JPH08283498A - Stabilized halogenated polymer - Google Patents

Abstract

PURPOSE: To obtain a stabilized polymer containing halogen having a good initial color, a color holding property and a long-time stability by blending a polymer containing a halogen or the like, a di- or poly-saccharide alcohol and an inorganic or organic zinc or the like.

CONSTITUTION: This polymer contains (A) a polymer containing a halogen or its recycled material, (B) a di- or poly-saccharide alcohol of the formula C₆H₁₁O₆(C₆H₁₀O₅)_nC₆H₁₃O₅ (wherein n is 0-5) (if it is a multitol, the combination of a calcium soap and a zinc soap is not included) and (C) an inorganic or organic zinc or aluminum or a rare earth compound.

COPYRIGHT: (C)1996,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a stabilized halogen-containing polymer or a regenerated product thereof, preferably polyvinyl chloride (PVC) or a regenerated product thereof, and a stabilizer mixture containing di- or polysaccharide alcohol, and The present invention relates to a method for producing a stabilized halogen-containing polymer.

[0002]

BACKGROUND OF THE INVENTION In addition to tin and lead compounds, PVC is a fatty acid salt known as metal soap, where the metal is usually barium, cadmium, zinc, magnesium or calcium. Can also be stabilized by using Considering the difference in stabilizing properties (initial color, color retention and long-term stability), a combination of two different metal soaps (eg Ba / Cd soaps) to achieve a balanced stabilization. , Used in each case. In order to avoid the use of barium-, lead- or cadmium-containing compounds, Ca / Zn soaps have also been proposed [in this respect, see, for example, "Plastics Additives Handbook" (Taschenbuch der Kunstst.
off-Additive) "R. Gaechter and H. Mueller, edited by Hanser Verlag, 3rd edition, 1990, 308-
309 pages, and "Plastics Handbook PV
C (Kunststoff-Handbuch PVC) "Volumes 1 and 2, Beck / Braun, Carl Hanser Verlag, Second Edition, 1985 /
1986].

Above all, it has also been proposed to use polyols or maltitol in the presence of a combination of calcium and zinc soaps as costabilizers for PVC; an example of which is Japanese patent application 63-63. No. 063737.

However, there is a need for a physiologically acceptable stabilizer system which at the same time allows a high degree of stabilization. In particular, stabilizer systems containing barium, lead or cadmium should be avoided.

[0005]

Certain di- or polysaccharide alcohols mixed with zinc, aluminum or rare earth compounds are superior to stabilized halogen-containing polymers with good initial color and color retention. It has now been found to provide long term stability.

Therefore, the present invention provides (a) a halogen-containing polymer or a regenerated product thereof, and (b) the following formula: C ₆ H ₁₁ O ₆ (C
₆ H ₁₀ O ₅ ) _n C ₆ H ₁₃ O ₅ (wherein n represents a number of 0 to 5), a di- or polysaccharide,
And (c) a stabilized halogen-containing polymer consisting of an inorganic or organic zinc, aluminum or rare earth compound, wherein component (b) is maltitol.
, The composition relates to a polymer that does not include a combination of calcium soap and zinc soap.

The halogen-containing polymer thus stabilized is preferably completely free of barium, lead or cadmium.

The halogen-containing polymer or its regenerated product is
Polymers preferably containing chlorine, such as vinyl chloride, vinyl resins containing vinyl chloride units in their structure, such as vinyl esters of vinyl chloride and fatty acids, especially vinyl acetate copolymers, vinyl chloride and acrylic and methacrylic acid esters. And acrylonitrile copolymers, vinyl chloride and diene compounds and unsaturated dicarboxylic acids or their anhydrides, for example vinyl chloride and diethyl maleate, diethyl fumarate or maleic anhydride copolymers, vinyl chloride post-chlorination Polymers and copolymers, vinylidene chloride and vinylidene chloride with unsaturated aldehydes, ketones and other such as acrolein, crotonaldehyde, vinyl methyl ketone, vinyl methyl ether and the like; polymers and salts of vinylidene chloride Copolymers of vinylidene with vinyl chloride and other polymerizable compounds; Copolymers of vinyl chloroacetate with dichlorodivinyl ether; Chlorinated polymers of vinyl acetate, chlorinated polymeric esters of acrylic acid with α-substituted acrylic acid; Chlorinated Polymers of styrene, such as dichlorostyrene; chlorinated rubbers; chlorinated polymers of ethylene; polymers of chlorobutadiene and post-chlorinated polymers, and copolymers of chlorobutadiene with vinyl chloride, rubber hydrogen chloride and chlorinated rubber hydrogen chloride; Polymers of each other or with other polymerizable compounds.

PVC with EVA, ABS and MBS
Graft polymers of are also suitable. Preferred substrates are furthermore mixtures of the abovementioned homopolymers and copolymers, especially vinyl chloride homopolymers with other thermoplastics and / or elastic polymers, in particular ABS, MBS, NBR, SAN, E.
VA, CPE, MBAS, PMA, PMMA, EPDM
And a blend with polylactone.

Suspension, bulk and emulsion polymers are also preferred.

Particularly preferred chlorine-containing polymers are polyvinyl chloride, especially emulsion and bulk polyvinyl chloride.

For the purposes of the present invention, PV of component (a)
C is also used to mean a copolymer or graft polymer of PVC with a polymerizable compound such as acrylonitrile, vinyl acetate or ABS, suspension, bulk or emulsion polymers can also be used for this purpose.
Preferred are PVC homopolymers and also combinations with polyacrylates.

For the purposes of the present invention, component (a) further comprises, in particular, regenerated products of halogen-containing polymers, which are the abovementioned polymers which have suffered damage due to processing, use or storage. Means Particularly preferred are:
It is a recycled PVC product. Recycled products may contain small amounts of foreign substances such as paper, pigments and additives, which are often difficult to remove. Said foreign substances may also come from contact with various substances in use or treatment, such as fuel residues, trace metals, initiator residues or trace moisture.

Di- which can be used in the present invention as component (b)
Alternatively, polysaccharide alcohols are generally known. Particularly preferred are disaccharide alcohols such as maltitol, malbitol, lactitol, palatinitol, isomaltitol, isomaltol, leucrose, dihydroleucrose, glucopyranosylsorbitol and lycasin (dehydrated). Very particularly preferably maltitol, lactitol,
Isomaltitol and palatinitol.

Di- which can be used in the present invention as component (b)
Alternatively, the polysaccharide alcohol is, for example, 0.01 to 1 with respect to 100 parts by weight of the halogen-containing polymer.
It may be used in an amount of 0 parts by weight, conveniently 0.01 to 5 parts by weight, particularly preferably 0.01 to 3 parts by weight.

Preferred is component (C), as described above.
Is at least one inorganic zinc compound, such as zinc oxide,
Zinc hydroxide, zinc chloride, zinc sulfide, or superbasic zinc oxide / zinc hydroxide addition compound, or the following system: aliphatic, carboxylate having 2 to 22 saturated carbon atoms, 3 to 22 unsaturated carbon atoms A carboxylate having 2 to 22 carbon atoms, which is substituted by at least one OH group or whose molecular chain is interrupted by at least one O atom, a ring having 5-22 carbon atoms or Bicyclic carboxylate, unsaturated, phenylcarboxylate substituted with at least one OH group and / or alkyl group having 1 to 16 carbon atoms, unsaturated or at least one O
A naphthylcarboxylate substituted with an H group and / or an alkyl group having 1 to 16 carbon atoms, phenyl-alkylcarboxylate having 1 to 16 carbon atoms, naphthyl-alkylcarboxylate having 1 to 16 carbon atoms, or A stabilized halogen-containing polymer which is an organozinc compound derived from a phenolate which is saturated or substituted with an alkyl group having 1 to 12 carbon atoms.

Examples in which the name may be mentioned are monocarboxylic acids,
For example, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, enanthic acid (heptanoic acid), octanoic acid, neodecanoic acid, 2-ethylhexanoic acid, pelargonic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, myristin Acid, palmitic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, 9,10-dihydroxystearic acid, 3,6-dioxaheptanoic acid,
3,6,9-trioxadecanoic acid, behenic acid, benzoic acid, p-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-di-tert-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid Acid, ethylbenzoic acid,
Zinc salts of n-propyl benzoic acid, salicylic acid, p-tertiary octyl salicylic acid, and sorbic acid; divalent carboxylic acids such as oxalic acid, malonic acid, succinic acid, curtaric 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, 3,6,9-trioxadecane-1,10-dicarboxylic acid, polyglycol dicarboxylic acid (n = 10-1
2), zinc salts of monoesters of phthalic acid, isophthalic acid, terephthalic acid and hydroxyphthalic acid; and diesters or triesters of tri- or tetravalent carboxylic acids, such as the monohydrates of hemimellitic acid, trimellitic acid, pyromellitic acid and citric acid. Zinc salt of ester; and Japanese Patent Application No. 3-27557
Zinc salts of mono- and diesterified phosphoric acid or monoesterified phosphorous acid as described in No. 0.

Preferred is that component (c) is an organozinc compound, especially an organozinc carboxylate (zinc soap) of a carboxylic acid having 7 to 18 carbon atoms, such as benzoates or alkanoates, preferably stearates, oleates. The above composition is laurate, palmitate, behenate, hydroxystearate, dihydroxystearate or (iso) octanoate. Stearate, oleate, benzoate and 2-
Particularly preferred is ethyl hexanoate.

In addition to the zinc compound, component (c) may be an inorganic or organic aluminum compound, in which case the related zinc compounds mentioned above may also be used. Further information on preferred aluminum compounds that may be used is
It is described in the specification of US 4060512.

In addition to the zinc compound, component (c) may be an inorganic or organic rare earth compound, in which case
The related zinc compounds described above may also be used. The term "rare earth compound" refers especially to the following elements: cerium, praseodymium,
Neodymium, samarium, europium, gadolinium,
It is understood as a compound of terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, lanthanum and yttrium, in particular a mixture with cerium is preferred. Further preferred rare earth compounds are described in the specification of EP-A-0108023.

Mixtures of zinc, aluminum, lanthanum or lanthanide compounds of different structures can also be used. Organic zinc, aluminum, lanthanum or lanthanide compounds can also be used for hydrotalcite, zeolite (zeo
lite), may be applied on dawsonite (see DE-A-4031818).

The inorganic or preferably organic zinc, aluminum or rare earth compounds are halogen-containing polymers 10
It may be used in an amount of 0.001 to 5 parts by weight, conveniently 0.01 to 3 parts by weight, particularly preferably 0.1 to 2 parts by weight, based on 0 parts by weight.

