FR2623514A1 - STABILIZED COMPOSITIONS BASED ON HALOGEN POLYMERS - Google Patents

Abstract

The invention relates to stabilized compositions based on halogenated polymers. They contain: a) 100 parts of a chlorinated thermoplastic, b) from 0.7 to 2 parts of thio-diethylene glycol bis-acetylacetate, body which corresponds to the formula: (H3 CCOCH2 -COOCH2 CH2) 2 S c) from 0 to 0.5 part of at least one Ca, Ba and / or Mg salt of a C8 -C2 4 aliphatic monocarboxylic or hydroxy-monocarboxylic acid or of benzoque acid or of a tert-butyl-benzoque acid, d) from 0.01 to 0.2 part of at least one Zn salt of a C8 -C2 4 aliphatic monocarboxylic or hydroxy-monocarboxylic acid or of benzoque acid or of a tert-butyl-benzoque acid, e) from 3 to 10 parts of epoxidized unsaturated fatty acid esters, and f) from 10 to 70 parts of at least one organic plasticizer. These compositions can be used in particular for the manufacture of sheets based on poly (vinyl chloride) intended for packaging of food products.

Description

The present invention relates to composi-

  stabilized compositions based on chlorinated thermoplastic

  compositions that contain an organic plasticizer

  and, as stabilizers, thio-diethylene acetylacetate

  glycol, epoxidized unsaturated fatty acid esters, zinc carboxylate

  and, optionally, a calcium, barium and / or magnesium carboxylate.

  By US Pat. No. 4,327,000 blends are known

  stabilizers consisting of P-keto carboxylic acid esters

  than diols or polyols with a thioether structure and

  stabilizers containing metals, such as carbons,

  xylates of Ca or Zn. These mixtures have a good

  Stabilizing compound in chloroplast thermoplastics

  such as in the PCV or in polymers containing

  from the PCV. The cited document indicates, among other things,

  Examples of β-keto carboxylic acid esters are

  acetylacetate of thio-diethylene glycol. Despite their

  The stabilizers described in US Pat. No. 4,327,000 have not been marketed so far because their action is really not sufficient to make them important in practice. In particular, the polymers which have been stabilized with these compounds yellow a little too strongly, especially when they are subjected to a heat stress of rather long duration. In

  in addition to the transparency of articles made with poly-

  stabilized mothers leaves something to be desired. These findings are also valid for the two stabilizing mixtures

2623 5 1 4

  described in detail in Application Examples A and B of US Pat. No. 4,327,000, especially with respect to initial color and color retention. Also known from JP A-54-11948 are analogous compositions which additionally contain free aromatic carboxylic acids. None of the two publications cited describe

  stabilized PCV compositions containing a plasma

  fying. They therefore only indicate the stabilization of the hard VCP, which differs fundamentally

  morphology, PCV containing a plasticizer.

  That being so, the present inventors have found that the properties of stabilizing mixtures containing constituents described in US Pat. No. 4,327,000 can be improved to the point of making these mixtures usable.

  industrially and make them particularly appro-

  for the stabilization of chlorinated thermoplastics containing plasticisers. This improvement can be achieved in a surprising way, namely in

  associating a well-defined P-keto-carboxylic acid ester

  with primary stabilizers consisting of a

  Zn boxylate and, optionally, carboxylates of Ca, Ba and / or Mg, in concentrations and in ratios,

  in the mixture, well determined.

  The subject of the present invention is

  stabilized polymer-based positions which contain: (a) 100 parts of a chlorinated thermoplastic material,

  b) from 0.7 to 2 parts of thio-diethyl bis-acetylacetate

  ethylene glycol, a body that responds to the formula

(H3CCOCH2COOCH2CH2) 2S,

  c) from 0 to 0.5 parts of at least one salt of Ca, Ba and / or

  of Mg of a monocarboxylic acid or hydroxy-monocarboxylic acid

  C8-C24 aliphatic xyl or benzoic acid or tertbutyl-benzoic acid, d) 0.01 to 0.2 parts of at least one Zn salt of an aliphatic monocarboxylic or hydroxy-monocarboxylic acid C8-C24 or benzoic acid or tert-butyl-benzoic acid, e) 3 to 10 parts of epoxidized unsaturated fatty acid esters and f) 10 to 70 parts of at least one organic plasticizer.

  Thio-diethylene glycol bis-acetylacetate

  col (component b) is contained in an amount which is preferably between 0.7 and 1.5, more particularly between 0.8 and 1.3 parts or, more preferably, which is equal to

about 1 part.

  Component c) is present in a quantity

  preferably between 0 and 0.4 parts, for example between 0 and 0.35 parts. It is good that there is

  componentc) in the compositions according to the invention.

  tion (concentration greater than 0). Component c) is then present in an amount which is for example between 0.001 and 0.5 parts, preferably between 0.01 and 0.5, more particularly between 0.05 and 0.4 or, better still, between 0.1 and 0.35 parts. We also get very

  good results with amounts from 0.05 to 0.15 part.

