DE29924285U1 - Cyanoacetylureas for stabilizing halogen-containing polymers - Google Patents

Description

Cyanoacetylureas for stabilizing halogen-containing polymers

The invention relates to compositions consisting of chlorine-containing polymers and cyanoacetylureas of the formula I shown below for stabilizing these polymers, in particular PVC.

PVC can be stabilized by a number of additives. Compounds of lead, barium and cadmium are particularly suitable for this purpose, but are currently controversial for ecological reasons or because of their heavy metal content (see "Kunststoffadditive", R. Gächter/H. Müller, Carl Hanser Verlag, 1st edition, 1989, pages 303-311, and "Kunststoff Handbuch PVC", Volume 2/1, W. Becker/D. Braun, Carl Hanser Verlag, 2nd edition, 1985, pages 531 - 538; and Kirk-Othmer: "Encyclopedia of Chemical Technology", ^4th Ed., 1994, Vol. 12, Heat Stabilizers, pp. 1071 -1091). The search is therefore continuing for effective stabilizers and stabilizer combinations that are free of lead, barium and cadmium.

Some of the compounds of formula I are new substances, others are known. Representatives of formula I have been described, for example, in US Patent 2,598,936 and J. Org. Chem. 16, 1879 -1890 (1951) and can be prepared by known methods in one or more process steps. The starting ureas are commercially available or can be prepared by known processes.

It has now been found that the cyanoacetylureas of the general formula I

,CO-CH ₂ -CN

R-NH-C-NO) .

&eegr;··:·M

-2-

where

X is oxygen or sulfur, and

RC ₂ -C ₂₂ -acyloxyalkyl or C ₁ -C ₁₂ -AIRyI, which may be interrupted by 1 to 3 oxygen atoms and/or substituted by 1 to 3 OH groups, C ₃ -C ₈ -alkenyl, C ₇ -C ₁₀ -phenylalkyl, Cs-Cg-cycloalkyl, C ₇ -C ₁₀ -alkylphenyl, phenyl or naphthyl, where the aromatic radical may be substituted in each case by -OH, C ₁ -C ₁₂ -A^yI and/or OC ₁ -C ₄ -AIKyI, and

R ₁ is hydrogen or has the meaning of R, are particularly suitable for the stabilization of chlorine-containing polymers such as PVC.

For compounds of formula I the following applies:

C _r C ₄ alkyl means e.g. B. methyl, ethyl, n-propyl, iso-propyl, n-, i-, see- or t-butyl.
C ₁ -C ₁₂ -AlKyI means, for example, in addition to the radicals just mentioned, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, i-octyl, decyl, nonyl, undecyl or dodecyl.

Preferred are C ₁ -C ₄ -alkyl, optionally interrupted by -CO ₂ -.

C ₅ -C ₈ -cycloalkyl means e.g. B. cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, preferably cyclohexyl.
C ₇ -C ₁₀ alkylphenyl means, for example, toyl, xylyl or mesityl, in particular toyl and xylyl.

C ₇ -C ₁₀ -Phenylalkyl is, for example, benzyl, 1- or 2-phenylethyl, 3-phenylpropyl, α,α-dimethylbenzyl or 2-phenylisopropyl, preferably benzyl and 2-phenethyl, in particular benzyl. If the aromatic radical is substituted, then preferably with three, two or in particular one substituent, and the substituents are in particular hydroxy, methyl, ethyl, methoxy or ethoxy.

C ₃ -C ₈ -Alkenyl means e.g. AIIyI, methallyl, 1-butenyl, 1-hexenyl, 1-octenyl

or 2-octenyl, preferably allyl or methallyl. 30

Examples of C ₂ -C ₂₂ acyloxyalkyl are branched or straight-chain radicals such as acetoxyethyl, propionyloxyethyl, acetoxypropyl, acetoxybutyl, propionyloxybutyl, benzoxyethyl, benzoxypropyl, benzoxybutyl, phenylpropionyloxyethyl, phenylpropionyloxypropyl, phenylpropionyloxybutyl, etc., where the phenyl radical can be substituted by 1 to 3 -OH and/or 1 to 3 C ₁ -C ₄ alkyl radicals (branched and unbranched). Acetoxyethyl and benzoxyethyl are preferred, for example.

Preference is given to compounds of formula I in which X is oxygen, as well as those in which the radicals R and R ₁ are identical.

Compounds in which X is sulfur are also useful.

Further preferred are compounds of the formula I in which R and R ₁ are C ₁ -C ₈ -alkyl, C ₃ -C ₅ -alkenyl, benzyl or 2-phenethyl. Particularly preferred are compounds of the formula I in which R and R ₁ are C ₁ -C ₄ -alkyl, allyl or benzyl.

To achieve stabilization in the chlorine-containing polymer, the compounds of formula I are advantageously used in an amount of 0.01 to 10% by weight, preferably 0.05 to 5% by weight, in particular 0.1 to 3% by weight.

Furthermore, combinations of compounds of the general formula I with other conventional additives or stabilizers can be used, for example with polyols and disaccharide alcohols and/or perchlorate compounds and/or glycidyl compounds and/or zeolitic compounds and/or layered lattice compounds (hydrotalcites) and, for example, light stabilizers. Examples of such additional components are listed and explained below.

-A-

Polyols and disaccharide alcohols

Examples of compounds of this type include: pentaerythritol, dipentaerythritol, tripentaerythritol, trimethylolethane, bistrimethylolpropane, inositol (cyclite), polyvinyl alcohol, bistrimethylolethane, trimethylolpropane, sorbitol (hexitol), maltitol, isomaltitol, cellobiitol, lactitol, lycasin, mannitol, lactose, leucrose, tris-(hydroxyethyl)-isocyanurate, tris-(hydroxypropyl)-isocyanurate, palatinite, tetramethylolcyclohexanol, tetramethylolcyclopentanol, tetramethylolcyclopyranol, xylitol, arabinitol (pentitol), tetrite, glycerol, diglycerol, polyglycerol, thiodiglycerol or 1-0-a-D-glycopyranosyl-D-mannitol dihydrate. Of these, the disaccharide alcohols are preferred.

Polyol syrups such as sorbitol, mannitol and maltitol syrup can also be used. The polyols can be used in an amount of, for example, 0.01 to 20, suitably 0.1 to 20 and in particular 0.1 to 10 parts by weight based on 100 parts by weight of PVC.

Perchlorate compounds

Examples are those of the formula M(CIO4) _n , where M stands for Li, Na, K, Mg, Ca, Sr, Ba, Zn, Al, La or Ce. The index η is 1, 2 or 3 depending on the valency of M. The perchlorate salts can be complexed or dissolved with alcohols (polyols, cyclodextrins), or ether alcohols or ester alcohols. Polyol partial esters are also included in the ester alcohols. In the case of polyhydric alcohols or polyols, their dimers, trimers, oligomers and polymers are also possible, such as di-, tri-, tetra- and polyglycols, as well as di-, tri- and tetrapentaerythritol or polyvinyl alcohol in various degrees of polymerization.

Other possible solvents include phosphate esters as well as cyclic and acyclic carbonic acid esters.

The perchlorate salts can be used in various common dosage forms; e.g. as a salt or solution in water or an organic solvent as such, or applied to a carrier material such as PVC, Ca silicate, zeolites or hydrotalcites, or incorporated by chemical reaction into a hydrotalcite or another layered lattice compound. Glycerol monoethers and glycerol monothioethers are preferred as polyol partial ethers.

Further embodiments are described in EP 0 394 547, EP 0 457 and WO 94/24200.

The perchlorates can be used in an amount of, for example, 0.001 to 5, advantageously 0.01 to 3, particularly preferably 0.01 to 2 parts by weight, based on parts by weight of PVC.

Glycidyl compounds

They contain the glycidyl group ^ ^H ( ^0�Igr; &EEacgr;, j | , which is directly

_{R1 R2 R3}

is bonded to carbon, oxygen, nitrogen or sulphur atoms, and wherein either Ri and R3 are both hydrogen, R2 is hydrogen or methyl and η = 0, or wherein Ri and R3 together are -CH2-CH2- or-CH2-CH2-CH2-, R2 is then hydrogen and
η = 0 or 1.

I) Glycidyl and ß-methylglycidyl esters obtainable by reacting a compound having at least one carboxyl group in the molecule and epichlorohydrin or glycerol dichlorohydrin or ß-methyl-epichlorohydrin. The reaction is conveniently carried out in the presence of bases.

-6-

Aliphatic carboxylic acids can be used as compounds with at least one carboxyl group in the molecule. 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, caproic, caprylic, lauric, myristic, palmitic, stearic and pelargonic acid, as well as the acids mentioned under organic zinc compounds. However, cycloaliphatic carboxylic acids can also be used, such as cyclohexanecarboxylic acid, tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid or 4-methylhexahydrophthalic acid.

Furthermore, aromatic carboxylic acids can be used, such as benzoic acid, phthalic acid, isophthalic acid, trimellitic acid or pyromellitic acid.

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

Further epoxy compounds which can be used in the context of this invention can be found in EP 0506 617.