The PVC stabilized according to the invention may contain further additives. These are, for example, inorganic or organic calcium or magnesium compounds, zeolites, hydrotalcites, dawsonites, magaziites, kenyaites, kanemite, 1,3-diketo compounds, polyols,
N-containing compounds such as β-aminocrotonates, α-phenylindoles, pyrroles, sterically hindered amines (HALS), dihydropyridines and polymers thereof, as described in EP 0465405, page 6, lines 9-14.
Perchlorate, epoxide, phenolic antioxidant [HANDBOOK OF PVC FORMULA
TING), E. Jay. EJ Wickson
, John Wiley & Sons, Inc., 1993, 5th
05-515], naphthol, thiophosphate, plasticizer [HANDBOOK OF PVC FOR
MULATING), E. Jay. Wickson (EJ Wicks
on), John Wiley & Sons, Inc., 1993, pp. 163-303], filler [HANDBOOK OF PVC FORMULATING], e. Jay. EJ Wickson, John Willey & Sons, John Wiley & Son
s, Inc.), 1993, pp. 393-449] and a toughening agent [TASCHENBUCH DER KUNSTSTOFF-ADDITIVE],
El. R. Gaechter and Har. H.Mue
ller), Carl Hanser, 1990
Pp. 549-615] (eg calcium carbonate,
Magnesium oxide, magnesium hydroxide, silicate,
Glass fiber, talc, kaolin, chalk, mica, metal oxides and hydroxides, carbon black or graphite), phosphites, chelating agents [Taschenbuch Deer Kunststoff-Additive (TASCHENBU
CH DER KUNSTSTOFF-ADDITIVE), Elle. Gechter (R. Gae
chter) and Ha. H. Mueller, Carl Hanser, 1990, 109-131
Pages], light stabilizers, UV absorbers [HANDBOOK OF PVC FORMULATING], e. Jay.
EJ Wickson, John Wiley & Sons, John Wiley & So
ns, Inc.), 1993, pp. 355-369], lubricant [HANDBOOK OF PVC FORMULA
TING), E. Jay. EJ Wickson
, John Wiley & Sons, Inc., 1993, 3rd.
69-393], impact modifier [IMPACT MODIFIERS FOR PCV], Jay. tea. JT Lutz and Day. El. Dunkelberger
(DL Dunkelberger), John Wiley & Sons, In
c.), 1992] and processing aids [Taschenbuch]
Der Kunststoff-Additive (TASCHENBUCH
DER KUNSTSTOFF-ADDITIVE), Elle. Gechter (R. Gaech
ter) and Ha. H. Mueller, Carl Hanser, 1990, 505-524
Page], fatty acid ester, paraffin, foaming agent [HANDBOOK OF PVC FORMULATING], e. Jay. EJ Wickson, John
Willay and Sons, Inc. (Joh
n Wiley & Sons, Inc.), 1993, 525-551.
Page], fluorescent whitening agent [TASCHENBUCH DER KUNSTSTOF
F-ADDITIVE), L. R. Gaechter and Har.
H. Mueller, Carl Hanse
r), 1990, p.807-821], gelling aid, dye [HANDBOOK OF PVC
FORMULATING), E. Jay. Wickson (EJ W
ickson), John Wiley & Sons, Inc., 1993
, 449-475], pigments [Taschenbuch
Der Kunststoff-Additive (TASCHENBUCH
DER KUNSTSTOFF-ADDITIVE), Elle. Gechter (R. Gaech
ter) and Ha. H. Mueller, Carl Hanser, 1990, No. 663-735
Page], flameproofing agent and smoke reducing agent [HANDBOOK OF PVC FORMULATING, E. Jay.
EJ Wickson, John Wiley & Sons, John Wiley & So
ns, Inc.), 1993, pp. 551-579], an antistatic agent [HANDBOOK OF PVC FOR
MULATING), E. Jay. Wickson (EJ Wicks
on), John Wiley & Sons, Inc., 1993, pp. 487-505], antifogging agent [HANDBOOK OF PVC FORMULATING], e. Jay. EJ Wickson, John Willey & Sons, John Wiley & Son
s, Inc.), 1993, pp. 475-487], microbicides, thiodipropionic acid and its esters, dialkyl disulfides [Handbook of PVC blending (HANDBOOK
OF PVC FORMULATING), E. Jay. Wickson
(EJ Wickson), John Willey & Sons, Inc. (John Wiley & Sons, Inc.)
1993, pp. 515-525], mercaptocarboxylic acid esters, peroxide scavengers, modifiers and other complexing agents for Lewis acids.

Suitable inorganic or organic calcium and magnesium compounds are similar to the compounds mentioned under zinc compounds. Preferred are organic calcium or magnesium compounds, especially calcium or magnesium soaps, and calcium oxide, calcium hydroxide,
And EP-0446685, 0394547 and 0
Superbasic calcium compounds as described in 279493.

In addition to components (b) and (c) of the present invention,
Epoxy compounds such as 1,2-epoxide and oxirane, for example, up to 10 parts by weight, conveniently up to 5 parts by weight, preferably 0.01 per 100 parts by weight of the composition.
It is also possible to use in amounts of up to 2 parts by weight. Examples are epoxidized polybutadiene, epoxidized soybean oil, epoxidized linseed oil, epoxidized fish oil, epoxidized tallow, methylbutyl or 2-ethylhexyl epoxy stearate, tris (epoxypropyl) isocyanurate, epoxidized castor oil, epoxidized Sunflower oil, 3
-(2-phenoxy) -1,2-epoxypropane, bisphenol A polyglycidyl ether, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide and 3,4-epoxycyclohexylmethyl 3,4
-Epoxycyclohexanecarboxylate.

Other epoxy compounds which may be used for the purposes of the present invention may have an aliphatic, aromatic, cycloaliphatic, araliphatic or heterocyclic structure; they are used as side groups. Contains epoxy groups. The epoxy groups are preferably linked to the rest of the molecule via ether or ester bonds as glycidyl groups, or they are N-glycidyl derivatives of heterocyclic amines, amides or imides.
Epoxy compounds of the above type are known in general terms and are commercially available.

The epoxy compound is at least one epoxy group, especially of formula II:

Embedded image [This is directly bonded to a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom, wherein R ₁ and R ₃ both represent a hydrogen atom, R ₂ represents a hydrogen atom or a methyl group, and n is 0, or, in the formula, R ₁ and R ₃ together form a —CH ₂ —CH ₂ — group or —CH ₂ —CH ₂
Represents a —CH ₂ — group, wherein R ₂ represents a hydrogen atom, and n represents 0 or 1].

Examples of epoxide compounds that may be mentioned are: I) Glycidyl and β-methylglycidyl ester obtained by reacting a compound containing at least one carboxyl group in the molecule with epichlorohydrin or glyceroldichlorohydrin or β-methylepichlorohydrin. The reaction is preferably carried out in the presence of a base.

The compound containing at least one carboxyl group in the molecule may be an aliphatic carboxylic acid. Examples of such carboxylic acids are glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid or dimerized or trimerized linoleic acid, acrylic acid, methacrylic acid, caproic acid, caprylic acid, lauric acid. Acids, myristic acid, palmitic acid, stearic acid and pelargonic acid, and the acids mentioned in the case of organozinc compounds.

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

It is also possible to use aromatic carboxylic acids such as benzoic acid, phthalic acid, isophthalic acid, trimellitic acid or pyromellitic acid.

It is likewise possible to use adducts which are end-capped with carboxyl groups, for example trimellitic acid and polyols such as glycerol or 2,2-bis (4-hydroxycyclohexyl) propane. is there.

Other epoxide compounds which can be used for the purposes of the present invention are described in the specification of EP-0506617.

II) Suitable substitution with compounds containing at least one free alcoholic hydroxyl group and / or phenolic hydroxyl group under alkaline conditions or by subsequent alkaline treatment in the presence of an acid catalyst. Glycidyl or β-methylglycidyl ether obtained by reaction with epichlorohydrin.

Ethers of the above type are, for example, ethylene glycol, diethylene glycol and higher poly (oxyethylene) glycols, propane-1,2-diols or poly (oxypropylene) glycols, propane-
1,3-diol, butane-1,4-diol, poly (oxytetramethylene) glycol, pentane-1,
5-diol, hexane-1,6-diol, hexane-2,4,6-triol, glycerol, 1,1,1
From acyclic alcohols such as trimethylolpropane, bistrimethylolpropane, pentaerythritol, sorbitol; and polyepichlorohydrin,
It is derived from butanol, amyl alcohol, pentanol; and from monofunctional alcohols such as isooctanol, 2-ethylhexanol, isodecanol and alkanols containing 7 to 9 carbon atoms and alkanols containing 9 to 11 carbon atoms.

However, they are, for example, 1,3
-Or 1,4-dihydroxycyclohexane, bis (4
-Hydroxycyclohexyl) methane, 2,2-bis (4-hydroxycyclohexyl) propane or 1,1
Also derived from cycloaliphatic alcohols such as -bis (hydroxymethyl) -3-cyclohexene, or they are N, N-bis (2-hydroxyethyl) aniline or p, p'-bis (2-hydroxy). It contains an aromatic ring such as ethylamino) diphenylmethane.

The epoxide compounds can also be derived from monocyclic phenols, for example phenols, resorcinols or hydroquinones; or they can be polycyclic phenols, for example bis (4-hydroxyphenyl) methane,
2,2-bis (4-hydroxyphenyl) propane,
Condensation products of formaldehyde and phenol obtained under acidic conditions, such as 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 4,4'-dihydroxydiphenyl sulfone, or phenol novolac. , Based.

Examples of other usable terminal epoxides are: glycidyl 1-naphthyl ether, glycidyl 2-phenyl phenyl ether, 2-biphenyl glycidyl ether, N- (2,3-epoxypropyl) phthalimide and 2,3-epoxy. Propyl 4-methoxyphenyl ether.

III) N-glycidyl compounds obtained by dehydrochlorinating the reaction product of epichlorohydrin and amine, which contains 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 with N, N, O-triglycidyl-m It may be aminophenol or N, N, O-triglycidyl-p-aminophenol.

However, the N-glycidyl compound is
Cycloalkylene urea N, N'-di-, N, N ',
N "-tri and N, N ', N", N "'-tetraglycidyl derivatives such as ethylene urea or 1,3-propylene urea, and N, N-diglycidyl derivatives of hydantoin such as 5,5-dimethyl Also included are hydantoin, or glycoluril and triglycidyl isocyanurate.

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

Wherein R ₁ and R ₃ together are --CH
₂ -CH ₂ - represents a group, and the epoxide compound containing a group of the formula II where n represents 0 are bis (2,3
-Epoxypentyl) ether, 2,3-epoxycyclopentylglycidyl ether or 1,2-bis (2,2
3-epoxycyclopentoxy) ethane. Where:
Epoxide compounds containing a group of the formula II in which R ₁ and R ₃ together represent a —CH ₂ —CH ₂ — group and n is 1 are, for example: (3 ′, 4′-epoxy- 6'-methylcyclohexyl) methyl 3,4-epoxy-6-methylcyclohexanecarboxylate.

Examples of suitable terminal epoxides are: a) Liquid bisphenol A diglycidyl ethers such as Araldit® GY240, Araldit® GY250, Araldit® GY260, Araldito.
ldit) GY266, Araldit
(Registered trademark) GY2600, Araldit (registered trademark) MY790; b) solid bisphenol A diglycidyl ethers such as Araldit (registered trademark) GT6071,
Araldit (registered trademark) GT7071, Araldit (registered trademark) GT7072, Araldit (registered trademark) GT6063, Araldit (A
raldit (R) GT7203, Araldit
it) (registered trademark) GT6064, Araldit
(Registered trademark) GT7304, Araldit (registered trademark) GT7004, Araldit (registered trademark) GT6084, Araldit (registered trademark)
GT1999, Araldit (registered trademark) GT
7077, Araldit (R) GT60
97, Araldit (R) GT709
7, Araldit (registered trademark) GT7008,
Araldit (registered trademark) GT6099, Araldit (registered trademark) GT6608, Araldit (registered trademark) GT6609, Araldit (A
c) liquid bisphenol F diglycidyl ethers, such as Araldit® GY281, Araldit® PY302, Araldit® PY306; d) raldit® GT6610; ) Solid polyglycidyl ethers of tetraphenylethane, eg CG Epoxy Resin® 0163; e) Solid and liquid polyglycidyl ethers of phenol-formaldehyde novolak, eg EPN113.
8, EPN1139, GY1180, PY307; f) Solid and liquid polyglycidyl ethers of o-cresol-formaldehyde novolac, such as ECN12.
35, ECN1280, ECN1299; g) Liquid glycidyl ethers of alcohols, such as Shell® glycidyl ether 162, Araldit® DY0390, Araldit® DY0391; h) carvone. Liquid glycidyl ethers of acids, such as Shell® Cardura E terephthalates, trimellitic acid esters, araldite (A
raldit (R), PY284; i) solid heterocyclic epoxy resins (triglycidyl isocyanurates), such as Araldit (R) PT810; j) liquid cycloaliphatic epoxy resins, such as Araldit (A).
raldit (R) CY179; k) liquid N, N, O-triglycidyl ether of p-aminophenol, such as Araldit (R) MY0510; l) tetraglycidyl-4,4'-methylenebenzamine. Or N, N, N ′, N′-tetraglycidyldiaminophenylmethane, such as Araldit® MY720, Araldit® M
Y721.

Epoxy compounds containing two functional groups are preferred. However, it is possible in principle to use epoxy compounds which contain one, three or more functional groups.

Diglycidyl compounds having an aromatic structure, for example a phenyl group, are used predominantly.

Mixtures of epoxy compounds of different structure can also be used if desired.

Particularly preferred polyfunctional epoxy compounds are
Bisphenols such as 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), bis (4-
Diglycidyl ethers based on a mixture of hydroxyphenyl) methane or bis (ortho / para-hydroxyphenyl) methane (bisphenol F).

