EP3110880A1 - Stabilizer composition - Google Patents

Stabilizer composition

Info

Publication number
EP3110880A1
EP3110880A1 EP14709895.8A EP14709895A EP3110880A1 EP 3110880 A1 EP3110880 A1 EP 3110880A1 EP 14709895 A EP14709895 A EP 14709895A EP 3110880 A1 EP3110880 A1 EP 3110880A1
Authority
EP
European Patent Office
Prior art keywords
parts
weight
containing polymer
component
halogen containing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP14709895.8A
Other languages
German (de)
French (fr)
Inventor
Walter Reith
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
IKA Innovative Kunststoffaufbereitung & CoKg GmbH
Original Assignee
IKA Innovative Kunststoffaufbereitung & CoKg GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by IKA Innovative Kunststoffaufbereitung & CoKg GmbH filed Critical IKA Innovative Kunststoffaufbereitung & CoKg GmbH
Publication of EP3110880A1 publication Critical patent/EP3110880A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/267—Magnesium carbonate

Definitions

  • the present invention relates to a stabilizer composition for a halogen- containing polymer, in particular such polymers which are resistant against e.g . weathering, thermal and/or photochemical degradation.
  • halogen-containing polymers are susceptible to degradation or decomposition if exposed to weather, thermal stress and high energy radiation, e.g. ultraviolet light.
  • An example of such a polymer is polyvinyl chloride (PVC).
  • compositions comprising isocyanurates containing hydroxyl groups and magnesium hydroxides for stabilizing organic plastics containing halogens against thermal and/or photochemical degradation.
  • An exemplary formulation of PVC stabilizing mixtures include calcium stearate, zinc stearate magnesium hydroxide and isocyanurate (THEIC).
  • WO 99/55777 Al relates to a stabilizer composition for degradation resistant halogen-containing thermoplastic resin compositions, in particular on the basis of polyvinyl chloride (PVC). It is provided a stabilizer composition for halogen- containing thermoplastic resins comprising calcium hydroxide and/or calcium oxide which may be surface-modified; and a hydroxyl group containing isocyanurate.
  • a stabilizer composition for halogen- containing thermoplastic resins comprising calcium hydroxide and/or calcium oxide which may be surface-modified; and a hydroxyl group containing isocyanurate.
  • the disclosed compositions include tris(hydroxyethyl)isocyan urate (referred to as THEIC) in an amount of 0.3 or 0.4 parts by weight with regard to the halogen-containing resin.
  • Further optional components of the examples include zinc stearate in an amount of 0.8 parts per weight with regard to the halogen-containing resin.
  • a stabilizer composition for a halogen containing polymer comprising : as a first component at least one of alkaline earth oxide, alkaline earth hydroxide, and calcinated dolomite; and, as a second component, at least one of a fatty acid zinc salt and a lead salt.
  • a stabilizer composition based on the first component and the second component can provide sufficient stabilization of a halogen-containing polymer while providing on the other hand cost efficiency.
  • the stabilizer composition comprises as a first component at least one of alkaline earth oxide, alkaline earth hydroxide, and calcinated dolomite.
  • the first composition consists of one of alkaline earth oxide, alkaline earth hydroxide, and calcinated dolomite while in another embodiment the first component consists of a mixture of two of alkaline earth oxide, alkaline earth hydroxide, and calcinated dolomite (e.g . of alkaline earth oxide and alkaline earth hydroxide), or, in another embodiment, the first component consists of a mixture of alkaline earth oxide, alkaline earth hydroxide and calcinated dolomite.
  • alkaline earth oxide includes "a single alkaline earth oxide” or, in another embodiment, "a mixture of two or more alkaline earth oxides”.
  • alkaline earth hydroxide includes “a single alkaline earth hydroxide” or, in another embodiment, “a mixture of two or more alkaline earth hydroxides”.
  • calcinated dolomit includes “a single calcinated dolomite” or, in another embodiment, “a mixture of two or more calcinated dolomits”.
  • the stabilizer composition comprises as the second component at least one of a fatty acid zinc salt and a lead salt, i.e. in other words the stabilizer composition comprises as the second component a fatty acid zinc salt and/or a lead salt.
  • the second component consists of a fatty acid zinc salt.
  • the second component consists of a lead salt.
  • the second component consists of a mixture of a fatty acid zinc salt and a lead salt.