II) Glycidyl or (ß-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 acidic 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, as well as from polyepichlorohydrins, butanol, amyl alcohol, pentanol, as well as from

»mm

monofunctional alcohols such as isooctanol, 2-ethylhexanol, isodecanol and C7-Cg-alkanol and Cg-Cn-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 they 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 phenol, resorcinol or hydroquinone; or they can be based on polynuclear phenols, such as bis-(4-hydroxyphenyl)-methane, 2,2-bis-(4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane, 4,4'-dihydroxydiphenyl sulfone or on condensation products of phenols with formaldehyde obtained under acidic conditions, such as phenol novolaks.

Other possible terminal epoxides are, for example: glycidyl 1-naphthyl ether, glycidyl 2-phenylphenyl ether, 2-biphenylglycidyl ether, N-(2,3-epoxypropyl)phthalimide and 2,3-epoxypropyl-4-methoxyphenyl ether. III) (N-glycidyl) compounds obtainable by dehydrochlorination of the reaction products of epichlorohydrin with amines which contain at least one 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 &Ngr;,&Ngr;,&Ogr;-triglycidyl-maminophenol or &Ngr;,&Ngr;,&Ogr;-triglycidyl-p-aminophenol.

The (N-glycidyl) compounds also include ν,ν'-di-, N,N',N"-tri- and N,N',N",N'"-tetraglycidyl derivatives of cycloalkylene ureas, such as ethylene urea or 1,3-propyleneurea, and ν,ν'-diglycidyl derivatives of hydantoins, such as 5,5-dimethylhydantoin or glycoluril and triglycidyl isocyanurate.

-8th-

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

V) Epoxy compounds containing a radical of formula I, in which Ri and R3 are

together are -CH2-CH2- and η is 0 are bis-(2,3-epoxycyclopentyl) ether, 2,3-epoxycyclopentyl glycidyl ether or 1,2-bis-(2,3-epoxycyclopentyloxy) ethane. An epoxy resin with a radical of the formula in which R 1 and R 3 together are -CH2-CH2- and η is 1 is, for example, S^-epoxy-ß-methyl-cyclohexanecarboxylic acid-^'^'-epoxy-e'-methyl-cyclohexylJ-methyl ester.

Suitable terminal epoxides are for example:

a) 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;

b) solid bisphenol A diglycidyl ethers such as Araldit®GT 6071, Araldit®GT 7071, Araldit®GT 7072, Araldit®GT 6063, Araldit®GT 7203, Araldit®GT 6064, Araldit®GT 7304, Araldit®GT 7004, Araldit ®GT 6084, Araldit®GT 1999, Araldit^GT 7077, AraldirOT 6097, AraldiPOT 7097, AraldirOT 7008, Araldit®GT 6099, Araldit®GT 6608, Araldit®GT 6609, Araldit®GT 6610;

c) liquid bisphenol F-diglycidyl ethers such as Araldit®GY 281, Araldit®PY 302, Araldit®PY 306;

d) solid polyglycidyl ethers of tetraphenylethane such as CG Epoxy Resin 0163;

(e) solid and liquid polyglycidyl ethers of phenol formaldehyde novolak such as EPN 1138, EPN 1139, GY 1180, PY 307;

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

(g) liquid glycidyl ethers of alcohols such as Shell Glycidyl Ether 162, AraldirOY 0390, AraldiPOY 0391;

(h) liquid glycidyl ethers of carboxylic acids such as Shell Cardura E terephthalic acid esters, trimellitic acid esters, Araldite PY 284;

-9-

(i) solid heterocyclic epoxy resins (triglycidyl isocyanurate) such as Araldit PT 810;

(R)

j) liquid cycloaliphatic epoxy resins such as Araldit CY 179; k) liquid &Ngr;,&Ngr;,&Ogr;-triglycidyl ethers of p-aminophenol such as Araldit MY 0510; i) tetraglycidyl-4-4'-methylenebenzamine or &Ngr;,&Ngr;,&Ngr;',&Ngr;'-tetraglycidyldiaminophenylmethane such as Araldit®MY 720, Araldit®MY 721.

Epoxy compounds with two functional groups are preferably used. However, epoxy compounds with one, three or more functional groups can also be used in principle.

Epoxy compounds, especially diglycidyl compounds, with aromatic groups are mainly used.

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

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

Hydrotalcites and (alkaline earth) aluminosilicates (zeolites)

The chemical composition of these compounds is known to the person skilled in the art, for example from the patents DE 3 843 581, US 4,000,100, EP 0 062 813 and WO 93/20135. Compounds from the series of hydrotalcites can be prepared by the following general
to be discribed,

the following general formula M ²⁺ 1- _X M ³⁺ _X (OH)2 (A ^b ")x/b · d H2O

where

M = one or more of the metals from the group Mg, Ca, Sr, Zn or Sn

M ³⁺ = Al, or B, A ⁿ is an anion with valence η, b is a number from 1 - 2,

0 < &khgr; < 0.5,

m is a number from 0-20.

Preference is
A ⁿ = OH', CIO4', HCO3", CH3COO", C6H5COO", CO3 ² ", (CHOHCOO)2 ² ", (CH2COO)2 ² ', CH3CHOHCOO", HPO3"or HPO4 ² "

represents;

Examples of hydrotalcites are Al2O3.6MgO.CO ₂ .12H2O (i), Mg ₄₎ 5Al2(OH)i3.CO3.3,5H2O (ii), 4MgO.AI2O3.CO2.9H2O (iii), 4MgO.AI2O3.CO2.6H2O, ZnO.3MgO.Al2O3.CO2.8-9H2O and ZnO.3MgO.Al2O3.CO2.5-6H2O. Types i, ii and iii are particularly preferred.

Zeolites (alkali or alkaline earth aluminosilicates)

They can be described by the following general formula Mx/n[(AIO2)x(SiO ₂ )y].wH2O, where η is 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 : χ 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

Nai2Ah2Sii2O48 ■ 27 H2O [zeolite A], Na6Al6Si6O ₂ 4 ■ 2 NaX . 7.5 H2O, X= OH, halogen, CIO4 [sodalite]; Na6Al6Si30O72 . 24 H2O; Na8Al8Si40Og6 .

H2O; Nai6Ah6Si24O80 · 16 H2O; Nai6Ali6Si32Og6 · 16 H2O; Na56Al56SM 360384 ■ 250 H2O [zeolite Y], Na86Al86Sii06O384 · 264 H2O [zeolite X];

or the zeolites which can be prepared by partial or complete replacement of the Na atoms by Li, K, Mg, Ca, Sr or Zn atoms, such as (Na,K)ioAMoSi22064 · 20 H ₂ O ; Ca4,5Na3[(AIO2)i2(SiO2)i2] · 30 H ₂ O; KgNa3[(AIO2)i2(SiO2)i2] · 27 H 2 O. Preferred zeolites correspond to the formulas ^Na 12 ^AI 12 ^Si 12°48 ■ 27 H ₂ O [zeolite A], Na6Al6Si6O ₂ 4 . 2NaX . 7.5 H ₂ O, X = OH, Cl, CIO4, I/2CO3 [sodalite] Na6Al6Si30O7 ₂ . 24 H ₂ O, Na8Al8Si40O96 ■ 24 H ₂ O, Nai6Ali6Si ₂ 4O80 ■ 16 H ₂ O, Nai6Ali6Si32O96. 16H ₂ O, Na56Al56Sii360384 · 250 H ₂ O [zeolite Y], Na86Al86Sii06O384 · 264 H ₂ O [zeolite X] and those X and Y zeolites with an Al/Si ratio of approximately 1:1. or the zeolites that can be prepared by partially or completely replacing the Na atoms with Li, K, Mg, Ca, Sr, Ba or Zn atoms, such as (Na,K)ifjAlioSi ₂₂ 064 · 20 H ₂ O Ca4,5Na3[(AIO ₂ )i ₂ (SiO ₂ )i ₂ ] . 30 H ₂ O K9Na3[(AIO ₂ )i ₂ (SiO ₂ )i ₂ ] . 27 H ₂ O The zeolites mentioned can also be lower in water or anhydrous. Other suitable zeolites are:

Na ₂ O-AI ₂ O3(2 to 5) SiO ₂ (3.5 to 10) H ₂ O [zeolite P] Na ₂ O-AI ₂ O3-2 SiO ₂ (3.5-1O)H ₂ O (zeolite MAP) or the zeolites which can be prepared by partial or complete replacement of the Na atoms by Li, K or &EEgr; atoms, such as

(Li ₁ Na ₁ K ₁ H) ₁ QAI ₁₀ Si ₂ 2O ₆ 4 ■ 20 H ₂ O .

