NO753579L - - Google Patents

Description

Liquid stabilizer mixture and there-

with stabilized chlorine-containing thermoplastics.

It is known to add stabilizers to chlorine-containing thermoplastics, for example polyvinyl chloride, in order to reverse damage and/or discoloration in the substrate caused by thermal stress. Generally, liquid and solid stabilizers are used, as liquid stabilizers have the advantage of good workability and distribution.

The most effective known thermostabilisers include, for example, organic metal compounds of magnesium, calcium, strontium, barium, zinc, cadmium, tin, lead and antimony. Mixtures of some of these compounds are also known. The heavy metals barium, cadmium and lead are relatively toxic and

there has therefore been no shortage of attempts to replace these metals with suitable stabilizer mixtures.

Thus, Japanese patent no. 4,840,843 mentions a combination of organotin maleate, calcium, zinc and potassium stearate and magnesium hydroxide. However, this mixture is only available in powder form. Furthermore, at higher temperatures, maleic acid can form maleic anhydride, known as an irritant, which is problematic in industrial toxicology.

American patent no. 3,644,246 mentions a mixture of dialkyltin carboxylates and sodium, magnesium, calcium or aluminum salts of half-esters of unsaturated dicarboxylic acids, for example maleic acid. In addition to the already mentioned anhydride formation, it is unfortunate that liquid stabilizers on this basis are not storage stable when combined with phosphites.

Orgahotinmercaptides, which additionally contain calcium, magnesium or barium compounds are proposed according to Japanese Patent No. 4,723-442, British Patent Nos. 1,229,521 and 1,229,522 and DOS 2,334,833. Of these combinations, however, it is known that they lead to odor formation during processing. A further disadvantage is eroded low light stabilizing effect.

The invention is based on that task

to provide a liquid storage-stable stabilizer that is sulphur-free, does not contain barium, cadmium and lead, while the processing hardly or does not develop volatile irritants and in chlorine-containing thermoplastics exerts an effective protection against degradation in heat with a good light-stabilizing effect at the same time.

The object of the invention is therefore a liquid stabilizer mixture, containing

a) salts 'of aliphatic saturated and branched monocarboxylic acids, aliphatic unsaturated linear or branched monocarboxylic acids, aliphatic substituted aromatic monocarboxylic acids and/or aliphatically substituted phenols and the cation zinc, calcium and R2Sn<IV->, where R means an alkyl group with 1 to 12 carbon atoms or the benzyl residue, the metal concentrations in the stabilizer mixture being 0.1 - 2.0% by weight zinc, 0.5 - 3.0% by weight calcium and 1.5 -

4.5 wt% tin and

b) a liquid organic phosphate.

Preferred are such stabilizer mixtures, in which

the aliphatic monocarboxylic acid is branched at the α-C atom and has 6 to 18 carbon atoms. Particularly preferred, the unsaturated aliphatic monocarboxylic acid contains 16 to 18 carbon atoms and the saturated aliphatic monocarboxylic acid 8 to 13 carbon atoms.

The aromatic monocarboxylic acids and likewise the phenols are preferably substituted with one or two, especially with an aliphatic group. The aliphatic group is preferably an alkyl group in the case of carboxylic acids especially with 1 to. 12 carbon atoms, which are particularly branched and in the case of phenols with 8 to 12 carbon atoms. Among the aromatic monocarboxylic acids, those which contain a phenyl residue as an aromatic residue are preferred, particularly, however, derivatives of benzoic acid.

The monocarboxylic acids and phenols are known compounds. Examples include:

1. Branched aliphatic monocarboxylic acids:

Isobutyric acid, 3-phenylbutyric acid, isovaleric acid, methylethylacetic acid, trimethylacetic acid, isooctanoic acid, isononanoic acid,

isodecanoic acid, isotridecanoic acid, 2-propylundecanoic acid, iso-palmitic acid, isostearic acid, 10-methylstearic acid and

those known as Versatic or neo acids are mixtures of branched monocarboxylic acids (manufacturer Shell or Esso).

2. Unsaturated monocarboxylic acids:

Crotonic acid, 2-ethyl-crotonic acid, oleic acid, liholic acid.

The saturated and unsaturated monocarboxylic acids are preferably short-chain branched, i.e. that the side chains

may contain 1-4 carbon atoms.