  Component c) is a salt of Ca, Ba or Mg or a mixture of such salts, preferably a salt of

  Ca or Mg, more particularly Ca, of a monohydric acid

  carboxylic acid or aliphatic hydroxy-monocarboxylic

  C8-C24 or benzoic acid or tert-butyl-

benzoic.

  Monocarboxylic and hydroxy-carboxylic acids

  aliphatic boxylics are saturated or unsaturated and they

  contain in particular from 8 to 22 carbon atoms.

  Hydroxycarboxylic acids are primarily acids

  hydroxy-stearic acids, such as 12-hydroxy stearic acid.

  Of the monocarboxylic acids, 2-ethyl hexanoic acid, neodecanoic acid, lauric acid, stearic acid and behenic acid are highly preferred. As component c), the "octoate" (that is to say, ethyl-2 hexanoate), the laurate, the stearate or the behenate of Ca, Ba and / or Mg are particularly preferred, preferably Ca and / or Mg. It goes without saying that we can also use

  mixtures of salts of different acids.

  Component d) is preferably contained in an amount of 0.05 to 0.2 parts, more preferably 0.1 to 0.2 parts. It is formed by the Zn salt of an aliphatic monocarboxylic or hydroxy-carboxylic acid in

  C8-C24 or benzoic acid or tert-butyl-

  benzoic. Monocarboxylic and hydroxycarboxylic acids

  aliphatic xylics are saturated or unsaturated and they

  contain in particular from 8 to 22 carbon atoms.

  The hydroxy carboxylic acids are primarily acids

  hydroxy-stearic acids, such as 12-hydroxy stearic acid.

  Among the monocarboxylic acids we like a lot

  2-ethyl hexanoic acid, lauric acid, stearic acid,

  arique and behenic acid. As components d), Zn octoate (or ethyl-2 hexanoate), Zn basic octoate, and Zn stearate, neodecanoate, laurate, behenate and benzoate are preferred, more particularly the octoate of Zn. Zn, the basic Zn octoate, the Zn neodecanoate, the

  Zn stearate and Zn benzoate. I1 is then particu-

  interesting to use Zn stearate in one

  amount of about 0.2 part, the Zn octoate in a quantity

  about 0.1 part and the basic Zn octoate in

  an amount of about 0.05 part.

  Component e) is in particular

  in a quantity of 4 to 7 parts, especially about 5 parts

  ties. It is preferably epoxidized soybean oil.

  The compositions according to the invention contain the component f) in an amount which is preferably between 15 and 70 parts, for example

  between 15 and 60 or, more particularly, between 20 and 50.

  The epoxidized fatty acid esters (component e) are

  also ranked in the category of plasticizers.

  But here, beware, these esters are not part of the set of plasticizers covered by the definition of the -component

  f). Components e) and f) are therefore different.

  Examples of organic plasticizers that may be used are those in the following groups: A) Phthalates (phthalic acid esters) Examples: dimethyl, diethyl, dibutyl, dihexyl, bis (2-ethylhexyl) phthalates ), di-n-octyl,

  diisooctyl, diiso-nonyl, di-iso-decyl, di--

  iso-dodecyl, dicyclohexyl, bis- (methylcyclohexyl), dimethylglycol, dibutylglycol, benzyl and

  butyl, and diphenyl, as well as phthalate mixtures.

  eg C 7 -C 9 and C 9 -C 14 alkyl phthalates mainly derived from linear alcohols, phthalates

  C6-C10 n-alkyls and C8-C10 n-alkyl phthalates.

  Among the esters cited phthalates are highly appreciated

  of dibutyl, dihexyl, bis (2-ethylhexyl), di-

  n-octyl, di-isooctyl, di-isononyl, diiso-

  and di-isotridecyl and benzyl phthalate and

  butyl, as well as the mentioned mixtures of phthalates from

  kyles. We particularly appreciate phthalate

bis- (2-ethylhexyl), or "DOP".

  B) Esters of aliphatic dicarboxylic acids, more specific

  esters of adipic acid, azelaic acid and sebacic acid

  Examples of plasticizers of this kind: bis (bis) adipate

  (2-ethylhexyl), di-isooctyl adipate (mixture),

  diisononyl adipate (mixture), diisopropyl adipate

  decylate (mixture), benzyl butyl adipate,

  benzyl and octyl paste, bis (2-ethylhexyl) azelate, bis (2-ethylhexyl) sebacate and

  di-isodecyl (mixture). Biphalic adipate is preferred.

  (2-ethylhexyl) and di-isooctyl adipate.