K ₉ Na ₃ I(AIO ₂ )I ₂ (SiO ₂ )I ₂ ] ■ 27 H ₂ O

K4AI ₄ Si4O-| ₆ -6H ₂ O [zeolite KF]

Na8Al8Si40.O96.24 H ₂ O [zeolite D], as described in Barreret al., J. Chem. Soc. 1952, 1561-71, and in US 2,950,952;

The following zeolites are also possible:

K-offretite as described in EP-A-400,961;

Zeolite R as described in GB 841,812;

Zeolite LZ-217 as described in US 4,503,023; Ca-free zeolite LZ-218 as described in US 4,333,859; zeolite T, zeolite LZ-220 as described in US 4,503,023; Na ₃ K ₆ AI ₉ Si ₂₇ O ₇₂ .21 H ₂ O [zeolite L];

Zeolite LZ-211 as described in US 4,503,023; Zeolite LZ-212 as described in US 4,503,023; Zeolite O, Zeolite LZ-217 as described in US 4,503,023; Zeolite LZ-219 as described in US 4,503,023; Zeolite Rho, Zeolite LZ-214 as described in US 4,503,023; Zeolite ZK-19 as described in Am. Mineral. 54 1607 (1969); Zeolite W (KM) as described in Barrer et al., J. Chem. Soc. 1956, 2882;

Na ₃ oAI ₃ rjSi660i9 ₂ . 98 H ₂ O [zeolite ZK-5, zeolite Q] Particular preference is given to using zeolite P types of the formula I in which χ is 2 to 5 and y is 3.5 to 10, very particular preference being given to zeolite MAP of the formula in which χ is 2 and y is 3.5 to 10. In particular, it is zeolite Na-P, ie M stands for Na. This zeolite generally occurs in the variants Na-P-1, NaP-2 and Na-P-3, which differ in their cubic, tetragonal or orthorhombic structure (RM Barrer, BM Munday, J.Chem.Soc. A 1971, 2909 - 14). The production of zeolite P-1 and P-2 is also described in the above-mentioned literature. Zeolite P-3 is very rare and therefore of little practical interest. The structure of zeolite P-1 corresponds to the

Gismondite structure known from the above-mentioned Atlas of Zeolite Structures. In more recent literature (EP-A-384 070) a distinction is made between cubic (zeolite B or P _c ) and tetragonal (zeolite Pi) P-type zeolites. Newer P-type zeolites with Si:Al ratios of less than 1.07:1 are also mentioned there. These are zeolites with the designation MAP or MA-P for "Maximum Aluminium P". Depending on the manufacturing process, zeolite P can contain small amounts of other zeolites. Very pure zeolite P has been described in WO 94/26662.
Within the scope of the invention, it is also possible to use finely divided, water-insoluble sodium aluminosilicates which have been precipitated and crystallized in the presence of water-soluble inorganic or organic dispersants. These can be introduced into the reaction mixture in any manner before or during precipitation or crystallization. Na zeolite A and Na zeolite P are particularly preferred.

The hydrotalcites and/or zeolites can be used in amounts of, for example, 0.1 to 20, advantageously 0.1 to 10 and in particular 0.1 to 5 parts by weight, based on 100 parts by weight of halogen-containing polymer.

The compositions according to the invention can also be mixed with other conventional additives, such as stabilizing agents, auxiliaries and processing agents, e.g. alkali and alkaline earth compounds, lubricants, plasticizers, pigments, fillers, phosphites, thiophosphites, ß-diketones, ß-keto esters, sterically hindered amines and thiophosphates, mercaptocarboxylic acid esters, epoxidized fatty acid esters, antioxidants, UV absorbers and light stabilizers, optical brighteners, impact modifiers and processing aids, gelling agents, antistatic agents, biocides, metal deactivators, flame retardants and blowing agents, antifogging agents, compatibilizers and antiplateout agents. (See "Handbook of PVC-Formulating" by E. J. Wickson, John Wiley & Sons, New York 1993). Examples of such additives follow:

. X

&Igr;. Fillers: Fillers (HANDBOOK OF PVC FORMULATING E. J. Wickson, John Wiley & Sons, Inc., 1993, pp. 393 - 449) and reinforcing agents (TASCHENBUCH der KUNSTSTOFFADDITIVE, R. Gächter & H. Müller, Carl Hanser, 1990, pp. 549 - 615) (such as calcium carbonate, dolomite, wollastonite, magnesium oxide, magnesium hydroxide, silicates, China clay, talc, glass fibers, glass beads, wood flour, mica, metal oxides or metal hydroxides, carbon black, graphite, rock flour, barite, glass fibers, talc, kaolin and chalk. Chalk is preferred. The fillers can be used in an amount of preferably at least 1 part, for example 5 to 200, expediently 10 to and in particular 15 to 100 parts by weight, based on 100 parts by weight of PVC.

II. Metal soaps: Metal soaps are mainly metal carboxylates, preferably of longer-chain carboxylic acids. Common examples are stearates and laurates, as well as oleates and salts of shorter-chain alkanecarboxylic acids. Alkylbenzoic acids are also considered metal soaps. Metals include: Li, Na, K, Mg, Ca, Sr, Ba, Zn, Al, La, Ce and rare earth metals. So-called synergistic mixtures are often used, such as barium/zinc, magnesium/zinc, calcium/zinc or calcium/magnesium/zinc stabilizers. The metal soaps can be used individually or in mixtures. An overview of common metal soaps can be found in Ullmann's Encyclopedia of Industrial Chemistry, ^5th Ed., Vol. A16 (1985), p. 361 ff.). It is expedient to use organic metal soaps from the series of aliphatic saturated C2-C22 carboxylates, aliphatic unsaturated C3-C22 carboxylates, aliphatic C2-C22 carboxylates substituted by at least one OH group, cyclic and bicyclic carboxylates with 5-22 C atoms, unsubstituted benzenecarboxylates substituted by at least one OH group and/or C1-C16-alkyl-substituted benzenecarboxylates, unsubstituted benzenecarboxylates substituted by at least one OH group and/or C1-C16-alkyl-substituted naphthalenecarboxylates.

boxylate, the phenyl-Ci-Ci6-alkyl ^{carboxy |ate} . the boxylate or the optionally Ci-C^-alkyl substituted phenolates, tallates and resinates.

By way of example, particular mention should be made of the zinc, calcium, magnesium or barium salts of monovalent carboxylic acids, such as acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, enanthic acid, octanoic acid, neodecanoic acid, 2-ethylhexanoic acid, pelargonic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, myristic acid, palmitic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, behenic acid, benzoic acid, p-tert-butylbenzoic acid, ν,ν,-dimethylhydroxybenzoic acid, 3,5-di-tert-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, n-propylbenzoic acid, salicylic acid, p-tert-octylsalicylic acid and sorbic acid; Calcium, magnesium and zinc salts of the monoesters of the divalent carboxylic acids, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, pentane-1,5-dicarboxylic acid, hexane-1,6-dicarboxylic acid, heptane-1,7-dicarboxylic acid, octane-1,8-dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid and hydroxyphthalic acid; and the di- or triesters of the tri- or tetravalent carboxylic acids, such as hemimellitic acid, trimellitic acid, pyromellitic acid, citric acid.

Calcium, magnesium and zinc carboxylates of carboxylic acids with 7 to 18 C atoms (metal soaps in the narrower sense) are preferred, such as benzoates or alkanoates, preferably stearate, oleate, laurate, palmitate, behenate, hydroxystearates, recinoleates, dihydroxystearates or 2-ethylhexanoate. Stearate, oleate and p-tert-butyl benzoate are particularly preferred. Overbased carboxylates such as overbased zinc octoate are also preferred. Overbased calcium soaps are also preferred.

If necessary, a mixture of carboxylates with different structures can also be used.
Preferred are compositions as described containing an organic zinc and/or calcium compound.

- 16-

In addition to the compounds mentioned, organic aluminum compounds are also possible, as well as compounds analogous to those mentioned above, in particular aluminum tri-stearate, aluminum distearate and aluminum monostearate, as well as aluminum acetate and basic derivatives derived therefrom. Further explanations of the usable and preferred aluminum compounds can be found in US 4,060,512 and US 3,243,394.

In addition to the compounds already mentioned, organic rare earth compounds, in particular compounds similar to those mentioned above, are also possible. The term rare earth compound refers primarily to compounds of the elements cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, lanthanum and yttrium, with mixtures with cerium being particularly preferred. Other preferred rare earth compounds can be found in EP-A-0 108 023.

If necessary, a mixture of zinc, alkali, alkaline earth, aluminum, cerium, lanthanum or lanthanoid compounds of different structures can be used. Organic zinc, aluminum, cerium, alkali, alkaline earth, lanthanum or lanthanoid compounds can also be coated on an alumino salt compound; see also DE-A-4 031 818.

The metal soaps or mixtures thereof can be used in an amount of, for example, 0.001 to 10 parts by weight, preferably 0.01 to 8 parts by weight, particularly preferably 0.05 to 5 parts by weight, based on 100 parts by weight of PVC. The same applies to the other metal stabilizers:

III. Other metal stabilizers: Organotin stabilizers are particularly important here. These can be carboxylates, mercaptides and

Sulfides. Examples of suitable compounds are described in US 4,743,640.

IV. Alkali and alkaline earth compounds: These primarily include the carboxylates of the acids described above, but also corresponding oxides or hydroxides or carbonates. Mixtures of these with organic acids are also possible. Examples are LiOH, NaOH, KOH, CaO, Ca(OH2), MgO, Mg(OH)2, Sr(OH) ₂ , Al(OH) ₃ , CaC03 and MgC03 (also basic carbonates such as magnesia alba and huntite) _as well as fatty acid Na and K salts. In the case of alkaline earth and Zn carboxylates, their adducts with MO or M( _OH2 (M=Ca, Mg, Sr or Zn), so-called "overbased" compounds, can also be used. In addition to the stabilizer combination according to the invention, alkali, alkaline earth and/or aluminum carboxylates are preferably used.

