The invention relates to a composition, which comprises the mixture of a polyglycerol ester of an unsaturated or saturated Ci ₂ -C ₃₀ carboxylic acid with a metal salt of a Ci ₂ -C ₂ oalkylcarboxylic acid. This mixture is useful as lubricant for shaping chlorine containing thermoplastic polymers, such as polyvinyl chloride (PVC). Shaping includes extrusion, calendering and injection-molding processes.

In some calendering processes a high-molecular weight emulsion PVC to which relatively large amounts of lubricants, particularly so-called lubricants, have been added, is processed by means of an extruder at a temperature below the melting range of the PVC. The product strain obtained is fully melted by brief heating to above 200°C. Finally, the product is stretched in order to give it the necessary mechanical strength.

Relatively large quantities of lubricants are needed processing of emulsion PVC substrates of high K-value. The lubricants are normally added in quantities of at least 4 phr (i.e., 4 parts by weight lubricant to 100 parts by weight synthetic resin) and more.

The diverse requirements which an effective PVC lubricant must meet may be illustrated by reference to the problems when calendering rigid PVC.

The choice of the lubricant is determined not only by the lubricating and release effect of the lubricant, but also by its compatibility with the substrate. Only few lubricants are compatible with rigid PVC in larger quantities of 4 to 5 or even 6 phr (= parts per hundred parts of resin). In addition, the lubricants used with emulsion PVC also have to be compatible with the emulsifier used for polymerization.

Suitable lubricants are esters of long-chain aliphatic carboxylic acids (montan acids) with dihydric or trihydric alcohols, e.g. ethylene glycol or glycerol, so-called montan waxes. Such lubricants are disclosed in, for example, German Published Pat. Application No. 1,907, 768. However, the availability of montan waxes and derivatives thereof is limited and subject to increases of price. For this reason alone, there is a need for alternative lubricants to replace these products.

EP-64 697 discloses a lubricant composition for shaping polyvinyl chloride, which contains esters of oligomers of trihydric, pentahydric or hexahydric aliphatic alcohols, having 3 or more monomer units, with saturated or unsaturated Ci ₆ -Ci ₈ fatty acids, from 30 to 100% of the alcoholic hydroxy groups being esterified. These compositions are disadvantageous in view of their high viscosity which results in the adhesion of substantial amounts on the metallic surfaces and obstruction of the machinery.

WO 95/06683 discloses internal lubricant mixtures for PVC films produced according to a low temperature process. These mixtures contain (A) partial esters of oligomers of trivalent or hexavalent aliphatic alcohols with at least 2 monomer units and monocarboxylic acids and (B) complex esters of (a) dicarboxylic acids with 2 to 22 C-atoms; (b) aliphatic polyols with 2 to 6 hydroxy groups and (c) monocarboxylic acids with 6 to 32 C-atoms.

The problem to which the present invention relates, is to find improved lubricant compositions for the processing of rigid PVC at higher temperatures, which is derived from a broader raw material base than is montanic acid, thus preventing substantial adhesion of the PVC composition on the metallic surfaces of the PVC processing equipment.

This problem has been solved with a novel lubricant composition that comprises several individual components. By using a multicomponent mixture, it is possible to apply the individual components in comparatively small quantities.

The present invention relates to a composition which comprises

a) A chlorine containing thermoplastic polymer;

b) A polyglycerol ester of an unsaturated or saturated Ci ₂ -C ₃ ocarboxylic acid; and c) A metal salt of a Ci ₂ -C ₂ oalkylcarboxylic acid.

A further embodiment relates to a composition, which comprises

d) Further additives which are customary for the processing and stabilizing of chlorine- containing polymers.

A preferred embodiment relates to a composition, which comprises

a) 65.0 to 95.0 wt.-% of a chlorine containing thermoplastic polymer;

b) 0.1 to 2.5 wt.-% of a polyglycerol ester of an unsaturated or saturated Ci ₂ -C ₃ ocarboxylic acid; and

c) 0.1 to 1.0 wt.-% of a metal salt of a Ci ₂ -C ₂₀ alkylcarboxylic acid; and, optionally, d) 0.01 to 30.0 wt.-% of further additives which are customary for the processing and stabilizing of chlorine-containing polymers;

provided that the sum of the weight percentages of all components amounts to 100 %.

A particularly preferred embodiment relates to a composition, which comprises

a) 85.0 to 95.0 wt.-% of a chlorine containing thermoplastic polymer;

b) 0.5 to 2.0 wt.-% of a polyglycerol ester of an unsaturated or saturated Ci ₂ -C ₃ ocarboxylic acid; and

c) 0.1 to 0.7 wt.-% of a metal salt of a Ci ₂ -C ₂₀ alkylcarboxylic acid; and, optionally, d) 0.1 to 10.0 wt.-% of further additives which are customary for the processing and stabilizing of chlorine-containing polymers; provided that the sum of the weight percentages of all components amounts to 100 %. A highly preferred embodiment relates to a composition, which comprises

a) A chlorine containing thermoplastic polymer;

b) A polyglycerol ester of a saturated Ci ₂ -C ₃ ocarboxylic acid; and

c) A metal salt of a Ci ₂ -C ₂ oalkylcarboxylic acid.

An embodiment of first choice relates to a composition, which comprises

a) A chlorine containing thermoplastic polymer;

b) A polyglycerol ester of stearic acid; and

c) Calcium stearate.

The compositions defined above are characterized by their improved lubricating properties. Therefore, they are particularly useful as lubricants, in the production of chlorine-containing polymers, such as PVC.

Component a)

The term chlorine-containing polymer comprises within its scope any polymer directly obtainable by the polymerization process for its production. The term also comprises within its definition worked-up polymer units or polymer fragments obtainable by standard methods for recycling, so called recyclates.