C) Esters of trimellitic acid

  Examples: tris (2-ethylhexyl) trimellitate, trimell-

  trisodecyl nitrate (mixture), tri-isotridecyl trimellitate, tri-isooctyl trimellitate (mixture) and trimellitates of tri (C 6 -C 8 alkyl), tri (C 6 -C 10) alkyls, tri- (C 7 -C 9 alkyl) and tri (C 9 -C 18 alkyl) groups. The last-mentioned trimellitates are formed by esterification of trimellitic acid with the corresponding alkanol mixtures. The trimellitate of

  bis (2-ethylhexyl) and the trimellitates mentioned which

  Many alkanol mixtures are the preferred trimellitates. D) Polyesters (Polymeric Plasticizers) A definition and examples of these plasticizers are given in "Plastics Additives Handbook", EditorsH. Gachter and H. Mler, Hanser Publishers, 1985, page 284, chapter 5.7.10, as well as in "PVC Technology", editor W.V. Titow, 4th edition, Elsevier Publ., 1984, pp. 165-170. The most common starting materials for the preparation of plasticizer polyesters are: dicarboxylic acids, such as adipic acid, phthalic acid, acid azelaic acid and sebacic acid; diols, such as 1,2-propanediol, 1,1,1-butanediol, 1,4-butanediol, 1,6-hexane-1,6-diol, neopentylglycol and diethylene glycol; glycol; monocarboxylic acids, such as acetic acid, hexanoic acid, octanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, nonanoic acid and benzoic acid ; monoalcohols, such as iso-octanol, 2-ethyl hexanol, isodecanol and mixtures of C 7 -C 9 alkanols and C 9 -C 13 alkanols. I1 is particularly

  advantage of using plasticizing polyesters which

  dicarboxylic acids and monohydric alcohols

  tioned. E) Esters of phosphoric acid A definition of these esters can be found in the book "Plastics Additives Handbook" mentioned above, page 271, chapter 5.7.2. Such phosphoric esters include, for example, tributyl phosphate, tris (2-ethylbutyl) phosphate, tris (2-ethylhexyl) phosphate, tris (chloroethyl) phosphate,

  (2-ethylhexyl) and diphenyl phosphate, phos-

  phaesyl and diphenyl phosphate, triphenylphosphate

  nyle, tricresyl phosphate and triphosphate

  xylenyl. Tris (2-ethylhexyl) phosphate is preferred.

  F) Hydrocarbons (paraffins) chlorinated G) Hydrocarbons H) Monoesters, eg butyl oleate, phenoxyethyl oleate, tetrahydrofurfuryl oleate and esters

alkanesulphonic acids.

  I) Glycol esters, for example diglycol benzoates.

  Definitions and examples

  of plasticisers of groups F) to I) in the following

  : "Plastics Additives Handbook", editors H. Gachter and H. Mueller, Hanser Publishers, 1985, page 284, chapter 5.7.11

  (group F)>, and chapter 5.7.13 (group G)).

  "PVC Technology", editor W.V. Titow, 4th edition, Else-

  see Publishers, 1984, pages 171-173, chapter 6.10.2 (group F)), page 174, chapter 6.10.5 (group G)), page 173, chapter 6.10.3 (group H)) and pages 173-174 chapter

6.10.4 (group I)).

  The plasticizers of groups A to E, more particularly groups A) to C), and especially the plasticizers which have been presented as preferred in these groups, are highly preferred. Bis (ethyl hexyl) phthalate, or "DOP", is particularly interesting.

  Chlorinated thermoplastic polymers (

  a) stabilized according to the invention are in particular

  bond homopolymers of vinyl chloride (PCV), copolymers of vinyl chloride with unsaturated comonomers (PCV copolymers), mixtures of the polymers mentioned together or mixtures of the polymers mentioned with

  other homopolymers or copolymers.

  Among the homopolymers and copolymers of vinyl chloride, mention should be made in particular of those prepared by suspension polymerization

  or in bulk as well as those that have been prepared by poly-

  emulsion merification. As comonomers for the copo-

  for example, vinyl acetate can be

  vinylidene chloride, trans-dichloroethylene,

  ethylene, propylene, butene, maleic acid, acrylic acid, fumaric acid and itaconic acid. As

  other suitable chlorinated polymers are the post-consumer PCV

  chlorinated polyolefins and also copoly-

  grafted PCV mothers with ABS, EVA and MBS. As

  In particular, those which are

  homopolymers or copolymers of PCV and ABS,

NBR, NAR, SAN and EVA.

  The compositions according to the invention may further contain conventional stabilizers for chlorinated thermoplastics. That's how they

  contain, for example, from 0 to 3 parts, more particularly

  0 to 1.5, or more preferably 0 to 1 part, of one or more phosphites. These phosphites may be contained approximately in an amount of from 0.01 to 3 parts, more particularly from 0.01 to 1.5, for example from 0.01 to 1, preferably from 0.1 to 0.6, for example of

  0.2 to 0.5 parts. Phosphites of this kind are notably

  those which answer the formulas: R20 --- and R '- P - \ - R2 R3 O /

1 2 3

  in which R, R and R each represent independently

  c6-C18alkyl, an alkenyl

  C6-C18, a substituted or unsubstituted phenyl or a cyclohexyl

C5-C7 alkyl.