V. Lubricants: Examples of lubricants that can be considered are: montan wax, fatty acid esters, PE waxes, amide waxes, chlorinated paraffins, glycerine esters or alkaline earth soaps. Usable lubricants are also described in "Kunststoffadditive, R.Gächter/H. Müller, Carl Hanser Verlag, 3rd edition, 1989, pages 478 - 488. Also worth mentioning are fatty ketones (as described in DE 4 204 887) and silicone-based lubricants (as described in EP 0 225 261) or combinations thereof, as listed in EP 0 259 783. Calcium stearate is preferred. The lubricants can also be applied to an aluminum salt compound; see also DE-A-4 031 818.

VI. Plasticizers Organic plasticizers may be those from the following groups:

A) Phthalic acid esters: Examples of such plasticizers are dimethyl, diethyl, dibutyl, dihexyl, di-2-ethylhexyl, di-n-octyl, di-iso-octyl, di-iso-nonyl,

&EEgr;·&ngr;

Di-iso-decyl, di-iso-tridecyl, dicyclohexyl, di-methylcyclohexyl, dimethyl glycol, dibutyl glycol, benzyl butyl and diphenyl phthalate as well as mixtures of phthalates such as C7-C9 and C8-Cn alkyl phthalates made from predominantly linear alcohols, C6-C10-n alkyl phthalates and Cs-C11-n alkyl phthalates. Preferred of these are dibutyl, dihexyl, di-2-ethylhexyl, di-n-octyl, di-iso-octyl, di-isononyl, di-iso-decyl, di-iso-tridecyl and benzyl butyl phthalate as well as the above-mentioned mixtures of alkyl phthalates. Particularly preferred are di-2-ethylhexyl, di-iso-nonyl and di-iso-decyl phthalate, which are also known by the common abbreviations DOP (dioctyl phthalate, di-2-ethylhexyl phthalate), DINP (diisononyl phthalate), DIDP (diisodecyl phthalate).

B) Esters of aliphatic dicarboxylic acids, in particular esters of adipic, azelaic and sebacic acid: Examples of such plasticizers are di-2-ethylhexyl adipate, di-isooctyl adipate (mixture), di-iso-nonyl adipate (mixture), di-isodecyl adipate (mixture), benzyl butyl adipate, benzyl octyl adipate, di-2-ethylhexyl azelate, di-2-ethylhexyl sebacate and di-iso-decyl sebacate (mixture). Di-2-ethylhexyl adipate and di-iso-octyl adipate are preferred.

C) Trimellitic acid esters, for example tri-2-ethylhexyltrimellithate, tri-isodecyltrimellithate (mixture), tri-iso-tridecyltrimellithate, tri-iso-octyltrimellithate (mixture) and tri-C6-C8-alkyl, tri-C6-Cio-alkyl, tri-Cz-Cg-alkyl and tri-Cg-Ci 1-alkyl trimellithates. The latter trimellithates are formed by esterification of trimellitic acid with the corresponding alkanol mixtures. Preferred trimellithates are tri-2-ethylhexyltrimellithate and the trimellithates mentioned 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 mainly epoxidized unsaturated fatty acids such as epoxidized soybean oil.

E) Polymer plasticizers: A definition of these plasticizers and examples of such are given in "Kunststoffadditive", R. Gächter/H. Müller, Carl Hanser Verlag,

3rd edition, 1989, chapter 5.9.6, pages 412 - 415, and in "PVC Technology", W.

V. Titow, ^4th Ed., Elsevier Publ., 1984, pages 165 -170. The most common starting materials for the production of polyester plasticizers are: dicarboxylic acids such as adipic, phthalic, azelaic and sebacic acid; diols such as 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and diethylene glycol.

F) Phosphoric acid esters: A definition of these esters can be found in the above-mentioned "Handbook of Plastics Additives" Chapter 5.9.5, pp. 408 - 412. Examples of such phosphoric acid esters are tributyl phosphate, tri-2-ethylbutyl phosphate, tri-2-ethylhexyl phosphate, trichloroethyl phosphate, 2-ethylhexyl diphenyl phosphate, cresyl diphenyl phosphate, triphenyl phosphate, tricresyl phosphate and trixylenyl phosphate. Tri-2-ethylhexyl phosphate and ®Reofos 50 and 95 (Ciba Specialty Chemicals) are preferred.

G) Chlorinated hydrocarbons (paraffins)
H) Hydrocarbons

I) Monoesters, e.g. butyl oleate, phenoxyethyl oleate, tetrahydrofurfuryl oleate and alkyl sulfonic acid esters.
J) glycol esters, e.g. B. Diglycol benzoates.

Definitions and examples of plasticizers in groups G) to J) can be found in the following handbooks: "Kunststoffadditive", R. Gächter/H. Müller, Carl Hanser Verlag, 3rd ed., 1989, chapter 5.9.14.2, pp.422 -425, (group G), and chapter 5.9.14.1, p. 422, (group H). "PVC Technology", WV Titow, 4 ^th " Ed., Elsevier Publishers, 1984, chapter 6.10.2, pages 171 -173, (group G), chapter 6.10.5 page 174, (group H), chapter 6.10.3, page 173, (group I) and chapter 6.10.4, pages 173-174 (group J).

Mixtures of different plasticizers can also be used. The plasticizers can be used in an amount of, for example, 5 to 20 parts by weight, preferably 10 to 20 parts by weight, based on 100 parts by weight of PVC. Rigid or semi-rigid PVC preferably contains up to 10%, particularly preferably up to 5% or no plasticizer.

» 9

VII. Pigments: Suitable substances are known to the person skilled in the art. Examples of inorganic pigments are T2O2, pigments based on zirconium oxide, _BaSO4 , zinc oxide (zinc white) and lithopone (zinc sulfide/barium sulfate), carbon black, carbon black-titanium dioxide mixtures, iron oxide pigments, SD2O3, (Ti,Ba,Sb)O2, Cr2O3, spinels such as cobalt blue and cobalt green, Cd( _S1Se ), ultramarine blue. Organic pigments are, for example, azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, diketopyrrolopyrrole pigments and anthraquinone pigments. T1O2 is also preferred in micronized form. A definition and further descriptions can be found in the "Handbook of PVC Formulating", EJWickson, John Wiley & Sons, New York, 1993.

VIII. Phosphites (phosphoric acid triesters): Examples are triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecylp entaerythritol&mdash;diphosphite , Bis-(2,4-di-tert-butylphenyl)-pentaerythritol diphosphite, Bis-(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite, Bis-isodecyloxy-pentaerythritol diphosphite, Bis-(2,4- di-tertbutyl-6-methylphenyl) pentaerythritol diphosphite, Bis-(2,4,6-tri-tert-butylphenyl)-pentaerythritol diphosphite, tristearyl sorbitol triphosphite, bis-(2,4-di-tert-butyl-6-methylphenyl)-methylphosphite, bis-(2, 4-di-tert-butyl-6-methylphenyl)-ethyl phosphite. Particularly suitable are trioctyl, tridecyl, tridodecyl, tritetradecyl, tristearyl, trioieyl, triphenyl, tricresyl, tris-p-nonylphenyl or tricyclohexyl phosphite and Particularly preferred are the aryl-dialkyl and the alkyl-diaryl phosphites, such as: B. Phenyldidecyl, (2,4-di-tert-butylphenyl)-didodecyl phosphite, (2,6-di-tert-butylphenyl)-di-dodecyl phosphite and the dialkyl and diaryl pentaerythritol diphosphites, such as distearylpentaerythritol diphosphite, and non-stoichiometric triarylphosphites, e.g. of the composition (H19C9-C6H ₄ )Oi ,5P(OCi 2,13H25,27)1,5 or (HsCi 7-C6H ₄ )O2P(i-C8Hi 7O) or

or

JC ₁₀ H ₂₁ O) ₂ PO _&Lgr;&Lgr; 0-P(Oi-C ₁₀ H ₂₁ ).

_{CH3 CH3}

Preferred organic phosphites are distearyl pentaerythritol diphosphite, trisnonylphenyl phosphite and phenyl didecyl phosphite. Other possible compounds are phosphorous acid diesters (with the above-mentioned residues) and phosphorous acid monoesters (with the above-mentioned residues), possibly also as alkali, alkaline earth, zinc or aluminum salts. These phosphorous acid esters can also be applied to an alumino salt compound; see also DE-A-4 031 818.

The organic phosphites can be used in an amount of, for example, 0.01 to 10, advantageously 0.05 to 5 and in particular 0.1 to 3 parts by weight, based on 100 parts by weight of PVC.

IX. Thiophosphites and thiophosphates: Thiophosphites and thiophosphates are understood to be compounds of the general type: (RS)3P, (RS)3P=O or (RS)3P=S, as described in the patents DE 2 809 492, EP 0 090 770 and EP 0 573 394. Examples of these compounds are: trithiohexyl phosphite, trithiooctyl phosphite, trithiolauryl phosphite, trithiobenzyl phosphite, trithiophosphorous acid tris-(carbo-ioctyloxy)-methyl ester. Trithiophosphorous acid tris-icarbo-trimethylcyclohexyloxy)-methyl ester, trithiophosphoric acid SSS-tris-icarbo-i-octyloxy)-methyl ester, trithiophosphoric acid SSS-tris-icarbo^-ethylhexyloxyJ-methyl ester, trithiophosphoric acid SSS-tris-i-icarbo-hexyloxyJ-ethyl ester, trithiophosphoric acid S,S,S-tris-1-(carbo-2-ethylhexyloxy)-ethyl ester, trithiophosphoric acid S,S,S-tris-2-(carbo-2-ethylhexyloxy)-ethyl ester.