Representative examples of chlorine-containing polymers or of the recyclates thereof 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 the anhydrides thereof, such as copolymers of vinyl chloride with diethyl maleate, diethyl fumarate or maleic acid anhydride, post-chlorinated polymers and copolymers of vinyl chloride, copolymers of vinyl chloride and vinylidene chloride with unsaturated aldehydes, ketones and others, such as acrolein, crotonaldehyde, vinyl methyl ketone, vinyl methyl ether, vinyl isobutyl ether and the like; polymers of vinylidene chloride and copolymers thereof with vinyl chloride and other poly- merisable compounds; polymers of vinyl chloroacetate and dichlorodivinyl ether; chlorinated polymers of vinyl acetate, chlorinated polymeric esters of acrylic acid and alpha-substituted acrylic acid; polymers of chlorinated styrenes, for example dichlorostyrene; chlorinated gum; chlorinated polymers of ethylene, polymers and post-chlorinated polymers of chlorobutadiene and the copolymers thereof with vinyl chloride, gum hydrochloride and chlorinated gum hydrochloride; and mixtures of the mentioned polymers with one another or with other polymerisable compounds. Also included are the graft polymers of PVC with EVA, ABS and MBS. Preferred substrates are also mixtures of the above-mentioned homo- and co-polymers, especially vinyl chloride homopolymers, with other thermoplastic and/or elastomeric polymers, especially blends with ABS, MBS, NBR, SAN, EVA, CPE, MBAS, PMA, PMMA, EPDM and polylactones.

Preference is given also to suspension and bulk polymers, and to emulsion polymers.

Polyvinyl chloride is especially preferred as the chlorine-containing polymer, especially in the form of a suspension polymer and of a bulk polymer.

Within the scope of this invention, PVC is also to be understood to include copolymers or graft polymers of PVC with polymerisable compounds such as acrylonitrile, vinyl acetate or ABS, which may be suspension, bulk or emulsion polymers. Preference is given to PVC

homopolymers also in combination with polyacrylates.

Within the scope of this invention are especially recyclates of chlorine-containing polymers, the polymers being those described in detail above, which have been damaged as a result of processing, use or storage. PVC recyclate is especially preferred. The recyclates may also contain small amounts of foreign substances, such as paper, pigments and adhesives, which are often difficult to remove. Those foreign substances may also originate from contact with various substances during use or working-up, such as propellant residues, traces of lacquer, traces of metal, and initiator radicals.

Component b)

Polyglycerol esters of unsaturated or saturated Ci2-C ₃₀ carboxylic acids are known and commercially available, such as the product Luwax®K obtainable from BASF SE.

The acid part of the ester is derived from a straight chain or branched, particularly straight chain Ci2-C ₃₀ alkylcarboxylic acid or from a unsaturated straight chain or branched Ci2-C ₃₀ alkenylcarb- oxylic acid with one to three double bonds (cis-, trans-forms included).

Examples of straight chain Ci2-C ₃₀ alkylcarboxylic acids are: lauric (C12), myristic (C14), palmitic (C16), stearic (C18), arachidic (C20), behenic (C22), lignoceric (C24) and cerotic (C26) acid.

Examples of unsaturated straight chain or branched Ci2-C ₃₀ alkenylcarboxylic acid with one to three double bonds are: myristoleic (C14), palmitoleic (C16) and oleic and elaidic acid (C18).

The alcohol part of the ester is derived from a polyglycerol obtainable by heating glycerol at 200° to 300°C, preferably at 250°C to 270°C in the presence of an alkaline catalyst, and distilling off the water liberated during the condensation. A suitable catalyst is sodium hydroxide used in an amount of about 2% by weight of the glycerol. The molecular weight of the polyglycerol can be determined approximately from the amount of water liberated during the reaction and from the hydroxyl content of the product or by ebullioscopic methods. A particular preferred polyglycerol is triglycerol (polyglycerol-3). Polyglycerol ester of unsaturated or saturated Ci ₂ -C ₃ ocarboxylic acids may be prepared by standard methods, such as the ones described in GB 817,041, e.g. by heating the oligomeric glycerol with at least one of the above-mentioned carboxylic acid or a reactive functional derivatice thereof, e.g. the acid chloride or anhydride, at temperatures, e.g. above 200°C. The esterifi- cation may be carried out at lower temperatures in the presence of suitable catalysts, such as sulphuric, p-toluenesulphonic or methane sulphonic acid.

Other catalysts are mentioned in EP 64 697, such as dibutylstannous(ll)-maleate or dibutylstan- nous(ll)-dilaurate.

A particular preferred polyglycerol ester is polyglycerol stearate.

Component b) is present in the composition in wide ranges, particularly 0.1 to 2.5 wt.-% and preferably 0.5 to 2.0 wt.-%, based on the weight of the composition.

Component c)

A suitable metal salt of a Ci ₂ -C ₂ oalkylcarboxylic acid is derived from the above-mentioned

Ci ₂ -C ₃ oalkylcarboxylic acids, such as lauric (C12), myristic (C14), palmitic (C16), stearic (C18), arachidic (C20), behenic (C22), lignoceric (C24) and cerotic (C26) acid.

Particularly preferred are the alkali metal or alkali earth metal salts, such as the lithium, sodium, potassium, calcium or magnesium salts, but also the zinc, copper, iron, manganese salts.

Metal salts of a Ci ₂ -C ₂ oalkylcarboxylic acid are known under the term metallic soaps. Particular reference is made to the entry Metallic Soaps in Ullmann's Encyclopedia of Industrial

Chemistry, Wiley-VCH Verlag Weinheim, Germany, and the numerous references cited therein.

A particularly preferred metal salt of a Ci ₂ -C ₂ oalkylcarboxylic acid is calcium stearate (CAS-No. 1592-23-0).

Component c) is present in the composition in wide ranges, particularly 0.1 to 1.0 wt.-% and preferably 0.2 to 0.5 wt.-%, based on the weight of the composition.

Component d)

The composition as defined above contains as optional components further additives which are customary for the processing and stabilizing of chlorine-containing polymers.