1,3-Diketo compounds which can be used are linear or cyclic dicarbonyl compounds. Formula III:

Embedded image [Wherein R ₁ is an alkyl group having 1 to 22 carbon atoms,
Hydroxyalkyl group having 5 to 10 carbon atoms, alkenyl group having 2 to 18 carbon atoms, phenyl group; OH
Group, alkyl group having 1 to 4 carbon atoms, 1 carbon atom
Phenyl group substituted with an alkoxy group having 4 to 4 carbon atoms or a halogen atom; a phenylalkyl group having 7 to 10 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms; substituted with an alkyl group having 1 to 4 carbon atoms A cycloalkyl group having 5 to 12 carbon atoms; or a —R ₅ —S—R ₆ or —R ₅ —O—R ₆ group, wherein R ₂ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a carbon atom. An alkenyl group having 2 to 12 atoms, a phenyl group, an alkylphenyl group having 7 to 12 carbon atoms, a phenylalkyl group having 7 to 10 carbon atoms, or -CO
-R ₄ group, R ₃ represents _one of the meanings given to R ₁ or an alkoxy group having 1 to 18 carbon atoms, R ₄ represents an alkyl group having 1 to 4 carbon atoms or a phenyl group R ₅ represents an alkylene group having 1 to 10 carbon atoms, and R ₆ represents an alkyl group having 1 to 12 carbon atoms, a phenyl group, 7 to 1 carbon atoms.
A diketo compound represented by an alkylphenyl group having 8 carbon atoms or a phenylalkyl group having 7 to 10 carbon atoms is preferable.

These are the hydroxy-containing diketones of EP-A-346279 and EP-A-307358.
Oxa and thiadiketones of the above specification.

Alkyl radicals R ₁ and R ₃ are in particular alkyl radicals having 1 to 18 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl. Represents a group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group or octadecyl group.

The hydroxyalkyl groups R ₁ and R ₃ are in particular represented by a — (CH ₂ ) _n —OH group (wherein n represents 5, 6 or 7).

The alkenyl radicals R ₁ and R ₃ are, for example, vinyl, allyl, methallyl, 1-butenyl, 1-hexenyl or oleyl, preferably allyl.

OH groups, alkyl groups, alkoxy groups or phenyl groups R ₁ and R substituted by halogen atoms
₃ may represent, for example, a tolyl group, a xylyl group, a tert-butylphenyl group, a methoxyphenyl group, an ethoxyphenyl group, a hydroxyphenyl group, a chlorophenyl group or a dichlorophenyl group.

The phenylalkyl radicals R ₁ and R ₃ in particular represent a benzyl radical. The cycloalkyl or alkylcycloalkyl radicals R ₁ and R ₃ represent in particular a cyclohexyl radical or a methylcyclohexyl radical.

The alkyl radical R ₂ may in particular represent an alkyl radical having 1 to 4 carbon atoms. 2 to 1 carbon atoms
The alkenyl group R ₂ of ₂ may in particular represent an allyl group.
The alkylphenyl radical R ₂ may in particular represent a tolyl radical. The phenylalkyl radical R ₂ may in particular represent a benzyl radical. R ₂ preferably represents a hydrogen atom. The alkoxy group R ₃ may represent, for example, a methoxy group, an ethoxy group, a butoxy group, a hexyloxy group, an octyloxy group, a dodecyloxy group, a tridecyloxy group, a tetradecyloxy group or an octadecyloxy group. The alkylene group R ₅ having 1 to 10 carbon atoms particularly represents an alkylene group having 2 to 4 carbon atoms. The alkyl radical R ₆ is in particular an alkyl radical having 4 to 12 carbon atoms, for example butyl, hexyl, octyl, decyl or dodecyl. The alkylphenyl radical R ₆ represents in particular a tolyl radical. The phenylalkyl radical R ₆ especially represents a benzyl radical.

Examples of the 1,3-dicarbonyl compound represented by the formula III are acetylacetone, acetylcyclopentanone, benzoylcyclopentanone, acetylbutyrolacetone, benzoylbutyroleacetone, butanoylacetone, heptanoylacetone and stearoyl. Acetone, palmitoylacetone, lauroylacetone,
7-tertiary nonylthioheptane-2,4-dione, benzoylacetone, dibenzoylmethane, lauroylbenzoylmethane, palmitoylbenzoylmethane, stearoylbenzoylmethane, 5-hydroxycaproylbenzoylmethane, tribenzoylmethane, bis (4-methyl Benzoyl) methane, benzoyl-p-chlorobenzoylmethane, bis (2-hydroxybenzoyl) methane, 4-methoxybenzoylbenzoylmethane, bis (4-methoxybenzoyl) methane, 1-benzoyl-
1-acetylnonane, benzoylacetylphenylmethane, stearoyl-4-methoxybenzoylmethane, bis (4-tert-butylbenzoyl) methane, benzoylformylmethane, benzoylphenylacetylmethane, bis (cyclohexanoyl) methane, di (pivaloyl) Methane; methyl, ethyl, hexyl, octyl, dodecyl or octadecyl acetoacetone; ethyl, butyl, 2
-Ethylhexyl, dodecylbenzoyl acetate or octadecylbenzoyl acetate; ethyl, propyl, butyl, hexyl or octyl stearoyl acetate and dihydroacetic acid, and their magnesium salts,
Calcium salt, zinc salt or aluminum salt.

1,3-diketo compound represented by the formula III: wherein R ₁ is an alkyl group having 1 to 18 carbon atoms,
A phenyl group; an OH group, a phenyl group substituted with a methyl group or a methoxy group; a phenylalkyl group having 7 to 10 carbon atoms or a cyclohexyl group, R ₂ represents a hydrogen atom, and R ₃ represents R ₁ . Represents one of the meanings given to.

Acetylacetonato magnesium, acetyl acetonato calcium, acetyl acetonato zinc, acetyl acetonato aluminum, stearoyl benzoyl methane, dibenzoyl methane, benzoyl octanoyl methane and tricetyl isocyanurate described in the specification of US Pat. No. 4,339,383. The triacetic acid ester of is particularly preferable. For a review of 1,3-diketo compounds, see EP
-6318, EP-0046161, EP-00352
68 and EP-0040286.

The 1,3-diketo compound is, for example, PVC1.
0.01 to 10 parts by weight, preferably 0.01 to 2 parts by weight, especially 0.05 to 1 part by weight, relative to 00 parts by weight
It may be used in an amount of parts by weight.

Other stabilizers that can be used are those of the formula IV:

Embedded image [Wherein n represents 1, 2, 3, 4 or 6, and n
When represents 1, R represents a phenyl group, and X represents an alkyl group having 10 to 20 carbon atoms, and when n represents 2, R represents 1 to 4 carbon atoms. Represents an alkyl group or a phenyl group having
And X 4 to 12 alkylene carbon atoms; at least one alkyl group having 1 to 8 carbon _{atoms, -CH 2 -CH 2 -S-CH} 2 -CH 2 -S-CH
₂ -CH ₂ - group or a _{-CH 2 -CH 2 -S-CH 2} -C
Represents an alkylene group having 2 to 12 carbon atoms substituted by a H _2- group, and when n represents 3, R represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, And X is CH ₃ CH ₂ C
When (CH ₂ —) ₃ is represented and n is 4, R is
Represents an alkyl or phenyl group having 1 to 4 carbon atoms, and X is of the formula:

[Chemical 4] (Wherein m represents 0 or 1), and when n represents 6, R represents an alkyl group having 1 to 4 carbon atoms or a phenyl group,
And X is the following formula:

Embedded image And a 1,3-ketoester represented by the formula:

R as an alkyl group having 1 to 4 carbon atoms is, for example, a methyl group, an ethyl group, a propyl group or a butyl group.

X as an alkyl group having 10 to 20 carbon atoms may be straight-chain or branched and is, for example, n-decyl, n-dodecyl or n.
An octadecyl group.

X as a C 4 -C 12 alkylene group or as a C 2 -C 12 alkylene group substituted by at least one C 1 -C 8 alkyl group is, for example, 1,2- Ditertiary butyl dimethylene group, tetramethylene group, hexamethylene group,
It is a 2,2-dimethyltrimethylene group, a 2-ethyl-2-butyltrimethylene group, a 2-methyl-2-propyltrimethylene group, an octamethylene group, a nonamethylene group, a decamethylene group or a dodecamethylene group.

The variable n is preferably EP-043323.
0, 1, or 3 as described in the specification.

Other further stabilizers which can be used are those of the formula V:

[Chemical 6] [Where X is the following formula:

[Chemical 7] Wherein R ₁ and R ₂ independently of each other represent an alkyl group having 1 to 20 carbon atoms, a hydroxy group and / or an alkyl group having 1 to 10 carbon atoms substituted with a halogen atom, carbon An alkenyl group having 3 to 20 atoms, a cycloalkyl group having 5 to 12 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms, a phenyl group or A ₁ Represents a mono-substituted or tri-substituted phenyl group, wherein the group A ₁ independently represents an alkyl group having 1 to 10 carbon atoms, a halogen atom, a hydroxy group, a methoxy group or an ethoxy group, and R ₁
And R ₂ further represents a phenylalkyl group having 7 to 10 carbon atoms which is unsubstituted or mono- or tri-substituted by A ₂ on the phenyl ring, wherein the group A ₂ is
Independently of each other, an alkyl group having 1 to 20 carbon atoms,
Halogen atom, a hydroxyl group, a methoxy group or an ethoxy group, and R ₃ represents a mono- to trisubstituted phenyl group by a phenyl group or A _3, wherein the group A ₃ independently of one another are C 1 -C To 10 alkyl group, halogen atom, hydroxyl group, methoxy group, ethoxy group or (alkyl having 1 to 8 carbon atoms) oxycarbonyl group, provided that at least one of the groups R ₁ and R ₂ is , Phenyl group or a phenyl group substituted as defined, and R ₁
Represents a methyl group when R ₂ represents a phenyl group].

The compounds of the above formula have a very good stabilizing effect on both heat- and light-induced decomposition. The long-term stabilizing action against thermal decomposition is particularly remarkable.

R ₁ preferably does not represent an alkyl group having 1 to 3 carbon atoms, especially an alkyl group having 1 to 20 carbon atoms, when R ₂ represents a phenyl group.

The halogen atom is preferably a chlorine atom.

Alkyl groups having up to 20 carbon atoms are, for example, methyl, ethyl, propyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, isooctyl, isononyl. , A decyl group, a dodecyl group, or an octadecyl group.

An alkyl group having 1 to 10 carbon atoms substituted with a hydroxy group and / or a halogen atom is
For example, it is a 5-hydroxypentyl group, a 2,3,5-trihydroxyphenylpentyl group or a 5-chloropentyl group.

An alkyl group having 3 to 20 carbon atoms is
For example, allyl group, 2-methallyl group, 3-methylbute-2
An -enyl group, a 3-methylbut-3-enyl group, a hexenyl group, a decenyl group, an undecenyl group, a heptadecenyl group or an oleyl group. Allyl, methallyl and oleyl groups are preferred.

The cycloalkyl group having 5 to 12 carbon atoms is, for example, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group or a cyclododecyl group. A cycloalkyl group having 5 to 7 carbon atoms, particularly a cyclohexyl group is preferable.

Alkyl groups having 1 to 4 carbon atoms, in particular cycloalkyl groups having 5 to 8 carbon atoms, which are substituted by methyl groups, are, for example, methylcyclohexyl groups or tert-butylcyclohexyl groups.