3. Substituted aromatic monocarboxylic acids: p-methylbenzoic acid, o-ethylbenzoic acid, 3~tert.-butyl-5-methylbenzoic acid, p-tert.butylbenzoic acid, isooctylbenzoic acid, tert.—

octylbenzoic acid, p-dodecylbenzoic acid, p-octadecylbenzoic acid, p-(tert., -butylphenyl)acetic acid, 3-(3,5-dimethylphenyl)-propionic acid. Particularly preferred is p-tert-butylbenzoic acid.

4. Substituted phenols:

Cresol, 4-ethylphenol, p-tert.^butylphenol, thymol, 4-methyl-2-(n-hexyl)phenol, p-isooctylphenol, nonylphenol, dodecylphenol, methyldecylphenol, didodecylphenol, p-tert-octylphenol.

Preferably, mixtures of saturated, unsaturated or aromatic monocarboxylic acids and/or phenols may also be contained in the stabilizer mixture.

The alkyl residues of the F^Sn groups preferably contain 1 to 8, especially 1 to 4 carbon atoms and furthermore R in this group is preferably a benzyl residue. The metal concentration in the stabilizer mixture is in particular 0.1 to 1.2% by weight

zinc, 0.5 to 2.5 wt# Ca and 2.0 to 4.0 wt% tin.

Of the liquid phosphites that serve as light stabilizers and solvents, the alkylaryl phosphites are preferred, especially alkylphenyl phosphites, as dialkylphenyl phosphites, especially those with 8 to 14 carbon atoms in the alkyl group, are particularly valuable. Phosphite is thereby usually present in amounts from 10 to 60, especially 15 to 40% by weight, referred to the total mixture. Phenyl may be substituted with preferably 1 to 2 alkyl radicals with 1 to 22, especially 1' to 18, carbon atoms.

Examples include: Trilaurylphosphite, tri-octadecylphosphite, diphenylhexylphosphite, diphenyldodecylphosphite, diphenyltetradecylphosphite, dioctylphenylphosphite, didecylphenylphosphite, didodecylphenylphosphite, dinonylphenyltetradecylphosphite, ditetradecylphenylphosphite, tri(nonylphenyl)-phosphite, isooctyldiphenylphosphite.

The stabilizer mixture according to the invention can preferably also contain, in addition to the liquid phosphite

. an additional solvent. Preferred solvents are glycol ethers such as ethyl glycol, diethylene glycol, propyl glycol, butyl glycol or as butylene glycol monomethyl ether, especially aromatic solvents such as benzene, toluene, xylene, ethyl benzene or isopropyl benzene. Usually

may be added up to 30, especially 5 to 30% by weight, referred to the total mixture of solvent.

Furthermore, the stabilizer mixture according to the invention can additionally contain antioxidants, also alongside a solvent. Preferred are sterically hindered alkyl-phenols, especially those whose alkyl groups are adjacent to the hydroxy group.

For economic reasons, the readily manufacturable and cheap 3,5-di-tertiary-butyl-4-hydroxytoluene (BHT) is particularly preferred. Up to 20, preferably 2 to 10% by weight of antioxidants can be added to the stabilizer mixture.

Examples of phenolic antioxidants should be mentioned: 1.1. 2, 6-dialkylphenols, such as

2-tert.butyl-4,6-dimethylphenol, 2,6-di-tert.butyl-4-methoxymethylphenol, 2,6-dioctadecyl-4-methylphenol.

1.2. Derivatives of alkylated hydroquinones, such as

2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amyl-hydro-quinone, 2,6-di-tert-butyl-hydroquinone, 2,5-di-tert-butyl-4-hydroxy -anisole, 3,5-di-tert.-butyl-4-hydroxy-anisole, tris(3,5-di-tert.butyl-4-hydroxyphenyl)-phosphite, 3,5-di-tert.butyl-4 -hydroxyphenyl stearate, bis-(3,5-di-tert.

butyl-4-hydroxyphenyl)-adipate.

1.3. Alkylidene bisphenols, such as..

2,2'-methylenebis-(6-tert.butyl-4-methylphenol), 2,2'-methylenebis-(6-tert^.buty 1-4-ethyl lf enol), 4,4'-methylenebis- (6-tert.butyl1-2-methylphenol), 4,4'-methylenebis-(2,6-di-tert.butylphenol),

2.6-di-(3-tert.butyl-5-methyl-2-hydroxybenzyl)-4-methyl-ferriol, 2,2'-methylenebis-i/~4-methyl-6-(a-methylcyclohexyl)-phenol/ , 1,1-bis-(3j5_dimethyl-2-hydroxyphenyl)butane, 1,1-bis-(5-tert.butyl-4-hydroxy^2-methylphenyl)-butane, 2,2-bis-(5-tert .butyl-4-hydroxy-2-methylphenyl)-butane, 2,2-bis-