Examples of suitable additives are listed in Handbook of PVC-Formulating edited by E. J.

Wickson, John Wiley & Sons, New York 1993, pp. 393-449 or in Taschenbuch der Kunst- stoff additive", Editors R. Gachter and H. Muller, Carl Hanser Verlag, 3rd Edition, 1989, pages 549-615.

PVC can be stabilized by a range of additives. Compounds of lead, of barium and of cadmium are particularly suitable for this purpose, but are nowadays controversial on ecological grounds, cf. the above-mentioned, see Taschenbuch der Kunststoff additive, and Kunststoff-Handbuch PVC, pages 531-538. The further additives can be used in an amount of, for example, from 0.01 to 50 parts by weight, preferably from 0.01 to 30 parts by weight, in particular from 0.01 to 10 parts by weight, based on 100 parts by weight of the polymer component a). If fillers are used, the upper limits stated can also be exceeded and, for example, up to 80 parts by weight of further additives can be used.

Suitable additives which are customary for the processing and stabilizing of chlorine-containing polymers are selected from the group consisting of epoxides and epoxidized fatty acid esters, phosphites, thiophosphites and thiophosphates, polyols, 1 ,3-dicarbonyl compounds, mercapto- carboxylic esters, dihydropyridines and polydihydropyridines, antioxidants; light stabilizers and UV absorbers, alkali metal and alkaline earth metal compounds, perchlorate salts, zeolites, hy- drotalcites and dawsonites.

Further additives which are customary for the processing and stabilizing of chlorine-containing polymers are selected from the group consisting of fillers, lubricants; plasticizers; impact modifiers; processing aids; blowing agents; antistats; biocides; antifogging agents; pigments and dyes; metal deactivators and flame proofing agents, cf. in this respect the above-mentioned Handbook of PVC Formulating.

Examples of such additives are known to the skilled worker and can be found in the technical literature. Without limitation, some representative additives and processing aids are listed below:

Epoxides and epoxidized fatty acid esters

Suitable epoxides and epoxidized fatty acid esters contain the glycidyl group

o

C _{H (C H} , \ , which is bonded directly to carbon, oxygen, nitrogen or sulphur atoms and wherein either R ₁ and R ₃ are both hydrogen, R ₂ is hydrogen or methyl and n=0, or R ₁ and R ₃ together are -CH ₂ -CH ₂ - or -CH ₂ -CH ₂ -CH ₂ -, in which case R ₂ is hydrogen and n=0 or 1. Suitable glycidyl compounds are glycidyl and β-methylglycidyl esters obtainable by reacting a compound having at least one carboxy group in the molecule with epichlorohydrin or glycerol dichlorohydrin or β-methyl-epichlorohydrin. The reaction is advantageously carried out in the presence of bases.

Glycidyl or (β-methylglycidyl) ethers obtainable by reacting a compound having 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 with subsequent treatment with an alkali.

Ethers of that type are derived, for example, from acyclic alcohols, such as ethylene glycol, di- ethylene 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, glycerol, 1 ,1 ,1-trimethylolpropane, bistrimethylolpropane, pentaerythritol, sorbitol, and from polyepichlorohydrins, n-butanol, amyl alcohol, pentanol, and from monofunctional alcohols, such as isooctanol, 2-ethylhexanol, isodecanol and C ₇ -C ₉ alkanol and C ₈ -Cnalkanol mixtures.

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

The epoxide compounds can also be derived from mononuclear phenols, such as phenol, res- orcinol or hydroquinone, or they are based on poly-nuclear phenols, such as bis(4-hydroxy- phenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)- propane, 4,4'-dihydroxydiphenylsulphone, or on condensation products of phenols with formaldehyde obtained under acid conditions, such as phenol novolaks.

N-Glycidyl compounds obtainable by dehydrochlorinating the reaction products of epichlorohy- drin with amines containing at least one amino hydrogen atom. Those amines are, for example, aniline, N-methyl aniline, toluidine, n-butylamine, bis(4-aminophenyl)methane, m-xylylene- diamine or bis(4-methylaminophenyl)methane, but also Ν,Ν,Ο-triglycidyl-m-aminophenol or Ν,Ν,Ο-triglycidyl-p-aminophenol.

The N-glycidyl compounds also include Ν,Ν'-di-, N,N',N"-tri- and N,N',N",N"'-tetra-glycidyl derivatives of cycloalkylene urea, such as ethylene urea or 1 ,3-propylene urea, and Ν,Ν'-diglycidyl derivatives of hydantoins, such as 5,5-dimethylhydantoin or glycoluril and triglycidyl isocyanu- rate.

S-Glycidyl compounds, such as di-S-glycidyl derivatives, that are derived from dithiols, such as ethane-1 ,2-dithiol or bis(4-mercaptomethylphenyl) ether.

Epoxide compounds containing a radical of formula I wherein Ri and R3 together are-CH ₂ -CH ₂ - and n is 0 are bis(2,3-epoxycyclopentyl) ether, 2,3-epoxycyclopentylglycidyl ether or 1 ,2-bis(2,3- epoxycyclopentyloxy)ethane. An epoxy resin containing a radical of formula I wherein R ₁ and R ₃ together are -CH ₂ -CH ₂ - and n is 1 is, for example, 3,4-epoxy-6-methylcyclohexanecarboxylic acid (3',4'-epoxy-6'-methylcyclohexyl)-methyl ester.