Examples of phenyl groups which are mono- or tri-substituted by the defined groups are o-, m- and p-methylphenyl groups, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2 , 5-dimethylphenyl group, 2,
6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2-methyl-6-ethylphenyl group, 2-methyl-4-tertiarybutylphenyl group, 2-ethylphenyl group, 2,6-diethylphenyl group, 2,6-diethyl-4-methylphenyl group, 2,6
-Diisopropylphenyl group, 4-tert-butylphenyl group, p-nonylphenyl group, o-, m- and p-chlorophenyl group, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group , 2,
6-dichlorophenyl group, 3,4-dichlorophenyl group, 2,4,5-trichlorophenyl group, 2,4,6-
Trichlorophenyl group, o-, m- and p-hydroxyphenyl group, o-, m- and p-methoxyphenyl group,
o- and p-ethoxyphenyl group, 2,4-dimethoxyphenyl group, 2,5-dimethoxyphenyl group, 2,5-
Diethoxyphenyl group, o-, m- and p-methoxycarbonyl group, 2-chloro-6-methylphenyl group, 3-
Chloro-2-methylphenyl group, 3-chloro-4-methylphenyl group, 4-chloro-2-methylphenyl group, 5
-Chloro-2-methylphenyl group, 2,6-dichloro-
3-methylphenyl group, 2-hydroxy-4-methylphenyl group, 3-hydroxy-4-methylphenyl group, 2
-Methoxy-5-methylphenyl group, 4-methoxy-2
-Methylphenyl group, 3-chloro-4-methoxyphenyl group, 3-chloro-6-methoxyphenyl group, 3-chloro-4,6-dimethoxyphenyl group and 4-chloro-
It is 2,5-dimethoxyphenyl.

The phenylalkyl group having 7 to 10 carbon atoms is, for example, a benzyl group or a 2-phenylethyl group. A benzyl group is preferred. When the phenyl group in these groups is mono- or tri-substituted by the defined radical, it can be defined as above. An alkyl group having 1 to 20 carbon atoms on the phenyl group,
A phenylalkyl group having 7 to 10 carbon atoms, which is preferably substituted by an alkyl group having 8 to 14 carbon atoms, is defined as above. Another example of interest is the dodecylbenzyl group. More detailed list is EP-0
In the specification of 465405.

Other further stabilizers which may be used are those of the formula VI:

Embedded image [In the formula, R ₁ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxycarbonylmethyl group, or α-
Hydroxyalkyl group, esterified α-hydroxyalkyl group, α-hydroxycycloalkylmethyl group, esterified α-hydroxycycloalkylmethyl group, α-hydroxyaralkyl group, esterified α-hydroxyaralkyl group, alkoxymethyl group, alkylthiomethyl Group, aryloxymethyl group, arylthiomethyl group,
Cycloalkoxymethyl group, cycloalkylthiomethyl group, aralkoxymethyl group, aralkylthiomethyl group,
Alkoxy group, alkylthio group, cycloalkoxy group,
Represents a cycloalkylthio group, an aralkoxy group, an arylalkylthio group, an aryloxy group, an arylthio group, a halogen atom, a mercapto group, a mercaptomethyl group or a hydroxyl group, and R ₂ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, α -Hydroxyalkyl group, esterified α-hydroxyalkyl group, alkylene group whose alkyl moiety is combined with R ₁ , α-hydroxycycloalkylmethyl group, esterified α-hydroxycycloalkylmethyl group, α-hydroxyaralkyl group , Esterified α-hydroxyaralkyl group, alkoxy group, cycloalkyloxy group, aralkoxy group, aryloxy group, alkylthio group, cycloalkylthio group, aralkylthio group, arylthio group, alkoxymethyl group, alkylthiomethyl group Group, aryloxymethyl group, arylthiomethyl group, cycloalkoxymethyl group, cycloalkylthiomethyl group, aralkoxymethyl group, arylalkylthiomethyl group, hydroxyl group,
Cyano group, carboxyl group, salted, esterified or amidated carboxyl group or acyl group, -CO-alkylene group in which the acyl group is combined with R ₁ (in the formula,
CO- is bonded at the 3-position), or a halogen atom, a mercapto group or a mercaptomethyl group, and R ₃ is an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a hydroxymethyl group or an esterified hydroxymethyl group. Group, alkoxymethyl group, alkylthiomethyl group, cycloalkoxymethyl group, cycloalkylthiomethyl group, aralkoxymethyl group, arylalkylthiomethyl group, aryloxymethyl group or arylthiomethyl group, alkoxy group, alkylthio group, cycloalkoxy group , A cycloalkylthio group, an aralkoxy group,
When an aralkylthio group, an aryloxy group, an arylthio group, a halogen atom, a mercapto group or a mercaptomethyl group is represented, or R ₂ is a salted carboxyl group, R ₃ represents a hydrogen atom and R ₁ Represents a meaning as defined above, or R ₃ represents a hydroxyl group, R ₁ represents a hydrogen atom, an alkyl group or an aryl group, and R ₂ represents a hydrogen atom, an alkyl group, an aryl group or an acyl group. Or a salt thereof]. A list of them is given in the specification of EP-0022087.

Other stabilizers which can be used are those of the formula VII:

[Chemical 9] [In the formula, n represents 1 or 2, R ₁ represents an alkyl group having 1 to 4 carbon atoms, and R ₂ represents formula IIa, IIb, II.
c or IId:

[Chemical 10] X ₁ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, 1 or 2 oxygen atoms or 3 carbon atoms interrupted by a sulfur atom and / or substituted by an OH group. To C6 to C6, C3 to C20 alkenyl, C5 to C12
Cycloalkyl group having 5 to 12 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms, phenyl group; alkyl group having 1 to 10 carbon atoms, chlorine atom, hydroxyl group, methoxy group as well as/
Or a phenyl group substituted by an ethoxy group; a phenylalkyl group having 7 to 10 carbon atoms or substituted on the phenyl group by an alkyl group having 1 to 20 carbon atoms, a chlorine atom, a hydroxyl group, a methoxy group and / or an ethoxy group Represents a phenylalkyl group having 7 to 10 carbon atoms, wherein X ₂ is an unsubstituted or mono- or tri-substituted phenyl group (wherein the substituent is 1 carbon atom).
To an alkyl group having 4 to 4 carbon atoms, a chlorine atom, a hydroxyl group, a methoxy group, an ethoxy group and an acetylamino group), X ₃ represents an alkyl group having 1 to 8 carbon atoms or a phenyl group, In the case where n represents 1, R ₃ has the following formulas IIIa to IIIg:

[Chemical 11] X ₀ represents an oxygen atom or a sulfur atom, Y ₁ and Y ₂ independently of each other are a —CN group, a benzoyl group, an alkanoyl group having 2 to 4 carbon atoms, or 2 to 4 carbon atoms. 4 represents an alkoxycarbonyl group, Y ₃ is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 3 to 20 carbon atoms, a phenyl group; an alkyl group having 1 to 4 carbon atoms, a chlorine atom, NO ₂ ,
A phenyl group substituted with a methoxy group and / or an ethoxy group; a 2-phenylethenyl group, a di (alkyl having 1 to 4 carbon atoms) amino group, a diphenylamino group, an alkylamino group having 1 to 20 carbon atoms, A cycloalkylamino group having 3 to 8 carbon atoms, a phenylamino group; an alkyl group having 1 to 4 carbon atoms on a phenyl ring, a chlorine atom, a hydroxyl group, a methoxy group and / or
Or a phenylamino group substituted with an ethoxy group; a benzylamino group, a benzenesulfonamide group or a toluenesulfonamide group, and Y ₄ is di (1
To 4 alkyl) amino groups, diphenylamino groups,
An alkylamino group having 1 to 8 carbon atoms, a phenylamino group; a phenylamino group substituted on the phenyl ring with an alkyl group having 1 to 4 carbon atoms, a chlorine atom, a hydroaxyl group, a methoxy group and / or an ethoxy group; Or a benzylamino group, Y ₅ is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 3 to 6 carbon atoms interrupted by 1 or 2 oxygen atoms, or a cycloalkyl having 5 to 12 carbon atoms. Base, carbon atom 1
A cycloalkyl group having 5 to 12 carbon atoms substituted with an alkyl group having 4 to 4 carbon atoms, a phenyl group, a phenylalkyl group having 7 to 10 carbon atoms or a phenyl group substituted with an alkyl group having 1 to 20 carbon atoms Represents a phenylalkyl group having 7 to 10 carbon atoms, Y ₆ is an alkoxy group having 1 to 4 carbon atoms,
On a phenylamino group or a phenyl group, an alkyl group having 1 to 4 carbon atoms, a chlorine atom, a hydroxyl group,
Represents a phenylalkyl group having 7 to 10 carbon atoms which is substituted with a methoxy group and / or an epoxy group, and Y
₇ Alkyl group having 1 to 4 carbon atoms, phenyl group or alkyl group having 1 to 4 carbon atoms, chlorine atom, NO ₂
Represents a phenyl group substituted by a -group, an (alkyl having 1 to 12 carbons) oxycarbonyl group and / or a phenoxycarbonyl group, and the groups Y ₈ each independently represent an alkoxy group having 1 to 4 carbon atoms; When an allyloxy group is represented and n is 2, R ₃ has the following formula IVa, IVb, IVc or IVd:

[Chemical 12] X ₀ has the same meaning as defined above, Z ₁ represents a direct bond, an alkylene group having 1 to 12 carbon atoms or a phenylene group, and Z 1
₂ represents an alkylene group having 2 to 12 carbon atoms or a 3-oxapentylene group, Z ₃ represents an alkylene group having 4 to 8 carbon atoms or a phenylene group, and Z
_{And 4} represents an alkoxy group having 1 to 4 carbon atoms or an allyloxy group].

An alkyl group having 1 to 20 carbon atoms is
For example, methyl group, ethyl group, propyl group, butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, isooctyl group, isononyl group, decyl group,
It is a dodecyl group or an octadecyl group.

R ₁ is preferably a straight-chain carbon atom of 1
Represents an alkyl group of 4 to 4, especially a methyl group.

The preferred meaning of X ₁ is C ₁ -C 18 alkyl, especially C 1 -C 12 alkyl, such as methyl or ethyl.

The alkyl group X ₃ preferably represents a methyl group or an ethyl group, in particular a methyl group.

The alkyl group X ₅ preferably has 1 to 4 carbon atoms. Methyl and ethyl groups particularly preferably represent the meaning of Y ₅ .

An alkoxy group having 1 to 4 carbon atoms is
For example, it is a methoxy group, an ethoxy group, a propoxy group or a butoxy group.

Alkyl groups having 3 to 6 carbon atoms interrupted by 1 or 2 oxygen atoms are, for example, 3-oxabutyl group, 3-oxapentyl group, 3-oxaheptyl group, 3,6-dioxaheptyl group. A group or a 3,6-dioxaoctyl group.

Alkyl groups having 3 to 6 carbon atoms interrupted by 1 or 2 oxygen atoms or sulfur atoms and / or substituted by OH are, for example, in addition to the groups mentioned in the preceding paragraph, 3- Thiabutyl group, 3-thiapentyl group, 3,6-dithiaheptyl group, 3,6-dithiaoctyl group, 5-hydroxy-3-oxapentyl group, 5-hydroxy-3-thiapentyl group or 4-hydroxybutyl group.

The alkenyl group having 3 to 20 carbon atoms is, for example, allyl group, 2-methallyl group, 3-methylbut-2-enyl group, 3-methylbut-3-enyl group, hexenyl group, decenyl group, undecenyl group, It is a heptadecenyl group or an oleyl group. Preferred meaning is an allyl group,
A methallyl group and an oleyl group.

Alkyl having 1 to 4 carbon atoms, especially 5 to 12 carbon atoms which may be substituted by a methyl group.
The cycloalkyl group of is, for example, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group,
It is a cyclodecyl group, a cyclododecyl group or a methylcyclohexyl group. Unsubstituted or substituted cycloalkyl groups having 5 to 8 carbon atoms, especially cyclohexyl groups are preferred.

Examples of preferably mono- or tri-substituted phenyl groups substituted by the defined groups are o
-, M- and p-chlorophenyl groups, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 2,6-dichlorophenyl group, 3,
4-dichlorophenyl group, 2,4,5-trichlorophenyl group, 2,4,6-trichlorophenyl group, o-, m
-And p-methylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3, 5-dimethylphenyl group, 2-
Methyl-6-ethylphenyl group, 2-methyl-4-tertiarybutylphenyl group, 2-ethylphenyl group, 2,6-diethylphenyl group, 2,6-diethyl-4-methylphenyl group, 2,6- Diisopropylphenyl group, 4-tert-butylphenyl group, p-nonylphenyl group, 2-chloro-6-methylphenyl group, 3-chloro-2-methylphenyl group, 3-chloro-4-methylphenyl group, 4- Chloro-2-methylphenyl group, 5-chloro-2-methylphenyl group, 2,6-dichloro-3-methylphenyl group,
o-, m- and p-methoxyphenyl groups, o- and p-
Ethoxyphenyl group, 2,4-dimethoxyphenyl group,
2,5-dimethoxyphenyl group, 2,5-diethoxyphenyl group, 2-methoxy-5-methylphenyl group, 4-
Methoxy-2-methylphenyl group, 3-chloro-4-methoxyphenyl group, 3-chloro-6-methoxyphenyl group, 3-chloro-4,6-dimethoxyphenyl group, 4-
Chloro-2,5-dimethoxyphenyl group, o-, m- and p-hydroxyphenyl group, 2-hydroxy-4-methylphenyl group, 3-hydroxy-4-methylphenyl group, o-, m- and p- Acetylaminophenyl group, o
-, M- and p-nitrophenyl groups, p- (alkyl having 1 to 12 carbon atoms) oxycarbonylphenyl group and p-phenyloxycarbonylphenyl group.

