Stabilising system for halogenated polymers

FIELD: chemistry.

SUBSTANCE: invention relates to a stabilising system for halogen-containing polymers, as well as a composition and article made from the composition which contains the stabilising system. The stabilising system for halogen-containing polymers contains component (A) in form of a calcium monocarbonate hydroxodialuminate of formula (A) Ca_mAl₂(OH)_6+2(m-1)CO₃*nH₂O (A), where m varies from 3.8 to 4.2 and n varies from 0 to 3, and component (B) in form of catena-2,2',2"-nitrile trisethanol perchlorate lithium or sodium coordination polymer (B1), having a monomer link of formula , where Mt denotes Li or Na, An denotes OCIO₃, q equals 1, and can additionally contain perchlorate of quaternary or tertiary ammonium or phosphonium (B2).

EFFECT: high heat-stabilising action.

17 cl, 19 tbl

The present invention relates to a stabilizing systems for halogenated polymers, and also to compositions and articles containing stabilizing system, as well as the application of systems and compositions.

It is known that halogenated plastics have a tendency to undesirable decomposition reactions and undesired degradation reactions when they are exposed to thermal stress during processing or during long-term use. This problem can be solved by applying a metal-containing stabilizers, and they are added to the halogenated polymers before or during processing. Among the known stabilizers are barium-cadmium stabilizers, lead stabilizers, organohalogen stabilizers, barium-zinc stabilizers and calcium-zinc stabilizers. However, all these groups of stabilizers containing heavy metals, and this impairs their compatibility with the environment.

Therefore, in recent years there has been increasing development of systems, known as organic systems, which do not contain heavy metals, and currently they are trading. They are solid stabilizers and mainly processed into molded form, more environment-friendly. Such systems are based on organic compounds, to depict ablaut a multicomponent mixture, the main component of which is, mainly, a member of the group of substances (magnesium aluminum hydroxycarbonate) hydrotalcites.

However, this class of compounds is relatively expensive to obtain because the affected source emissions. The method of obtaining, in addition, is accompanied by significant amounts of wastewater, due to the fact that use salts of magnesium and aluminium salts.

Compositions that do not contain heavy metals, which act as stabilizers for PVC containing hydrotalcite and accordingly hydrocalumite (catot), described by example in EP 1046668 B1 and EP 0930332 B1.

Therefore, the need remains to find substances that are less expensive and which, moreover, can be synthesized in a way compatible with the environment, without the use of expensive tools.

The cost of the starting substances for the calcium monochromatization makes them promising thermal stabilizers for PVC. However, they are very expensive for industrial production. In the German patent application with the application number DE 10 2006 055214.8 described method for obtaining compounds of this class. This method can demonstrate environmentally friendly obtain for a low price, because it uses source materials at a low price and if estvo emerging wastewater is only small.

Internal systems such as triethanolamine-metal in the form of the coordination polymers are also described in WO-A 2006/0136191 as additives for synthetic polymers.

Despite existing system stabilizers there is a need for alternative systems that may possess superior stabilizing properties, as well as the aforementioned benefits.

Therefore, the present invention is to provide such a stabilizing system.

The task was successfully performed using a stabilizing system for halogenated polymers comprising as component (A) calcium monochromatization formula (A)

where m is from 3.8 to 4.2, and n is from 0 to 3, and

as component (C) Catena-2,2',2"-nitrilotriacetonitrile or sodium coordination polymer (B1)having a monomer link of the formula

,

where Mt denotes Li or Na, An means OClO₃and q is 1, and/or ammonium Quaternary or tertiary ammonium or phosphonium (B2).

In particular, we discovered that the combination of components (a) and (b) lead to an increase in " oven " de the acts, especially in PVC. Further increase is obtained by adding component (C).

Component (A) is a calcium monochromatization formula (A). Obtaining such a compound is described by way of example in the German patent application with the application number DE 10 2006 055214.8.

Component (C) contains a compound (B1) and/or (B2).

Compounds (B1) are coordination polymers and contain the following Monomeric link:

,

where Mt denotes Li or Na, An means OClO₃and q is 1.

In WO-A 2006/0136191 described compounds as such and described their receipt.

Compounds (B2) are the perchlorates of Quaternary or tertiary ammonium and corresponding phosphonium.

Preferably, there is a perchlorate of the formula R¹R²₃XClO₄where X is P or N, R¹means N or R²and each R²regardless of the other, represents a saturated or unsaturated hydrocarbon radical of a branched or unbranched, cyclic or acyclic, or cyclic or acyclic structure, having from 1 to 20 carbon atoms.

Such Quaternary salts obtained by anion metathesis perchlorates of alkali metals (mainly sodium compounds) with salts of Quaternary ammonium Il is of phosphonium (mainly the halides or nitrates in the water, where the Quaternary onevia perchlorate is obtained in the form of filterable precipitates. Tertiary onevia perchlorate is obtained by protonation of tertiary amines or Fofanov water perchloro acid.

The amount of component (C), based on component (A)is preferably from 1 to 10% by mass.

The stabilizing system of the invention, in addition, may also contain components (C), and they represent a nitrogen-containing organic compounds or calcium hydroxide.

Here, it is preferable that the component (C) contains a nitrogen-containing organic compound (C), which are substituted cyanoacetylene (1), substituted 6-aminouracil (C-2, C-3, C-4, C-5 and C-6), substituted mono - or poly-1,4-dihydropyridine (C-7) and 3-aminocrotonate esters (C-8), which have the following structure:

* structure of substituted poly-1,4-dihydropyridine described in WO 2006/0136191,

in which

R³means₁-C₂₀-alkyl, C₃-C₆alkenyl,₇-C₉-phenylalkyl, unsubstituted phenyl or phenyl substituted from 1 to 3, C₁-C₄-alkyl, C₁-C₄-alkoxy or hydroxy groups and

R⁴OSN which includes R ³or N,

R⁵means H or hydroxy-C₂-C₄-alkyl, hydroxyphenyl,₁-C₄-alkoxyphenyl,

R⁶means₁-C₂₀-alkyl,

R⁷means N or the following radicals:₁-C₁₄-alkyl, C₂-C₄alkenyl, optionally substituted C₄-C₈-cycloalkyl,₆-C₁₀-aryl, C₇-C₁₀-alkylaryl,₇-C₁₀-arylalkyl, -CH₂-O-R⁹where

R⁹means₁-C₁₀is an alkyl radical or₂-C₄-alkanniny radical, or With₄-C₈-cycloalkyl, if appropriate, containing oxirane ring,

R⁸represents a C₂-C₂₀-alkylen unbranched or branched structure, which can be chains of 1 to 4 atoms of O or S and/or may be substituted by from 1 to 4, HE-groups, or dimethylcyclohexane-1,4-diyl, polyethylene (or propylene)glycol-α,ω-diyl (poly, preferably, means from Tetra to DECA), polyglyceryl-α,ω-diyl (poly, preferably, means from Tetra to DECA) or glycerites, trimethylated-(or propane)trial, pentaerythritol three(or Tetra)Il, bestemmelser- (or propane)three(or Tetra)Il, diglyceride(or Tetra)Il, Tetra-tetraol, triglyceride(or Tetra or Penta)Il, penitential, dipentaerythritol(or hexa)silt and exitex the sludge; and

p is from 2 to 6.