  • a fatty acid zinc salt includes "a single fatty acid zinc salt” or, in another embodiment, “a mixture of two or more fatty acid zinc salts”.
  • a lead salt includes "a single lead salt” or, in another embodiment, "a mixture of two or more lead salts”.
  • the first component comprises calcium oxide and/or calcium hydroxide. According to a further embodiment, the first component comprises alkaline earth double carbonate lime of the formula A
  • M 1 and M 2 are different alkaline earth metals
  • the fatty acid zinc salt is zinc carboxylate.
  • These may be compounds of the set of aliphatic saturated and unsaturated Ci- 22 carboxylates (with 1 to 22 C atoms), the aliphatic saturated or unsaturated C 2 - 22 carboxylates which are substituted with at least one OH group or the chain of which is interrupted with at least one or more O atoms (oxa acids), the cyclic and bicyclic carboxylates with 5 to 22 C atoms, the unsubstituted, with at least one OH group substituted and/or Ci-ie alkyl- substituted phenyl carboxylates, the phenyl-Ci-e-alkylcarboxylates, or the eventually with Ci-i 2 alkylsubstituted phenolates, or the abietic acid.
  • Examples are zinc salts of monovalent carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanonic acid, enantic acid, octanoic acid, neodecanonic acid, 2-ethylhexanonic acid, peiargonic acid, decanonic acid, undecanonic acid, dodecanonic acid, tridecanonic acid, myristic acid, palmitic acid, lauric acid, isostearic acid, stearic acid, 12- hydroxystearic acid, 9,10-dihydroxystearic acid, oleic acid, ricinoieic acid, 3,6- dioxaheptanonic acid, 3,6,9- trioxadecanoic acid, behenic acid, benzoic acid, p-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-di-tert-butyl-4- hydroxybenzoic acid, toluenic acid,
  • the lead salt comprises or consists of a lead carboxylate, e.g . of the carboxylate type described above with regard to the zinc salts.
  • the lead salt comprises or consists of a fatty acid lead salt.
  • the fatty acid lead salt is of a type disclosed above with regard to the fatty acid zinc salt.
  • the lead salt is a lead salt of monovalent carboxylic acids as disclosed herein, lead salts of divalent carboxylic acids as disclosed herein, respectively its monoesters, etc.
  • the lead salt comprises or consists of lead stearate (CsehboC ⁇ Pb) or dibasic lead stearate (CsehboC ⁇ Pb ⁇ Pb0 2 ).
  • the lead salt comprises or consists of a mixture of lead stearate and dibasic lead stearate (CseHyoC Pb ⁇ Pb0 2 ).
  • the weight ratio of the first component to the second component is from 0.01 : 2 to 2 : 0.05.
  • the weight ratio of the first component to the second component is from 0.2 : 1 to 0.5 : 0.6.
  • the weight ratio of the first component to the second component is 0.3 : 0.8.
  • the weight ratio of the fatty acid zinc salt to the lead salt is from 0.05 : 2.5 to 2 : 0.05. According to a further embodiment, the weight ratio of the fatty acid zinc salt to the lead salt is from 0.3 : 1.2 to 0.5 : 0.8. For example, according to a further embodiment the weight ratio of the fatty acid zinc salt to the lead salt is 0.4 : 1.
  • the first component comprises or consists of calcium hydroxide; and the second component comprises or consists of at least one of zinc stearate and lead stearate.
  • the first component is calcium hydroxide and the second component consists of zinc stearate and/or lead stearate.
  • the second component consists (only) of lead stearate. According to a further embodiment, the second component consists only of zink stearate. According to a still further embodiment, the second component consists zinc stearate and lead stearate.
  • a stabilizer composition for a halogen-containing polymer comprising : calcium hydroxide, Ca(OH) 2 (as a first component), and at least one of zinc stearate, Zn(Ci8H 350 2 ) 2 and lead stearate, e.g. C36H7o0 4 Pb (as a second component).
  • a stabilizer composition based on calcium hydroxide and at least one of zinc stearate and lead stearate can provide sufficient stabilization of a halogen-containing polymer while providing on the other hand cost efficiency.