If Y ₃ , Y ₄ and Y ₆ are phenylamino radicals which are substituted, preferably mono- or trisubstituted, on the phenyl radical by a defined radical, the substituted phenyl radical is, for example: It may represent what is defined above.

The phenylalkyl group having 7 to 10 carbon atoms is, for example, a benzyl group or a 2-phenylethyl group. A benzyl group is preferred. If the phenyl groups in these radicals are substituted, preferably mono- or tri-substituted by the defined radicals, they can be defined as above. An alkyl group having 1 to 20 carbon atoms on the phenyl group, preferably 8 to 1 carbon atoms
7 to 1 carbon atoms substituted by an alkyl group of 4
A phenylalkyl group of 0 is one of the preferred meanings. The dodecylbenzyl group may be noted as another example.

The alkanoyl group having 2 to 4 carbon atoms is, for example, an acetyl group, a propanoyl group or a butanoyl group. Acetyl is preferred.

The alkoxycarbonyl group having 2 to 4 carbon atoms is, for example, a methoxycarbonyl group, an ethoxycarbonyl group or a propoxycarbonyl group. A methoxycarbonyl group and an ethoxycarbonyl group are preferred.

The di (C1-C4 alkyl) amino group is, for example, a dimethylamino group, a diethylamino group, a dipropylamino group or a dibutylamino group.

An alkylamino group having 1 to 20 carbon atoms, preferably an alkylamino group having 1 to 8 carbon atoms, particularly an alkylamino group having 4 to 8 carbon atoms is
For example, it is a butylamino group, a pentylamino group, a hexylamino group, a heptylamino group or an octylamino group.

The cycloalkylamino group having 3 to 8 carbon atoms is, for example, a cyclopropylamino group, a cyclohexylamino group or a cyclooctylamino group.

Alkylene groups having up to 12 carbon atoms are, for example, methylene, dimethylene, trimethylene, butylene, pentamethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene. Alkylene groups having up to 8 carbon atoms are preferred. The specification of US 5155152 contains a review.

Other usable stabilizers which can be used are the following formulas a and b:

[Chemical 13] [Wherein R ¹ is an alkyl group having 1 to 22 carbon atoms,
Phenyl group, phenyl group substituted by mono- or di (alkyl group having 1 to 9 carbon atoms), 5 carbon atoms
To a cycloalkyl group represented by the following formula A or B:

Embedded image Or R ¹ is a group represented by the following formula ca or c
b:

[Chemical 15] Wherein R ² and R ³ are each independently substituted by an alkyl group having 1 to 20 carbon atoms, a phenyl group, a mono- or di- (alkyl group having 1 to 9 carbon atoms). Represents a phenyl group or a cycloalkyl group having 5 to 7 carbon atoms, and R ⁴ represents an alkylene group having 2 to 12 carbon atoms]. A more detailed description, examples and selections are given in the specification of EP-224438.

Another stabilizer is of the formula:

Embedded image [Wherein R ₁ is a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 2 to 6 carbon atoms, a mercapto group, an alkylthio group having 1 to 6 carbon atoms, -SC
H ₂ —COOH group or —S—CH ₂ —COO— (alkyl having 1 to 6 carbon atoms) group, X is a thio group,
Methylene group, -COO- group or a -S-CH ₂ -COO-
Represents a group, in each case an alkyl group is bound via an ester oxygen atom, m represents an integer from 1 to 20, n represents 1 or 2 and R ₂ is monovalent, Represents a hydrogen atom, a hydroxyl group or a mercapto group, and when divalent, represents a direct bond, an imino group, an alkylimino group having 1 to 6 carbon atoms, an oxy group, a thio group or a methylene group, and R ₃ represents hydrogen atom, an amino group, a mercapto group or an alkylthio group having 1 to 12 carbon atoms, and when R ₃ represents a hydrogen atom, R ₄ represents a hydrogen atom, a -COOR _5, wherein, R ₅ Represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a —CH ₂ —COO— (alkyl having 1 to 8 carbon atoms) group, or an —S—R ₆ group, and R ₆ represents a hydrogen atom or a carbon atom. 1 to 12 Alkyl group, -CH ₂ -
COO- (C1-8 alkyl) group or C1-12 alkylthio group or the following formula:

[Chemical 17] Represents a group represented by: wherein X'is -CO-NH
-Alkylene-NH-CO- group, -CO-alkylene-
Represents an S-alkylene-CO- group (in each case having 1 to 12 carbon atoms in the alkylene chain) or (an alkylene group having 1 to 12 carbon atoms), and R ₃ represents NH ₂ . In this case, R ₄ is an alkyl group having 1 to 4 carbon atoms, a mercapto group, an alkylthio group having 1 to 4 carbon atoms or the following formula:

Embedded image Where R ₃ represents a mercapto group, R ₄ represents an unsubstituted or substituted phenyl group, and R ₃ Represents an alkylthio group having 1 to 12 carbon atoms, R ₄ represents an alkyl group having 1 to 4 carbon atoms, an alkylthio group having 1 to 12 carbon atoms or an unsubstituted or substituted phenyl group] Is a triazole represented by.

These stabilizers, other aspects, examples and selections are given in the specification of DE-3048659.

A) The following formula VIII:

[Chemical 19] [In the formula, n represents 0 or 1, and R is an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms. Represents an aryl group having 6 to 10 carbon atoms, and R ₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, each X as a repeating unit is the same or different from another, and Hydrogen atom or the following formula:

Embedded image Represents a group represented by and each Y as a repeating unit
Is the same as or different from the others, and is an alkylene group having 1 to 6 carbon atoms or the following formula:

[Chemical 21] In represents a group represented by wherein, - (CH _{2) m} - group is attached to an oxygen atom, and R ₂ is a hydrogen atom or the following formula:

[Chemical formula 22] And n is 1 to 4 and p is 0 to 3, Z is an alkylene group having 1 to 6 carbon atoms or the following formula:

[Chemical formula 23] A) a thioether represented by the formula: b) a stabilizer consisting of a metal from the group consisting of zinc, calcium, magnesium and antimony, or a stabilizer consisting of zinc further mixed with at least one of said metals. A mixture may be mentioned.

Other details, examples and preferences related to this are given in the specification of EP-19576.

The following equation IX:

[Chemical formula 24] [In the formula, m represents 0, 1 or 2, and n is 0, 2 or 3
And p represents 1 or 2 and Hal represents-
Represents F, -Cl, -Br or -I, and X is -NH
₂ group, -NHCH ₃ group and / or -OCH ₃ or OC ₂
Represents a H ₅ group, Y represents a —CO— group or a —SO ₂ — group, and R represents —H, —OH group, —NH ₂ group, unsubstituted or, for example, 1 to 3 HO— groups and / or Or an alkyl group having 1 to 18 carbon atoms substituted by an alkoxy group having 1 to 4 carbon atoms or a phenoxy group, a phenyl group, a benzyl group or a phenethyl group, or R is further represented by the following formula:

[Chemical 25] (In the formula, X, Y, m, n and Hal represent the meanings defined above)]. A detailed description, examples and selections are given in the specifications EP 122228 and EP 174412.

At least one of the following formulas X:

[Chemical formula 26] [Wherein, X represents an O atom or an S atom, n represents an integer of 1 to 5, and R represents a linear or branched alkyl group having 1 to 18 carbon atoms or a substituted or unsubstituted alkyl group. A compound represented by a cyclohexyl group] is added to at least one PVC stabilizer of the Me (II) carboxylate and / or Me (II) phenoxide type [wherein M is
e (II) represents one or more metals from the group consisting of Ba, Sr, Ca, Mg, Zn and Cd] and is mixed with a stabilizer mixture [in this case PCV] In contrast, 0.01 to 2% by weight of formula I
And a compound of 0.1 to 4 wt% Me
(II) carboxylate and / or Me (II) phenoxide are used]. Said stabilizer mixture is disclosed in the specification of EP-90770, which also gives examples and options.

Examples of suitable organic plasticizers are from the following groups. Examples of A) phthalate (esters of phthalic acid) These plasticizers of phthalic acid, dimethyl, diethyl, dibutyl, dihexyl, di-2-ethylhexyl,
Di-n-octyl, diisooctyl, diisononyl, diisodecyl, diisotridecyl, dicyclohexyl, dimethylcyclohexyl, dimethyl glycol, dibutyl glycol, benzyl butyl and diphenyl esters and mixtures of phthalates, for example carbon of phthalic acid obtained mainly from linear alcohols. These are alkyl esters having 7 to 9 atoms and 9 to 11 carbon atoms, phthalic acid (n-alkyl having 6 to 10 carbon atoms) ester and phthalic acid (alkyl having 8 to 10 carbon atoms) ester. Phthalic acid dibutyl, dihexyl, di-2-
Ethylhexyl, di-n-octyl, diisooctyl,
Diisononyl, diisodecyl, diisotridecyl and benzyl butyl esters, and mixtures of said phthalic acid alkyl esters are preferred. The di-2-ethylhexyl ester, diisononyl ester and diisodecyl ester of phthalic acid are particularly preferred.

B) Esters of aliphatic dicarboxylic acids , especially of adipic acid, azelaic acid and sebacic acid Examples of these plasticizers are di-2-ethylhexyl adipate, diisooctyl adipate (mixture), diisononyl adipate ( Mixture), diisodecyl adipate (mixture), benzyl benzyl adipate, benzyl octyl adipate, di-2-ethylhexyl azelate, di-2-ethylhexyl sebacate and diisodecyl sebacate (mixture). Di-2-ethylhexyl adipate and diisooctyl adipate are preferred.

C) Esters of trimellitic acid For example, tri-2-ethylhexyl trimellitate, triisodecyl trimellitate (mixture), triisotridecyl trimellitate, tri-isooctyl trimellitate (mixture) and tri-mellic acid having 6-carbon atoms. Through 8
Alkyl-, tri-alkyl having 6 to 10 carbon atoms, tri-alkyl having 7 to 9 carbon atoms and tri-alkyl having 9 to 11 carbon atoms. The trimellitic acid ester described below is formed by esterifying trimellitic acid with a suitable alkanol mixture. A preferred trimellitic acid ester is the trimellitic acid ester prepared from a mixture of tri-2-ethylhexyl trimellitic acid and an alkanol.

D) Epoxy plasticizers , such as 1,2-epoxides and oxiranes, examples being epoxidized polybutadiene, epoxidized soybean oil, epoxidized linseed oil, epoxidized fish oil, epoxidized tallow, methylbutyl or 2-ethylhexylepoxysteare. Rate, tris (epoxypropyl) isocyanurate, epoxidized castor oil, epoxidized sunflower oil, 3
-(2-phenoxy) -1,2-epoxypropane, bisphenol A polyglycidyl ether, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide and 3,4-epoxycyclohexylmethyl 3,4
-Epoxycyclohexanecarboxylate.

E) Polymer Plasticizers The definitions and examples of these plasticizers are given in the following document: "TASCHENBUCH DER KUNSTSTOFF-ADDITI.
VE), Elle. R. Gaechter and Har. Muller
(H.Mueller), Hanser Verlak
ag), 1990, p. 412, chapter 5.9.6, "and" Polyvinyl Chloride Technology (PVC Technology), Double.
V. Fourth Edition, edited by WV Titow. , Elsevier Publ., 1984, No. 165-1
70 pages. The most common starting materials for the production of polyester-based plasticizers are dicarboxylic acids such as adipic acid, phthalic acid, azelaic acid and sebacic acid; 1,2-propanediol, 1,3-butanediol, 1, Diols such as 4-butanediol, 1,6-hexanediol, neopentyl glycol and diethylene glycol; such as acetic acid, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, pelargonic acid and benzoic acid. Monocarboxylic acid; isooctanol, 2
Monofunctional alcohols such as ethylhexanol, isodecanol and mixtures of C 7 -C 9 alkanols and C 9 -C 11 alkanols. Particularly advantageous are polyester plasticizers prepared from the above dicarboxylic acids and monofunctional alcohols.