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

a) Liquid diglycidyl ethers of bisphenol A, such as Araldite™GY 240, GY 250, GY 260, GY 266, GY 2600, MY 790; b) Solid diglycidyl ethers of bisphenol A, such as Araldite™GT 6071 , GT 7071 , GT 7072, GT 6063, GT 7203, GT 6064, GT 7304, GT 7004, GT 6084, GT 1999, GT 7077, GT 6097, GT 7097, GT 7008, GT 6099, GT 6608, GT 6609, GT 6610;

c) Liquid diglycidyl ethers of bisphenol F, such as Araldite™GY 281 , PY 302, PY 306;

d) Solid polyglycidyl ethers of tetraphenylethane, such as CG Epoxy Resin^OieS;

e) Solid and liquid polyglycidyl ethers of phenol formaldehyde novolak, such as EPN 1 138, EPN 1 139, GY 1 180, PY 307;

f) Solid and liquid polyglycidyl ethers of o-cresol formaldehyde novolak, such as ECN 1235, ECN 1273, ECN 1280, ECN 1299;

g) Liquid glycidyl ethers of alcohols, such as Shel Bglycidyl ether 162, Araldite™DY 0390, DY 0391 ;

h) Liquid glycidyl ethers of carboxylic acids, such as Shell^Cardura E terephthalic acid ester, trimellitic acid ester, Araldite™PY 284;

i) Solid heterocyclic epoxy resins (triglycidyl isocyanurate), such as Araldite^PT 810;

k) Liquid cycloaliphatic epoxy resins, such as Araldite^CY 179;

I) Liquid Ν,Ν,Ο-triglycidyl ethers of p-aminophenol, such as Araldite^MY 0510;

m) Tetraglycidyl-4,4'-methylenebenzamine or Ν,Ν,Ν',Ν'-tetraglycidyl-diaminophenylmethane, such as Araldite™MY 720, MY 721 .

Preference is given to the use of epoxide compounds having two functional groups. Epoxide compounds having one, three or more functional groups may be used, too.

There are used predominantly epoxide compounds, especially diglycidyl compounds, having aromatic groups.

Where appropriate, a mixture of different epoxide compounds can also be used.

Further examples are epoxidized linseed oil, epoxidized fish oil, epoxidized tallow, methylbutyl or 2-ethylhexyl epoxystearate, tris(epoxypropyl)isocyanurate, epoxidized castor oil, epoxidized sunflower oil, 3-phenoxy-1 ,2-epoxypropane, bisphenol A diglycidyl ether, vinylcyclohexene di- epoxide, dicyclopentadiene diepoxide and 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane- carboxylate.

Especially preferred as terminal epoxide compounds are diglycidyl ethers based on 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).

Phosphites Suitable phosphites are known co-stabilizers for chlorine-containing polymers. Examples are trioctyl, tridecyl, tridodecyl, tritridecyl, tripentadecyl, trioleyl, tristearyl, triphenyl, tricresyl, trisnonylphenyl, tris-2,4-t-butylphenyl or tricyclohexyl phosphite.

Further suitable phosphites are various mixed aryl dialkyl and alky diarylphosphites, such as phenyl dioctyl, phenyl didecyl, phenyl didodecyl, phenyl ditridecyl, phenylditetradecyl, phenyl dipentadecyl, octyl diphenyl, decyl diphenyl, undecyl diphenyl, dodecyldiphenyl, tridecyl diphe- nyl, tetradecyl diphenyl, pentadecyl diphenyl, oleyl diphenyl, stearyl diphenyl and dodecyl bis- 2,4-di-t-butylphenyl phosphite.

Furthermore, phosphites of various diols and polyols can also be used advantageously; exam- pies are tetraphenyldipropylene glycol diphosphite, polydipropylene glycol phenyl phosphite, tetramethylolcyclohexanol decyl diphosphite, tetramethylolcyclohexanol butoxyethoxyethyl diphosphite, tetramethylolcyclohexanol nonylphenyl diphosphite, bisnonylphenyl di-trimethylol- propane diphosphite, bis-2-butoxyethyl di-trimethylolpropane diphosphite, trishydroxyethyl iso- cyanurate hexadecyl triphosphite, didecylpentaerythritol diphosphite, distearyl pentaerythritol diphosphite, bis-2,4-di-t-butylphenyl pentaerythritol diphosphite, and also mixtures of these phosphites and aryl/alkyl phosphite mixtures of the statistical composition

(OCi2,i3H ₂₅ ,27)i.5 or [C ₈ Hi7-C6H4-0-]2P[i-C ₈ Hi70] or (OC ₉ ,iiHi ₉ ,23)i.5. Thiophosphites and thiophosphates

Suitable thiophosphites and thiophosphates are compounds of the general formula: (RS) ₃ P, (RS) ₃ P=0 and (RS) ₃ P=S, as described in the patent literature in DE 2 809 492, EP 090 770 and EP 573 394. Examples are: trithiohexyl phosphite, trithiooctyl phosphite, trithiolauryl phosphite, trithiobenzyl phosphite, tris[carboxy-i-octyloxy]methyl trithiophosphate, S,S,S-tris[carbo-i- octyloxy]methyl trithiophosphate, S,S,S-tris[carbo-2-ethylhexyloxy]methyl trithiophosphate, S,S,S,-tris-1 -[carbohexyloxy]ethyl trithiophosphate, S,S,S-tris-1 -[carbo-2-ethylhexyloxy]ethyl trithiophosphate, S,S,S-tris-2-[carbo-2-ethylhexyloxy]ethyl trithiophosphate.

Polyols

Examples of suitable compounds of this type are: pentaerythritol, dipentaerythritol, tripentae- rythritol, bistrimethylolpropane, trimethylolethane, bistrimethylolethane, trimethylolpropane, sorbitol, maltitol, isomaltitol, lactitol, lycasine, mannitol, lactose, leucrose, tris(hydroxyethyl) isocy- anurate, palatinite, tetramethylolcyclohexanol (TMCH), tetramethylolcyclopentanol, tetra- methylolcyclopyranol, glycerol, diglycerol, polyglycerol, thiodiglycerol, or 1 -O-a-D-glycopyran- osyl-D-mannitol dihydrate, and also polyvinyl alcohol and cyclodextrins. Among these, TMCH and the disaccharide alcohols are preferred. 1,3-Dicarbonyl compounds