  • the weight ratio of calcium hydroxide to zinc stearate is from 0.01 : 2 to 2 : 0.05. According to an embodiment, the weight ratio of calcium hydroxide to zinc stearate is from 0.1 : 2 to 1 : 0.3. According to a further embodiment, the weight ratio of calcium hydroxide to zinc stearate is from 0.2 : 1 to 0.5 : 0.6. According to a further embodiment, the weight ratio of calcium hydroxide to zinc stearate is from 0.2 : 1 to 0.5 : 0.6. According to a further embodiment, the weight ratio of calcium hydroxide to zinc stearate is 0.3 : 0.8.
  • the zinc stearate content is reduced if the lead stearate content is increased while still providing suitable stabilizer functionality of the stabilizer composition .
  • the weight ratio of zinc stearate to lead stearate is from 0.05 : 2.5 to 2 : 0.05.
  • the weight ratio of zinc stearate to lead stearate is from 0.1 : 2.5 to 2 : 0.5.
  • the weight ratio of zinc stearate to lead stearate is from 0.3 : 1.2 to 0.5 : 0.8.
  • the weight ratio of zinc stearate to lead stearate is 0.4 : 1.
  • the stabilizer composition is substantially free from isocyanurate.
  • the stabilizer composition is (absolutely) free of isocyanurate.
  • the stabilizer composition consists of the first component and the second component.
  • the stabilizer composition comprises the first component, the second component and at least one further component.
  • the stabilizer composition is adapted for providing the functionality of one or more of the embodiments disclosed herein and/or for providing the functionality as required by one or more of the herein disclosed embodiments, in particular of the embodiments of the second aspect described below.
  • a composition comprising : a halogen-containing polymer; and a stabilizer composition according to the first aspect or an embodiment thereof.
  • a content specified herein is given is by weight with respect to 100 parts of the halogen containing polymer (also referred to as parts per hundred resin, phr).
  • the content of the first component is from 0.01 parts by weight to 2 parts by weight with respect to 100 parts of the halogen containing polymer, in particular the content of the first component is from 0.2 parts by weight to 0.5 parts by weight with respect to 100 parts of the halogen containing polymer.
  • the content of the second component in the composition is from 0.05 parts by weight to 4 parts by weight with respect to 100 parts of the halogen containing polymer, in particular from 0.05 parts by weight to 2.5 parts by weight with respect to 100 parts of the halogen containing polymer, in particular from 0.6 parts by weight to 1.5 parts by weight with respect to 100 parts of the halogen containing polymer.
  • the fatty acid zinc salt content is from 0.05 parts by weight to 2 parts by weight with respect to 100 parts of the halogen containing polymer, in particular from 0.3 parts by weight to 1 parts by weight with respect to 100 parts of the halogen containing polymer, in particular from 0.3 parts by weight to 0.5 parts by weight with respect to 100 parts of the halogen containing polymer, e.g. if the second component includes the lead salt, or from 0.7 parts by weight to 0.9 parts by weight with respect to 100 parts of the halogen containing polymer, e.g. if the second component consists of the fatty acid zinc salt (and hence does not include a lead salt).
  • the lead salt content is from 0.05 parts by weight to 2.5 parts by weight with respect to 100 parts of the halogen containing polymer, in particular from 0.8 parts by weight to 1.2 parts by weight with respect to 100 parts of the halogen containing polymer.
  • the first component comprises or consists of calcium hydroxide.
  • the calcium hydroxide content is from 0.01 parts by weight to 2 parts by weight with respect to 100 parts of the halogen-containing polymer.
  • the calcium hydroxide content is from 0.1 parts by weight to 1 parts by weight with respect to 100 parts of the halogen- containing polymer.
  • the calcium hydroxide content is from 0.2 parts by weight to 0.5 parts by weight with respect to 100 parts of the halogen-containing polymer.
  • the fatty acid zinc salt is zinc stearate.
  • the zinc stearate content is from 0.05 parts by weight to 2 parts by weight with respect to 100 parts of the halogen-containing polymer.
  • the zinc stearate content is from 0.3 parts by weight to 2 parts by weight with respect to 100 parts of the halogen- containing polymer.
  • the zinc stearate content is from 0.6 parts by weight to 1 parts by weight with respect to 100 parts of the halogen- containing polymer, e.g. 0.8 parts by weight with respect to 100 parts of the halogen-containing polymer, e.g . in a lead stearate free composition.
  • the lead salt is lead stearate.
  • the lead stearate content is from 0.05 parts by weight to 2.5 parts by weight with respect to 100 parts of the halogen-containing polymer.