F) Esters of Phosphoric Acid The definition of these esters is as defined above in “Taschenbuch der Kunststoff-Additive”.
CH DER KUNSTSTOFF-ADDITIVE), pp. 408, 5.
9.6 ". Examples of these phosphates include tributyl phosphate, tri-2-ethylbutyl phosphate, tri-2-ethylhexyl phosphate, trichloroethyl phosphate, 2-ethylhexyl phosphate. Diphenyl, cresyl diphenyl phosphate, triphenyl phosphate, tricresyl phosphate and trixylenyl phosphate Tri-2-ethylhexyl phosphate and Reophos (registered trademark;
Reofos) 50 is preferred.

G) Chlorinated hydrocarbons or chlorinated paraffins

H) Hydrocarbon (paraffin)

I) Monoesters, for example esters of butyl oleate, phenoxyethyl oleate, tetrahydrofurfuryl oleate and alkylsulphonic acids.

J) Esters of glycols, for example diglycol benzoates, or full or partial esters of conventional polyols.

Definitions and examples of plasticizers of groups G) to J) are given in the handbooks below.

[TASCHENBUCHDER KUNSTSTOFF-ADD [Taschenbuch Der Kunststoff-Additive
ITIVE), El. R. Gaechter and Har. Edited by H. Mueller, Hanser Ferluk
Verlag), 1990, p. 422, 5.9.14.
Chapter 2 (Group G) and Chapter 5.9.14.1 (Group H) "

“Polyvinyl Chloride Technology (PVC Technology),
W. V. Fourth Edition, edited by WV Titow. ，
Elsevier Publ., 1984, 171-173, Chapter 6.10.2 (Group G), 17th.
P. 4, chapter 6.10.5 (group H), p. 173, p.
Chapter 10.3 (Group I) and pp. 173-174, 6.1
Chapter 0.4 (Group J).

Preference is given to plasticizers of the groups A) to F), in particular of the groups A) to D) and F), especially the plasticizers within the groups mentioned as being preferred.

It is also possible to use mixtures of different plasticizers.

The plasticizer is used in an amount of 1 to 120 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of PVC.
It may be used in an amount of 0 parts by weight, especially 2 to 70 parts by weight.

Suitable dihydropyridines are monomeric and oligomeric compounds, for example EP-0362012,
It is described in each specification of EP-0286887 and EP-0024754.

Suitable perchlorates are alkali metal perchlorates and alkaline earth metal perchlorates and zinc perchlorates and aluminum perchlorates, or their cations being the surfactant ammonium or A perchlorate composed of a phosphonium cation, for example, US
It is also possible to apply it to a support as described in the specification of 5034443. It is also possible to use adducts of these perchlorates with monohydric and polyhydric alcohols.

Examples of suitable antioxidants are: 1. Alkylated monophenols such as 2,6-di-tert-butyl-4-methylphenol, 2-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-isobutylphenol, 2,6-dicyclopentyl-4-methylpheno -L, 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2,6
-Dioctadecyl-4-methylphenol, 2,4,6
-Tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6-
(1'-methylundeci-1'-yl) phenol,
2,4-Dimethyl-6- (1'-methylheptadecyl-
1'-yl) phenol, 2,4-dimethyl-6-
(1'-Methyltridec-1'-yl) phenol and mixtures thereof.

2. Alkylthiomethylphenol, for example, 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-
Ethylphenol and 2,6-di-dodecylthiomethyl-4-nonylphenol.

3. Hydroquinone and alkylated hydroquino
Emissions For example, 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 Tributyl-4-hydroxyphenyl stearate, bis (3,5-di-tert-butyl-
4-hydroxyphenyl) adipate.

4. Hydroxylated thiodiphenyl ether
Le for example 2,2'-thiobis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thiobis (6-tert-butyl -
3-methylphenol), 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-thiobis (3,6-di-second-amylphenol), 4,4'-
Bis (2,6-dimethyl-4-hydroxyphenyl)-
Disulfide.

5. Alkylidene bisphenols such as 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- (α-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 (4,4)
6-di-tert-butylphenol), 2,2'-ethylidene-bis (6-tert-butyl-4-isobutylphenol), 2,2'-methylene-bis [6- (α-methylbenzyl) -4-nonylphenol ], 2,2′-Methylene-bis [6- (α, α-dimethylbenzyl) -4-nonylphenol], 4,4′-methylene-bis (2,6
-Di-tert-butylphenol), 4,4'-methylene-
Bis (6-tert-butyl-2-methylphenol), 1,
1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3-tert-butyl-
5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-tert-butyl-4-)
Hydroxy-2-methylphenyl) butane, 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecylmercaptobutane, ethylene glycol bis [3,3-bis (3 ′ -Tert-butyl-
4'-hydroxyphenyl) butyrate], bis (3-
Tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, bis [2- (3'-tert-butyl-
2'-Hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1,1
-Bis (3,5-dimethyl-2-hydroxyphenyl)
Butane, 2,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-
n-dodecyl mercaptobutane, 1,1,5,5-tetra- (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane.

6. O-, N- and S-benzyl compounds such as 3,5,3 ', 5'-tetra-tert-butyl-
4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl-mercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tertiary Tributyl-3-hydroxy-2,6-dimethylbenzyl)-
Dithioterephthalate, bis (3,5-di-tert-butyl-
4-hydroxybenzyl) sulfide, isooctyl-
3,5-Ditert-butyl-4-hydroxybenzyl-mercaptoacetate.

7. Hydroxybenzylated malonate, for example, dioctadecyl 2,2-bis (3,5-ditert-butyl-2-hydroxybenzyl) malonate, dioctadecyl 2- (3-tert-butyl-4-hydroxy-5-).
Methylbenzyl) malonate, didodecylmercaptoethyl 2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, di [4- (1,1,3,3)
-Tetramethylbutyl) phenyl] 2,2-bis (3,
5-di-tert-butyl-4-hydroxybenzyl) malonate.

8. Hydroxybenzyl aromatic compound, for example, 1,3,5-tris (3,5-di-tert-butyl-
4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-ditert-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2, 4,6-Tris (3,5-di-tert-butyl-
4-hydroxybenzyl) phenol.

9. Triazine compounds such as 2,4-bis-octylmercapto-6-
(3,5-di-tert-butyl-4-hydroxyanilino)-
1,3,5-triazine, 2-octyl mercapto-
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,
3,5-Tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-Tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate , 2,4,6-Tris (3,5-di-tert-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.

10. Phosphonate, Sulfite
Tellurium and phosphonite, for example, dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4
-Diethyl hydroxybenzylphosphonate, 5-tertiary-
Dioctadecyl butyl-4-hydroxy-3-methylbenzylphosphonate, dioctadecyl 3,5-di-tert-butyl-4-hydroxy-3-methylbenzylphosphonate; 3,5-di-tert-butyl-4- Calcium salt of hydroxybenzylphosphonic acid monoethyl ester; triphenyl phosphite, diphenylalkyl phosphite, phenyldialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, di Stearyl pentaerythritol diphosphite, tris (2,4-ditert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol diphosphite, Bis (2,6-di-tert-butyl-4-methylphenyi ) Pentaerythritol diphosphite, bis-isodecyloxy pentaerythritol diphosphite, bis (2,4-di-tert-butyl-6
Methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tritert-butyl-6-methylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-ditert-butylphenyl) ) -4,4'-Biphenylenediphosphonite, 6-isooctyloxy-2,
4,8,10-Tetra-tert-butyl-12H-dibenz [d, g] -1,3,2-dioxaphosphocin, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-
Methyldibenz [d, g] -1,3,2-dioxaphosphocin, bis (2,4-di-tert-butyl-6-methylphenyl) methyl phosphite, bis (2,4-di-phosphite) tert-butyl-6-methylphenyl) ethyl, (C ₉ H ₁₉ -C
_{6 H 4) 1.5 -P- (O} -C 12-13 H 25-27) 1.5.

11. Acylaminophenols for example, lauric acid 4-hydroxyanilide, stearic acid 4-hydroxyanilide, carbamate N-(3,
5-di-tert-butyl-4-hydroxyphenyl) octyl ester.

12. β- (3,5-di-tert-butyl-4-
The following monovalent or poly (hydroxyphenyl) propionic acid
Esters with polyhydric alcohols, for example, methanol, ethanol, octadecanol,
1,6-hexanediol, 1,9-nonanediol,
Ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) 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.

13. β- (5-tert-butyl-4-hydro
The following monovalents of xy-3-methylphenyl) propionic acid
Or an ester with a polyhydric alcohol, for example, methanol, ethanol, octadecanol,
1,6-hexanediol, 1,9-nonanediol,
Ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) 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.

14. β- (3,5-di-cyclohexyl
-4-Hydroxyphenyl) propionic acid monovalent
Or an ester with a polyhydric alcohol, for example, methanol, ethanol, octadecanol,
1,6-hexanediol, 1,9-nonanediol,
Ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) 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.

15.3,5-Di-tert-butyl-4-hydr
The following monovalent Rokishifeniru acetic acid or a polyhydric alcohol
Ester of, for example, methanol, ethanol, octadecanol,
1,6-hexanediol, 1,9-nonanediol,
Ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) 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.

16. β- (3,5-di-tert-butyl-4-
Hydroxyphenyl) propionic acid amides such as N, N'-bis (3,5-ditert-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.

17. Thiodiacetic acid and thiodipropionic acid
Esters preferred are antioxidants from the group 5, 10 and 14, in particular, 2,2-bis (4-hydroxyphenyl) propane, 3,5-di-tert-butyl-4-hydroxy-phenylpropionic acid and octa Esters with decanol or pentaerythritol, and tris (2,4-ditert-butylphenyl) phosphite. Mixtures of antioxidants of different structure may also be used if desired. The antioxidant is, for example, 0.01% with respect to 100 parts by weight of PVC.
It may be used in an amount of from 1 to 10 parts by weight, preferably 0.1 to 10 parts by weight, especially 0.1 to 5 parts by weight.

Examples of suitable UV absorbers and light stabilizers are: 1.2- (2'-hydroxyphenyl) benzotriazo
Lumpur For example, 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-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-5'-tert-butyl-2'-hydroxyphenyl) benzo Triazole, 2
-(2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2- (3 ', 5'-ditertiary amyl-
2'-hydroxyphenyl) benzotriazole, 2-
(3 ', 5'-bis (α, α-dimethylbenzyl)-
2'-hydroxyphenyl) benzotriazole; 2-
(3'-tert-butyl-2'-hydroxy-5 '-(2'
-Octyloxycarbonylethyl) phenyl) -5-
Chlorobenzotriazole, 2- (3'-tert-butyl-
5 '-[2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-(2- Methoxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3 '
-Tert-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl) benzotriazole,
2- (3'-tert-butyl-2'-hydroxy-5'-
(2-Octoxycarbonylethyl) 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) phenylbenzo Mixture of triazoles; 2,2'-methylenebis [4- (1,1,3,
3-tetramethylbutyl) -6-benzotriazole-
2-ylphenol]; 2- [3'-tert-butyl-5 '
- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] transesterification product of benzotriazole with polyethylene glycol 300; [R-CH ₂ CH
_{2 -COO (CH 2) 3 -} ] 2 - ( wherein, R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazole-2-yl - phenyl).

2. 2-Hydroxy-benzophenone, for example 4-hydroxy-, 4-methoxy-, 4-octoxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 4,2 ', 4 ′ -Trihydroxy- or 2′-hydroxy-4,4′-dimethoxy derivative.

3. Substituted and unsubstituted benzoic acid esters
Ter, for example, 4-tertiary butyl phenyl salicylate, phenyl salicylate, octyl phenyl salicylate, dibenzoyl resorcinol, bis (4-tertiary butyl benzoyl) resorcinol, benzoyl resorcinol,
2,4-Ditert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-
Di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5
-Di-tert-butyl-4-hydroxybenzoate.