(3'5-di-tert-butyl-4-hydroxyphenyl)-propane, 1,1,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane, 2,2-bis- (5-tert.butyl-4-hydroxy-2-methylphenyl)-butane, 1,1,5,5-tetra-(5-tert.butyl-4-hydroxy-2-methylphenyl)-pentane, ethylene glycol-bis- _/ 3, 3-bis-(3'-tert.butyl-4'-hydroxy-phenyl)-butyrate/. 1.4. O- and N- benzyl compounds, such as e.g. 3 » 5» 3.' 3 5 ' - te tr a-t ert .butyl-4, 4 '-dihydroxydibenzyl ether, tris-(3,5-di-tert.butyl-4-hydroxybenzyl)-amine. 1.5. H ydroxybenzylated malon esters, such as e.g.

2,2-bis-(3»5-di-tert.butyl-2-hydroxybenzyl)-malonic acid dioctadecyl ester, 2-(3-tert.butyl-4-hydroxy-5-methyl-benzyl)-malonic acid dioctadecyl ester, 2, 2-bis-(3,5-di-tert.butyl-4-hydroxybenzyl)-rnalonic acid di-/_ 4-(1,1,3»3_

tetramethylbutyl)-phenyl/-ester.

1.6. H ydroxybenzyl-aromatic er-, s if e.g.

1,3,5-tri-(3,5-di-tert.butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-di-(3»5-di-tert.butyl-4 -hydroxy-benzyl)-2,3,5»6-tetramethylbenzene, 2,4,6-tri-(3',5-di-tert.butyl-4-hydroxybenzyl)-phenol.

1.7. s- triazine compounds, such as e.g.

2,4-bis-octoxy-6-(33 5-di-tert.butyl-4-hydroxyanilino)-s-triazine, 2-octoxy-4,6-bis-(3>5-di-tert.butyl- 4-hydroxyanilino)-s-triazine, 2-octoxy-4,6-bis-(35 5_ di-tert.butyl-4-hydroxy-phenoxy)-s-triazine, 2,4,6-tris-( 3 j 5-di-tert.butyl-4-hydroxyphenoxy)-s-triazine, 2,4,6-tris-(3,5-di-tert.butyl-4-hydroxyphenylethyl)-s-triazine, 1*3 » 5_tris-(3,• 5-di-tert.butyl-4-hydroxybenzyl)-isocyanurate.

1.8. A amides of g-(3»5-di-tert.butyl-4-hydroxyphenyl)-propionic acid, such as e.g. 1» 3» 5-tris-(3,5-di-tert.butyl-4-hydroxyphenyl-propionyl)-hexahydro-s-triazine, N,N'-di-(3,5-di-tert.butyl- 4-hydroxyphenyl-propionyl)-hexamethylenediamine.

1.9. Esters of g-(.3,5-di-tert.butyl-4-hydroxyphenyl)-propionic acid with monohydric or polyhydric alcohols., such as e.g. with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonane-diol, ethylene glycol, 1,2-propanediol, diethylene glycol, neopentyl glycol, pentaerythritol, trimethylhexanediol, trimethylol-ethane, trimethylol-propane, tris-hydroxyethyl-isocyanurate, 4 -

hydroxymethyl-1-phos fa-2 , 6 , 7-trioxabicyclo//2 >2,27-octane.

1.10. Ester of g-(5-tert.butyl-4-hydroxy-3-methylphenyl)-propionic acid' with. single, or, f ler.verdi.ge alcohols such as e.g. with

methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonane-diol, ethylene glycol, 1,2-propanediol, diethylene glycol, neopentyl glycol, pentaerythritol, trimethylhexanediol, trimethylolethane, trimethylolpropane, trishydroxyethyl isocyanurate, 4-hydroxymethyl-l- phosph a-2,6,7-trioxabicyclo/_ 2,2,2/- octane.'

1.11. East of 3,. 5- di- tert. butyl-4-hydroxyphenylacetic acid

with monohydric or polyhydric alcohols such as e.g. with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, diethylene glycol, neopentyl glycol, pentaerythritol, ■trimethylhexanediol, tri-methylolethane, trimethylolpropane, tris-hydroxyethyl iso-cyanurate, 4- hydroxymethyl-1-phospha-2,6,7-trioxabicyclo _/~2,2, 27-octane.