Especially preferred that the substituted cyanoacetylene represents a 1,3-dimethylcyclohexylamine that substituted 6-aminouracil represents 1,3-dimethyl-6-aminouracil, 1,3-diallyl-6-aminouracil or 5,5'-[S₄-C₁₈-alkyliden]-bis-1,3-dimethyl-6-aminouracil, substituted 1,4-dihydropyridines is a 2,6-dimethyl-3,5-bicarboxylic-1,4-dihydropyridines and complex 3-aminocrotonate ether is a 1,4-butanediols-3-aminocrotonate or 2,2'-timecalendar-3-aminocrotonate.

Substance classes from (1) to (6) described in more detail in EP 0768336, EP 1510545, EP 0967209, EP 0967208, EP 0962491 and EP 1044968.

Particular preference is given to the following compounds as components (a) to (C).

(A): keturahnalley monochromatization and its hydrates

(In): katana-2,2',2"-nitrilotriacetate

(C): (C-1) 1,3-dimethylcyclohexylamine

(P-2) 1-[S₃-C₂₂-alkyl]- or 1-benzyl-6-aminouracil

(3) bis-1,3-C₁-C₂₂-alkyl - or 1,3-dibenzyl-6-aminouracil

(C-4) 6-[2-hydroxyethylamino]-, 6-[2(3,4)-hydroxyimino]- or 6-[2(3,4)-m(et)acetanilide]-1,3-dimethyluracil

(5) 5,5'-[S₄-C₁₈-alkyliden]bis-1,3-dimethyl-6-aminouracil

(C-6) 1-methyl(phenyl, benzyl)-3-[2-hydroxybutyl]-6-aminouracil or

1-methyl(phenyl, benzyl)-3-[2-hydroxy-2-allyl shall xitil]-6-aminouracil

(7) 2,6-dimethyl-3,5-bicarboxylic-1,4-dihydropyridines

(C-8) 1,4-butanediols-3-aminocrotonate or

2,2'-timecalendar-3-aminocrotonate.

Among (With) the most particular preference is given:

1,3-dimethyl-6-aminouracil, 1,3-dibenzyl-6-aminouracil (C-3),

1,3-dimethyl-6-[2-hydroxyanisol]uracil (C-4),

5,5'-pentylidene-1,3-dimethyl-6-aminouracil,

5,5'-hexylidene-1,3-dimethyl-6-aminouracil,

5,5'-reptilians-1,3-dimethyl-6-aminouracil,

5,5'-Actividades-1,3-dimethyl-6-aminouracil,

5,5'-undecylenic-1,3-dimethyl-6-aminouracil or

5,5'-dodecylamino-1,3-dimethyl-6-aminouracil (C-5),

1-methyl-3-[2-hydroxybutyl]-6-aminouracil or

1-benzyl-3-[2-hydroxybutyl]-6-aminouracil (C-6),

2,6-dimethyl-3,5-bicarboxylic-1,4-dihydropyridines (C-7)

and

1,4-butadienestyrene or

2,2'-todeteriorate (C-8),

the calcium hydroxide.

The stabilizing system of the invention can, if appropriate, to further contain the following additives, such as:

- magnesium hydroxide and alkaline earth metal soap

- polyols and sugar alcohols or trihydroxyacetophenone

- esters of phosphorous acid (phosphites)

- Picadilly connection and epoxydecane esters of fatty acids

- spatial-employed amines (HALS) and aminoalcohols

- β-diket the HN and complex β-ketoesters

antioxidant

UV absorbers and light stabilizers

optical brighteners

antistatic agents

- biocidal tools

- pigments

- fillers

- foaming agents

- grease

- plasticizers.

The present invention therefore additionally provides a composition of the invention, which also contains one or more of such compounds.

It is preferable that the stabilizing system of the invention also contains at least one antioxidant and/or one alcohol selected from polyols, sugar alcohols and trihydroxyacetophenone or aminoalcohols.

Hydroxides of alkaline earth metals and the alkaline earth metal soap

Preference is given to calcium hydroxide and calcium stearate.

The polyols and sugar alcohols

Examples of compounds of this type that can be applied are: pentaerythritol, dipentaerythritol, tripentaerythritol, trimethylacetyl, bestemmingsplan, Inositol, polyvinyl alcohol, bestemmelser, trimethylolpropane, sorbitol ▫ maltitol, isomaltol, likacin, mannitol, lactose, leucrose, Tris(hydroxyethyl)isocyanurate (THEIC), palatinol, tetramethylcyclobutane, tetramethylcyclobutane, tetramethylsilane, glycerin, diglycerin, polyglycerins, thiodiglycol or 1-O-α-D-glucopyranosyl-D-mannitol dehydrate. PR is dpochtenie given disaccharide glycosides of alcohols. Also applicable syrups polyols, and examples are sorbitol syrup, syrup mannitol and syrup maldita. Example number in which you can apply polyols, represents from 0.01 to 20 parts by weight, applicable, from 0.1 to 20 parts by weight and, particularly, from 0.1 to 10 parts by weight based on 100 parts by weight of PVC. Preferred is Tris(hydroxyethyl)isocyanurate.

Esters of phosphorous acid (phosphites)

Examples in accordance with the original are trioctyl, tridecyl, tridodecyl, tetradecyl, tapentadol, triolein, tristearin, triphenyl, dilauryl, Tricresyl, trigonelline, Tris-2,4-tert-butylphenyl or tricyclohexylphosphine. Other suitable phosphites are different mixture kildalkey or alkylarylphosphites, i.e. feildmaster, vinyldimethyl, feniletinil, phenyltetrazol, phenyltetrazole, phenylpiperazines, octyldiphenyl, deciliter, undecadienal, dodecylphenyl, tridecylamine, tetradecyltrimethyl, pentadecanedioic, reeldirty, steroidogenic and modellus-2,4-di-tert-butylphenylphosphine. Also preferred application of different phosphites di - or polyalcohol, such as tetraferriphlogopite, poly(dipropyleneglycol)phenylphosphate, tetrasociological, creditrepairloanswith, tetrameth is aziklovirmonofosfat, tetramethylcyclopropanecarboxylate, tetramethylcyclopentadienyl, binaryformatter.serialize, bis-2-butoxycarbonylmethylene, trihydroxyethylrutoside, dimetilparafenilendiamina, distearoylphosphatidylcholine, bis-2,4-di-tert-butylbenzylphthalate, as well as mixtures of these phosphites, and mixtures of these phosphites and mixtures of aryl/alkylphosphates statistical composition (H₁₉With₉-C₆H₄)O_1,5P(OS_12,13H_25,27)_1,5or (C₈H₁₇-C₆H₄-Oh)₂P(ISO-C₈H₁₇O),(N₁₉With₉-C₆H₄)O_1,5P(OS_9,11H_19,23)_1,5. Available in industry examples are Naugard P, Mark CH300, Mark CH301, Mark CH302 and Mark CH55 (manufacturer: Chemtura Corp. USA). Example number in which you can apply organic phosphites, is from 0.01 to 10 parts by weight, applicable, from 0.05 to 5 parts by weight, especially from 0.1 to 3 parts by weight based on 100 parts by weight of PVC.