4. Acrylate, for example, ethyl α-cyano-β, β-diphenyl acrylate, isooctyl α-cyano-β, β-diphenyl acrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, Butyl α-cyano-β-methyl-p-methoxycinnamate, methyl α-carbomethoxy-p-methoxycinnamate, and N- (β-carbomethoxy-β
-Cyanovinyl) -2-methylindoline.

5. Nickel compound, for example, 2,2'-thiobis [4- (1,1,3,3-
Tetramethylbutyl) phenol] nickel complexes, eg 1: 1 or 1: 2 complexes, optionally with other ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel. Dibutyldithiocarbamate; nickel salts of monoalkyl esters such as methyl or ethyl esters of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid; ketoxime such as nickel complexes of 2-hydroxy-4-methyl-phenylundecylketoxime. ; 1
A nickel complex of phenyl-4-lauroyl-5-hydroxy-pyrazole, optionally with other ligands.

6. Sterically hindered amines such as bis (2,2,6,6-tetramethylpiperidyl) sebacate, bis (2,2,6,6-tetramethylpiperidyl) succinate, bis (1,2,2,6,6)
-Pentamethylpiperidyl) sebacate, bis (1,
2,2,6,6-Pentamethylpiperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, 1- (2-hydroxyethyl) -2,2,6
Condensation product of 6-tetramethyl-4-hydroxypiperidine and succinic acid, N, N'-bis (2,2,6,6-
Tetramethyl-4-piperidyl) hexamethylenediamine and 4-tertiary octylamino-2,6-dichloro-1,
Condensation product with 3,5-s-triazine, tris (2,2
2,6,6-Tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1,1 ′-(1,2-ethanediyl) -bis (3,3,5,5-tetramethylpiperazinone), 4-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-ditert-butylbenzyl) malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2, 4-dione, bis (1-octyloxy-2,
2,6,6-Tetramethylpiperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, N, N′-bis (2,2
2,6,6-Tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro-
Condensation product with 1,3,5-triazine, 2-chloro-
4,6-di (4-n-butylamino-2,2,6,6-
Condensation product of tetramethylpiperidyl) -1,3,5-triazine and 1,2-bis (3-aminopropylamino) ethane, 2-chloro-4,6-di (4-n-butylamino-1, 2,2,6,6-pentamethylpiperidyl)
Condensation product of -1,3,5-triazine and 1,2-bis (3-aminopropylamino) ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,
3,8-triazaspiro [4.5] decane-2,4-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 and timasorb (trade name; Chimassorb) 966.

7. Oxamide, for example 4,4'- dioctyloxyoxanilide ,
2,2'-Dioctyloxy-5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethoxanilide, N, N ' -Bis (3-dimethylaminopropyl)
Oxamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and the compound and 2-ethoxy-2'-
A mixture with ethyl-5,4'-ditertiary butoxanilide,
And mixtures of o- and p-methoxy-disubstituted oxanilides and o- and p-ethoxy-disubstituted oxanilides.

8.2- (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-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-butoxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl)-
1,3,5-triazine, 2- [2-hydroxy-4-
(2-Hydroxy-3-octyloxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl)
-1,3,5-triazine.

Examples of suitable peroxide scavengers are esters of β-thiodipropionic acid, for example lauryl ester, stearyl ester, myricyl ester or tridecyl ester, mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole. , Zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis (β-dodecylmercapto) propionate and ethylene glycol bismercaptoacetate.

Examples of suitable lubricants are eg DE-420.
Montan wax described in the specification of 4887,
Fatty acid esters, PE waxes, amide waxes, polyol partial esters, partially hydrolyzed PE waxes, so-called complex esters, chlorinated paraffins, glycerol esters, alkaline earth metal soaps and aliphatic ketones. Lubricants that can be used are "Taschen Buch der Kunststoff-Additive (TASCHEN
BUCH DER KUNSTSTOFF-ADDITIVE) ”, El. Gechter
(R. Gaechter) and Har. H. Mueller Edition, Hanser Verlag, 3rd Edition, 199
Year 0, pp. 443-503. Other lubricants, especially combinations thereof, are described in EP-00628.
13 and EP-0336289.

Examples of suitable polyols are pentaerythritol, dipentaerythritol, tripentaerythritol, trimethylolethane, bistrimethylolethane, trimethylolpropane, bistrimethylolpropane, sorbitol, mannitol, xylitol, lactose, lauculose, tris (hydroxyethyl). )
Isocyanurate, tris (dihydroxypropyl) isocyanurate, inositol, tetramethylol cyclohexanol, tetramethylol cyclopentanol, tetramethylol cyclopyranol, glycerol, diglycerol, polyglycerol, thiodiglycol, thiodiglycerol, bishydroxyethyl tartar Amide, hexakis (hydroxyethyl) melamine, bistrihydroxymethyloxamide, tristrihydroxymethylcitramide and α-, β- and γ-
Cyclodextrin.

The polyol is, for example, 0.01 to 20 parts by weight, preferably 0.1 to 20 parts by weight, particularly 0.1 to 10 parts by weight, particularly preferably 0.1 to 10 parts by weight, relative to 100 parts by weight of PVC. It can be used in an amount of 3 parts by weight.

Suitable compounds from the system consisting of hydrotalcites, zeolites, dawsonites, magaziites, kenyaites and kanemite are both natural minerals and synthetic compounds.

Compounds from the system consisting of hydrotalcites have the general formula XIII:

[Chemical 27] [In the formula, M ²⁺ is Mg, Ca, Sr, Zn and / or Sn
And M ³⁺ represents Al, B or Bi, and A 3
^n- represents an anion having n valence, and n is 1 to 4
, X represents a number from 0 to 0.5, and m represents a number from 0 to 2, and A ^n- preferably has the formula:

[Chemical 28] Represents a group represented by].

Another example of hydrotalcite is DE-41
06403.

Other hydrotalcites which may preferably be used are of the general formula XIIIa:

[Chemical 29] Wherein M ²⁺ represents at least one metal from the group consisting of Mg and Zn, preferably Mg, A ⁿ⁻ is an anion, preferably a CO ₃ ²⁻ group,

Embedded image Represents an anion from a system consisting of a group represented by, an OH ⁻ group and an S ²⁻ group, where n represents the valency of the anion, m represents a positive number, preferably 0.5 to 5,
And x and z represent positive numbers, x preferably represents 2 to 6, and z preferably represents a number less than 2.].

Formula XIII:

[Chemical 31] [ ^Wherein M ²⁺ represents Mg or a solid solution of Mg and Zn, A ⁿ⁻ represents a CO ₃ ²⁻ group, and x represents 0 to 0.5.
And m is a number from 0 to 2], and compounds from the system consisting of hydrotalcites are preferred.

The following equation:

Embedded image The hydrotalcite represented by is very particularly preferred.

Zeolites have the general formula XIV:

[Chemical 33] [In the formula, n represents the valence of the cation M, and M is I or II.
Represents an element from the main group or represents a zinc atom,
y: x is a number between 0.8 and infinity, preferably 0.
Represents a number between 8 and 10.5, and W represents a number between 0 and 300].

Further, the zeolite which can be used is “Atlas of Zeolite Structure Type”.
pes) ", WM Meier and DH Olson, Butterworths, 3rd Edition, 1992.

Zeolite in a broad sense also includes aluminum phosphite having a zeolite structure.

Known preferred zeolites are 3 to 5
It has an effective pore diameter of Å and can be manufactured by known methods. A NaA-type zeolite having an effective pore size of 4Å, that is known as zeolite 4A, is preferred.

Particularly preferred is crystalline sodium aluminosilicate, the particle size of which is at least mainly in the range 1-10 μm.

In a preferred embodiment of the present invention, sodium alumosilicate with rounded corners and edges may also be used.

The following equation:

Embedded image Or a compound represented by the following formula:

Embedded image Preference is given to zeolites which can be prepared by replacing all or some of the sodium atoms with lithium, potassium, magnesium, calcium, strontium or zinc atoms, such as

Suitable dawsonites or more generally alumo salt compounds are for example those of the formula XV: {(Mt ₂ O) _{m
· (Al 2 O 3) n} · Z o · pH 2 O} wherein, Mt is H, Na, K, Li, Mg 1/2, Ca 1/2, the Sr _1/2 or Zn _1/2 Representation; Z is CO ₂ , SO ₂ , (Cl ₂ O
₇ ) _1/2 , B ₄ O ₆ , S ₂ O ₂ (thiosulfate) or C ₂ O ₂ (oxalate); m is 1 to 3
N is a number from 1 to 4; o is a number from 2 to 4; and p is a number from 0 to 30]; these are natural minerals or synthetic compounds. May be The metals may be partially replaced with each other. Dawsonite is crystalline, partially crystalline or amorphous or in the desired gel form. Dawsonite may be a rare crystalline modification. The method for producing said compound is described in the specification of EP-0394670. Examples of natural alumo salt compounds are indigirite, tunisite, alumohydrocalsite, para-alumohydrocalsite, strontiodresserite and hydro-strontiothio. It is a dresserite (hydro-strontio dresserite). Other examples of alumo salt compound potassium alumo carbonates _{{(K 2 O) · (} Al 2 O 3) is · (CO _{2) 2} · ₂
H ₂ O}, sodium alumosulfate {(Na
₂ O) ・ (Al ₂ O ₃ ) ・ (S ₂ O ₂ ) ₂・ 2H
₂ O}, potassium alumosulsulfite {(K ₂ O)
. (Al ₂ O ₃ ). (SO ₂ ) ₂ .2H ₂ O}, calcium alumoxalate {(CaO). (Al ₂ O ₃ ).
_{· (C 2 O 2) 2} · 5H 2 O}, the following equation:

Embedded image It is magnesium almotetraborate represented by.

The following formula: Na ₂ Si ₁₄ O ₂₉ · nH ₂ O or N
Magadite represented by a ₂ Si ₈ O ₁₇ .nH ₂ O [where n represents a number of 0 to 30] is suitable.

Kenyaite represented by the following formula: Na ₂ Si ₂₂ O ₄₅ .nH ₂ O [wherein n represents a number of 0 to 30] is suitable.

The following formula: Na ₂ Si ₂ O ₅ .nH ₂ O, Na
HSi ₂ O ₅ · nH ₂ O or Na ₂ Si ₄ O ₉ · nH ₂
Kanemite represented by O [wherein n represents a number of 0 to 30] is suitable.

The magadiite, kenyaite and kanemite which can be used can be natural minerals or synthetic compounds.
The method for producing the compound is described in, for example, EP-047214.
4, EP-0615955, EP-0615956, E
P-0627383 and DE-4107955.

The mixed alumo salt compounds can be obtained in a known manner, preferably by cation exchange from alkali metal alumo salt compounds or by coprecipitation (see for example US Pat. No. 5,194,458).

Preferred is the formula XV [wherein Mt is N
represents a or K; Z is CO ₂ , SO ₂ or (Cl ₂ O
₇ ) _1/2 ; m represents a number from 1 to 3; n represents a number from 1 to 4; o represents a number from 2 to 4; and p represents a number from 0 to 20]. It is represented. Z particularly preferably represents CO ₂ .

Another preferred compound has the formula:

Embedded image [In the formula, Mt is a metal, for example, Na, K, Mg _1/2 , Ca
_1/2 , Sr _1/2 or Zn _1/2 , and p represents a number from 0 to 12].

[0172] the following equation: Na kenyaite also preferably represented by ₂ Si ₁₄ Magajiito represented by O ₂₉ · 6H ₂ O and _{Na 2 Si 22 O 45 · 7H} 2 O.

(A) PVC or a recycled product thereof, (b) the following formula: C ₆ H ₁₁ O ₆ (C ₆ H ₁₀ O ₅ ) _n C ₆ H ₁₃ O ₅ (where n is a number from 0 to 5) Represents a di- or polysaccharide alcohol, and (c) one of PVC
0.001-5.0 parts by weight per 100 parts by weight of an inorganic or organic zinc compound, and optionally 0.1-per 100 parts by weight of a phenolic antioxidant, especially PVC.
A stabilized halogen-containing polymer consisting of 5.0 parts by weight of a phenolic antioxidant is preferred.