1.12. A cylaminophenols, such as

N-(3,5-di-tert-butyl-4-hydroxyphenyl)-stearic acid amide, N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenyl)-bisacetamide.

1.13. Benzylphosphonates such as e.g.

3,5-di-tert.butyl-4-hydroxybenzylphosphonic acid dimethyl ester, 3,5-di-tert.butyl-4-hydroxybenzylphosphonic acid diethyl ester, 3,5-di-tert.butyl-4-hydroxybenzylphosphonic acid -dioctadecyl ester, 5-tert.butyl-4-hydroxy-3-methylbenzyl-phosphonic acid dioctadecyl ester.

The stabilizer mixture according to the invention can be prepared by mixing the individual components, possibly by simultaneous heating. The individual components are commercial goods or can be produced using known methods. The salts of the monocarboxylic acid of the phenols are obtained, for example, by reaction of oxides or hydroxides of the metals zinc and calcium and of dialkyl resp. dibenzyltin oxides with the corresponding monocarboxylic acids or phenols in a suitable solvent while removing formed water. They, for example, by direct reaction of tin with alkyl halides or benzyl chloride by hydrolytic processing formed dialkyl resp. dibenzyltin oxides can also contain smaller amounts of monoorganotin oxides (stannonic acids). Particularly preferred organotin oxides are dimethyl-, di-n-butyl-,

di-n-octyl and dibenzyltin oxides.

In a particularly preferred embodiment, the

the salts are placed in a solvent, which can additionally be contained in the stabilizer mixture, as it can then. a liquid phosphite and possibly an antioxidant are dissolved. On

in this way the particularly preferred mixtures of the corresponding salts, a phosphite, a solvent and an antioxidant are obtained.

The stabilizer mixture according to the invention is

suitable for stabilizing chlorine-containing thermoplastics against degradation caused by heat or light.

A further object of the invention is there-

for a stabilized mixture containing a chlorine-containing thermoplastic polymer and 0.5 to 10 wt#, referred to the overall mixture, especially 1 to 5 wt# of a stabilizer mixture according to the invention.

Thermoplastics of or on a basis are preferred

of vinyl chloride, esp. polyvinyl chloride, especially those produced by mass or suspension polymerization. Furthermore, it is preferred that the chlorine-containing thermoplastic

holds an emollient. Polyvinyl chloride, which contains a plasticizer, is particularly preferred.

Suitable comonomers for vinyl chloride are e.g. ethylene, propylene, 1,2-butene, vinylidene chloride, acrylonitrile, acrylic acid ester or styrene.

Compared to known calcium/zinc stabilizers, the stabilizer mixture according to the invention has a higher thermostabilizing effect, in particular a better long-term stability. Advantageous is its relation to the selection of the metals

very low toxicity and that during processing they do not form volatile and irritating anhydrides, such as diorganotin maleic acid half-esters. Moreover, the thermostabilizing effect is higher, especially with regard to the initial stability, than with the latter organotin maleates. The light-stabilizing effect is very good and better than, for example, with diorganotinmercaptides, which also

derer to formation of mercaptide odor. A further advantage is the high storage stability, without thereby losing the good effect, which is surprising, since when storing diorganotin maleic acid half-esters with phosphites, a thermostability is reduced

gazing. effect.

It is known that calcium/zinc carboxylates in combination with phosphites convey a relatively good initial stability, but for a longer Torarbeidselsen one too little long-term stability.

Diorganotin carboxylates of monocarboxylic acids stabilize, as is generally known, insufficiently with regard to initial and long-term stability. Surprisingly, the combination according to the invention of both stabilizers also leads to an improved long-term stability, next to the already indicated improvement of the initial stability.

The invention shall be explained in more detail with the help of some examples where the stated percentages are % by weight and the parts are parts by weight.

. Manufacturing examples.

Example A.

205.7 g of p-t-butylbenzoic acid, 137.4 g of isostearic acid and 160.0 g of butyl glycol are heated in a 2 liter three-necked flask to 80°C. While stirring, 63.0 g of dibutyltin oxide, 12.4 g of ZnO and 29.4 g of Ca(OH)2 are added and reacted at 130°C while separation of reaction water. 362.9 g of ditetradecylphenyl phosphite and 50.0 g of 3,5- di-tert.butyl-p-hydroxytoluene. The filtered solution is a storage-stable clear liquid. Metal concentration: About 1.6% by weight, Zn 1.0% by weight, Sn 3.0% by weight.

Example B.