  As C6-C18 alkyl, 2 or R is, for example, an n-hexyl, n-octyl or n-nonyl radical,

  decyl, dodecyl, tetradecyl, hexadecyl or octadecyl.

  Alkyls containing 8 to 18 carbon atoms are preferred. As substituted phenyl, R, R2 or R is, for example, tolyl, ethylphenyl, xylyl, cumyl, cymyl, cresyl, 4-methoxyphenyl, 2,4-dimethoxyphenyl, ethoxyphenyl, butoxyphenyl, n-octyl-4 phenyl,

  n-nonyl-4-phenyl or n-dodecyl-4-phenyl.

  Particularly suitable phosphites are the phosphites of trioctyl, tridecyl,

  tridodecyl, tri-tetradecyl, tri-stearyl, tri-tetradecyl

  oleyl, triphenyl, tricresyl, tris (nonyl-4-phenyl)

  nyl) and tricyclohexyl; we really like the phos-

  aryl and dialkyl phites as well as alkyl and diaryl phosphites, such as phenyl and didecyl phosphite, (2,4-di-tert-butyl-2,4-phenyl) phosphite and di-dodecyl phosphite, and phosphite of 2,6-ditert-butyl

  phenyl) and didodecyl, as well as dialkyl and diaryl-

  pentaerythrol-diphosphites, such as bis (stearyloxy) -3.9

  tetraoxa-2,4,8,10 diphospha-3,9 spiroZ5,57undecane.

  The preferred organic phosphites are bis (stearyloxy) -3,9-tetraoxa-2,4,8,10-diphospha-3,9-spiro-5,7 -undecane, tris (nonylphenyl) phosphite, and

  Phenyl and didecyl phosphite.

  In addition, there may be

  according to the invention, other co-stabilizers

  naked, for example in an amount of 0 to 2 parts, more

  especially 0 to 1.5 parts. It is then preferable that they are present in an amount of from 0.01 to 2 parts, more preferably from 0.05 to 1.5, for example from 0.1 to 1, and especially from 0.1 to 0.5 parts. . These costabilizers are

  including amino-crotonic esters, dehydro-

  dioxo-1,3 compounds, 2,4-dihydroxybenzophenyl

  none, 2,4-dihydroxy-tert-butyl-4'-benzophenone and

  derivatives of pyrrole, the latter being those which one prefers.

  As amino-crotonic esters it is possible

  especially those derived from mono-alcohols

  C8-C20, especially C12-C18, and / or butane-1,3-diol or 1,4-diol and / or 1,2-dipropylene glycol

and / or thio-diethylene glycol.

  The dioxo-1,3 compounds which can be used as co-stabilizers are, in particular, those described in DE B 2,600,516 and EP A 35,268, for example those corresponding to the formula given in the DE B 2,600 claim. 516. Preferred dioxo-1,3 compounds are (benzoyl) (stearoyl) methane, alkyl esters (eg

  example the ethyl ester) of benzoyl-2 acetylacetic acid

tick and triacyl-methanes.

  As the co-stabilizers deriving from pyrrole, particular mention should be made of those described in EP A 22 087 and in GB A 2,078,761, in particular those which correspond to the formula I indicated in these documents, preferably derivatives. pyrrole

  which are defined in claims 2 to 9 of EP A

  For example, 2-methylcyclohexyloxy-

3-carbonyl-4-phenyl-1H-pyrrole.

  In addition to or instead of the optional co-stabilizers mentioned above the compositions in accordance

  to the invention may contain other optional constituents

  particularly organotin stabilizers, such as

  that butylthio-stannonic acid, mono- (n-octyl) -tin

  iso-octyl tris (thioglycolate), di-n-octyltin-bis-

  (isooctyl thioglycolate), dibutyltin sulfide,

  dibutyltin thioglycolate or monohydrogen sulfide

  tyl-tin, as well as mono- (methyl) -tin-tris- (thiogly-

  alkyl colates), mono- (n-butyl) -tin-tris- (thiogly-

  alkyl colates), mono- (n-butoxycarbonyl-ethyl) -tin

  tris- (thioglycolates of alkyls), dimethyltin-bis-

  (thioglycolates of alkyls), di-n-butyl-tin-bis- (thio-

  alkyl glycolates), bis (n-butoxycarbonyl-ethyl) -

  tin-bis- (alkyl thioglycolates), mono-methyl-tin-

  tris- (thiopropionates of alkyls), mono- (n-butoxycarbonyl)

  nyl-ethyl) -tin-tris- (thiopropionates of alkyls),

  dimethyltin-bis- (thiopropionates of alkyls), di-n-

  butyl-tin-bis- (thiopropionates of alkyls), bis- (n-

  butoxycarbonyl-ethyl) -tin-bis- (thiopropionates of alkyls), in which the alkyl is for example a 2-ethylhexyl, dodecyl, tridecyl or tetradecyl radical, and also organotin carboxylates, more particularly maleates or maleic half-esters, or mixtures of the organotin stabilizers mentioned above, or organic compounds of antimony, such as

  antimony-tris- (isooctyl thioglycolate) (by "iso-

  octyl is understood to mean the 2-ethyl hexyl radical).