  • the lead stearate content is from 0.5 parts by weight to 2.5 parts by weight with respect to 100 parts of the halogen- containing polymer. According to a still further embodiment, the lead stearate content is from 0.8 parts by weight to 1.2 parts by weight with respect to 100 parts of the halogen-containing polymer, e.g. 1 part by weight with respect to 100 parts of the halogen-containing polymer.
  • the second component consists of lead stearate and zinc stearate (in the following the composition is referred to as zinc and lead stearate containing composition) wherein the zinc stearate content is from 0.05 parts by weight to 2 parts by weight with respect to 100 parts of the halogen-containing polymer.
  • the zinc stearate content is from 0.1 parts by weight to 1 parts by weight with respect to 100 parts of the halogen-containing polymer.
  • the zinc stearate content is from 0.3 parts by weight to 0.5 parts by weight with respect to 100 parts of the halogen-containing polymer, e.g. e.g . 0.4 parts by weight with respect to 100 parts of the halogen-containing polymer.
  • the composition is substantially free from isocyanurate.
  • the term "substantially free from isocyanurate” in particular means that the isocyanurate content is below 0.1 parts by weight with respect to 100 parts of the halogen containing polymer.
  • isocyanurate in particular means that the isocyanurate content is below 0.05, below 0.01, or below 0.005 parts by weight with respect to 100 parts of the halogen containing polymer. According to an embodiment, the composition is (absolutely) free of isocyanurate.
  • the composition is a thermoplastic composition. According to another embodiment, the composition is a thermosetting composition. According to other embodiments, the composition comprises the halogen containing polymer and, additionally, a polymer which does not contain a halogen.
  • halogen containing polymer examples are chlorine containing polymers, in particular of vinyl chloride as well as of vinylidene chloride, vinyl resins comprising vinyl chloride units in their structure, as copolymers of vinyl chloride and vinyl ester of aliphatic acids. Further examples are those described in EP 2 110 405 Al which are incorporated herein by reference.
  • the composition according to embodiments of the herein disclosed subject-matter comprises, in addition to the halogen- containing polymer and the stabilizer composition according to the first aspect (or one or more embodiments thereof), further additives, e.g . one or more of the following additives:
  • lithium intracomplexes respectively lithium or sodium perchlorates (triflates) in dissolved or supported form
  • impact modifier e.g . on the basis of acrylate or CPE or mixtures thereof
  • processing aids e.g. melt flow enhancers
  • additives may be those disclosed in EP 2 110 405 Al which is incorporated herein by reference.
  • examples of a composition according to embodiments of the herein disclosed subject matter have been prepared and investigated, wherein details of the examples are provided in table 1 below.
  • Table 1 exemplary compositions (No. 1 and 2) according to embodiments without isocyanurate (THEIC) and of comparison examples (No. 3 and 4) with isocyanurate.
  • the given numbers specify the weight of the respective component in parts by weight with respect to 100 parts of the halogen containing polymer (PVC K- value 68 in the present examples).
  • the amount of 0.3 calcium hydroxide in table 1 means that per 100 parts by weight of the halogen containing polymer 0.3 parts by weight of calcium hydroxide are added .
  • compositions have been prepared in a heating / cooling mixer comination FML 10/KM23 of the firm Reimelt Henschel at a temperature of 120 °C/ 35°C.
  • compositions 1 to 4 have been plasticized on a laboratory rolling mill Polymix 150P of the firm Swabenthan for 5 minutes at 200 degrees Celsius.
  • the thus obtained foils have been used for further investigations.
  • Table 2 colorimetry results for the investigated compositions
  • the b* value is a measure for the yellow-blue axis. The lower the b* value, the more blue is the color. For a good stabilization, a low b* value is advantageous.
  • compositions No. 1 and 2 which implement embodiments of the herein disclosed subject matter and which do not contain isocyanurate, show a lower b* value than the comparison compositions containing isocyanurate.
  • compositions according to embodiments of the herein disclosed subject matter provide a much higher cost efficiency than similar compositions with isocyanurate.
  • Sufficient stabilization of the halogen containing polymers according to embodiments of the herein disclosed subject matter is achieved by the advantageous combination of calcium hydroxide and zinc stearate (and optionally lead stearate).