In an analogous reaction to example A of 399.9 g of isostearic acid with 46.9 g of dibutyltin oxide, 9.9 g of ZnO and 24.7 g of Ca(OH)2 using 150.0 g of butyl glycol, 350.0 g of ditetradecylphenyl phosphite and 50 .0 g of 3,5-di-tert.butyl-p-hydroxy-toluene yields a liquid stabilizer of the following composition:

16.5$ dibutyltin diisostearate

7.7% Zn isostearate

20.8% Ca isostearate

35.0% ditetradecylphenyl phosphite

5.0% 3,5-di-tert.butyl-p-hydroxytoluene

15.0% butyl glycol.

Metal concentration:- About 1.3% by weight, Zn 0.8% by weight, Sn 2.1% by weight. Oak sample C.

The components 1 to 10 are mixed according to the following procedure and reacted: (1) 43.0 g of methyl branched Cn-monocarboxylic acid (trade name "Cekanoic 8") (2) 91.0 g of benzene acid<:>;

(3) . 71.4 g of oleic acid

(4) 41.1 g of butyl glycol

(5) - 164.5 g cycloaliphatic hydrocarbon, boiling range l80-210°C (trade name ESSO "Vårsol" 180/210 E)

(6) 62.9 g of dibutyl dimoxide

(7) 55.6 g zinc-(2-ethylhexoate)

(8) .2.9.5 g of calcium hydroxide

(9) 40.0 g BHT

(10) 420.0 g of diphenylmyristyl phosphite.

(1), (2), (3), (4) and (5) are mixed and heated to 80°C. Then add (6) and react for 30 minutes at 110°C (reflux cooler, water separator). Then add (8) at 80°C, react at 120 to 130°C and remove the water

under low vacuum. After mixing with (7) and (9) at 80°C, filter over Celite.

Calcium content: 1.6% Zinc content: 1.0% Tin content: 3.0%.

Application examples.

Example 1.

The stabilizing effect of the according to examples A resp. B produced stabilizers according to the invention are compared in a permanent roll test suitable as a test method for calender preparation to a commercially available Ba/Cd/Zn stabilizer suitable for calender preparation with a metal content of approx. 5.3% barium, 3.2% cadmium, and 0.5% zinc ("Irgastab" BC 231). For this, 100 g of suspension PVC (KW 70) are mixed with 50 g of dioctyl phthalate (DOP), 0.5 g of paraffin wax and 2.0 g of stabilizer in a fast-running mixer and the mixture is submitted to a 190°C hot laboratory rolling mill for the thermal examination. . A sample is taken from the formed roll at intervals of 5 minutes, the degree of discoloration of which is determined by determining the yellowness index. The results are listed in table 1.

According to table 1, the stabilizer produced according to example A proves to be superior to comparison stabilizers3 with regard to the lightness of the foils produced from it in the practically important phases of permanent rolling samples, while the stabilizer mentioned in example B has a. in relation to the comparative stabilizer, a slightly increased degree of discoloration results in a clearly higher long-term stability.

Example 2.

To investigate the applicability of the stabilizer according to the invention for the stabilization of PVC pastes, 100 g of suitable for paste processing PVC of K-value 68 are mixed together -

72 with 65 g of DOP and 2 g of stabilizer into a paste 3 The paste is spread to a film of uniform thickness (035 mm) on a flat glass plate and submitted to an oven at the constant temperature of 170°C for a heat test. For this, samples are taken from the oven at intervals of 15 minutes, the discoloration of which is measured (Yellowness Index). As comparative stabilizers, a liquid Ca/Zn rod suitable for pasta processing was used. about. 2.6% calcium and 2.k% zinc ("Irgastab" CZ 57). The results is shown in table 2..

Table 2 shows the superiority of the stabilizer according to the invention.

Example 5.

In 2 paste PVC types (Pasta type I with KW 68 - 72

and paste type II with KW 70) likewise takes place in the heat test according to example 2, a comparison of a comparative stabilizer (18.6% -Sn) based on dibutyltin-maleic acid dibutyl esters with a stabilizer according to the invention produced according to example A, in which ditetradecylphenylphosphite was replaced with didecylphenylphosphite fit. The amounts of dibutyltin-maleic acid half-esters used amounted to 1%, the stabilizer according to the invention 2%. The results are shown in table 3.

From table 3 it can be seen that the initial stability, which is important for the production of bright finished articles, can easily be achieved with the stabilizer type according to the invention.

Example 4.