  The compositions in accordance with the invention may also contain conventional antioxidants, such as those of the following list: 1.1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tertbutyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tertbutyl 4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (2-methylcyclohexyl) -6,6-dimethylphenol, 2-dioctadecyl , 6-methyl-4-phenol, 2,4,6-tricyclohexylphenol and

  2,6-di-tert-butyl-4-methoxymethylphenol.

  1.2. Alkylated hydroxyquinones, for example 2,6-di-tert-butyl-4-methoxyphenol, di-tert-butyl-2,5-hydroquinone, di-tert-pentyl-2,5-hydroquinone and

  2,6-diphenyl-4-octadecyloxyphenol.

  1.3. Hydroxylated diphenyl sulphides, for example thio-2,2 'bis- (6-tertbutyl-4-methylphenol), thio-2,2'-bis (4-octylphenol), thio-4,4'bis (tert- butyl 6-methyl-3-phenol) and

  thio-4,4'-bis- (tert-butyl-6-methyl-2-phenol).

  1.4. Alkylidene-bis-phenols, for example: methylene-2,2'bis- (tert-butyl-4-methylphenol), methylene-2,2'bis- (tert-butyl-6-ethyl-4-phenol), methylene-2 2 'Bis [methyl-4 (i-methylcyclohexyl) -6-phenol; methylene-2,2' bis- (4-methyl-6-cyclohexyl) phenol) methylene-2,2 'bis- (nonyl-6-methyl) phenol), 2,2'-methylenbis (4,6-di-tert-butyl) phenol, 2,2'-ethylidene bis (4,6-di-tert-butyl) phenol, 2,2-ethylidene bis (6-tert-butyl-4-isobutyl) phenol, methylene-2,2'-bis [(d-methylbenzyl) -6-nonyl-4-phenol], methylene-2,2'-bis (t, 6-dimethylbenzyl) ) -6-nonyl-4-phenol-2, 4,4'-methylenbis (2,6-di-tert-butyl) -phenol), 4,4'-methylenbis (6-tertbutyl-2-methylphenol), bis- ( tert-butyl-5-hydroxy-2-methyl-2-phenyl) -1,1-butane, bis (3-tert-butyl-5-methyl-2-hydroxy-benzyl) -2,6-methyl-4-phenol, tris- (tert-butyl) 5-hydroxy-4-methyl-2-phenyl) -1,3-butane,

  bis- (tert-butyl-5-hydroxy-2-methyl-phenyl) -1,1-n-dodecyl-

  3-thio-butane, bis-bis- (tert-butyl-3-hydroxy-4-phenyl) -3,3-butyrate] ethylene glycol,

  bis- (tert-butyl-3-hydroxy-4-methyl-5-phenyl) -dicyclopenta

  diene and bis (tert-butyl-3-hydroxy-2-methyl-5-benbenzyl) terephthalate

  zyl) -2 tert-butyl-6-methyl-4-phenyl7.

  1.5. Benzyl compounds, for example:

  tris (di-tert-butyl-3,5-hydroxy-4-benzyl) -1,3,5-trimethyl-

  2,4,6 benzene, bis (3,5-di-tert-butyl-4-hydroxy-4-benzyl) sulfide, (iso-octyl 3-tert-butyl-4-hydroxy-benzylthio) -acetate,

  bis (tert-butyl-4-hydroxy-3-dimethyl) dithiol terephthalate

  2,6 benzyl), tris- (3,5-di-tert-butyl-4-hydroxy-4-benzyl) isocyanurate, tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate,

  dioctyl di (tert-butyl-3,5-hydroxy-4-benzyl) phosphonate

decyle, and

  calcium salt mono-ethyl ester of (di-tert-butyl-

3,5-hydroxy-4-benzyl) -phosphonic.

  1.6. Acylaminophenols, for example: lauroylamino-4-phenol, stearoylamino-phenol, bis-octylthio-2,4-di (tert-butyl-3,5-hydroxy-4-anilino) -6-triazine-1, 3,5 and

  N- (octyl-tert-butyl-3-hydroxy-4-phenyl) -carbamate.

  1.7. Esters of 3,5-di-tert-butyl-3-hydroxy-4-phenylpropionic acid which are derived from monoalcohols or polyols,

these alcohols being for example:

  methanol, octadecanol, hexane-1,6-diol, neopentyl-

  glycol, thio-diethylene glycol, diethylene glycol,

  triethylene glycol, pentaerythrol, trisocyanate isocyanurate

  (hydroxyethyl) and N, N'-bis (hydroxyethyl) oxalamide.