The stabilizing system of the invention may contain an amount of approximately 30% by weight, in particular up to 10% by weight described fofanah connections.

Glycidaldehyde and epoxydecane esters of fatty acids

Example is and epoxy compounds are epoxydecane soybean oil, epoxydecane olive oil, epoxydecane linseed oil, epoxydecane castor oil, epoxydecane peanut butter, epoxydecane corn oil and epoxydecane cottonseed oil.

Examples of glycidaldehyde are compounds having glycidyloxy group:

which can have a direct link with the carbon atoms, oxygen atoms, nitrogen atoms or sulfur atoms, and in which or both of R₃and R₅are hydrogen, R₄is hydrogen or stands, and n is 0, or in which R₃and R₅together represent-CH₂-CH₂- or-CH₂-CH₂-CH₂-, and R₄then represents hydrogen and n is 0 or 1.

I) Glycidyloxy and β-methylglycerol esters obtained by a reaction between compounds having at least one carboxypropyl in the molecule and epichlorohydrin and accordingly glyceraldehyde and consequently β-methylephedrine. The reaction of interaction is successfully performed in the presence of bases.

Compounds that can be used which have at least one carboxypropyl in the molecule, represent aliphatic carboxylic acid. Examples of such carboxylic acids are glutaric acid, adipe the OIC acid, Emelyanova acid, subernova acid, azelaic acid, sabotinova acid or diarizonae or trimmeresana linoleic acid, acrylic and methacrylic acid, hexanoic acid, Caprylic acid, pelargonia acid, lauric acid, myristic acid, palmitic acid and stearic acid.

However, it is also possible to use cycloaliphatic carboxylic acids, for example cyclohexanecarbonyl acid, tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid or 4-methylhexahydrophthalic acid.

It is also possible to use aromatic carboxylic acid, and examples include benzoic acid, phthalic acid, isophthalic acid, trimellitate acid or pyromellitate acid.

It is also possible to use adducts with end carboxypropyl, for example trimellitic acids and polyols, such as glycerol or 2,2-bis(4-hydroxycyclohexyl)propane.

In EP 0506617 described more epoxysilane that you can apply for the purposes of this invention.

II) Glycidyloxy or β-methylglycerol ethers, available by the reaction between compounds having at least one free alcoholic hydroxy-group and/or a phenolic hydroxy-group, with acceptable replaced epichlorhydrine the under alkaline conditions or in the presence of an acid catalyst with subsequent alkali treatment.

Ethers of this type get, as an example, from acyclic alcohols such as ethylene glycol, diethylene glycol and higher poly(oksietilenom)glycols, propane-1,2-diol or poly(oxypropylene)glycols, propane-1,3-diol, butane-1,4-diol, poly(oxytetracyline)glycols, pentane-1,5-diol, hexane-1,6-diol, hexane-2,4,6-triol, glycerol, 1,1,1-trimethylolpropane, bestemmingsplan, pentaerythritol or sorbitol, or even from polyepichlorohydrins, butanol, amyl alcohol or pentanol, or even from monohydroxy alcohols, such as isooctanol, 2-ethylhexanol or isodecanol, or more of a mixture With₇-C₉-alcohols and mixtures With₉-C₁₁-alcohols.

However, they also receive, as an example, from cycloaliphatic alcohols, such as 1,3 - or 1,4-dihydrocyclopenta, bis(4-hydroxycyclohexyl)methane, 2,2-bis(4-hydroxycyclohexyl)propane or 1,1-bis(hydroxymethyl)cyclohex-3-ene, or they may have an aromatic ring, and examples include N,N-bis(2-hydroxyethyl)aniline or p,p'-bis(2-hydroxyethylamino)difenilmetana.

Epoxysilane also can be obtained from managernew 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'-dihydroxydiphenylsulfone recondensation, obtained in acidic conditions, of phenols with formaldehyde, such as phenol novolaks.

Examples of other possible epoxides with end epoxypropoxy are: simple glycidyl-1-nattily ether, simple glycidyl-2-phenylphenolate ether, a simple 2-biphenyldiol ether, N-(2,3-epoxypropyl)phthalimide and simple 2,3-epoxypropyl-4-methoxyphenacyl ether.

III) N-Glycidaldehyde obtained by dehydrochlorinating the reaction products of epichlorohydrin with amines containing at least one amine hydrogen atom. Examples of such amines are aniline, N-methylaniline, toluidine, n-butylamine, bis(4-AMINOPHENYL)methane, m-Cialdini and bis(4-methylaminophenol)methane, N,N,O-triglycidyl-m-aminophenol and N,N,O-triglycidyl-p-aminophenol.

However, among the N-glycidaldehyde are also N,N'-di-N,N',N"-tri - and N,N',N",N"-tetraphenylphosphonium of cycloalkylation, such as etilenmocevina or 1,3-propylenimine and N,N'-diglyceride hydantoins, for example, 5,5-dimethylhydantoin or glycoluril, tripyridyltriazine.

IV) S-Glycidaldehyde, such as di-S-glycidylester, in those cases, when they receive from the developed, such as ethane-1,2-dithiol or bis(4-mercaptoethanol) simple ether.

V) Epoxysilane having a radical of the above formula in which R₁and R₃together who appoints-CH ₂-CH₂and n is 0, are simple bis(2,3-amoxicillinbuy) ether, 2,3 simple-amoxicillingeneric ether or 1,2-bis(2,3-amoxicillinamoxil)ethane. Example epoxy resin having the radical of the above formula in which R₁and R₃together denote-CH₂-CH₂and n is 1, is 3',4'-epoxy-6'-methylcyclohexyl-3,4-epoxy-6-methylcyclohexanecarboxylic.

Examples of suitable epoxides with end epoxypropoxy are

a) simple liquid bisphenol-A-diglycidyl ethers, such as Araldit®GY240, Araldit®GY 250, Araldit®GY 260, Araldit®GY 266, Araldit®GT 2600, Araldit®MY 790 and Epicote® 828 (BADGE);

b) simple solid bisphenol-A-diglycidyl ethers, such as Araldit®GT 6071, Araldit®GT 7071, Araldit®GT 7072, Araldit®GT 6063, Araldit®GT 7203, Araldit®GT 6064, Araldit®GT 7304, Araldit®GT 7004, Araldit®GT 6084, Araldit®GT 1999, Araldit®GT 7077, Araldit®GT 6097, Araldit®GT 7097, Araldit®GT 7008, Araldit®GT 6099, Araldit®GT 6608, Araldit®GT 6609, Araldit®GT 6610 and Epicote® 1002;

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

d) solid simple polyglycidyl esters of tetraphenylmethane, such as CG Epoxy Resin®0163;

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

f) solid and liquid simple polyglycidyl esters o-crazyforbargains of novolak, such as ECN 1235, ECN 1273, ECN 1280, ECN 1299 (NODGE);

g) liquid is a simple glycidyloxy esters of alcohols, such as Shell Glycidylether® 162, Araldit®DY 0390, Araldit®DY 0391;

h) liquid and solid complex glycidyloxy esters of carboxylic acids, and examples are Shell Cardura® E complex terephthalic esters, complex trimellitate esters, and mixtures thereof, Araldit®PY 284 and Araldit® P811;

i) solid heterocyclic epoxy resins (tripyridyltriazine), such as Araldit®PT 810;

(j) liquid cycloaliphatic epoxy resins, such as Araldit®CY 179;

k) simple liquid N,N,O-triglycidyl ethers of p-aminophenol, such as Araldit®MY 0510;

l) tetraglycidyl-4,4'-methylenediamine or N,N,N',N'-tetrachlorodibenzofuran, such as Araldit®MY 720, Araldit®MY 721.