  • the stabilizer composition is adapted for providing the functionality of one or more of the embodiments disclosed herein and/or for providing the functionality as required by one or more of the herein disclosed embodiments, in particular of the embodiments of the first aspect described above and of the third aspect described below.
  • a stabilizer composition according to the first aspect or an embodiment thereof for stabilizing a halogen-containing polymer.
  • the use of a stabilizing composition according to the first aspect or an embodiment thereof results, according to a respective embodiment, in a composition according to the second aspect or an embodiment thereof.
  • the halogen containing polymer is a chlorine containing polymer, in particular polyvinyl chloride as mentioned above.
  • the halogen containing polymer is stabilized against at least one of heat, moisture, radiation, oxidative stress, mechanical stress, aging, thermal cycling .
  • the halogen containing polymer is stabilized in terms of waterproofing, oxidation resistance, wear resistance.
  • the stabilizer composition is adapted for providing the functionality of one or more of the embodiments disclosed herein and/or for providing the functionality as required by one or more of the herein disclosed embodiments, in particular of the embodiments of the first aspect and the second aspect described above.
  • an article in particular an extruded or a molded article manufactured from or containing a composition according to the second aspect or an embodiment thereof.
  • the article may be e.g . a window profile.
  • Further examples of an article are e.g . cables, wallpapers, floorings, foils, housings, etc., e.g. articles as described in EP 2 110 405 Al .
  • the article further comprises a protective layer on the composition.
  • the protective layer forms an outer surface of the article.
  • the protective layer may be configured for protecting the composition according to embodiments of the herein disclosed subject matter from environmental influences.
  • a window frame is manufactured from the composition according to one or more embodiments of the herein disclosed subject matter and provided thereon with a protecting layer.
  • a window frame is produced with the composition according to one or more embodiments of the herein disclosed subject matter and a further
  • composition e.g . an even more stabilized composition
  • This embodiment has the advantage of being cost-efficient and providing nevertheless a good stabilization of the article.
  • Providing a halogen-containing polymer with a polymer composition according to one or more embodiments of the herein disclosed subject matter is advantageous in many applications, e.g . in an application where the polymer is subjected to decomposition, in particular decomposition due to aging or thermal cycling.
  • Using a stabilizer composition according to one or more embodiments of the herein disclosed subject matter provides a cost efficient stabilizer for halogen containing polymers such as PVC.
  • the term “comprising” stands for “consisting of”. Hence each use of the term “comprising” discloses two embodiments, one with “comprising” in the sense of “comprising inter alea” and one with
  • an embodiment describes the first component as being calcium hydroxide with content of 0.3 parts by weight per 100 parts of the halogen containing polymer and a further embodiment describes the second component as being zinc stearate with a content of 0.8 parts by weight per 100 parts of the halogen containing polymer
  • a composition comprising calcium hydroxide with a content of 0.3 parts by weight per 100 parts of the halogen containing polymer and zinc stearate with a content of 0.8 parts by weight per 100 parts of the halogen containing polymer is also disclosed by this application.
  • a stabilizer composition for a halogen containing polymer comprising : as a first component at least one of alkaline earth oxide, alkaline earth hydroxide, and calcinated dolomite; and, as a second component, at least one of a fatty acid zinc salt and a lead salt.
  • An exemplary stabilizer composition comprises calcium hydroxide; zinc stearate and/or lead stearate. According to an embodiment, the stabilizer composition or, in another embodiment, a composition comprising the stabilizer
  • composition is substantially free from isocyanurate.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Disclosed is a stabilizer composition for a halogen containing polymer, the stabilizer composition comprising: as a first component at least one of alkaline earth oxide, alkaline earth hydroxide, and calcinated dolomite; and, as a second component, at least one of a fatty acid zinc salt and a lead salt. An exemplary stabilizer composition comprises calcium hydroxide; zinc stearate and/or lead stearate. According to an embodiment, the stabilizer composition or, in another embodiment, a composition comprising the stabilizer composition is substantially free from isocyanurate.

Description

Stabilizer composition
Field of the invention The present invention relates to a stabilizer composition for a halogen- containing polymer, in particular such polymers which are resistant against e.g . weathering, thermal and/or photochemical degradation.
Background
It is known that halogen-containing polymers are susceptible to degradation or decomposition if exposed to weather, thermal stress and high energy radiation, e.g. ultraviolet light. An example of such a polymer is polyvinyl chloride (PVC).