  1.8. Esters of 5-tert-butyl-4-hydroxy-3-methylphenylpropionic acid which are derived from monoalcohols or polyols, these alcohols being for example:

  methanol, octadecanol, hexane-1,6-diol, neopen-

  tyl-glycol, thio-diethylene glycol, diethylene glycol, triethylene glycol, pentaerythrol, isocyanurate,

  tris (hydroxyethyl) and N, N'-bis (hydroxyethyl) oxalamide.

  1.9. Amides of 3- (3-di-tert-butyl-3-hydroxy-phenyl) propionic acid, for example:

  N, N'-bis (3,5-di-tert-butyl-4-hydroxy-4-phenylpropionyl)

hexamethylenediamine,

* N, N '-bis- (di-tert-butyl-3,5-hydroxy-4-phenylpropionyl) -

trimethylenediamine and

  N, N '-bis- (di-tert-butyl-3,5-hydroxy-4-phenylpropionyl) -

hydrazine.

  Depending on the application we have in view

  may incorporate additional additives into the composi-

  in accordance with the invention, such as lubricants

  (eg montan waxes or glycerol esters)

  cerol), esters of fatty acids, paraffins, car-

  carbon black, asbestos, kaolin, talc, fiberglass, optical brighteners, pigments, light stabilizers, ultraviolet absorbers, flame retardants and / or antistatic agents, more particularly lubricants, pigments, processing aids, fillers, antioxidants

  and / or light stabilizers.

  It is preferable that the compositions

  forms of the invention do not contain carboxylic acids

  free aromatic substances, in particular such as

  described as component (d) in JP A 54 11948.

  With the compositions according to the invention

  it is possible to manufacture molded objects by the formative methods, such as extrusion,

262 3 5 1 4

  injection molding, calendering or shell molding known as "slush mold" (powders or plastisols). They can also be used as plastisols. With the compositions of the invention, it is advantageous to manufacture PCV foils for packaging intended for

to food products.

  The following examples illustrate the invention.

  Unless otherwise indicated, the parts and percentages referred to in these examples and in the

  remainder of the description and in the claims

tooth by weight.

Example 1 to 4

  The PCV-based compositions indicated below are prepared by mixing the various components (the amounts are given in parts by weight):

Table 1

Composition Example n Ex.

1 2 3 4 comp.

  PCV prep suspension (K value: 70) (Corvic 571/102) 100 100 100 100 l100 Dioctyl phthalate 20 20 50 50 20

  Thio-diethyl bis-acetylacetate

Iene-glycol 1 2 1 2 -

  Epoxidized soybean oil (ESO) 5 5 5 5 -

  Zinc oleate 0.15 0.15 0.15 0.15 0.15 Tert-butyl-4 barium benzoate 0.35 0.375 0.375 0.375 0.375 Phosphite of diisodecyl and phenyl 0.525 0.525 0.525 0.525 0.525 Di-tert- butyl-2,6-methyl-4-phenol 0.075 0.075 0.075 0.075 0.075 Shellsol A (= mixture of aromatic solvents) 0.375 0.375 0.375 0.375 0.375

2623 5 14

Heat test

  We work for 5 minutes on a laminate

  Mixtures are prepared at 180 ° C., and the mixtures are indicated in Table 1. On the 0.3 mm thick sheet provided by the rolling, samples are taken and exposed to a thermal stress at 180 ° C. an experimental furnace ((R) Mathis Thermotakter type LTF-ST). At the end

  the time intervals indicated in Table 2 we de-

  finishes, on a sample, the YI index (Yellowness Index) by the method ASTM 'D 1925-70 (of

  high values of yellowness index mean that discoloration is important and, by

  therefore, stability is low).

Table 2

  Example n YI after a constraint of a duration, in minutes, of

0 5 10 15 20 25 30 35 40

  1 1.9 2.0 2.1 2.4 3.2 4.4 6.4 8.7 12.1

  2 2.2 2.2 2.9 3.0 3.1 4.1 4.7 6.0 8.1

  3 1.2 1.2 1.3 1.6 2.3 3.8 5.0 7.5 9.5

  4 0.9 1.2 1.4 1.5 2.1 2.8 3.9 6.1 8.2

  Witness 15.8 16.5 19.4 22.3 28.7 33.3 37.0 42.4 43.6 Molded plate

  We work for 5 minutes on a laminate

  The mixtures indicated in Table 1 are mixed at 180 ° C. With the obtained rolled sheet, a molded plate 3 mm thick is made by compression at 180 ° C. under 150 bar for 3 minutes. On this one also determines the yellowness index (YI). of the

  described above. The values obtained are considered

shown in Table 3.

Table 3

Ex. N YI ("initial color)

1 19.3

2 16.2

3 13.9

4 13.7

witness 67.5

Examples 5 to 8

  By mixing the various components (the amounts are given in parts by weight) the PCV compositions are prepared which are shown below:

Table 4

Composition Example n Ex.

