, for example stearic acid or Hydroxystearic acid, α-olefins, wax esters, d. H. Long chain esters 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 of 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 carbon atoms and Polyols with 2 to 6 carbon atoms and 2 to 6 hydroxyl groups per molecule in Contain at least one free polyol hydroxyl group. Can be used furthermore the mixed esters described in DE-C-19 07 768 with hydroxyl or Acid numbers in the range from 0 to 6 from aliphatic, cycloaliphatic or aromatic dicarboxylic acids with 2 to 22 carbon atoms in the molecule, aliphatic Polyols with 2 to 6 hydroxyl groups in the molecule and aliphatic Monocarboxylic acids with 12 to 30 carbon atoms in the molecule. examples for this are Mixed ester from maleic acid-pentaerythritol-behenic acid, mixed ester from adipic acid Pentaerythritol oleic acid and mixtures of adipic acid-pentaerythritol-stearic acid. Such lubricants or release agents can be used within the scope of the present invention both individually and in combination with each other, as well as in combination with the above calcium, magnesium or aluminum salts are used.

With regard to examples of suitable compounds d10), be explicit on page 29, line 20 to page 30, line 26, of EP-A-768 336 cited above. The Plasticizers mentioned therein are incorporated in the disclosure of the present invention expressly included.

With regard to examples of suitable compounds d11), be explicit on page 30, line 28 to page 30, line 35, of EP-A-768 336 cited above. The Pigments mentioned therein are incorporated in the disclosure of the present invention expressly included. Titanium dioxide is preferred as pigment d11).  

With regard to examples of suitable compounds d12), be explicit on page 30, line 37 to page 30, line 43, of EP-A-768 336 cited above. The Fillers mentioned there are in the disclosure of the present invention expressly included. Titanium dioxide is preferred as pigment d11). Both Fillers d12) are calcium carbonate (chalk), talc, kaolin and the like prefers. Chalk is particularly preferred.

With regard to examples of suitable compounds d13), be explicit on page 30, line 45 to page 31, line 3, of EP-A-768 336 cited above. These Phosphites mentioned in the disclosure of the present invention expressly included.

With regard to examples of suitable compounds d14), be explicit on page 31, line 5 to page 31, line 19, of EP-A-768 336 cited above. These mentioned thiophosphites and thiophosphates are in the disclosure of the the present invention expressly included.

With regard to examples of suitable compounds d15), be explicit on page 31, line 21 to page 31, line 25, of EP-A-768 336 cited above. The Mercaptocarboxylic acid esters mentioned there are in the disclosure of the present Invention expressly included.

With regard to examples of suitable compounds d16), be explicit on page 31, line 27 to page 31, line 32, of EP-A-768 336 cited above. The there epoxidized fatty acid esters are in the disclosure of the present invention expressly included.

With regard to examples of suitable compounds d17), be explicit on page 33, line 6 to page 34, line 7, of EP-A-768 336 cited above. These  UV absorbers and light stabilizers mentioned in the disclosure of the present invention expressly included.

With regard to examples of suitable compounds d18), be explicit on page 35, line 9 to page 35, line 12, of EP-A-768 336 cited above. These blowing agents mentioned in the disclosure of the present invention expressly included.

With regard to compound d19), it should be noted that this is urea and is therefore a substance of a defined structure known to the person skilled in the art.

Halogenated organic plastics

In the case of halogen-containing organic plastics which are compatible with the invention To stabilize compositions, it is particularly chlorine-containing Polymers or their recyclates. Examples of such chlorine-containing to be stabilized 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 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 others polymerizable compounds; Polymers of vinyl chloroacetate and dichlorodivinyl; chlorinated polymers of vinyl acetate, chlorinated polymeric Esters of acrylic acid and 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 others polymerizable compounds.

Also included are the graft polymers of PVC with EVA, ABS and MBS. Preferred substrates are also mixtures of the homo- and Copolymers, especially vinyl chloride homopolymers, with others thermoplastic and / or 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 Emulsion polymers.

Polyvinyl chloride is particularly preferred as the chlorine-containing polymer, in particular Suspension polymer and bulk polymer.

In the context of this invention, copolymers or Graft polymers of PVC with polymerizable compounds such as acrylonitrile, To understand vinyl acetate or ABS, where it is suspension, bulk or Emulsion polymers can act. PVC homopolymer is also preferred in Combination with polyacrylates.

Furthermore, stabilization also comes in particular within the scope of this invention Recyclates of chlorine-containing polymers in question, which are the ones detailed above described polymers, which are processed, processed or stored have suffered damage. PVC recyclate is particularly preferred. In the Recyclates can also contain small amounts of foreign substances, e.g. B. Paper, pigments, adhesives that are often difficult to remove. These foreign substances can also result from contact with various substances during use or  Work up come, such. B. fuel residues, paint, traces of metal and Initiator residues.

The invention also relates to a method for stabilizing halogen-containing in particular chlorine-containing polymers, these being an inventive one Add stabilizer composition and the components in suitable Equipment intimately mixed.