Particularly preferred are those in which component (b) is a disaccharide alcohol.

Very particular preference is given to component (b)
Is maltitol, lactitol, isomaltitol or palatinitol.

Further preferred are β-diketones and /
Or a stabilized halogen-containing polymer further containing its Mg salt, Ca salt or Zn salt, or β-keto ester.

Even more preferred are stabilized halogen containing polymers which further comprise an epoxide.

Further preferred are halogen-containing polymers which further comprise monomeric, oligomeric or polymeric dihydropyridines.

Further preferred are stabilized halogen-containing polymers which further comprise an inorganic or organic calcium compound.

Further preferred are stabilized halogen-containing polymers which further comprise phosphites, perchlorate compounds, polyols, hydrotalcites, zeolites, dawsonite, magaziite, kenyaite or kanemite.

Particularly preferred are β-diketones and /
Alternatively, a halogen-containing polymer further containing a Mg salt, a Ca salt or a Zn salt thereof, or a β-ketoester, and a monomeric, oligomeric or polymeric dihydropyridine.

Particular preference is further given to β-diketones and / or their Mg, Ca or Zn salts, or β-ketoesters, as well as polyols, hydrotalcites, zeolites, dawsonites, magazites, kenyaites or kanemite. Is a halogenated polymer.

Particularly preferred are also stabilized halogen-containing polymers which further comprise perchlorate compounds and polyols, hydrotalcites, zeolites, dawsonites, magaziites, kenyaites or kanemite.

Particularly preferred are also stabilized halogen-containing polymers which additionally contain epoxide and perchlorate compounds.

The two last-mentioned formulations may additionally comprise β-diketones, their Mg, Ca or Zn salts, or β-ketoesters, or mixtures thereof.

All formulations may further comprise calcium soap and / or lubricant.

The present invention further provides the following formula: C ₆ H ₁₁ O ₆ (C ₆
H ₁₀ O ₅ ) _n C ₆ H ₁₃ O ₅ (in the formula, n represents a number of 0 to 5) and a di- or polysaccharide alcohol, and an inorganic or organic zinc, aluminum or rare earth compound Stabilizer mixture, wherein when the disaccharide alcohol is maltitol, the mixture relates to a mixture that does not include a combination of calcium soap and zinc soap. The above selections apply to the individual mixture components, and the stabilizer mixture may include other components as described above.

The present invention further provides the following formula: C ₆ H ₁₁ O ₆ (C ₆
H ₁₀ O ₅ ) _n C ₆ H ₁₃ O ₅ (in the formula, n represents a number of 0 to 5) and a di- or polysaccharide alcohol, and an inorganic or organic zinc, aluminum or rare earth compound Stabilizer mixture, wherein when the disaccharide alcohol is maltitol, the mixture is a halogen-containing polymer or polymer recycle of a mixture that does not include a combination of calcium soap and zinc soap. It relates to a method of use for stabilization. The above-mentioned choices apply to the individual stabilizers and to the halogen-containing polymer itself, and may also use one of the other constituents mentioned above.

The stabilized halogen-containing polymer of the present invention may be produced by a known method, and the final stabilizer and, if desired, other stabilizer may be mixed with the halogen-containing polymer in a calender, a mixer, a compounding machine, Mixing is done using known equipment such as extruders and the like.

The halogen-containing polymers stabilized according to the invention can be converted into the desired shape by known methods.
Methods of this kind are, for example, grinding (milling), calendering, extrusion, injection molding, sintering or spinning (spinning), and also extrusion blow molding or conversion by the plastisol method. The stabilized PVC may be converted into foam.

The halogen-containing polymers of the present invention are particularly suitable for semi-rigid and flexible formulations, especially those in the form of flexible formulations for wire sheaths and cable insulation. In the form of semi-rigid formulations,
The halogen-containing polymer of the present invention is particularly suitable for cosmetic sheet materials, foams, agricultural sheet materials, tubes, sealing profiles and office films.

In the form of hard formulations, the halogen-containing polymers stabilized according to the invention can be used for hollow articles (bottles), packaging films (thermoforming films), blown films, safety pad films (automobiles). ,
Particularly suitable for tubes, foams, heavy profiles (window frames), light wall profiles, architectural profiles, siding, fittings, office films and equipment housings (computers and household appliances).

Examples of the use of the halogen-containing polymers according to the invention as plastisols are artificial leather, floor coverings, textile coatings, wall coatings, coil coatings and automotive basecoats.

Sintering applications for halogen-containing polymers stabilized according to the invention are slush, slush molding and coil coatings.

[0195]

EXAMPLES AND EFFECTS OF THE INVENTION The present invention will be explained in more detail by the following examples without any limitation. Unless stated otherwise, parts and percentages are by weight below.

Examples 1-4: As shown in Table 1 below, PVC compounds are prepared by mixing the individual components (amounts by weight).

Homogenization in a mixing roll for 5 minutes at 180 ° C. gives a film with a thickness of 0.3-0.5 mm.

The long-term stability is determined according to DIN 53381 [in this case the sample is stored in a test oven at 180 ° C. and then the time to failure of this sample is determined (Table 1)].

Another measure of stability is determined by the dehydrochlorination test, which is carried out according to DIN 53381, in which the time until the dehydrochlorination curve rises (conductivity> 200 μm) is 180 ° C. (Table 2).

Another measure of stability is 180 ° C. and 200 b
It was determined by pressing the film in ar for 2 minutes to obtain a sheet with a thickness of 2 mm, whose yellowness index is ASTM
Determined according to D1925-70 (Table 3).

[0201]

[Table 1]

The new PVC mixture shows a higher stability than the comparative samples (Comparative Example 1 and Comparative Example 2).

Examples 5 and 6: As shown in Table 2 below,
The PVC compound is prepared by mixing the individual components (quantity by weight).

Homogenization in a mixing roll for 5 minutes at 180 ° C. gives a film with a thickness of 0.3-0.5 mm.

Long-term stability is determined according to DIN 53381 (in which case the sample is stored in a test oven at 180 ° C. and then the yellowness index is measured).

[0206]

[Table 2]

After 85 minutes, the sample of Comparative Example 4 had a YI value of 90.
0, whereas the new samples (Example 5 and Example 6) only have YI values of 80.7 and 74.0, respectively. Comparative Example 3 becomes dark in only 60 minutes.

Examples 7-10: As shown in Table 3 below,
The PVC compound is prepared by mixing the individual components (quantity by weight).

Homogenization in a mixing roll for 5 minutes at 170 ° C. gives a film with a thickness of 0.3-0.5 mm.

The thermal stability is determined according to DIN 53381 (in this case the sample is stored in a test oven at 170 ° C. and then the time to failure of this sample is determined).

[0211]

[Table 3]

The sample of Comparative Example 5 turned dark after 20 minutes, while the new sample (Examples 7-10) had a dark color of 5.
Only dark after 0 minutes.

The following substances are used in the above examples. PVC1: Evipol SH7020 (SP
VC, K value 71) Ca1: calcium stearate DOP: dioctyl phthalate DSA1: maltitol DSA2: lactitol DSA3: isomaltitol DSA4: palatinitol ESO: epoxidized soybean oil L1: lubrication Agent Loxiol G16 L2: PE wax MSA: Sorbitol Zn1: Zinc stearate

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08L 101/04 KAD C08L 101/04 KAD (72) Inventor Rolf Drewes, Federal Republic of Germany, 64678 Lindenfers, Am Buchacker 1 (72) Inventor Karl Joseph Kuhn Germany, 64686 Lautertal, Nibelgengenstraße 774 (72) Inventor Hans-Jürgen Zander Germany, 64653 Lorsch, Magnolieenstraße 25 (72) Inventor Marx Körp Germany, 68723 Planckstadt, Mozartstraße 48

Claims (16)

[Claims] 1. A halogen-containing polymer or a regenerated product thereof, and (b) the following formula: C ₆ H ₁₁ O ₆ (C ₆ H ₁₀ O ₅ ) _n C.
Stabilized by a di- or polysaccharide alcohol represented by ₆ H ₁₃ O ₅ (wherein n represents a number from 0 to 5), and (c) an inorganic or organic zinc, aluminum or rare earth compound. A halogen-containing polymer, wherein when the component (b) is maltitol, the composition does not include a combination of calcium soap and zinc soap. 2. The component (a) is polyvinyl chloride (PVC).
The stabilized product according to claim 1, which is a regenerated product thereof and, if desired, a phenolic antioxidant, particularly 0.1 to 5.0 parts by weight of phenolic antioxidant per 100 parts of polyvinyl chloride (PVC). Halogen-containing polymer. 3. A stabilized halogen-containing polymer according to claim 1, wherein component (b) is a disaccharide alcohol. 4. The component (b) is maltitol,
Lactitol, isomaltitol
ol) or palatinitol.
A stabilized halogen-containing polymer as described. 5. β-diketone and / or its magnesium (Mg) salt, calcium (Ca) salt or zinc (Zn)
The stabilized halogen-containing polymer according to claim 1, further comprising a salt or a β-keto ester. 6. The stabilized halogen-containing polymer of claim 1, further comprising an epoxide. 7. The stabilized halogen-containing polymer according to claim 1, further comprising a monomeric, oligomeric or polymeric dihydropyridine. 8. The stabilized halogen-containing polymer according to claim 1, further comprising an inorganic or organic calcium compound. 9. Phosphite, perchloate
rate) compounds, polyols, hydrotalcite (hydrota
lcite), zeolite (zeolite), dawsonite (dawsoni)
te), magadiite, kenyaite
Alternatively, the stabilized halogen-containing polymer of claim 1, further comprising kanemaite. 10. β-diketone and / or its magnesium (Mg) salt, calcium (Ca) salt or zinc (Z
n) salts or β-ketoesters, as well as monomers,
The stabilized halogen-containing polymer of claim 1, further comprising an oligomeric or polymeric dihydropyridine. 11. β-diketone and / or its magnesium (Mg) salt, calcium (Ca) salt or zinc (Z
n) salts or β-ketoesters, and polyols,
Hydrotalcite, zeolite (zeolit
e), dawsonite, magadiit
e), Kenyaite or kanemaite
The stabilized halogen-containing polymer of claim 1, further comprising: 12. A perchlorate compound and a polyol, hydrotalcite, hydrotalcite, zeolite (zeolite), dawsonite (dawsonite), magadiite (kenaite) or kenyaite (kanemaite). The stabilized halogen-containing polymer according to 1. 13. Epoxide and perchlorate (perch)
The stabilized halogen-containing polymer of claim 1, further comprising a lorate) compound. 14. The following formula: C ₆ H ₁₁ O ₆ (C ₆ H ₁₀ O ₅ )
_n C ₆ H ₁₃ O ₅ (wherein n represents a number from 0 to 5)
A stabilizer mixture consisting of a di- or polysaccharide alcohol represented by: and an inorganic or organic zinc, aluminum or rare earth compound, wherein the disaccharide alcohol is maltitol (mal
titol), the mixture does not include a combination of calcium soap and zinc soap. 15. The following formula: C ₆ H ₁₁ O ₆ (C ₆ H ₁₀ O ₅ )
_n C ₆ H ₁₃ O ₅ (wherein n represents a number from 0 to 5)
A stabilizer mixture consisting of a di- or polysaccharide alcohol represented by: and an inorganic or organic zinc, aluminum or rare earth compound, wherein the disaccharide alcohol is maltitol (mal
titol), the mixture is a mixture containing no combination of calcium soap and zinc soap for use in stabilizing a halogen-containing polymer or a polymer regenerated product. 16. Using equipment such as calenders, mixers, compounders, extruders and the like, having the formula: C ₆ H ₁₁ O ₆ (C ₆ H ₁₀ O ₅ ) _n C ₆ H ₁₃ O
_A stabilizer mixture comprising a di- or polysaccharide alcohol represented by the formula ₅ (wherein n represents a number from 0 to 5) and an inorganic or organic zinc, aluminum or rare earth compound, wherein: The saccharide alcohol is maltitol (mal
titol), the mixture does not include a combination of calcium soap and zinc soap, in the form of a mixture as described above or its individual components and, optionally, another additive, halogen-containing. A method of making a stabilized halogen-containing polymer comprising mixing with a polymer or polymer reclaim.