X. Mercaptocarboxylic acid esters: Examples of these compounds are:

Esters of thioglycolic acid, thiomalic acid, mercaptopropionic acid, mercaptobenzoic acid or thiolactic acid, mercaptoethyl stearate and oleate, as described in patents FR 2 459 816, EP 0 090 748, FR 2 552 440, EP 0 365 483

·

·

·

-22-

The gen. mercaptocarboxylic acid esters also include polyol esters or their partial esters, as well as thioethers derived therefrom.

Xl. Epoxidized fatty acid esters and other epoxy compounds: The stabilizer combination according to the invention can additionally preferably contain at least one epoxidized fatty acid ester. Esters of fatty acids from natural sources (fatty acid glycerides), such as soybean oil or rapeseed oil, are particularly suitable for this. However, synthetic products such as epoxidized butyl oleate can also be used. Epoxidized polybutadiene and polyisoprene, optionally also in partially hydroxylated form, or glycidyl acrylate and glycidyl methacrylate as homopolymer or copolymer can also be used. These epoxy compounds can also be applied to an alumino salt compound; see also DE-A-4 031 818.

XII. Antioxidants: Examples of such antioxidants include:

Alkvlated monophenols, e.g. E.g. 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-iso-butylphenol, 2,6-di-cyclopentyl-4-methylphenol 2-(alpha -Methylcyclohexyl)-4,6-dimethylphenol, 2,6-di-octadecyl-4-methylphenol, 2,4,6-tri-cyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1 '-methyl-undec-1 '-yl)-phenol 2,4-dimethyl- 6-(1 ^! -methyl-heptadec-1'-yl)-phenol, 2,4-dimethyl-6-(1'-methyl-tridec-1'-yl)-phenol, octylphenol, nonylphenol, dodecylphenol and mixtures thereof. Alkylthiomethylphenols, e.g. B. 2,4-Di-octylthiomethyl-6-tert-butylphenol, 2,4-di-octylthiomethyl-6-methylphenol, 2,4-di-octylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol.

Alkaline hydroquinones, e.g. B. 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amyl-hydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2, 6-Di-tert-butyl-hydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-

Di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis-(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

Hydroxylated thiodiphenyl ethers, e.g. B. 2,2'-thio-bis-(6-tert-butyl-4-methylphenol), 2,2'-thio-bis-(4-octylphenol), 4,4'-thio-bis-(6 -tert-butyl-3-methylphenol), 4,4'-thio-bis-(6-tert-butyl-2-methylphenol), 4,4'-thio-bis-(3,6-di-sec. -amylphenol), 4,4'-bis-(2,6-dimethyl-4-hydroxyphenyl) disulfide.

Alkvlidene bisphenols. e.g. 2,2'-methylene-bis-(6-tert-butyl-4-methylphenol), 2,2'-methylene-bis-(6-tert-butyl-4-ethylphenol), 2,2'-methylene-bis-[4-methyl-6-(alpha-methylcyclohexyl)-phenol], 2,2'-methylene-bis-(4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis-(6-nonyl-4-methylphenol), 2,2'-methylene-bis-(4,6-ditert-butylphenol), 2,2'-ethylidene-bis-(4,6-di-tert-butylphenol), 2,2'-ethylidene-bis-(6-tert-butyl-4-isobutylphenol), 2,2'-Methylen-bis-[6-(alpha-methylbenzyl)-4-nonylphenol], 2,2'-Methylen-bis-[6-(alpha,alpha-dimethylbenzyl)-4-nonylphenol], 4,4'-Methylen-bis-(2,6-di-tert-butylphenol), 4,4'-Methylen-bis-(6-tert-butyl-2-methylphenol), 1,1-Bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butan, 2,6-Bis-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-Tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butan, 1,1-Bis-(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutan, Ethylene glycol-bis-[3,3-bis-(3'-tert-butyl-4'-hydroxyphenyl)-butyrate], bis-iS-tert-butyl^-hydroxy-S-methyl-phenylJ-dicyclopentadiene, bis-[2-(3'-tert-butyl-2'-hydroxy-5'-methyl-benzyl)-6-tert-butyl-4-methyl-phenyl] terephthalate, 1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)-butane, 2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)-propane, 2,2-bis-(4-hydroxyphenyl)-propane, 2,2-bis-(5-tert-butyl^-hydroxy^-methylphenyl^-n-dodecylmercapto-butane, 1,1,5,5-Tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

Benzyl compounds, e.g. B. 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl^-hydroxy-S.ö-dimethylbenzyl-mercaptoacetate, tris-(3,5-di-tertbutyl-4 -hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, isooctyl- 3,5-ditert-butyl-4-hydroxybenzyl mercaptoacetate.

15.· * \ &psgr;*

Hydroxvbenzylated malonates, ζ. B. Dioctadecyl 2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl) malonate, di-octadecyl^-iS-tert-butyM-hydroxy-S-methylbenzyl) malonate, di&mdash; dodecylmercaptoethyl^^-bis-iS.S-di-tert-butyM-hydroxybenzyl)-malonate, di-[4-(1,1,3,3-tetramethylbutyl)-phenyl]-2,2-bis-(3, 5-di-tert-butyl-4-hydroxybenzyl) malonate.

Hydroxybenzyl aromatics, e.g. B. 1,3,5-Tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-bis-(3,5-di-tert-butyl -4-hydroxybenzyi)-2,3,5,6-tetramethylbenzene, 2,4,6-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

Triazine compounds, e.g. E.g. 2,4-bis-octylmercapto-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis-(3,5 -di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis-(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3, 5-triazine, 2,4,6-Tris-(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,SS-Tris-iS.S-di-tert- butyl^-hydroxybenzylJ-isocyanurate, 1,3,5-Tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-isocyanurate, 2,4,6-Tris-(3,5-ditert-butyl-4-hydroxyphenylethyl)- 1,3,5-triazine, 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine, 1,3,5-tris- (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

Phosphonates and phosphonites , &zgr;. B. Dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonat, Diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonat, Dioctadecyl-S.ö-di-tert-butyl^-hydroxybenzylphosphonat, Dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonat, Ca-SaIz des 3,5-Di-tert-butyl-4-hydroxybenzyl-phosphonsäure-monoethyleste rs, Tetrakis-(2,4-di-tert-butylphenyl)-4,4'-biphenylen&mdash;diphosphonit, e-lsooctyloxy^Ae.iO-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin, e-Fluor^^.S.IO-tetra-tert-butyl-^- methyl-dibenz[d,g]-1,3,2-dioxaphosphocin.

Acvlaminophenols , e.g. 4-hydroxy-lauric anilide, 4-hydroxystearic anilide, N-iS^-di-tert-butyl^-hydroxyphenyO-carbamic acid octyl ester.

Esters of beta-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid with mono- or polyhydric alcohols, such as methanol, ethanol, octanol, octadecanoi, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl-

glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, dipentaerythritol, tris-(hydroxyethyl)-isocyanurate, N ₁ N'-bis-(hydroxyethyl)-oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, di-trimethylolpropane, 4-Hydroxymethyl-1-phospha^.ö.Z-trioxabicyclo-[2.2.2]-octane.

Esters of beta-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols, such as with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris-(hydroxy)ethyl isocyanurate, N,N'-bis-(hydroxyethyl)-oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo-[2.2.2]-octane.

Esters of beta-(4-[(5-hydroxyethyl)-dicyclohexyl)phenyl]propionic acid with mono- or polyhydric alcohols, such as with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris-(hydroxy)ethyl isocyanurate, N,N'-bis-(hydroxyethyl)-oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo-[2.2.2]-octane.

Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with mono- or polyhydric alcohols, such as with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris-(hydroxy)-ethyl isocyanurate, N,N'-bis-(hydroxyethyl)-oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo-[2.2.2]-octane.

Amides of beta-(3,5-di-tert-butyl-4 -hydroxyphenylpropionyl)-hexamethylenediamine, N,N'-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-trimethylenediamine, N _, N'-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine.

Vitamin E (tocopherol) and derivatives

Preferred antioxidants are those of groups 1-5, 10 and 12, in particular 2,2-bis-(4-hydroxyphenyl)-propane, esters of S^-di-tert-butyl-hydroxyphenylpropionic acid with octanol, octadecanol or pentaerythritol or tris-(2,4-di-tert-butyl phenyl)-phosphite.

If necessary, a mixture of antioxidants with different structures can also be used.

The antioxidants can be used in an amount of, for example, 0.01 to 10 parts by weight, advantageously 0.1 to 10 parts by weight and in particular 0.1 to 5 parts by weight, based on 100 parts by weight of PVC.