The stabilizer compositions according to the invention can expediently be incorporated by the following methods:

• - As an emulsion or dispersion (One possibility is, for example, the form of a pasty one Mixture. One advantage of the combination according to the invention is that Dosage form in the stability of the paste.);
• - As a dry mix while mixing additional components or Polymer mixtures;
• - by adding directly to the processing equipment (e.g. calender, mixer, Kneader, extruder and the like) or
• - as a solution or melt.

Another object of the invention is a stabilized PVC, in one stabilizer composition according to the invention was incorporated. Such one Stabilized PVC can be manufactured in a manner known per se, which can be found under Use of devices known per se, such as the one mentioned above Processing equipment the stabilizer combination according to the invention and if necessary, other additives mixed with the PVC. Here, the Stabilizers are added individually or in a mixture or in the form so-called masterbatches.  

The invention thus also relates to a method for producing stabilized PVC, using equipment such as calenders, mixers, Kneaders, extruders and the like, the components a) described above, b), c) and optionally d) and other additives mixed with PVC.

The PVC stabilized according to the present invention can be prepared in known manner desired shape can be brought. Such processes are, for example, grinding, Calendering, extruding, injection molding, sintering or spinning, and further Extrusion blow molding or processing according to the plastisol process.

Extrusion and injection molding are processes for processing the PVC stabilized according to the invention is particularly preferred.

The stabilized PVC can also be processed into foams. You put as Blowing agent azodicarbonamide, it is advantageous if no 1,3-diketones can also be used.

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

The hard formulations are preferred. In the form of hard recipes is suitable PVC stabilized according to the invention especially for hollow bodies (bottles), Packaging films (thermoformed films), blown films, pipes, foams, heavy profiles (Window frames), light wall profiles, building profiles, sidings, fittings, office foils and Equipment housing (computers, household appliances).

PVC rigid foam moldings and PVC pipes as for are preferred Drinking or waste water, gas pipes, cable duct and cable protection pipes, pipes for Industrial pipes, drainage pipes, drain pipes, gutter pipes and drainage pipes.  

For more information see "PVC Plastic Handbook", Volume 2/2, W. Becker / H. Brown, 2nd ed., 1985, Carl Hanser Verlag, pages 1236-1277.

Examples of soft formulations are wire jackets, crash pad foils (Automobiles) and cable insulation.

The PVC stabilized according to the invention is suitable for the semi-hard formulations especially for decorative films, foams, agricultural films, hoses, Sealing profiles and office foils.

Examples of the use of the PVC according to the invention as plastisol are Synthetic leather, floor coverings, textile coatings, wallpaper, protective gloves, Coil coatings and underbody protection for motor vehicles.

Examples of sintered PVC applications of the PVC stabilized according to the invention are Slush, slush mold and coil coatings.  

Examples Substances used

In Tables 1 to 4 below:
Evipol SH 6030 = S-PVC (k-value = 60)
Hydrocarb 95 T = chalk
Ca stearate = calcium stearate
Loxiol G 32 = commercially available lubricant
Loxiol G 40 = commercially available lubricant
Compound a) = N, N'-dimethyl-N-cyanoacetylurea
Compound b) = sodium perchlorate solution, 50% by weight in water
Compound c) = in test series α → zeolite A
in test series β → Alcamizer 2 (commercially available hydrotalcite)
in test series γ → Bärostab RB 3061 (commercially available CHAP connection) δ
Zn stearate = zinc stearate
DOP = dioctyl phthalate.

Tables 1 to 4

Tables 1 to 4 below show the individual formulation components of the examined test recipes, on the other hand the determined test results shown. The respective test numbers are in the first line of the table specified. The proportions of the individual components are given in phr; phr means "part per hundred resin" and indicates how many parts by weight of the each substance after adding the composition in PVC - based on 100 parts by weight of PVC are present. Accordingly, the recipes contain 100 parts each PVC (Evipol SH 6030).

Three measurements were carried out for each of the test formulations:

1) Stability test under thermal stress

According to the recipes Rolled skins produced and the static thermal stability at 180 ° C determined. The The rolled skins were produced by using the PVC powder mixture and the recipe components mentioned on a laboratory rolling mill for 5 minutes  170 ° C homogenized and plasticized. From the thus produced about 0.5 mm thick rolled skins became test pieces (test specimens) measuring 17 × 17 mm cut out. The test specimens were opened at 180 ° C in the heating cabinet Glass plates placed on rotating trays and again every 15 minutes taken until all samples were "burned" (i.e. blackened had)

Color measurement on the rolled skin

In addition, for the rolled skins for further Characterization of the expert. known L *, a *, b * method (compare DIN 6174). The L value indicates the brightness. During the measurements came a commercial device called "Micro Color" (Dr. Long).

Stability test using the Congo Red method

Furthermore, the Rolled skins for further characterization the Congo red Method according to the Euro standard EN 60811-3-2: 1995 para. 9 used. For this small samples (50 ± 5 mg) were taken from the rolled skins and in the corresponding glass tube in a metal block at 200 ° C (± 0.5 ° C) heated. A strip was made into the top of the glass tube Universal indicator paper introduced. The time until the color of the indicator paper just turned red was measured in minutes.  