Preferably the application of the epoxy compounds having two functional groups. However, it is also possible, in essence, the use of epoxy compounds having one or three or more functional groups.

Mainly used compounds are epoxysilane, in particular, dipicolylamine having an aromatic group.

It is also possible, if appropriate, the use of mixtures of various epoxy compounds.

Spatial-employed amines (HALS) and aminoalcohols

Spatial-employed amines are typically compounds containing the following group

in which A and V, independently of one another, represent the th _1-8-alkyl, C_3-8alkenyl,_5-8-cycloalkyl or_7-9-phenylalkyl, or together, if appropriate, form a_2-5-alkylen, if appropriate, containing in-chain O, NH or CH₃-N, or spatial hindered amine may be cyclic, in particular, a compound from the class of alkyl - or polyalkylimide, especially tetramethylpiperidine containing the following group

Examples of such polyalkylimide compounds are the following (where, in the case of oligomeric or polymeric compounds, n and r are in the range from 2 to 200, preferably in the range from 2 to 10, especially from 3 to 7). A complete list of such compounds is EP 0796888 B1.

For the purposes of one particularly preferred variant implementation of the present invention applied aminoalcohols include heterocyclic compounds. Examples of compounds are: EO-, RHO -, and THE reaction products of ethylene - and propylenoxide, Paramonovo acid, hydantoins, barbituric acids, glycoluril and isocyanuric acids. For the purposes of the present invention is particularly preferably the use of Tris(hydroxyethyl)isocyanurate (THEIC) or Tris(hydroxypropyl)isocyanurate as an integral part of the stabilizing system of the invention.

The content of THEIC in stabilizing the system from which bretania is, as an example, approximately 0.01 to approximately 10% by mass.

β-Diketones and complex β-ketoesters

1,3-Dicarbonyl compounds that can be used are dicarbonyl compounds unbranched or cyclic structure. Preferably the application of the dicarbonyl compounds of the formula R'₁COCHR'₂-COR'₃in which R'₁represents a C₁-C₂₂-alkyl, C₅-C₁₀-hydroxyalkyl,₂-C₁₈alkenyl or phenyl, or phenyl substituted IT WITH₁-C₄-alkyl, C₁-C₄-alkoxy or halogen, or represents C₇-C₁₀-phenylalkyl or₅-C₁₂-cycloalkyl or₁-C₄-alkyl substituted With₅-C₁₂-cycloalkyl, or a group-R'₅-S-R'₆or-R'₅-O-R'₆; R'₂represents hydrogen, C₁-C₈-alkyl, C₂-C₁₂alkenyl, phenyl, C₇-C₁₂-alkylphenyl,₇-C₁₀-phenylalkyl or the group-CO-R'₄; R'₃means R'₁or means₁-C₁₈-alkoxy, R'₄represents a C₁-C₄-alkyl or phenyl; R'₅represents a C₁-C₁₀-alkylene and R'₆represents a C₁-C₁₂-alkyl, phenyl, C₇-C₁₈-alkylphenyl or₇-C₁₀-phenylalkyl.

the Redi such compounds diketones, containing hydroxy-group are in the patent EP 0346279 A1, and oxa and dedicatory in patent EP 0307358 A1 and complex ketoesters on the basis of the isocyanuric acid in the patent US 4339383.

R'₁and R'₃as the alkyl can be, in particular, With₁-C₁₈-alkyl, such as stands, ethyl, n-propylene, isopropyl, n-bootrom, tert-bootrom, Pentium, hexyl, heptyl, actilon, decyl, dodecyl or octadecyl.

R'₁and R'₃as hydroxyalkyl are, in particular, the group -(CH₂)_n-OH, in which n is 5, 6 or 7.

R'₁and R'₂as of alkenyl can be, as an example, vinyl, allyl, Metallica, 1-butanolom, 1-hexenyl or Oleron, preferably, allyl.

R'₁and R'₃as HE-, alkyl-, alkoxy - or halogen-substituted phenyl can be, as an example, talila, xilian, tert-butylphenyl, methoxyphenyl, ethoxyphenyl, hydroxyphenyl, chlorophenyl or dichlorophenyl.

R'₁and R'₃as phenylalkyl are, in particular, benzyl. R'₂and R'₃as cycloalkyl or alkylcyclohexane are, in particular, cyclohexyl or methylcyclohexyl.

R'₂as the alkyl can be, in particular, With₁-C₄-alkyl. R'₂as With₂-C₁₂-al is Anila maybe in particular allyl. R'₂as alkylphenyl can be, in particular, talila. R'₂as phenylalkyl can be, in particular, benzyl. It is preferable that R'₂represents hydrogen. R'₃as alkoxy may be, as an example, methoxy, ethoxy, butoxy, hexyloxy, octyloxy, dodecyloxy, tridecylamine, tetradecane or octadecylamine. R'₅as With₁-C₁₀-alkylene represents, in particular, With₂-C₄-alkylen. R'₆as the alkyl is, in particular, With₄-C₁₂-alkyl, such as butyl, hexyl, octyl, decyl or dodecyl.

R'₆as alkylphenyl represents, in particular, tolyl. R'₆as phenylalkyl represents, in particular, benzyl.

Examples of 1,3-dicarbonyl compounds of the above General formula, and chelates of alkali metals, alkaline earth chelates metals and chelates of zinc are acetylacetone, butanolate, heptanoate, staurolite, palmitoylation, laurolactam, 7-tert-nonlitigated-2,4-dione, benzoylacetone, dibenzoylmethane, lauroylsarcosinate, palmitoylation, stearoylbenzoylmethane, isooctylphenol, 5-hydroxypropylmethacrylate, dibenzoylmethane, bis(4-methylbenzoyl)methane, benzoyl-p-Chlorobenzilate, bis(2-hydroxybenzoyl)methane 4-methoxybenzothiazole, bis(4-methoxybenzoyl)methane, 1-benzoyl-1-acetylene, benzoylacetonitrile, stearoyl-4-methoxybenzoate, bis(4-tert-butylbenzoyl)methane, benzoylformate, benzylpenicillin, bicyclogermacrene, dipivaloylmethane, 2-acetylcyclopentanone, 2-benzoylthiophene, methyl, ethyl and allyl esters diacetoxy acid, methyl and ethyl esters benzoyl, propionyl and butyrolacetone acid, triazolylmethyl, methyl, ethyl, hexyl, oktilovom, dodecyloxy or octadecylamine esters of acetoacetic acid, methyl, ethyl, butyl, 2-ethylhexyloxy, dodecyloxy or octadecylamine esters benzoyloxy acid, and also With₁-C₁₈-alkalemia esters propionyl and butyryloxy acid. Ethyl, propyl, butyl, hexyl or oktilovom esters starorusyny acids and polynuclear complex of β-ketoesters, described in the patent EP-A 0433230, and DHA, as well as their zinc, magnesium salts or alkali metal salts. Preference is given to CA, Mg and Zn salts of acetylacetone and DHA.