  6 7 8 comp. PCV prepared in suspension (K value: 70) (1orvic 571/102) 100 100 100 100 100 Dioctyl phthalate 20 20 50 50 20 Zinc oleate 0.15 0, 15 0.15 0.15 0.15 Tert-butyl -4 Ca benzoate 0.375 0.375 0.375 0.375 0.337

Bis-acetylacetate of thio-di-

thylene glycol 1 2 1 2 -

  Epoxidized soybean oil (ESO) 5 5 5 5 -

  Di-isodecyl and phenyl phosphite 0.525 0.525 0.525 0.525 0.525 Ditert-butyl-2,6-methyl-4-phenol 0.075 0.075 0.075 0.075 0.075 thellsol A (= mixture of aromatic solvents) 0.375 0.375 0.375 0.375 0.375 It is good to prepare the compositions of the

  examples 1 to 8 and those of the comparative examples (

  witness statements) as follows: we start with

2623 5 1 4

  mixing the metal carboxylates with ESO, diisodicyl and phenyl phosphite and Shellsol A to obtain a stabilizing mixture, and then incorporating it, with thio-diethylene glycol bis-acetylacetate and the plasticizer (dioctyl phthalate), in the PCV. By operating as described in Examples 1 to 4, a sheet laminated with the blends is produced.

  defined in Table 4, the sheet is exposed to

  thermal stress and its yellowness index is determined

  (YI) at intervals of 5 minutes.The results obtained

  held are shown in Table 5.

Table 5

  I Example no YI after a duration of the constraint. in minutes, from

0 5 10 15 20 25 30 35 40

  3.1 1.5 1.7 2.3 2.5 3.0 4.2 6.5 14.5

  6 1.1 1.6 1.9 1.8 2.3 3.1 4.2 6.6 10.8

  7 0.9 1.1 1.1 1.3 1.7 2.3 3.0 5.8 11.4

  8 1.1 1.1 1.1 1.4 1.6 2.0 3.2 6.2 13.3

  Control 3.6 4.3 5.6 9.6 14.4 17.3 22.5 47.5 121.8 By operating as described in Examples 1 to 4, a plate molded with the blends of Table 4 is prepared. the yellowness index (YI) of the plate is determined. The values obtained are given in the

table 6.

Table 6

Ex. No YI ("initial color")

14.6

6 14.5

7 10.9

8 10.6

  control 24.2 Examples 9 and 10 By mixing the various components (the amounts are given in parts by weight) the PCV compositions are prepared which are indicated below:

Table 7

Composition Example n Ex.

9 10 comp.

  PCV prepared in suspension (K value: 70) (kCorvic S71 / 102) 100100 100 100 Dioctyl phthalate 20 50 20 Zn stearate 0.1 0.1 0.1

  Thio-diethyl bis-acetylacetate

  lene-glycol 1 1 Epoxidized soybean oil (ESO) 5 5 In the same way as in the examples

  1 to 4 a laminated sheet is produced with each of the

  As defined in Table 7, this sheet is exposed to thermal stress and its yellowness index (YI) is determined at 5 minute intervals. The

  The results obtained are shown in Table 8.

Table 8

  Example n YI after a duration of the stress, min of 25 minutes

9 1.2 1.5 1.7 2.9 4.3 6.8 9.3

1.4 1.5 2.0 3.0 5.4 9.9 12.2

control 4.4 5.0 8.2 25.1 31.9 - -

  By operating as in Examples 1 to 4, each of the mixtures of Table 7 are worked in such a way as to

  make a molded plate and determine the index of

  of it. The values obtained are given

in Table 9.

Table 9

Example no YI ("initial color")

9 13.0

10.8

  control 29.8 Examples 11 to 13 By mixing the various components (the amounts are given in parts by weight) the PCV compositions are prepared which are indicated below:

Table 10

Composition Example no

he Ex.

11 12 comp.

  comp. PCV prepared in suspension PIinoflex 56514) 100 100 100 Dioctyl phthalate 18 18 18 Zn oleate 0.2 0.2 0.2 Tert-butyl-4 benzoate Ba 0.5 0.5 0.5

  Thio-diethylene bis-acetylacetate

0.7 0.7 -

  Epoxidized soybean oil (ESO) 3 3 3 Di-isodecyl phosphite 0.7 0.7 0.7 Di-tert-butyl-2,6-methyl-4-phenol 0.1 0.1 0.1 Ohellsol A (= mixture of aromatic solvents) 0.5 0.5 0.5 2-Methylcyclohexyloxycarbonyl-3

4-phenyl-1H-pyrrole - 0.2 -

  The compositions defined in Table 10 are worked on a mixer mill at 190 ° C. for minutes. Samples are cut from the 0.3 mm thick sheet provided by the rolling and exposed to thermal stress at 190 ° C.

  an experimental furnace (Mathis Termotakter LTF-ST). Wave-

  finishes the yellowness index (YI) of the samples in

  operating as in Examples 1 to 4. The results obtained

  are shown in Table 11.