XIII. UV absorbers and light stabilizers: Examples are:

2-(2'-Hvdroxvphenyl)-benzotriazole . such as E.g. 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-benzotriazole, 2-(5'-tert-butyl -2'-hydroxyphenyl)-benzotriazole, 2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)-benzotriazole, 2-(3',5'-di-tert-butyl -2'-hydroxyphenyl)-5-chlorobenztriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5-chloro-benzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)-benzotriazole,2-(2'-hydroxy-4'-octoxyphenyl)-benzotriazole,2-(3',5'-Di-tert-amyl-2'-hydroxyphenyl)-benzotriazole,2-(3',5'-bis-(alpha,alpha-dimethylbenzyl)-2'-hydroxyphenyl)-benzotriazole, Mixture of 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-5'-[2- (2-ethylhexyloxy)-carbonylethyl]-2'--hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5- chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)-benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl ]-2'-hydroxyphenyl)-benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)-benzotriazole, and 2-(3'-tert-butyl-2'-hydroxy-5' -(2-isooctyloxycarbonylethyl)phenyl-benzotriazole, 2,2'-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-yl-phenol]; transesterification product of 2-[3 '-tert&mdash;

Butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxy-phenyl]-benzotriazole with polyethylene glycol 300; [R-CH ₂ CH ₂ -COO-CH ₂ CH ₂ -]- with R = 3'-tert-butyl-4'-

hydroxy-5'-2H-benzotriazol-2-yl-phenyl.

2-Hydroxybenzophenones , such as B. the 4-hydroxy-, 4-methoxy-, 4-octoxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 4,2',4 ^> -trihydroxy-, 2'-hydroxy-4 '4'-dimethoxy derivative.

Esters of optionally substituted benzoic acids , such as 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis-(4-tert-butylbenzoyl)-resorcinol, benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di-tert-butylphenyl ester, S.δ-di-tert-butyl^-hydroxybenzoic acid hexadecyl ester, S.δ-di-tert-butyl^-hydroxybenzoic acid octadecyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2-methyl-4,6-di-tert-butylphenyl ester.

Acrylates , such as alpha-cyano-beta.beta-diphenylacrylic acid ethyl ester or isooctyl ester, alpha-carbomethoxy-cinnamic acid methyl ester, alpha-cyanobeta-methyl-p-methoxy-cinnamic acid methyl ester or butyl ester, alpha-carbomethoxy-p-methoxy-cinnamic acid methyl ester, N-(beta-carbomethoxy-b-cyanovinyl)-2-methyl-indoline.

Nickel compounds , such as nickel complexes of 2,2'-thio-bis-[4-(1,1,3,3-tetramethylbutyl)-phenol], such as the 1:1 or 1:2 complex, optionally with additional ligands, such as n-butylamine, triethanolamine or N-cyclohexyl-diethanolamine, nickel dibutyldithiocarbamate, nickel salts of 4-hydroxy-3,5-ditert-butylbenzylphosphonic acid-monoalkyl esters, such as the methyl or ethyl ester, nickel complexes of ketoximes, such as 2-hydroxy-4-methyl-phenylundecyl ketoxime, nickel complexes of i-phenyl^-lauroyl-δ-hydroxy-pyrazole, optionally with additional ligands.

Oxalic acid diamides , such as 4,4'-di-octyloxy-oxanilide, 2,2'-di-octyloxy-5,5'-di-tert-butyl-oxanilide, 2,2'-di-dodecyloxy-5,5'-di-tert-butyl-oxanilide, 2-ethoxy-2'-ethyl-oxanilide, N,N'-bis-(3-dimethylaminopropyl)-oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyl-

oxanilide, mixtures of o- and p-methoxy- as well as o- and p-ethoxy-disubstituted oxanilides.

2-(2-HydroxvphenvO-1,3,5-triazines , such as 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2- Hydroxy-4-octyloxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl). )-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy- 4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 2-(2-Hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butyloxy -propyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)- 1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]- 4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

Sterically hindered amines , such as: B. Bis(2,2,6,6-tetramethyl-piperidin-4-yl) sebacate, bis(2,2,6,6-tetramethyl-piperidin-4-yl) succinate, bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonic acid bis(1,2,2,6,6-pentamethylpiperidyl) ester, condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensation products of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tert-Octylamino-2,6-dichloro-1,3,5-s-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl)-nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetraoate, 1,1'-(1,2-ethanediyl)-bis(3,3,5,5 -tetramethyl-piperazinone), A- benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl) malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, bis(1-octyloxy^^^.e-tetramethylpiperidyO-sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)-succinate, linear or cyclic condensation products of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, condensation product of 2-chloro-4,6-di-(4-nbutylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, condensation product of 2-Chloro-4,6-di-(4-n-butylamino-

&bull;&Lgr; * Äff &bgr; * _&bgr;

-29-

1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)-ethane, e-acetyl-S-dodecyl-T.Z.Q.Q-tetramethyl-I.S.e-triazaspiro^.öjdecan^^- dione, 3-dodecyl-1 -(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)-pyrrolidine-2,5-dione, mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, condensation product of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, condensation product of 1,2-bis(3-aminopropylamino)-ethane and 2,4,6-trichloro-1,3,5-triazine and 4-butylamino-2,2,6,6-tetramethyl-piperidine (CAS Reg. No. [136504-96-6]); N-(2,2,6,6-tetramethyl-piperidyl)-n-dodecylsuccinimide, N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4,5]decane, reaction product of 2J^.g-tetramethyl^-cycloundecyl-ioxa-3,8-diaza-4-oxospiro[4,5]decane and epichlorohydrin, 1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)-ethene, N,N'-bisformyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine, diester of 4-methoxy-methylene-malonic acid with 1 ^^^,e-pentamethylM-hydroxy-piperidine, poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]-siloxane, reaction product of maleic anhydride-a-olefin copolymer and 2,2,6,6-tetramethyl-4-aminopiperidine or 1^^Ae-pentamethyl^-aminopiperidine.

XIV. Blowing agents: Blowing agents include organic azo and hydrazo compounds, tetrazoles, oxazines, isatoic anhydride, as well as soda and sodium bicarbonate. Azodicarbonamide and sodium bicarbonate and mixtures thereof are preferred. Definitions and examples of impact modifiers and processing aids, gelling agents, antistatic agents, bio-edges, metal deactivators, optical brighteners, flame retardants, antifogging agents and compatibilizers are described in "Kunststoffadditive", R. Gächter/H. Müller, Carl Hanser Verlag, 3rd ed., 1989, and in the "Handbook of Polyvinyl Chloride Formulating" E. J. Wickson, J. Wiley & Sons, 1993, and in "Plastics Additives" G. Pritchard, Chapman & Hall, London, 1st ed., 1998. Impact modifiers are also described in detail

described in "Impact Modifiers for PVC", J. T. Lutz/D. L. Dunkelberger, John Wiley & Sons, 1992.

XV. beta-diketones, beta-ketoesters: Usable 1,3-dicarbonyl compounds can be linear or cyclic dicarbonyl compounds. Dicarbonyl compounds of the following formula are preferably used: R'-|CO CHR2'-COR'3 _i in which r'i is Ci-C22-alkyl, C5-Cio-hydroxyalkyl, C2-C<|8-alkenyl, phenyl, phenyl substituted by OH, Ci-C4-alkyl, C-|-C4-alkoxy or halogen, C7-Cio-phenylalkyl, C5-Ci2-cycloalkyl, substituted by Ci-C4-alkyl-

I J J J

tes Cö-C^-cycloalkyl or a group -R 5-S-R 6 or -R 5-O-R 6, R 2 is hydrogen, Ci-Ce-alkyl, C2-Ci2-alkenyl, phenyl, C7-Ci2-alkylphenyl, C7-

&igr;&igr;&igr;

Ci o-phenylalkyl or a group -CO-R 4, R 3 has one of the meanings given for R 1 or is C jC-js-alkoxy, R 4 is C 1-C 4 alkyl or phenyl, R 5 is Ci-C 10 -alkylene and R 6 is Ci-C 12 alkyl, phenyl, C 7-C 18 alkylphenyl or C 7-C 1 nP ^nen ylalkyl.

These include the hydroxyl-containing diketones of EP 0 346 279 and the oxa- and thia-diketones of EP 0 307 358 as well as the isocyanic acid-based ketoesters of US 4,339,383. R 1 and R 3 as alkyl can in particular be C-|-C-|8-alkyl, such as methyl, ethyl, n-propyl, isopropyl, η-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl or octadecyl.

R 1 and R 3 as hydroxyalkyl represent in particular a group -(CH2)n-OH, where η is 5, 6 or 7.
R 1 and R 3 as alkenyl can be, for example, vinyl, allyl, methallyl, 1-butenyl, 1-hexenyl or oleyl, preferably allyl.

R 1 and R 3 as phenyl substituted by OH, alkyl, alkoxy or halogen can be, for example, toyl, xylyl, tert-butylphenyl, methoxyphenyl, ethoxyphenyl, hydroxyphenyl, chlorophenyl or dichlorophenyl. R 1 and R 3 as phenylalkyl are in particular benzyl. R 2 and R 3 as cycloalkyl or alkylcycloalkyl are in particular cyclohexyl or methylcyclohexyl.