Particular preference is given to 1,3-dichlooethene above formula, in which R'₁represents a C₁-C₁₈-alkyl, phenyl or phenyl substituted IT, stands or methoxy, or PR is dstanley a ₇-C₁₀-phenylalkyl or cyclohexyl, R'₂represents hydrogen, and R'₃represents as indicated for R'₁. Among such compounds are heterocyclic 2,4-diones, such as N-phenyl-3-acetylpyrrolidine-2,4-dione. In the patent EP 0734414 A1 describes other representatives of this class. A number of examples in which you can apply dimethocaine are from 0.01 to 10 parts by weight, effectively, from 0.01 to 3 parts by mass, and particularly from 0.01 to 2 parts by weight, based on 100 parts by weight PVC.

Antioxidants

Among the compounds are spatial-employed phenols, such as alkylated monophenol, for example 2,6-di-tert-butyl-4-METHYLPHENOL, alkyltrimethylenedi, for example 2,4-dioctylfluorenyl-6-tert-butylphenol, alkylated hydrochinone, for example 2,6-di-tert-butyl-4-methoxyphenol, gidroksilirovanii thiodiphenylamine ethers, for example 2,2'-THIOBIS(6-tert-butyl-4-METHYLPHENOL), alcaligenaceae, for example 2,2'-Methylenebis(6-tert-butyl-4-METHYLPHENOL), benzylamine, for example simple 3,5,3',5'-Tetra-tert-butyl-4,4'-dihydroxydiphenyl ether, hydroxybenzylidene malonate, such as dioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, hydroxybenzeneacetic compounds, for example 1,3,5-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylpent is l, triazine compounds, for example 2,4-biochimique-6-(3,5-di-tert-butyl-4-hydroxyanisole)-1,3,5-triazine, phosphonates and phosphonites, for example dimethyl-2,5-di-tert-butyl-4-hydroxyethylphosphonate, aceraminophen, for example 4-hydroxylamino anilide, esters of beta-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, beta-(5-tert-butyl-4-hydroxy-3-were)propionic acid, beta-(3,5-DICYCLOHEXYL-4-hydroxyphenyl)propionic acid, esters of 3,5-di-tert-butyl-4-hydroxyphenylarsonic acid with one or polynuclear alcohols, amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, for example N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionic)hexamethylenediamine were, vitamin E (tocopherol) and derivatives thereof, as well as D,L-ascorbic acid. Examples of quantities that can be applied antioxidants comprise from 0.01 to 10 parts by weight, effectively, from 0.1 to 10 parts by mass and, particularly, from 0.1 to 5 parts by weight, based on 100 parts by weight PVC.

UV absorbers and light stabilizers

Examples of these compounds are 2-(2'-hydroxyphenyl)benzotriazoles, for example 2-(2'-hydroxy-5'-were)benzotriazol, 2-hydroxybenzophenones, esters of optionally substituted benzoic acids, for example 4-tert-butylanisole, fenilsalitsilat, acrylates, Nickel compounds, oxolamine, for example ,4'-dioctylamine, 2,2'-dioctyloxy-5,5'-di-tert-butylacetamide, 2-(2-hydroxyphenyl)-1,3,5-triazine, for example 2,4,6-Tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimetilfenil)-1,3,5-triazine, spatial-employed amines on the basis of tetramethylpiperidine and accordingly tetramethylpiperidine or tetramethylpiperidine, for example bis(2,2,6,6-tetramethylpiperidine-4-yl)sebacate, bis(2,2,6,6-tetramethylpiperidine-4-yl)succinate, as well as benzoxazinone, such as 1,4-bisbenzimidasoles.

Optical Brightener

Examples of such compounds are babinsa(1,4)oksazolov, fenalcomine and bacterivory, for example 4-methyl-7-diethylaminocoumarin, 3-phenyl-7-(4-methyl-6-butoxybenzoate)coumarin, 4,4'-bis(benzoxazol-2-yl)stilbene and 1,4-bis(benzoxazol-2-yl)naphthalene. The advantage of given solutions of optical brighteners in plasticizers such as DOP.

Antistatic agents

Antistatic agents are divided into classes: non-ionic (a), anionic (b), cationic (C) and amphoteric (d). Among (a) are ethoxylates of fatty acids, esters of fatty acids, ethoxylated fatty alkylamines followed, diethanolamine fatty acids and ethoxylated phenols and alcohols, as well as complex monetary fatty acids of polyglycols. Among (b) are fatty alkanesulfonyl alkali metals and salts of alkaline metal is low complex bis(fatty alcohol)esters of phosphoric acid. Among (with) are Quaternary salt (bold) alkylamine, and among (d) are (bold) alkylbetaine and (fatty) alkylimidazole. Typical preferred compounds are diethanolamide lauric acid, myristiciformis, octadecylsilane Na and biostatistical Na.

Biocides

Biocides which may be mentioned are: derived isothiazolin-3-one, such as 2-n-octyl-4-isothiazolin-3-one (OIT) and 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (DCOIT), Ag-Zn zeolite, N-trichloromethylthio-4-cyclohexene-1,2-dicarboximide, 2,3,5,6-tetrachloro-4-(methylsulphonyl)pyridine, 10,10'-exibitionism (OWRA), salts of Quaternary ammonium and phosphonium, 3-iodine-2-propynylbutylcarbamate (IPBC), methylbenzimidazole-2-carbamate, simple 2,4,4'-trichloro-2'-hydroxydiphenyl ether, N-oxide, bis-2-pyridinethiol zinc (zinc pyrithione) and 1,2-benzisothiazolin-3-one, N-butylbenzothiazole-3-one and 2-(4-thiazolyl)benzimidazole (thiabendazole).

Pigments

Pigments are another suitable integral part of the stabilizing system of the invention. Specialist in the field of engineering known suitable agents. Examples of inorganic pigments are TiO₂pigments based on zirconium oxide, BaSO₄zinc oxide (zinc white) and lithopone (zinc sulfide/barium sulfate), carbon black, a mixture of carbon-dioxide Titus is a, micaceous iron pigments, Sb₂O₃, (Ti, Ba, Sb)O₂, Cr₂O₃, spinels, such as cobalt blue and cobalt green, Cd(S, Se), ultramarine blue. Examples of organic pigments are azo pigments, phthalocyanine pigments, quinaqridone pigments, Pereladova pigments, diketopiperazine pigments and antrahinonovye pigments. Preference is given TiO₂also in micronized form. Designation and additional descriptions are given in “Handbook of PVC Formulating”, E.J. Wickson, John Wiley & Sons, New York, 1993.