From WO 2005/054358 Al it is known to use compositions comprising isocyanurates containing hydroxyl groups and magnesium hydroxides for stabilizing organic plastics containing halogens against thermal and/or photochemical degradation. An exemplary formulation of PVC stabilizing mixtures include calcium stearate, zinc stearate magnesium hydroxide and isocyanurate (THEIC).
WO 99/55777 Al relates to a stabilizer composition for degradation resistant halogen-containing thermoplastic resin compositions, in particular on the basis of polyvinyl chloride (PVC). It is provided a stabilizer composition for halogen- containing thermoplastic resins comprising calcium hydroxide and/or calcium oxide which may be surface-modified; and a hydroxyl group containing isocyanurate. Examples of the disclosed compositions include tris(hydroxyethyl)isocyan urate (referred to as THEIC) in an amount of 0.3 or 0.4 parts by weight with regard to the halogen-containing resin. Further optional components of the examples include zinc stearate in an amount of 0.8 parts per weight with regard to the halogen-containing resin.
Summary of the invention
In view of the above, there still exits a need for a cost-efficient stabilizer composition for a halogen-containing polymer which are efficient regarding the stabilization of the polymer with respect to decomposition, e.g. with respect to at least one of thermal stress, thermal cycling, aging, weathering, etc.
This need may be met by the subject-matter according to the independent claims. Advantageous embodiments of the herein disclosed subject-matter are described by the dependent claims.
According to an embodiment of a first aspect of the herein disclosed subject- matter, there is provided a stabilizer composition for a halogen containing polymer, the stabilizer composition comprising : as a first component at least one of alkaline earth oxide, alkaline earth hydroxide, and calcinated dolomite; and, as a second component, at least one of a fatty acid zinc salt and a lead salt. Embodiments of the herein disclosed subject-matter are based on the idea that a stabilizer composition based on the first component and the second component can provide sufficient stabilization of a halogen-containing polymer while providing on the other hand cost efficiency. According to an embodiment, the stabilizer composition comprises as a first component at least one of alkaline earth oxide, alkaline earth hydroxide, and calcinated dolomite. Hence, in an embodiment, the first composition consists of one of alkaline earth oxide, alkaline earth hydroxide, and calcinated dolomite while in another embodiment the first component consists of a mixture of two of alkaline earth oxide, alkaline earth hydroxide, and calcinated dolomite (e.g . of alkaline earth oxide and alkaline earth hydroxide), or, in another embodiment, the first component consists of a mixture of alkaline earth oxide, alkaline earth hydroxide and calcinated dolomite. It is noted that the term "alkaline earth oxide" includes "a single alkaline earth oxide" or, in another embodiment, "a mixture of two or more alkaline earth oxides".
Further, the term "alkaline earth hydroxide" includes "a single alkaline earth hydroxide" or, in another embodiment, "a mixture of two or more alkaline earth hydroxides". Further, the term "calcinated dolomit" includes "a single calcinated dolomite" or, in another embodiment, "a mixture of two or more calcinated dolomits".
According to an embodiment, the stabilizer composition comprises as the second component at least one of a fatty acid zinc salt and a lead salt, i.e. in other words the stabilizer composition comprises as the second component a fatty acid zinc salt and/or a lead salt. For example, in an embodiment the second component consists of a fatty acid zinc salt. According to a further embodiment, the second component consists of a lead salt. According to a further an embodiment, the second component consists of a mixture of a fatty acid zinc salt and a lead salt. It is noted that the term "a fatty acid zinc salt" includes "a single fatty acid zinc salt" or, in another embodiment, "a mixture of two or more fatty acid zinc salts". Further, the term "a lead salt" includes "a single lead salt" or, in another embodiment, "a mixture of two or more lead salts".
According to an embodiment, the first component comprises calcium oxide and/or calcium hydroxide. According to a further embodiment, the first component comprises alkaline earth double carbonate lime of the formula A
( M 10)m* ( M20)n-m*(C02)o* ( H20)p (A)
wherein M1 and M2 are different alkaline earth metals;
m= 0.9 to 1.1;
n = 1.9 to 2.1 and p=0 to 2.1 or n = 3.9 to 4.1 and p = 0 to 4.1
o=0 to 1.1, e.g . a dolomite quicklime of the formula (A2)
(CaO)m*(MgO)n-m*(C02)o (A2) with m = 0.9 to 1.1; n = 1.9 to 2.1 and o=0 to 1.1.