Examples of 1 ,3-dicarbonyl compounds are acetylacetone, butanoylacetone, heptanoylacetone, stearoylacetone, palmitoylacetone, lauroylacetone, 7-tert-nonylthioheptane-2,4-dione, ben- zoylacetone, dibenzoylmethane, lauroylbenzoylmethane, palmitoylbenzoylmethane, stea- roylbenzoylmethane, isooctylbenzoylmethane, 5-hydroxycapronylbenzoylmethane, tribenzoyl- methane, bis(4-methylbenzoyl)methane, benzoyl-p-chlorobenzoylmethane, bis(2-hydroxy- benzoyl)methane, 4-methoxybenzoyl-benzoylmethane, bis(4-methoxybenzoyl)methane, 1 - benzoyl-1 -acetylnonane, benzoyl-acetylphenylmethane, stearoyl-4-methoxybenzoylmethane, bis(4-tert-butylbenzoyl)methane, benzoylformylmethane, benzoylphenylacetylmethane, bis(cyclohexanoyl)methane, di(pivaloyl)methane, acetoacetic methyl, ethyl, hexyl, octyl, dodecyl or octadecyl ester, benzoylacetic ethyl, butyl, 2-ethylhexyl, dodecyl or octadecyl ester, stearoy- lacetic ethyl, propyl, butyl, hexyl or octyl ester and dehydroacetic acid, and the zinc, alkali metal, alkaline earth metal or aluminium salts thereof.

Mercaptocarboxylic esters

Examples of these compounds are: esters of thioglycolic acid, thiomalic acid, mercaptopropionic acids, of mercaptobenzoic acids and of thiolactic acid, as are described in FR 2 459 816, EP 90 748, FR 2 552 440 and EP 365 483. The mercaptocarboxylic esters also embrace corre- sponding polyol esters and their partial esters.

They can be present in the chlorine-containing polymer expediently in proportions of from 0.01 to 10.0%, preferably from 0.1 to 5.0% and, in particular, from 0.1 to 1.0%, based on the weight of the polymer.

Dihydropyridines and polydihydropyridines

Suitable monomeric dihydropyridines are compounds as described, for example, in FR

2 039 496, EP 362 012 and EP 24 754. Preference is iven to those of the formula in which Z is

CO2CH3, C0 ₂ C2H _5! C0 ₂ ⁿ Ci2H ₂ 5 or -CC^HU-S^C^Hzs in which n is zero or a numeral from 1 to 20.

Particularly suitable polydihydropyridines are compounds of the following formula in which T is unsubstituted Ci_i ₂ alkyl,

L is as defined for T,

m and n are numbers from 0 to 20,

k is O or l ,

R and R' independently of one another are ethylene, propylene, butylene or an alkylene- or cy- cloalkylenebismethylene group of the type -(-CpH2p-X-)tCpH ₂ p-,

p is from 2 to 8,

t is from 0 to 10, and

X is oxygen or sulphur.

Compounds of this kind are described in more detail in EP 0 286 887.

Particular preference is given to thiodiethylenebis[5-methoxycarbonyl-2,6-dimethyl-1 ,4- d i hyd ropy ri d i n e-3-carboxyl ate] .

Antioxidants; light stabilizers and UV absorbers

Preferred specific antioxidants include octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (IRGANOX 1076), pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxypheny l)propionate] (IRGANOX 1010), tris(3,5-di-tert-butyl-4-hydroxyphenyl)isocyanurate (IRGANOX 31 14), 1 ,3,5- trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benze ne (IRGANOX 1330), triethylenegly- col-bis[3-(3- tert-butyl-4-hydroxy-5-methylphenyl)propionate] (IRGANOX 245), and N,N'-hexane- 1 ,6-diyl-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamid e] (IRGANOX 1098), tris(2,4-di-tert- butylphenyl)phosphite (IRGAFOS 168), 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9- diphosphaspiro[5.5]undecane (IRGAFOS 126), 2,2',2"-nitrilo[triethyl-tris(3,3',5,5'-tetra-tert-butyl- 1 ,1 '-biphenyl-2,2'-diyl)]phosphite (IRGAFOS 12), and tetrakis(2,4-di-tert-butylphenyl)[1 ,1 - biphenyl]-4,4'-diylbisphosphonite (IRGAFOS P-EPQ). Specific light stabilizers include 2-(2H- benzotriazole-2-yl)-4,6-bis(1 -methyl-1 -phenylethyl)phenol (TINUVIN 234), 2-(5-chloro(2H)- benzotriazole-2-yl)-4-(methyl)-6-(tert-butyl)phenol (TINUVIN 326), 2-(2H-benzotriazole-2-yl)-4- (1 ,1 ,3,3-tetramethylbutyl)phenol (TINUVIN 329), 2-(2H-benzotriazole-2-yl)-4-(tert-butyl)-6-(sec- butyl)phenol (TINUVIN 350), 2,2'-methylenebis(6-(2H-benzotriazol-2-yl)-4-(1 ,1 ,3,3-tetramethyl- butyl)phenol) (TINUVIN 360), and 2-(4,6-diphenyl-1 ,3,5-triazin-2-yl)-5-hexyloxy-phenol

(TINUVIN 1577), 2-(2'-hydroxy-5'-methylphenyl)benzotriazole (TINUVIN P), 2-hydroxy-4- (octyloxy)benzophenone (CHIMASSORB 81 ), 1 ,3-bis-[(2'-cyano-3',3'-diphenylacryloyl)oxy]-2,2- bis-{[(2'-cyano- 3',3'-diphenylacryloyl)oxy]methyl}-propane (UVINUL 3030, BASF), ethyl-2- cyano-3,3-diphenylacrylate (UVINUL 3035, BASF), and (2-ethylhexyl)-2-cyano-3,3- diphenylacrylate (UVINUL 3039, BASF).

Alkali metal and alkaline earth metal compounds

By these terms are meant principally the carboxylates of the above-described acids, or also corresponding oxides and hydroxides, carbonates or basic carbonates. Also suitable are mixtures thereof with organic acids. Examples are NaOH, KOH, CaO, Ca(OH ₂ ), MgO, Mg(OH) ₂ , CaC0 ₃ , MgC0 ₃ , dolomite and huntite.