Fillers

The fillers which may be mentioned are: calcium carbonate, dolomite, calcium sulfate, talc, kaolin, mica, feldspar, nepheline, syenite, wollastonite, barium sulfate, heavy spar (barite), aluminum hydroxide, magnesium hydroxide, carbon black and graphite.

Foaming agents

Examples of foaming agents are organic azo - and hydrazobenzene, tetrazole, oxazine, satinay anhydride, N-methylisatoic anhydride, as well as soda and sodium bicarbonate. Preference given to azodicarbonamide and bicarbonate, as well as their mixtures. Most particular preference is given satyavolu anhydride or N-metalization anhydride, particularly in flexible PVC or semi-rigid PVC.

Lubrication

The stabilizing system of the invention can also contain lubricants.

The stabilizing system of the invention may contain about 70% by weight, in particular up to approximately 40% by weight of the above residue.

Plasticizers

Organic plasticizers are also suitable additives for stabilizing system of the present invention. Examples of organic plasticizers that can be used are the plasticizers of the following groups:

(i) a compound of phthalic esters, and preferred examples are di-2-ethylhexyl, diisononyl and diisodecylphthalate, which is also known familiar abbreviations DOP (dioctylphthalate, di-2-ethylhexylphthalate), DINP (diisononylphthalate) and DIDP (diisodecylphthalate),

(ii) esters of aliphatic dicarboxylic acids, in particular esters of adipic, azelaic and sabatinovka acid, with preference given to di-2-ethylhexyladipate and diisooctylphthalate,

(iii) esters trimellitic acid, such as tri-2-ethylhexylacrylate, tristellateia (mix), christrebellion the ITAT, triisostearate (mix), and three With₆-C₈-alkyl, tri-C₆-C₁₀-alkyl, tri-C₇-C₉-alkyl and tri-C₉-C₁₁-alkyltrimethyl; known abbreviations are TOTM (trioctyltrimellitate, three 2-ethylhexylacrylate), TIDTM (tristellateia) and TITDTM (treasurerelect),

(iv) epoxy plasticizers; there are mainly epoxydecane unsaturated fatty acids, for example epoxydecane soybean oil,

(v) polymeric plasticizers: the most famous source materials for the production of plasticizers are dicarboxylic acids such as adipic, phthalic, azelaic and sabotinova acid, and diols, such as 1,2-propandiol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentylglycol and diethylene glycol (see ADMEX® grades from Velsicol Corp. and PX-811 from Asahi Denka),

(vi) esters of phosphoric acid: the description of such esters can be found on pages 408-412 Chapter 5.9.5 “TASCHENBUCH der Kunststoffadditive” [Plastics additives handbook]. Examples of such complex phosphate esters are tributyl phosphate, tri-2-ethylbutyrate, three 2-ethylhexanoate, trichlorethylene, 2-ethylhexylcarbonate, cresyldiphenyl, resorcinolphthalein, triphenyl, tricresylphosphate and trichilemmomas; preference is given to tri-2-ethylhexanoate and Reofos® 50 and 95 see Ciba Spezialitatenchemie),

(vii) chlorinated hydrocarbons (paraffins),

(viii) hydrocarbons,

(ix) a compound monetary, such as butylurea, Phenoxyethanol, tetrahydrofurfurylamine and complex alkylsulfonate ethers,

(x) a complex of glycolic esters, such as dipicolinate,

(xi) esters of citric acid, such as tributyltin and triboelectricity, as described in patent WO 02/05206,

(xii) complex perhydrofluorene, isophthalic and terephthalic esters, and targetirovannye glycol and dipicolinate; preference given targetirovannoy diisononylphthalate (Hexamoll® DINCH - manufacturer: BASF), as described in the patent DE 19756913 A1, DE 19927977 A1, DE 19927978 A1 and DE 19927979 A1,

(xiii) plasticizers based on castor oil (Soft-N-Safe®, manufacturer: DANISCO),

(xiv) ester cyanoethylene terpolymer: Elvaloy® KEE, (Elvaloy® 741, Elvaloy® 742, manufacturer: DuPont).

A description of these plasticizers and examples of plasticizers are given on pages 412-415 Chapter 5.9.6 “TASCHENBUCH der Kunststoffadditive” [Handbook of plastics additives], R. Gachter/H. Muller, Carl Hanser Verlag, 3^thedn., 1989, pages 165-170 “PVC Technology”, W.V. Titow, 4^thedn., Elsevier Publ., 1984. Example number, which can contain plasticizers, is about to 99.5% by weight, in particular approximately 30% by weight to approximately 20% by weight or up to about 10% by weight. For the purposes of one preferred the additional option of implementing the present invention, the lower limit for such plasticizers as integral parts of the stabilizing system of the invention is approximately 0.1% by weight or more, for example, about 0.5% by weight, 1% by weight, 2% by weight or 5% by mass.

Descriptions and examples of other additives such as impact resistance modifiers, and processing AIDS, gelling agents, biocides, metal deactivators, flame retardant tools, agents against turbidity, as well as agents for compatibility are described in “Handbook der Kunststoffadditive” [Plastics additives handbook], R. Gachter/H. Muller, Carl Hanser Verlag, 3^thedn., 1989, 4^thedn., 2001, and in “Handbook of Polyvinil Chloride Formulating” E.J. Wickson, J. Wiley & Sons, 1993, and in “Plastics Additives” G. Pritchard, Chapman & Hall, London, 1^stedn., 1998. More detailed description for impact modifiers found in “Impact Modifiers for PVC”, J.T. Lutz, L. Dunkelberger, John Wiley & Sons, 1992.

The invention further provides compositions that contain a chlorine-containing polymer and a stabilizing system of the invention.

Effective the following intervals concentrations for the use of components (A)+(B) in such compositions, in order to stabilize the chlorine-containing polymer:

per 100 parts by weight of halogenated polymer.

In addition, it is preferable that the used amount of the compounds of formula (a) is from 0.01 to 3.0 hours 100 hours of the polymer, preferably from 0.05 to 1.5 hours at 100 g polymer, and particularly preferably from 0.1 to 1.0 hours per 100 g polymer.

Intervals of concentrations that can be used to optionally present component (C), are:

per 100 parts by weight of halogenated polymer.

In addition, it is preferable that the used amount of the component (C) is from 0.01 to 10 hours per 100 g polymer, preferably, from 0.01 to 5.0 hours 100 hours of the polymer and, particularly preferably, from 0.01 to 2.0 hours at 100 h p is limera.

The composition of the invention may of course also contain additional compounds that are mentioned above as a component of the stabilizing system of the invention.

The present application therefore also provides a composition that contains at least one of the following compounds: magnesium hydroxide and alkaline earth metal soap, polyols or sugar alcohols, or trihydroxyethylrutoside (THEIC), esters of phosphorous acid, glycidaldehyde, epoxydecane esters of fatty acids, spatial-employed amines (HALS), antioxidants, UV absorbers and light stabilizers, optical brighteners, antistatic agents, biocides, pigments, fillers, foaming agents, lubricants, plasticizers, impact resistance modifiers and processing AIDS.