According to an embodiment, the fatty acid zinc salt (zinc soap) is zinc carboxylate. These may be compounds of the set of aliphatic saturated and unsaturated Ci-22 carboxylates (with 1 to 22 C atoms), the aliphatic saturated or unsaturated C2-22 carboxylates which are substituted with at least one OH group or the chain of which is interrupted with at least one or more O atoms (oxa acids), the cyclic and bicyclic carboxylates with 5 to 22 C atoms, the unsubstituted, with at least one OH group substituted and/or Ci-ie alkyl- substituted phenyl carboxylates, the phenyl-Ci-e-alkylcarboxylates, or the eventually with Ci-i2 alkylsubstituted phenolates, or the abietic acid.
Examples are zinc salts of monovalent carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanonic acid, enantic acid, octanoic acid, neodecanonic acid, 2-ethylhexanonic acid, peiargonic acid, decanonic acid, undecanonic acid, dodecanonic acid, tridecanonic acid, myristic acid, palmitic acid, lauric acid, isostearic acid, stearic acid, 12- hydroxystearic acid, 9,10-dihydroxystearic acid, oleic acid, ricinoieic acid, 3,6- dioxaheptanonic acid, 3,6,9- trioxadecanoic acid, behenic acid, benzoic acid, p-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-di-tert-butyl-4- hydroxybenzoic acid, toluenic acid,dimethylbenzoic acid, ethylbenzoic acid, n- propylbenzoic acid, salicylic acid, p-tert-octylsalicylic acid, and sorbic acid, cinnamic acid, mandelic acid, glycolic acid; zinc salts of divalent carboxylic acids respectively its monoesters such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, pentane-l,5-dicarboxylic acid, hexane-l,6-dicarboxylic acid, heptane-1 ,7-dicarboxylic acid, octane-1,8- dicarboxylic acid, 3,6,9-trioxadecane-l, 10-dicarboxylic acid, lactic acid, malonic acid, maleic acid, tartaric acid, malic acid, salicylic acid, Polyglycol- dicarboxylic acid (n = 10-12), phthalic acid, isophthalic acid, terephthalic acid and hydroxyphthalic acid; and the di- or triester of the tri-oder tetravalent carboxylic acid, such as hemimellitic acid, trimellitic acid, pyromellitic acid, citric acid as well as so-called overbased zinc carboxylates or zinc lauryl mercaptide, zinc thioglycolate, zinc thiosalicylate, zinc-bis-i-octylthioglycolate, zinc mercaptopropionate, zinc thiolactate, zinc thiomalate, zinc-bis- octylmercaptopropionate, zinc-bis-isooctylthiolactate and zinc- bislaurylthiomalate. Further examples and methods for preparation are disclosed in
EP 2 110 405 Al, the contents of which is incorporated herein by reference.
According to an embodiment, the lead salt comprises or consists of a lead carboxylate, e.g . of the carboxylate type described above with regard to the zinc salts. According to an embodiment, the lead salt comprises or consists of a fatty acid lead salt. For example, in an embodiment, the fatty acid lead salt is of a type disclosed above with regard to the fatty acid zinc salt. For example, according to an embodiment, the lead salt is a lead salt of monovalent carboxylic acids as disclosed herein, lead salts of divalent carboxylic acids as disclosed herein, respectively its monoesters, etc.
According to an embodiment, the lead salt comprises or consists of lead stearate (CsehboC^Pb) or dibasic lead stearate (CsehboC^Pb ■ Pb02). According to an embodiment, the lead salt comprises or consists of a mixture of lead stearate and dibasic lead stearate (CseHyoC Pb ■ Pb02). According to an embodiment, the weight ratio of the first component to the second component is from 0.01 : 2 to 2 : 0.05. According to a further embodiment, the weight ratio of the first component to the second component is from 0.2 : 1 to 0.5 : 0.6. For example, according to an embodiment the weight ratio of the first component to the second component is 0.3 : 0.8.
According to an embodiment, the weight ratio of the fatty acid zinc salt to the lead salt is from 0.05 : 2.5 to 2 : 0.05. According to a further embodiment, the weight ratio of the fatty acid zinc salt to the lead salt is from 0.3 : 1.2 to 0.5 : 0.8. For example, according to a further embodiment the weight ratio of the fatty acid zinc salt to the lead salt is 0.4 : 1.