The stabilizers listed in Table 4 are examined at 180°C in a heat test according to example 1. The recipe consists of 100 parts PVC (KW 70) and 50 parts dioctyl phthalate, with 2 parts stabilizer always being added. For comparison, the result with a liquid Ba/Cd/Zn stabilizer ("Irgastab" BC 231) is shown.

Butyl glycol was used as solvent

(B), as phosphite dimyristyl phosphite (D) and as antioxidant 3,5-di-tert.-butyl-p-4-hydroxytoluene (BHT). The quantity of these

constituents (by weight) are also indicated in table 4 (B : D :

BHT). As an organotin group, it contains the dibutyltin group.

E xample 5-

In a recipe of 100 parts polyvinyl chloride (KW 70), 50 parts dioctyl phthalate and 2 parts of the stabilizer mixtures detailed in Table 5, the dependence of the stabilizer effect on the organotin group is determined. It is carried out according to example. 1 a heat test at 180°C, the Yellowness index being determined after every 15 minutes. The results are listed in table 5 - The amount in weight% of solvent

(B), phosphite (D) and antioxidant (BHT) are also indicated.

Claims (24)

1. Liquid stabilizer mixture, containing a) salts of aliphatic saturated and branched monocarboxylic acids, aliphatic unsaturated linear or branched monocarboxylic acids, aliphatically substituted aromatic monocarboxylic acids and/or aliphatically substituted phenols and the cations zinc, calcium and the residue R2 Sn <IV-> , where R means an alkyl group with 1 to 12 carbon atoms or benzyl ester, the metal concentration in the stabilizer mixture being 0.1 - 2.0 wt% zinc, 0.5 - 3.0 wt% calcium and 1.5 - 4.5 wt% tin and b) a liquid organic phosphite. 2. Mixture according to claim 1, characterized in that the aliphatic monocarboxylic acid is branched at the α-carbon atom. 3. Mixture according to claim 1, characterized in that the aliphatic monocarboxylic acid contains 6 to 18 carbon atoms. 4..Mixture according to claim 1, characterized in that the unsaturated aliphatic monocarboxylic acid contains 16 to 18 carbon atoms. 5- Mixture according to claim 1, characterized in that the aliphatic monocarboxylic acid is saturated and contains 8 to 13 carbon atoms. 6. Mixture according to claim 1, characterized in that the aromatic monocarboxylic acids and phenols are mono- or disubstituted. 7. Mixture according to claim 1, characterized in that the aromatic carboxylic acid is substituted with 1 or 2 alkyl groups. 8. Mixture according to claim 7, characterized in that the alkyl groups contain 1 to 12 carbon atoms. 9. Mixture according to claim 8, characterized in that the alkyl group is branched. 10. Mixture according to claim 9, characterized in that it contains p-tert-butylbenzoic acid. 11. Mixture according to claim 1, characterized in that the phenol is substituted with 1 or 2 alkyl groups. ' 12. Mixture according to claim 11, characterized in that the alkyl residue contains 8 to 12 carbon atoms. 13. Mixture according to claim 1, characterized in that R means an alkyl group with 1 to 8 carbon atoms or the benzyl group. 14. Mixture according to claim 1, character, eri-s e r t in that it contains 0.1 - 1.2 wt% zinc, 0.5 - 2.5 wt% Ca and 2.0 to 4.0 wt% tin . 15. Mixture according to claim 1, characterized in that an alkyl-aryl phosphite is contained as component b). 16. Mixture according to claim 15, characterized in that it contains a dialkylphenyl phosphite. 17- Mixture according to claim 15, characterized in that the alkyl groups contain 8 to 14 carbon atoms. 18. Mixture according to claim 17, characterized in that it contains ditetradecylphenylphosphite, didecylphenylphosphite, dimyristylphenylphosphite, myristyldiphenylphosphite or (dinonylphenyl)isotridecylphosphite. 19. Mixture according to claim 1, characterized in that it also contains a solvent. 20. Mixture according to claim 1 or 19, characterized in that an antioxidant is also contained. 21. A stabilized mixture, containing a chlorine-containing thermoplastic polymer and .0.5 to 10% by weight of the stabilizer mixture according to claim 1, 19 or 20, referred to the overall mixture. 22. Stabilized mixture according to claim 21, characterized in that it contains a polymer of or based on vinyl chloride. 23. Stabilized mixture according to claim 22, k a r a k - .terized in that the mixture also contains a plasticizer. 24. Stabilized mixture according to claim 22, characterized in that the polymer is suspension or mass polyvinyl chloride.