In the case of carboxylates of alkaline earth metals and of Zn, it is also possible to employ ad- ducts thereof with MO or M(OH) ₂ (M = Ca, Mg, Sr or Zn), so-called overbased compounds.

Perch lorate salts

Examples are those of the formula M(CI0 ₄ ) _n where M is Li, Na, K, Mg, Ca, Ba, Zn, Al, Ce or La. The index n is, in accordance with the valency of M, 1 , 2 or 3. The perchlorate salts can be pre- sent as complexes with alcohols or ether alcohols. In this context, the respective perchlorate can be employed in various common forms in which it is supplied; for example as a salt or aqueous solution applied to a carrier material such as PVC, Ca silicate, zeolites or hydrotalcites, or obtained by chemical reaction of hydrotalcite with perchloric acid.

Hydrotalcites and zeolites

The chemical composition of these compounds is known to the skilled worker, for example from the patent literature, such as DE 3 843 581, US 4,000, 100, EP 062 813, WO 93/20135.

Representative examples of hydrotalcites are

AI ₂ Cv6 MgOC0 ₂ -12 H ₂ 0, Mg _{4 5} AI ₂ -(OH) ₁₃ C0 ₃ -3.5 H ₂ 0, 4 MgOAI ₂ 0 ₃ C0 ₂ -9 H ₂ 0,

4 MgO-AI ₂ 0 ₃ C0 ₂ -6 H ₂ 0, ZnO-3 MgO-AI ₂ 0 ₃ C0 ₂ -8-9 H ₂ 0 and ZnO-3 MgO-AI ₂ 0 ₃ -C0 ₂ -5-6 H ₂ 0. Examples of zeolites are sodium alumosilicates of the formulae

Nai ₂ AI ₁₂ Sii ₂ 0 ₄₈ 27 H ₂ 0 [zeolite A], Na ₆ AI ₆ Si ₆ 0 ₂₄ 2 NaX 7.5 H ₂ 0, X= OH, halogen, CI0 ₄ [sodalite]; Na ₆ AI ₆ Si ₃ o0 ₇₂ 24 H ₂ 0; Na ₈ AI ₈ Si ₄ o0 ₉ 6 24 H ₂ 0; Nai ₆ AI ₁₆ Si ₂₄ 0 ₈ o 16 H ₂ 0; Nai ₆ AI ₁₆ Si ₃₂ 0 ₉ 6 16 H ₂ 0; Na ₅₆ AI ₅₆ Sii ₃₆ 0 ₃₈₄ 250 H ₂ 0 [zeolite Y], Na ₈₆ AI ₈₆ Sii ₀ 6O ₃₈₄ 264 H ₂ 0 [zeolite X];

or the zeolites which can be prepared by partial or complete exchange of the Na atoms by Li, K, Mg, Ca, Sr or Zn atoms, such as

(Na, K) ₁₀ AI ₁₀ Si ₂₂ O ₆₄ 20 H ₂ 0; Ca _{4 5} Na ₃ [(AI0 ₂ )i ₂ (Si0 ₂ )i ₂ ] 30 H ₂ 0; K ₉ Na ₃ [(AI0 ₂ )i ₂ (Si0 ₂ )i ₂ ] 27 H ₂ 0.

Other suitable zeolites are: Na ₂ 0-AI ₂ 0 ₃ (2 to 5)Si0 ₂ (3.5 to 10) H ₂ 0 [zeolite P], Na ₂ OAI ₂ 0 ₃ 2 SiO ₂ (3.5-10)H ₂ O (zeolite MAP) or the zeolites which can be prepared by partial or complete exchange of the Na atoms by Li, K or H atoms, such as

(Li,Na,K,H) ₁₀ AI ₁₀ Si ₂₂ O ₆ 420 H ₂ 0, K ₉ Na ₃ [(AI0 ₂ )i ₂ (Si0 ₂ )i ₂ ] 27 H ₂ 0, K4AI4S14O166 H ₂ 0 [zeolite K- F], Na ₈ AI ₈ Si4o096-24 H ₂ 0 zeolite D, as described in Barrer et al., J. Chem. Soc. 1952, 1561-71, and in US 2,950,952;

Preference is given to Na-zeolite A and Na-zeolite P.

The hydrotalcites and zeolites can be naturally occurring minerals or synthetically prepared compounds.

Dawsonites (alkali metal alumocarbonates)

These compounds can be represented by the formula

{(M ₂ 0) _m (AI ₂ 0 ₃ ) _n Z _oP H ₂ 0},

in which M is H, Li, Na, K, Mg _1/2 , Ca _V 2, Sr _1/2 or Zn _1/2 ; Z is C0 ₂ , S0 ₂ , (CI ₂ 0 ₇ )i/ ₂ , B ₄ 0 ₆ , S ₂ 0 ₂ (thio- sulphate) or C ₂ 0 ₂ (oxalate); m, if M is Mg _1/2 or Ca-i/ ₂ , is a number between 1 and 2, in all other cases a number between 1 and 3; n is a number between 1 and 4; or is a number between 2 and 4; and p is a number between 0 and 30.