R 2 as alkyl can be in particular C-|-C4-alkyl. R 2 as C2-C-|2-alkenyl can

! 1

in particular AIIyI. R 2 as alkylphenyl can in particular be toIyI. R 2 as phenylalkyl can in particular be benzyl. R 2 is preferably hydrogen. R 3 as alkoxy can be, for example, methoxy, ethoxy, butoxy, hexyloxy, octyloxy,

dodecyloxy, tridecyloxy, tetradecyloxy or octadecyloxy. R 5 as C-|-Cio-alkylene is in particular C2-C4-alkylene. R 6 as alkyl is in particular C4-C"|2-alkyl, such as butyl, hexyl, octyl, decyl or dodecyl. R 6 as alkylphenyl is in particular toyl. R 6 as phenylalkyl is in particular benzyl. Examples of 1,3-dicarbonyl compounds of the above formula and their alkali metal, alkaline earth metal, zinc chelates and aluminum chelates are acetylacetone, butanoylacetone, heptanoylacetone, stearoylacetone, palmitoylacetone, lauroylacetone, 7-tert-nonylthio-heptanedione-2,4, benzoylacetone, dibenzoylmethane, lauroylbenzoylmethane, palmitoylbenzoylmethane, stearoylbenzoylmethane, isooctylbenzoylmethane, 5-hydroxycapronylbenzoylmethane, tribenzoylmethane, bis(4-methylbenzoyl)methane, benzoyl-p-chlorobenzoylmethane, Bis(2-hydroxybenzoyl)methane, 4-methoxybenzoylbenzoylmethane, bis(4-methoxybenzoyl)methane, 1-benzoyl-i-acetylnonane, benzoylacetylphenylmethane, stearoyl-4-methoxybenzoylmethane, bis(4-tert-butylbenzoyl)methane, benzoylformylmethane, benzoylphenylacetylmethane, biscyclohexanoylmethane, dipivaloylmethane, 2-acetylcyclopentanone, 2-benzoylcyclopentanone, methyl, ethyl and allyl diacetoacetate, methyl and ethyl benzoyl, propionyl and butyryl acetoacetate, triacetylmethane, methyl, ethyl, hexyl, octyl, dodecyl or octadecyl acetoacetate, methyl, ethyl, butyl benzoylacetate, -2-ethylhexyl, -dodecyl or -octadecyl esters, and also propionyl and butyrylacetic _acid C ₁₈ -alkyl esters. Stearoylacetic acid ethyl, propyl, butyl, hexyl or octyl esters and polynuclear ß-keto esters as described in EP 0 433 230 and dehydroacetic acid and their aluminum, zinc, alkaline earth or alkali metal salts. Preference is given to 1,3-diketo compounds of the above formula in which R 1 is C1-C18-alkyl, phenyl, phenyl substituted by OH, methyl or methoxy, C7-C10-

phenylalkyl or cyclohexyl, R 2 is hydrogen and R 3 has one of the meanings given for R 1.

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

Examples of the chlorine-containing polymers to be stabilized are: polymers of vinyl chloride, vinylidene chloride, vinyl resins containing vinyl chloride units in their structure, such as copolymers of vinyl chloride and vinyl esters of aliphatic acids, in particular vinyl acetate, copolymers of vinyl chloride with esters of acrylic and methacrylic acid and with acrylonitrile, copolymers of vinyl chloride with diene compounds and unsaturated dicarboxylic acids or their anhydrides, such as copolymers of vinyl chloride with diethyl maleate, diethyl fumarate or maleic anhydride, post-chlorinated polymers and copolymers of vinyl chloride, copolymers of vinyl chloride and vinylidene chloride with unsaturated aldehydes, ketones and others, such as acrolein, crotonaldehyde, vinyl methyl ketone, vinyl methyl ether, vinyl isobutyl ether and the like; polymers of vinylidene chloride and copolymers thereof with vinyl chloride and other polymerizable compounds; Polymers of vinyl chloroacetate and dichlorodivinyl ether; chlorinated polymers of vinyl acetate, chlorinated polymeric esters of acrylic acid and alpha-substituted acrylic acid; polymers of chlorinated styrenes, for example dichlorostyrene; chlorinated rubbers; chlorinated polymers of ethylene; polymers and post-chlorinated polymers of chlorobutadiene and their copolymers with vinyl chloride, chlorinated natural and synthetic rubbers, and mixtures of the polymers mentioned with each other or with other polymerizable compounds. In the context of this invention, PVC is also understood to mean copolymers with polymerizable compounds such as acrylonitrile, vinyl acetate or ABS, which can be suspension, bulk or emulsion polymers. A PVC homopolymer is preferred, also in combination with polyacrylates.

Graft polymers of PVC with EVA, ABS and MBS are also suitable. Preferred substrates are also mixtures of the above-mentioned homopolymers and copolymers, in particular vinyl chloride homopolymers, with other thermoplastic and/or elastomeric polymers, in particular blends with ABS, MBS, NBR, SAN, EVA, CPE, MBAS, PMA, PMMA, EPDM and polylactones.

Examples of such components are compositions of (i) 20-80 parts by weight of a vinyl chloride homopolymer (PVC) and (ii) 80-20 parts by weight of at least one thermoplastic copolymer based on styrene and acrylonitrile, in particular from the group ABS, NBR, NAR, SAN and EVA. The abbreviations used for the copolymers are familiar to the person skilled in the art and mean the following: ABS: acrylonitrile-butadiene-styrene; SAN: styrene-acrylonitrile; NBR: acrylonitrile-butadiene; NAR: acrylonitrile-acrylate; EVA: ethylene-vinyl acetate. Styrene-acrylonitrile copolymers based on acrylate (ASA) are also particularly suitable. Preferred components in this context are polymer compositions which contain, as components (i) and (ii), a mixture of 25-75% by weight of PVC and 75-25% by weight of the copolymers mentioned. Examples of such compositions are: 25-50% by weight of PVC and 75-50% by weight of copolymers or 40-75% by weight of PVC and 60-25% by weight of copolymers. Preferred copolymers are ABS, SAN and modified EVA, in particular ABS. NBR, NAR and EVA are also particularly suitable. One or more of the copolymers mentioned can be present in the composition according to the invention. Of particular importance as components are compositions which contain (i) 100 parts by weight of PVC, and (ii) 0-300 parts by weight of ABS and/or ABS modified with SAN and 0-80 parts by weight of the copolymers NBR, NAR and/or EVA, but in particular EVA.

Furthermore, recyclates of chlorine-containing polymers are also suitable for stabilization within the scope of this invention, whereby these are the polymers described in more detail above, which are obtained by processing,

have been damaged during use or storage. PVC recyclate is particularly preferred. Recyclates can also contain small amounts of foreign substances, such as paper, pigments, adhesives, which are often difficult to remove. These foreign substances can also come from contact with various substances during use or processing, such as fuel residues, paint particles, traces of metal and initiator residues.

The stabilization according to the invention is particularly advantageous for PVC formulations, such as those commonly used for pipes and profiles. The stabilization can be carried out without heavy metal compounds (Sn, Pb, Cd, Zn stabilizers). This property offers advantages in certain areas because heavy metals - with the possible exception of zinc - are often undesirable for ecological reasons both in the production and in the use of certain PVC articles. The production of heavy metal stabilizers also often causes problems from an industrial hygiene perspective. The smelting of ores containing heavy metals is also very often associated with serious impacts on the environment, with the environment including the biological system of humans, animals (fish), plants, air and soil. For these reasons, the incineration or landfilling of plastics containing heavy metals is also controversial.

The invention also relates to a process for stabilizing PVC, characterized in that at least one of the above-mentioned stabilizer combinations is added thereto.

The stabilisers can be conveniently incorporated using the following methods: as an emulsion or dispersion (one possibility is, for example, the form of a pasty mixture. An advantage of the combination according to the invention in this dosage form is the stability of the paste.); as a dry mix during the mixing of additional components or polymer mixtures;

by direct addition to the processing equipment (e.g. calender, mixer, kneader, extruder and the like) or as a solution or melt. The PVC stabilized according to the invention, which also relates to the invention, can be produced in a manner known per se, for which purpose the stabilizer combination according to the invention and optionally further additives are mixed with the PVC using devices known per se such as the processing equipment mentioned above. The stabilizers can be added individually or as a mixture or also in the form of so-called masterbatches.

The PVC stabilized according to the present invention can be shaped into the desired form in known ways. Such processes include grinding, calendering, extrusion, injection molding or spinning, as well as extrusion blow molding. The stabilized PVC can also be processed into foams.

A PVC stabilized according to the invention is particularly suitable for hollow bodies (bottles), packaging films (thermoforming films), blown films, pipes, foams, heavy profiles (window frames), light wall profiles, construction profiles, sidings, fittings, office films and equipment housings (computers, household appliances) as well as panels.

PVC rigid foam moldings and PVC pipes such as those for drinking water or waste water, pressure pipes, gas pipes, cable duct and cable protection pipes, pipes for industrial lines, seepage pipes, drain pipes, gutter pipes and drainage pipes are preferred. For more information, see "Plastics Handbook PVC", Volume 2/2, W. Becker/H. Braun, 2nd edition, 1985, Carl Hanser Verlag, pages 1236 -1277.

The compounds of formula I are prepared by known methods [US Patent 2,598,936 and J. Org. Chem. 16, 1879 - 1890 (1951)], as explained in more detail in the following Examples 1 to 3. Here, as in the rest of the text, parts and percentages are by weight unless otherwise stated.