Examples of halogenated polymers for stabilization are chlorine-containing polymers, in particular, and most especially preferred polymers of vinyl chloride, as well as vinylidenechloride, 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 the compounds and unsaturated dicarboxylic acids or their anhydrides, for example, copolymers of vinyl chloride with diethylmaleate, diethylfumarate or maleic anhydride, post-chlorinated polymers and copolymers of vinyl chloride, copolymers of vinyl chloride and vinylidenechloride with unsaturated aldehydes and ketones, and other compounds, such as acrolein, CROTONALDEHYDE, vinylmation, simple vinylmations ether, simple minimizebutton ether, and the like; polymers of vinylidenechloride and their copolymers with vinyl chloride and with other curable compounds; polymers of vinylchloride and simple dichlorodiphenyl ether; chlorinated polymers of vinyl acetate, chlorinated polymeric esters of acrylic acid and alpha-substituted acrylic acid; polymers of chlorinated sterols, such as dichlorostyrene, chlorinated rubbers; chlorinated polymers of ethylene; polymers and post-chlorinated polymers of chloroprene and copolymers with vinyl chloride, chlorinated natural and synthetic rubbers, and mixtures of the aforementioned polymers within this group, or with other curable compounds. For the purposes of this invention the term PVC also includes copolymers of vinyl chloride with the polymerized compounds, such as Acrylonitrile or vinyl acetate or ABS, and substances there may be a suspension of the polymer, the polymer block p is liberizatsii or emulsion polymers.

Preference given to homopolymer PVC, also in combination with polyacrylates or polymethacrylates.

It is also possible to use graft polymers of PVC with EVA, ABS and MBS, as well as it is possible to use graft polymers of PVC with emission spectra obtained for pure. Other preferred substrates are mixtures of the abovementioned Homo - 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, in particular, from the group of ABS, NBR, NAR, SAN and EVA. Abbreviations related to the copolymers, well-known specialist in the field of machinery and their value is as follows: ABS: Acrylonitrile-butadiene-styrene; SAN: styrene-Acrylonitrile; NBR: Acrylonitrile-butadiene; NAR: Acrylonitrile-acrylate; EVA: ethylene-vinyl acetate. Special another substance that can be used is a copolymer of styrene-Acrylonitrile-based acrylate (ASA). The preferred component in this regard presents a polymeric compositions which include as components (i) and (ii)a mixture of from 25 to 75% by weight of PVC and from 75 to 25% by weight of the above-mentioned copolymers. A particularly important component presents compositions derived from (i) 100 parts by weight of PVC and (ii) from 0 to 300 parts by weight of ABS and/or SAN-modified ABS and 0 to 80 parts by weight of apolima is offering NBR, NAR and/or EVA, but especially EVA.

Chlorine-containing polymers used for stabilization, for the purposes of this invention can in particular contain polymers processing for recycling, and they are polymers described above in more detail, which decompose during processing, use or storage. PVC processing for the secondary use of particularly preferred. Another application of the stabilizing combinations of the invention consists in the ability to provide antistatic properties of the target object is made of a rigid or flexible PVC. Therefore, it is possible to reduce the use of expensive anti-static agents. For this application, preference is given to flexible PVC or semi-solid PVC.

The invention further provides products, such as consumer goods, which include the composition of the invention.

Preference is also given to the use of consumer products, which are characterized by particularly fine foam structure. This applies to rigid, flexible and semi-rigid PVC. This aspect is particularly important in the panel partitions and floor coverings made from flexible PVC. To achieve fine foam typically required "pushers", which are compounds of heavy m is the metal, for example Zn stabilizers or Sn stabilizers. Suddenly discovered that the internal complexes TEAP exert a pushing action on satinay anhydride or N-methylsalicylate anhydride, ensuring the achievement of fine foam structure.

There are some surprising properties of the electrical resistance of materials of national consumption, which contain internal complexes Thea formula (I) as a component, are significantly improved, and this is confirmed by a special advantage in the manufacture of cables and insulators, and in applications in the field of semiconductors.

Such objects (mainly cables), in addition, have an excellent property of stability under the action of water, because the compositions do not contain zinc soap and therefore, when processing not produce a chloride of zinc, which, after migration to the surface of the plastic degrades electrical properties.

It is also possible that the zinc-containing fungicides add when sensitive to zinc application area have an urgent need for a biocidal properties, mainly in part of flexible PVC (examples of the existence of foil and protective coatings for roofs), and there are strict limitations on the use of calcium-zinc stabilizers.

Compounds that can be used in conjunction, and t is the train of chlorine-containing polymers are well known to the expert in the field of technology and is described in detail in "HANDBUCH DER KUNSTSTOFFADDITIVE" [Plastics additives handbook], R. Gachter/H. Muller, Carl Hanser Verlag, 3^rdedn., 1989 and 4^thedn. 2001, DE 19741778 A1 and EP 0967245 A1, and such publication entered here by reference.

The stabilizing system of the invention is suitable not only for chlorine-containing polymer compositions, which are unplasticized or not containing a plasticizer or essentially does not contain plasticizer composition, but also for plasticized compositions. Particular preference is given to applications in rigid PVC or semi-rigid PVC.

Compositions of the invention are particularly suitable in the form of rigid formulations for hollow bodies (bottles), foil, including packaging foil (foil molded sheet thermoplastic), foil obtained by foaming, foil "airbag" (cars) and foil in the office sector, pipes, foams, profiles, including profiles for heavy duty (window frames), the profiles of luminous walls and structural profiles, bubble transparent packaging (including packaging, obtained by the method Luvitherm), siding, fittings, tubes for margarine, packaging for chocolates and casings for devices for buildings computer, insulators and integral part of home equipment, and they are also suitable for applications in electronics, particularly in parts of semiconductors. They are also more especially under Odesa for the production of window profiles with intense whiteness and luster of surface.

There are other preferred compositions in the form of semi-solid or elastic composition for shell wire, cable insulation, decorative foil, foil roofing materials, foams, foils for agriculture, hoses, profiles, gaskets, materials, floor coverings, wall coverings, auto parts, elastic foil, molding (injection molding with foaming), foil for office sectors and foil designs for aviation support stands. Examples of the application of the compositions of the invention as plastisols are products for children (rotary pressing), synthetic leather, floor coverings, textile coatings, coating materials for walls, use to cover the coil (coil) and remedies of the bottom of the body of the car, and examples of applications of the compositions of the invention for the sintered PVC are grease, viscous mass to form and application of coatings spirals, as well as in EPVC, to foil produced by the method Luvitherm. More details in this regard see “KUNSTSTOFFHANDBUCH PVC“ [Plastics handbook: PVC], volume 2/2, W. Becker/H. Braun, 2^thedn. 1985, Carl Hanser Verlag, pp. 1236-1277.

The present invention further proposes the use of a stabilizing system of the invention for the stabilization of halogen-containing polymer, and the use of a composition of the invention to obtain a product which ia of the invention.

Examples

Molchanie rolled sheet material

Each of the obtained mixtures in table 1.2 (a-2, b-2), 2.1 (S-2, D-2), 3.1 (E-2, F-2) and 4.1 (G-2, H-2, J-2, K-2), 5.1 (L-2, M-2) and 6.1 (N-2, O-2, P-2, R-2) plastificator at a given temperature for 5 minutes to test the system Collin laboratory-roll-mill (COLLIN: W100E, BJ: 2005) (roller diameter: 110 mm, 10 rpm, friction: -10%). The obtained foil (thickness 0.3 mm) transmit next for the next test.