Trial series α)

Table 1

Test recipe with zeolite as component c)

Test series β)

Table 2

Test recipe with hydrotalcite as component c)

Test series γ)

Table 3

Check recipe with CHAP as component c)

Test series δ)

Table 4

Test recipe with mixtures of different components c)

Claims (24)

1. Containing stabilizer compositions for halogen-containing organic plastics

• a) one or more cyanoacetylureas of the formula (A)
  NC-CH ₂ -CO-N (R ¹ ) -CO-NH-R ² (A)
  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 C atoms or an aryl radical having 6 to 18 C atoms, which may be one or more alkyl radicals each having 1 to 6 C atoms can be substituted, mean in an amount of 0.01 to 0.5 parts by weight,
• b) one or more perchlorates in an amount of 0.001 to 0.5 parts by weight and
• c) one or more compounds selected from the group of zeolites, cationic layered lattice compounds, calcium hydroxy aluminum hydrogen phosphites and katoites in an amount of 0.1 to 3.0 parts by weight,

where the stated proportions of components a), b) and c) each relate to 100 parts by weight of chlorine-containing thermoplastic material to be stabilized and the additional proviso that the compositions do not contain zinc soaps. 2. The composition of claim 1, wherein component a) in an amount of 0.1 up to 0.4 parts by weight - based on 100 parts by weight of the stabilized chlorine-containing thermoplastic - is included.   3. Composition according to claim 1 or 2, wherein component b) in an amount from 0.01 to 0.1 part by weight - based on 100 parts by weight stabilizing chlorine-containing thermoplastic - is included. 4. Composition according to one of claims 1 to 3, wherein component c) in an amount of 0.2 to 1.0 part by weight based on 100 parts by weight stabilizing chlorine-containing thermoplastic - is included. 5. Composition according to one of claims 1 to 4, wherein as further Component d1) one or more glycidyl compounds are contained. 6. Composition according to one of claims 1 to 5, wherein as further Component d2) contain one or more beta-diketones and / or beta-keto esters are. 7. Composition according to one of claims 1 to 6, wherein as further Component d3) one or more dihydropyridines and / or polyhydropyridines are included. 8. Composition according to one of claims 1 to 7, wherein as further Component d4) contain one or more polyols and / or disaccharide alcohols are. 9. Composition according to one of claims 1 to 8, wherein as further Component d5) one or more sterically hindered amines are contained. 10. Composition according to one of claims 1 to 9, wherein as further Component d6) one or more dawsonites are contained. 11. The composition according to any one of claims 1 to 10, wherein as further Component d7) one or more compounds from the group of the alkali and / or alkaline earth metal hydroxides, bicarbonates and carbonates are contained. 12. The composition according to any one of claims 1 to 11, wherein as further Component d8) one or more antioxidants are contained.   13. The composition according to any one of claims 1 to 12, wherein as further Component d9) one or more release agents and / or lubricants are contained. 14. The composition according to any one of claims 1 to 13, wherein as further Component d10) one or more plasticizers are contained. 15. The composition according to any one of claims 1 to 14, wherein as further Component d11) one or more pigments are contained. 16. The composition according to any one of claims 1 to 15, wherein as further Component d12) one or more fillers are contained. 17. The composition according to any one of claims 1 to 16, wherein as further Component d13) one or more phosphites are contained. 18. Composition according to one of claims 1 to 17, wherein as further Component d14) one or more thiophosphites and / or thiophosphates are included. 19. The composition according to any one of claims 1 to 18, wherein as further Component d15) one or more mercaptocarboxylic acid esters are contained. 20. The composition according to any one of claims 1 to 19, wherein as further Component d16) one or more epoxidized fatty acid esters are contained. 21. The composition according to any one of claims 1 to 20, wherein as further Component d17) contain one or more UV absorbers and light stabilizers are. 22. The composition according to any one of claims 1 to 21, wherein as further Component d18) one or more blowing agents are contained. 23. The composition according to any one of claims 1 to 22, wherein as further Component d19) urea is included.   24. A method for stabilizing halogen-containing organic plastics, wherein compositions are incorporated into the halogen-containing plastics

• a) one or more cyanoacetylureas of the formula (A)
  NC-CH ₂ -CO-N (R ¹ ) -CO-NH-R ² (A)
  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 C atoms or an aryl radical having 6 to 18 C atoms, which may be one or more alkyl radicals each having 1 to 6 C atoms can be substituted, mean in an amount of 0.01 to 0.5 parts by weight,
• b) one or more perchlorates in an amount of 0.001 to 0.5 parts by weight and
• c) one or more compounds selected from the group consisting of zeolites, cationic layered lattice compounds, calcium hydroxy aluminum hydrogenphosphites and katoites in an amount of 0.1 to 3.0 parts by weight,

contain, where the stated proportions of components a), b) and c) each relate to 100 parts by weight of chlorine-containing thermoplastic material to be stabilized and the additional proviso that the compositions do not contain zinc soaps.