Example 1 : Cyanoacetyldibenzylurea

IlCO-CH ₂ -CN

Ph-CH ₂ -NH-CN

_CH2 -Ph

36.0 g (0.15 mol) of dibenzylurea, 15.3 g (0.18 mol) of cyanoacetic acid and 30.6 g (0.3 mol) of acetic anhydride are stirred for 2 hours at 80 - 85°C. After cooling, the reaction mixture is stirred into 600 ml of water, the precipitate is filtered off with suction and then dried to constant weight.
10

Yield : 44.7 g ( ^ 96.9 % of theory)

For purification, the crude product is recrystallized from 150 ml of n-propanol. This gives white crystals with a melting point of 86 - 87°C. 15

Il CO-CH ₂ -CN Example 2 : Cyanoacetyldimethylurea CH -NH-CN

³ \

_CH3

Cyanoacetyldimethylurea is prepared analogously to Example 1. Dimethylurea is used instead of dibenzylurea. The product is worked up by removing the acetic anhydride/acetic acid mixture under reduced pressure on a rotary evaporator. The residue thus obtained is recrystallized from water.

Yield : 90% of theory, white crystals with a melting point of 75 - 76°C.

-37-

Example 3 : N-cyanoacetyl-N-benzyl-N'^-acetoxyethyl-urea/ N '-cyanoacetyl-N '^-acetoxyethyl-N-benzyl-urea

XO-CH ₂ -CN

Ph-CH ₂ -N

CO-NH-CH ₂ -Ch ₂ -O-CO-CH ₃

XO-CH ₂ -CN

CH ₃ -CO-O-CH ₂ -CH ₂ -N _n

CO-NH-CH ₂ -Ph

Example 3 is prepared analogously to Example 1. Instead of N ₁ N'-dibenzylurea, the acetylated N'-(2-hydroxyethyl)-N-benzylurea is used. The mixture is worked up by distilling off the acetic anhydride/acetic acid mixture to a residue. The residue is dissolved in dichloromethane. The organic solution is washed with water and sodium hydrogen carbonate solution, dried over sodium sulfate and concentrated again to a residue on a rotary evaporator.

Yield : 96.7% of theory, honey-colored, viscous liquid

According to ¹ H-NMR the distribution is as follows: 55.4 mol% of compound (7)

20 37.6 mol% of the compound @ and

6.9 mol% starting urea

Example 4 : Static heat test

A dry mixture consisting of
5

100.0 parts Evipol SH 5730 = PVC K-value 57

5.0 parts BTA III N 2 = MBS modifier

0.5 parts Paraloid K 120 N = Acrylate processing aid

0.5 parts Paraloid K 175 = acrylate processing aid

0.3 parts wax E = ester wax (Montan wax)

3.0 parts ESO = epoxidized soybean oil

1.0 parts Loxiol G 16 = fatty acid partial ester of glycerin

and one of the stabilizer mixtures specified in Tables 1a) and 1b)

is rolled on a mixing mill for 5 minutes at 180 ⁰ C. Test foil pieces of 0.3 mm thickness are taken from the rolled sheet formed. The foil samples are thermally stressed in an oven at 190 ⁰ C. The yellowness index (Yl) is determined in accordance with ASTM D-1925-70 at intervals of 3 minutes. The results can be found in Table 1 [a) and b)]. Low Yl values mean good stabilization.

Table 1a )

Mixture A Mixture B Mixture C Stabilizers 1.0 parts Stabilizer 1 1.0 parts Minutes Ca stearate 0.8 parts Manomet 200 0.8 parts Ca stearate 0.8 parts Malbit CH 16385 Malbit CH 16385 0.4 parts 0.4 parts O Yl61,63 Yl15.89 Yl15,13 3 64.89 16.23 16.53 6 78.37 19.24 19.52 9 107.90 24.51 25.51 12 145.69 31.33 32.55 15 38.05 43.45 18 46.43 61.94 21 61.37 86.83 24 81.30 108.34 27 125.65 134.38

-40-

Tableb )

Mixture D Mixture E Mixture F Stabilizer 2 1.0 parts Stabilizer 2 1.0 parts Stabilizer3 1.0 parts Minutes Manomet 200 0.8 parts Ca stearate 0.1 parts Ca stearate 0.8 parts Malbit CH 16385 Malbit CH 16385 0.1 parts 0.4 parts 0 Yl16.05 Yt 12,00 Yl12.48 3 20,21 21.88 13.97 6 22.03 25.89 15.55 9 24.38 27.86 18,21 12 26.37 27.17 22.37 15 29.57 32.75 28.67 18 39.20 39.88 38.79 21 61.72 52.58 53.48 24 97,00 71.61 70.38 27 141.75 103.51 90.33 30 113.93 33 141.82

Legend for Example 4 / Table 1 :

see table see table see table see table see table

Manomet 200 = overbased Ca stearate

Malbit CH 16385 = Maltitol (polyol)

Stabilizer 1 = Cyanoacetyldibenzylurea (Example 1)

Stabilizer 2 = Cyanoacetyldimethylurea (Example 2)

Stabilizer 3 = N-cyanoacetyl-N-benzyl-N'^-acetoxyethyl-urea/

N '-cyanoacetyl-N '^-acetoxyethyl-N-benzyl-urea

(Example 3)

Compared to the comparison mixture (A), the mixtures according to the invention (B to F) show a drastic improvement in thermal stability both with regard to initial colour, colour retention and long-term stability.

Example 5 :

A dry mixture consisting of
10

100.00 parts Norvinyl S 6775 = S-PVC

2.00 parts Omyalite 95T = chalk

0.80 parts Ca stearate
0.70 parts IRGAWAX 367 = paraffin wax

0.60 parts Hoechst wax PE 520 = ester wax (= partially saponified

Montanic acid esters) ex Hoechst

0.15 parts Allied AC 629 A = Oxidized homopolymer ex Allied Signal

0.05 parts Allied AC 316 = Oxidized Polyethylene ex Allied Signal

1.00 parts Wessalith P = Na-Zeolite A
0.40 parts Malbit CH 16385 = maltitol

0.20 parts Mark 6045 J = mixture of 9% NaCIO ₄ , 45% CaCO ₃ ,

40% _CaSiO3 , 6% _H2O

and the stabilizer specified in Table 2 is rolled on a mixing mill for 5 minutes at 200 ⁰ C. Test film pieces 0.3 mm thick are taken from the rolled sheet formed. The film samples are thermally stressed in an oven at 190 ⁰ C. The Yellowness Index (Yl) is determined in accordance with ASTM D-1925-70 at intervals of 3 minutes. The results can be found in Tables 1 and 2 below. Low Yl values mean good stabilization.

-42-

Table 2

Mixture G Mixture H Minutes without additional stabilizer Stabilizer 2 0.2 parts O Yl98.18 Yl30.79 3 100.53 32.35 6 101.56 35.74 9 102.21 42.17 12 103.59 49.78 15 105.50 59.89 18 116.70 72.61 21 83.86 24 99.09 27 113.04

Legend to Table 2

Stabilizer 2 = Cyanoacetyldimethylurea (Example 2)

Compared with the comparison mixture (G), the composition (H) according to the invention shows a very good improvement in the stabilizer effect both with regard to initial color and color retention and with regard to long-term stability.

Claims (20)

1. Composition comprising a chlorine-containing polymer and at least one compound of the general formula I


where
X is oxygen or sulfur, and
RC ₂ -C ₂₂ -acyloxyalkyl or C ₁ -C ₁₂ -alkyl, which may be interrupted by 1 to 3 oxygen atoms and/or substituted by 1 to 3 OH groups, C ₃ -C ₈ -alkenyl, C ₇ -C ₁₀ -phenylalkyl, C ₅ -C ₈ -cycloalkyl, C ₇ -C ₁₀ -alkylphenyl, phenyl or naphthyl, where the aromatic radical may be substituted in each case by -OH, C ₁ -C ₁₂ -alkyl and/or OC ₁ -C ₄ -alkyl, and
R ₁ is hydrogen or has the meaning of R. 2. Composition according to claim 1, wherein
X is oxygen. 3. Composition according to claim 1, wherein
X is sulfur. 4. Composition according to claim 1, wherein
R is equal to R ₁ . 5. Composition according to claim 1, wherein
Around
R ₁ is C ₁ -C ₈ alkyl, C ₃ -C ₅ alkenyl, benzyl or 2-phenethyl. 6. Composition according to claim 5, wherein
Around
R ₁ is C ₂ -C ₄ alkyl, allyl or benzyl. 7. Composition according to claim 1 containing at least one epoxidized fatty acid ester. 8. Composition according to claim 1 containing at least one zinc and/or alkali and/or alkaline earth carboxylate and/or aluminum carboxylate. 9. Composition according to claim 1 containing at least one further substance from the groups of phosphites, antioxidants, beta-dicarbonyl compounds, plasticizers, fillers, lubricants or pigments. 10. Composition according to claim 1 containing chalk as filler. 11. Composition according to claim 1 containing calcium stearate as a lubricant. 12. Composition according to claim 1 containing titanium dioxide and/or zirconium oxide and/or barium sulfate as pigment. 13. Composition according to claim 1 containing at least one polyol and/or one disaccharide alcohol. 14. Composition according to claim 1 containing at least one glycidyl compound. 15. Composition according to claim 1 containing at least one perchlorate compound. 16. Composition according to claim 1 containing at least one zeolitic compound. 17. Composition according to claim 1 containing at least one layered lattice compound (hydrotalcite). 18. Stabilizer combinations for chlorine-containing polymer comprising a compound of the general formula I according to any one of the preceding claims 1 to 6 and at least one further additive/stabilizer known per se. 19. A molded article of chlorinated polymer comprising a composition or stabilizer combination according to any one of the preceding claims. 20. Moulded part according to claim 19, characterized in that it is a tube, profile, plate or film.