II. The method of testing dehydrochlorination (DHC)

DHC measured in the allocation of HCl from PVC when it is heated. Distilled water with nitrogen gas used for flushing released hydrochloric acid in the collector, where they measure the conductivity increases in microsiemens per centimeter (µs/cm). Applied indexes represent a combined value in minutes [min], which are summarized in table. The longer the time required to achieve a certain conductivity, the greater thermal stability of the PVC sample.

Equipment: PVC Thermomat 763 (Metrohm)

Tests performed in accordance with DIN 53381, part 1, method: conductivity measurements.

Parameter:

Sample mass: 500±0.5 mg (destructible rolled sheet)

Temperature: °C (as specified in the examples)

Flow: 7 l/h (nitrogen 5,0)

Absorption volume: 60 ml (deionized water)

Rating: t₁ , t₅₀and t₂₀₀(conductivity of 10, 50 and 200 µs/cm data in numerical value, minutes)

III. Method static heat test (SHT)

Test strips (15×15 mm) were cut from the rolled sheet obtained in I. was Heated at a given temperature in the oven Heraeus tray up until no significant discoloration. Then determined YI (yellowness index) in accordance with DIN 53381, using measuring equipment Spectro-Guide color (BYK-GARDNER), and this was compared with YI unheated rolled sheet (zero minutes). The results were brought to the table. The smaller the YI at the moment, the better the characteristic (indicator) staining.

IV. Time-consuming method of testing roller car (SRT)

Dynamic thermal testing was performed on roller (SRT) machine COLLIN W110E (roller diameter: 110 mm, 10 rpm, friction: -10%).

The mixture homogenized for 5 minutes at a given temperature on a roller machine. Then the processing roller machine continued at this temperature, and test samples (t=0.3 mm, 25×38 mm) was taken out at intervals of 5 minutes, and the yellowness (YI) was determined in accordance with ASTM D1925 using equipment for measuring color BYK GARDNER (Spectro Guide Sphere Gloss).

Example 1(Elastic PVCpainted foil)

Mixture a-1 and b-1 homogenized in the GT universe is flax mixer (ROTH, Karlsruhe) (table 1.1)

A mixture of a-1 is a mixture of the invention. The mixture In-1 corresponds to the prior art. 2.2 g of each of the above mixtures are used for the following compounds (table 1.2).

Set values in table 1.3 was measured on the cut rolled sheet obtained from compositions a-2 and b-2.

The higher the value, in minutes, the better the effect.

The establishment of the NT was performed on the test strips obtained with composition a-2 and b-2 (table 1.4).

The smaller the YI and the higher the value, in minutes, the better the index.

When used identical mass stabilizing mixtures, found a clear and significant improvement in the result of dehydrocorydaline and the static heat test, not only in terms of thermal stability values (10, 50 and 200 µs/cm), but also in respect of the initial coloring - IC (0 to 20 min) and color-strength - CF (from 40 to 80 min) and long-term stability - LTS (100 to 120 min) to a-2 (containing SAENS) in comparison with the prior art for In-2 (containing hydrotalcite).

Example 2(elastic PVC, industrial foil)

We have received the following dry powder mixture (table 2.1).

Composition C-2 represents the composition of the invention. Composition D-2 corresponds to the prior art. The following values DHC was measured on the resulting compositions C-2 and D-2 (table 2.2).

The results dehydrochlorinating show that when using an identical weight of the stabilizing components of the indicator composition containing SAENS (2), certainly better than the indicator composition containing hydrotalcite (D-2).

The test strips obtained with compositions C-2 and D-2 were tested in terms of color (table 2.3).

As you can see the C table 2.3, values DHC composition C-2, containing SANZ, indicate the best color profile than the values for composition D-2 containing hydrotalcite, static heat test.

Example 3(hard PVCtransparent foil)

Received the following mixed substances E-2 and F-2 (table 3.1).

The composition of the E-2 represents the composition of the invention. Composition F-2 corresponds to the prior art. Formulations F-2 and F-2 can be characterized by the following values DHC (table 3.2).

These dehydrochlorinating undoubtedly shows that when the applied amount of the stabilizing components are identical, the indicator composition E-2 containing SANZ, significantly better than the composition F-2 containing hydrotalcite.

The test strips obtained with the composition of the E-2 and F-2 were subjected SHT (table 3.3).

Static heat test similar to confidently shows that E-2 is superior to F-2.

Example 4(hard PVCthe composition profile)

Received the following dry powder mixture (table 4.1).

The composition G-2 represents the composition of the invention. The compositions of N-2 and, accordingly, the J-2 and K-2 corresponds published and therefore unpublished prior art.

The obtained rolled sheet of composition G-2, H-2, J-2 and K-2 were described as follows by its values DHC (table 4.2).

G-2 represents the composition of the invention. H-2, J-2 and C-2 represent prior art. N-2 is a Ca/Zn-stabilized composition obtained commercially (single package I) and used in the recommended instruction concentration of 3.6 hours per 100 g polymer. Single packing II is the same as a single package I, except that instead of Alkamizer P93 used identical content by weight SANZ.

The results dehydrochlorinating demonstrate that the G-2 (SANZ in the composition, not containing heavy metal) exceeds a commercial product N-2 containing heavy metal, with a noticeable reduction of the applied amount (3,31 compared with 3.6 hours per 100 g polymer).

Similar discussions were applied to the structures J-2 and K-2, which include the SENS in combination with calcium and zinc Soaps containing heavy metal, and which are optimized further adding dipentaerythritol, dihydropyridines and laurate zinc. On the other hand, in this comparison used the increased total concentrations (4.1 and 4,65 hours 100 hours of the polymer in comparison with 3,31 hours at 100 g polymer).

The results of testing compounds G-2, H-2, J-2 and K-2 in long-term test on the mA roller is ine were as follows below (table 4.3).

Here again the comparison of the G-2 c H-2 in the composition window profile using approximately the same mass (3,31 compared with 3.6 hours per 100 g polymer) shows that G-2 is the best in relation to IC, CF and LTS (i.e. in the transverse direction is taken as a whole painted profile).

Example 5(hard PVCthe composition of the foil)

We have received the following dry powder mixture (dry mixture) (table 5.1).

The composition of the L-2 is a composition of the invention, and the composition M-2 corresponds to the prior art. Both composition containing DHP to improve IC, and therefore they can be compared directly with example 3, which contains DMAU to improve IC.

Values DHC compositions are the following (table is CA 5.2).

These data provide a very good indication of the superiority of L-2 on M-2.

SRT on the composition of L-2 and M-2 gives the following result (table 5.3).

The values suggest that the composition L-2 of the invention are considerably superior to the composition M-2, corresponding to the prior art, and not only in relation to IC, CF and LTS: unexpected result in SRT is a strong decrease in M-2 in comparison with example 3, which specifies the action Sorbacid 911 (F-2) in SHT.

Example 6: (elastic PVCcable structure)

We have received the following dry mixture (table 6.1).