The alumo salt compounds of the formula above can be naturally occurring minerals or synthetically prepared compounds. The metals can be partially substituted by one another. The above-mentioned alumo salt compounds are crystalline, partially crystalline or amorphous or can be present in the form of a dried gel. A process for preparing such compounds is specified in EP 394 670. Examples of naturally occurring alumo salt compounds are indigirite, tunisite, alumohydrocalcite, para-alumohydrocalcite, strontiodresserite and hydro-strontiodresserite. Further examples of alumo salt compounds are potassium alumocarbonate

{(K ₂ 0)(AI ₂ 0 ₃ )(C0 ₂ ) ₂ -2H ₂ 0}, sodium alumothiosulphate {(Na ₂ 0)(AI ₂ 0 ₃ )(S ₂ 0 ₂ ) ₂ -2H ₂ 0}, potassium alumosulphite {(K ₂ 0)(AI ₂ 0 ₃ )(S0 ₂ ) ₂ -2H ₂ 0}, calcium alumooxalate {(CaO)(AI ₂ 0 ₃ )(C ₂ 0 ₂ ) ₂ -5H ₂ 0}, magnesium alumotetraborate {(MgO)(AI ₂ 0 ₃ )(B ₄ 0 ₆ ) ₂ -5H ₂ 0},

{([Mg _0.2 Nao.6] ₂ 0)(AI ₂ 0 ₃ )(C0 ₂ ) ₂ -1 H ₂ 0}, {([Mgo _.2 Na ₀ .6] ₂ 0)(AI ₂ 0 ₃ )(C0 ₂ ) ₂ -3H ₂ 0} and

{([Mgo _.3 Nao.4] ₂ 0)(AI ₂ 0 ₃ )(C0 ₂ ) _2.2 .9H ₂ 0}.

Preferred alumo salt compounds are those of the above formula in which M is Na or K; Z is C0 ₂ , S0 ₂ or (CI ₂ 0 ₇ )i/ ₂ ; m is 1 -3; n is 1 -4; o is 2-4 and p is 0-20. Z is particularly preferably C0 ₂ .

Particular preference is given to sodium alumodihydroxycarbonate (DASC) and the homologous potassium compound (DAPC).

The composition according to the invention contains as optional components further additives which are customary for the processing and stabilizing of chlorine-containing polymers. These additives are selected from the group consisting of lubricants; plasticizers; impact modifiers; processing aids; blowing agents; antistatics; biocides; antifogging agents; pigments and dyes; metal deactivators and flame-proofing agents.

Examples of such additives are known to the skilled worker and can be found in the technical literature. Without limitation, some representative additives and processing aids are listed be- low:

Fillers

Suitable fillers are based on minerals commonly found in nature, such as aluminium oxides, alumino silicates, calcium sulphate, barium sulphate, titanium oxide, calcium carbonate, dolomite, wollastonite, magnesium oxide, magnesium hydroxide, silicates, phosphates, talc, kaolin, chalk, mica, or other metal oxides and metal hydroxides, preference is being given to calcium carbonate.

Other fillers or reinforcing agents derived from the minerals mentioned above, such as carbon black or graphite or glass fibre materials, are also possible.

Lubricants

Examples of suitable lubricants are: fatty alcohols, fatty acid amides, polyethylene(PE) waxes, amide waxes, chlorinated paraffins and silicone-based lubricants as described in EP 0 225 261. Lubricants which can be used are also described in the above-mentioned Taschenbuch der Kunststoffadditive.

Plasticizers

Representative examples of suitable plasticizers are those from the following groups:

A) Phthalic esters

Examples of such plasticizers are dimethyl, diethyl, dibutyl, dihexyl, di-2-ethylhexyl, di-n-octyl, di-isooctyl, di-isononyl, di-isodecyl, di-isotridecyl, dicyclohexyl, di-methylcyclohexyl, dimethylgly- col, dibutylglycol, benzyl butyl and diphenyl phthalate, and also mixtures of phthalates, such as C7-9- and C _9- nalkyl phthalates from predominantly linear alcohols, C _6- io-n-alkyl phthalates and Cs-io-n-alkyl phthalates. Among these, preference is given to dibutyl, dihexyl, di-2-ethylhexyl, di- n-octyl, di-isooctyl, di-isononyl, di-isodecyl, di-isotridecyl and benzyl butyl phthalate and to the abovementioned mixtures of alkyl phthalates. Particular preference is given to di-2-ethylhexyl, di-isononyl and di-isodecyl phthalate, which are also known under the common abbreviations DOP (dioctyl phthalate, di-2-ethylhexyl phthalate), DINP (diisononyl phthalate), and DIDP (di- isodecyl phthalate).

B) Esters of aliphatic dicarboxylic acids, especially esters of adipic, azelaic and sebacic acid

Examples of such plasticizers are di-2-ethylhexyl adipate, di-isooctyl adipate (mixture), di- isononyl adipate (mixture), di-isodecyl adipate (mixture), benzyl butyl adipate, benzyl octyl adipate, di-2-ethylhexyl azelate, di-2-ethylhexyl sebacate and di-isodecyl sebacate (mixture). Preference is given to di-2-ethylhexyl adipate and di-isooctyl adipate.

C) Trimellitic esters

for example tri-2-ethylhexyl trimellitate, tri-isodecyl trimellitate (mixture), tri-isotridecyl trimellitate, tri-isooctyl trimellitate (mixture) and also tri-C _6-8 alkyl, tri-C _6- ioalkyl, tri-C ₇ - ₉ alkyl and tri-C _9- nalkyl trimellitates. The latter trimellitates are formed by esterification of trimellitic acid with the corresponding mixtures of alkanols. Preferred trimellitates are tri-2-ethylhexyl trimellitate and the abovementioned trimellitates from alkanol mixtures. Common abbreviations are TOTM (trioctyl trimellitate, tri-2-ethylhexyl trimellitate), TIDTM (triisodecyl trimellitate) and TITDTM (triisotridecyl trimellitate).

D) Epoxy plasticizers

These are principally epoxidized unsaturated fatty acids such as epoxidized soybean oil.

E) Polymer plasticizers

The most common starting materials for the preparation of the polyester plasticizers are: dicar- boxylic acids such as adipic, phthalic, azelaic and sebacic acid; and diols such as 1 ,2-propane- diol, 1 ,3-butanediol, 1 ,4-butanediol, 1 ,6-hexanediol, neopentylglycol and diethylene glycol.