Table 11

  Example n DYI after a duration of the constraint, min, of:

20 30 40 50

It 1,0 2,3 2,6 3,1 5,4

12 0.9 2.1 2.4 2.3 5.8

  control 11.4 15.0 15.1 12.7 10.9 In addition, with each of the compositions of Table 10, a molded plate is manufactured by compression, as described in Examples 1 to 4, the index of which is determined. yellowing. The values obtained are given

in table 12.

Table 12

  Example n YI ("initial color") ll 24.7

12 24.5

64.7

Example 13

  By mixing the various components, the following PCV-based composition was prepared: 100 parts by weight of a PCV prepared by suspension polymerization (K value: 64) parts by weight of dioctyl phthalate 0.04 parts by weight of Zn neodecanoate

  0.7 parts by weight of thio-diethyl bis-acetylacetate

  ethylene glycol parts by weight of epoxidized soybean oil (ESO) and 0.3 part by weight of 2-methylcyclohexyloxycarbonyl)

4-phenyl-1H-pyrrole.

  Operating as described in the examples

  1 to 4, a laminate sheet is produced with this composition.

  This is exposed to heat stress and its yellowness index (YI) is determined at 5 minute intervals. YI values obtained below are given below: Time (in minutes) 5 10 15 20 25 30 35

YI 0.4 1.6 2.5 4.0 6.4 9.8 13.4.

2623 5 1 4

Claims (17)

  1. Composition based on stable polymers   which contains: (a) 100 parts of a chlorinated thermoplastic material,   (b) from 0.7 to 2 parts of thio-diethyl bis-acetylacetate   ethylene glycol, a body that responds to the formula: (H3CCOCH2COOCH2CH2) 2 S,   c) from 0 to 0.5 parts of at least one salt of Ca, Ba and / or   of Mg of a monocarboxylic acid or hydroxy-monocarboxylic acid   C8-C24 aliphatic xyl or benzoic acid or tertbutyl-benzoic acid, d) 0.01 to 0.2 parts of at least one Zn salt of an aliphatic monocarboxylic or hydroxy-monocarboxylic acid C8-C24 or benzoic acid or a tert-butyl-benzoic acid, e) 3 to 10 parts of epoxidized unsaturated fatty acid esters and   f) from 10 to 70 parts of at least one organic plasticizer.   2. Composition according to claim 1   wherein component c) is a salt of Ca and / or Mg.   3. Composition according to one of the claims   1 and 2, in which the thermoplastic   Chloride is a homopolymer of vinyl chloride, a co-   polymer of vinyl chloride with unsatisfactory comonomers   a mixture of the polymers mentioned with each other or a   mixtures of the polymers mentioned with other homopolymers or copolymers.   4. Composition according to one of the claims   1 and 2 in which the component b) is contained in one amount of 0.8 to 1.5 parts.   5. Composition according to one of the claims   1 and 2 in which the component c) is contained in an amount of 0.01 to 0.5 part, more particularly from 0.05 to 0.4 parts.   6. Composition according to any one of   claims 1, 2 and 5, wherein the component c) is a salt of Ca.   7. Composition according to any one of   claims 1, 2, 5 and 6, wherein the component   c) is a salt of lauric acid, 2-ethyl-hexahydrate   no, stearic acid or behenic acid.   8. Composition according to one of the claims   1 and 2, wherein component d) is contained in an amount of 0.05 to 0.2 parts, more particularly 0.1 to 0.2 parts.   9. Composition according to one of the claims   1 and 2, wherein component d) is zinc octoate (2-ethylhexanoate), basic zinc octoate, stearate zinc or zinc benzoate.   10. Composition according to one of the claims   1 and 2, wherein component e) is contained in an amount of 4 to 7 parts, more particularly parts. 11. Composition according to any one of   claims 1, 2 and 10, wherein the component e) is an epoxidized soybean oil.   12. Composition according to any one of   claims 1 and 2, wherein the component f) is   contained in an amount of 15 to 60 parts, more particularly firstly from 20 to 50 parts.   13. Composition according to any one of   claims 1, 2 and 12, wherein the component f)   is a plasticizer taken from the group consisting of phthalates, esters of aliphatic dicarboxylic acids, trimellitates, polymeric plasticizers (polyesters), phosphates, hydrocarbons, chlorinated hydrocarbons,   monoesters and / or esters of glycols.   14. Composition according to claim 13   wherein the plasticizer is a phthalate, a trimellate   tate, adipate, azelate or sebacate.   15. Composition according to any one of   claims 1 to 13 which contains at most 3 parts of a   stabilizing organic phosphite, more particularly 0.1 to 1 part.   16. Composition according to any one of   claims 1 to 14 which contains at most 1.5 parts of least another co-stabilizer.   The composition of claim 16 wherein the one or more co-stabilizers is or are   taken from the group consisting of aminocroto-   niques, dehydracetic acid, 1,3-dioxo compounds, 2,4-dihydroxybenzophenone, 2,4-dihydroxy-tert-butyl-4 '   benzophenone and pyrrole derivatives.