F) Phosphoric esters

Examples of such phosphoric esters are tributyl phosphate, tri-2-ethylbutyl phosphate, tri-2- ethylhexyl phosphate, trichloroethyl phosphate, 2-ethylhexyl diphenyl phosphate, cresyl diphe- nyl phosphate, triphenyl phosphate, tricresyl phosphate and trixylenyl phosphate. Preference is

®

given to tri-2-ethylhexyl phosphate and to Reofos 50 and 95 (from FMC).

G) Chlorinated hydrocarbons (paraffin)

H) Hydrocarbons

I) Monoesters, for example butyl oleate, phenoxyethyl oleate, tetrahydrofurfuryl oleate and al- kylsulphonic esters

J) Glycol esters, for example diglycol benzoates.

It is also possible to employ mixtures of different plasticizers.

Suitable plasticizers which can be used are also described in the above-mentioned Taschen- buch der Kunststoffadditive.

Pigments

Suitable pigments are known to the skilled worker. Examples of inorganic pigments are Ti0 ₂ , carbon black, Fe ₂ 0 ₃ , Sb ₂ 0 ₃ , (Ti, Ba, Sb)0 ₂ , Cr ₂ 0 ₃ , spinels, such as cobalt blue and cobalt green, Cd(S, Se), ultramarine blue. Preference is given to Ti0 ₂ , including its micronized form. Examples of organic pigments are azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, pyrrolopyrrole pigments and anthraquinone pigments. Further details are to be found in the above-mentioned Handbook of PVC Formulating.

A further embodiment of the invention relates to the use of a mixture, which comprises

b) A polyglycerol ester of an unsaturated or saturated Ci ₂ -C ₃ ocarboxylic acid; and c) A metal salt of a Ci ₂ -C ₂ oalkylcarboxylic acid;

as a lubricant for improving the slip properties of a chlorine containing thermoplastic polymer.

The present invention specifically provides for the use of the above-described mixture as granules, extrudate or paste for stabilizing a halogen-containing polymer or polymer recyclate. For the individual stabilizers and for the halogen-containing polymer itself, the preferences expressed above apply; similarly, one of the above-described additional constituents can be employed.

A particularly preferred embodiment relates to the use of a mixture, which comprises

b) A polyglycerol ester of stearic acid; and

c) Calcium stearate.

as a lubricant for improving the slip properties of a chlorine containing thermoplastic polymer.

A further embodiment of the invention relates to a process for the preparation of chlorine

containing thermoplastic polymer compositions, which comprises adding to the chlorine containing thermoplastic polymer a mixture of

b) A polyglycerol ester of an unsaturated or saturated Ci ₂ -C ₃ ocarboxylic acid; and c) A metal salt of a Ci ₂ -C ₂₀ alkylcarboxylic acid; and, optionally,

d) Further additives which are customary for the processing and stabilizing of chlorine containing polymers.

A particularly preferred embodiment relates to a process according to, which comprises adding to the chlorine containing thermoplastic polymer a mixture of

b) A polyglycerol ester of stearic acid; and

c) Calcium stearate; and, optionally,

d) Further additives which are customary for the processing and stabilizing of chlorine containing polymers.

The mixture defined above can be added to the polymer in a known manner, the above mentioned components and, if desired, further additives being mixed with the halogen-containing polymer by using known machinery, such as mixers, compounders, extruders, mills and the like. In this context the components can be added individually or as a mixture or else in the form of so-called master batches.

The invention also relates to the polymer compositions comprising the mixture defined above. They can be processed into the desired form, such as granulates, by known methods. Exam- pies of such methods are calandering, extrusion, injection moulding, sintering or spinning, and also extrusion blow moulding or processing by the plastisol process. The polymer compositions can also be processed to foams.

The invention also relates to the use of the polymer compositions for preparing mouldings which can be prepared from halogen-containing polymer. The polymer compositions are suitable for semi-rigid and flexible formulations, for example for flexible formulations for wire sheathing and cable insulation. In the form of semi-rigid formulations, the polymer compositions are suitable for decorative films, foams, agricultural films, hoses, sealing profiles, office films, extruded profiles and sheets, flooring films and sheets, coated products and synthetic leathers, and also crash- pad sheets, e. g. for use in the automotive sector).

In the form of rigid formulations, the polymer compositions are suitable for hollow articles (bottles), packaging films (thermoform films), blown films, crash-pad sheets (cars), pipes, foams, heavy profiles (window frames), transparent wall profiles, construction profiles, sidings, fittings and apparatus enclosures (computers, domestic appliances) and also other injection-moulded articles.

Examples of the use of the polymer compositions are artificial leathers, flooring, textile coatings, wallpapers, coil coatings and under body protection for motor vehicles.

Examples of sinter applications of the polymer compositions stabilized in accordance with the invention are slush, slush mould and coil coatings.

The Examples below illustrate the invention in more detail without restricting it. As in the re- mainder of the description, parts and percentages are by weight unless stated otherwise.

Materials and Methods

PVC (K-value of 60): Solvin® 260 F (Solvay)

CaC03: Hydrocarb® 95T (Omya)

Thermal stabilizer: Mono-/Dioctyl stannous thioester, e.g. Thermolite® 890 F (Arkema)

Flow agent Vinuran® 3833 (BASF)

Impact modifier: Vinuran® DS 2391 (BASF)

Ester wax 1 : Ester wax according to the invention, polyglycerol stearate

Ester wax 2: Glycerol fatty acid ester (> 40 % Stearinsauremonoester): Loxiol® G12-40 (Emery Oleochemicals) A precursory mixture is prepared with a mixing device (Henschel, type FM 10 L) at 120°C and a retention time of 5 min. The characterizing data are determined in a plastographic torsion angle metering device of the type Plasticorder PL 330 obtainable from Brabender Co. (filling amount: 60 g, filling temperature160°C, rotational speed: 40 min- ¹ )

Table

Table ctd (1).

Table ctd (2).

Table ctd (3)

Ref.: Referential Composition [phr] Inv.: Inventive Composition [phr] AN: Acid number [mg KOH/g]