According to a further embodiment, the first component comprises or consists of calcium hydroxide; and the second component comprises or consists of at least one of zinc stearate and lead stearate. For example, in an embodiment the first component is calcium hydroxide and the second component consists of zinc stearate and/or lead stearate.
According to an embodiment, the second component consists (only) of lead stearate. According to a further embodiment, the second component consists only of zink stearate. According to a still further embodiment, the second component consists zinc stearate and lead stearate.
According to an embodiment of the first aspect, there is provided a stabilizer composition for a halogen-containing polymer, the stabilizer composition comprising : calcium hydroxide, Ca(OH)2 (as a first component), and at least one of zinc stearate, Zn(Ci8H 3502)2 and lead stearate, e.g. C36H7o04Pb (as a second component). Such embodiments of the herein disclosed subject-matter are based on the idea that a stabilizer composition based on calcium hydroxide and at least one of zinc stearate and lead stearate can provide sufficient stabilization of a halogen-containing polymer while providing on the other hand cost efficiency. According to an embodiment, the weight ratio of calcium hydroxide to zinc stearate is from 0.01 : 2 to 2 : 0.05. According to an embodiment, the weight ratio of calcium hydroxide to zinc stearate is from 0.1 : 2 to 1 : 0.3. According to a further embodiment, the weight ratio of calcium hydroxide to zinc stearate is from 0.2 : 1 to 0.5 : 0.6. According to a further embodiment, the weight ratio of calcium hydroxide to zinc stearate is from 0.2 : 1 to 0.5 : 0.6. According to a further embodiment, the weight ratio of calcium hydroxide to zinc stearate is 0.3 : 0.8.
In accordance with an embodiment, starting from an exemplary embodiment of a stabilizer composition comprising calcium hydroxide and zinc stearate, the zinc stearate content is reduced if the lead stearate content is increased while still providing suitable stabilizer functionality of the stabilizer composition .
According to an embodiment, the weight ratio of zinc stearate to lead stearate is from 0.05 : 2.5 to 2 : 0.05.
For example, according to an embodiment, the weight ratio of zinc stearate to lead stearate is from 0.1 : 2.5 to 2 : 0.5. According to a further embodiment, the weight ratio of zinc stearate to lead stearate is from 0.3 : 1.2 to 0.5 : 0.8. According to an exemplary embodiment, the weight ratio of zinc stearate to lead stearate is 0.4 : 1. According to an embodiment, the stabilizer composition is substantially free from isocyanurate. According to an embodiment, the term "substantially free from isocyanurate" in particular means that the weight ratio of isocyanurate to the second component is below 0.5 : 1, e.g . below 0.1 : 1, below 0.05 : 1, below 0.01 : 1 or below 0.005 : 1.
According to an embodiment, the stabilizer composition is (absolutely) free of isocyanurate. According to an embodiment, the stabilizer composition consists of the first component and the second component. According to a further embodiment, the stabilizer composition comprises the first component, the second component and at least one further component.
According to embodiments of the first aspect, the stabilizer composition is adapted for providing the functionality of one or more of the embodiments disclosed herein and/or for providing the functionality as required by one or more of the herein disclosed embodiments, in particular of the embodiments of the second aspect described below.
According to embodiments of a second aspect, there is provided a composition (polymer composition) comprising : a halogen-containing polymer; and a stabilizer composition according to the first aspect or an embodiment thereof. According to an embodiment, a content specified herein is given is by weight with respect to 100 parts of the halogen containing polymer (also referred to as parts per hundred resin, phr).
According to an embodiment, the content of the first component is from 0.01 parts by weight to 2 parts by weight with respect to 100 parts of the halogen containing polymer, in particular the content of the first component is from 0.2 parts by weight to 0.5 parts by weight with respect to 100 parts of the halogen containing polymer.
According to a further embodiment, the content of the second component in the composition is from 0.05 parts by weight to 4 parts by weight with respect to 100 parts of the halogen containing polymer, in particular from 0.05 parts by weight to 2.5 parts by weight with respect to 100 parts of the halogen containing polymer, in particular from 0.6 parts by weight to 1.5 parts by weight with respect to 100 parts of the halogen containing polymer. According to a further embodiment, the fatty acid zinc salt content is from 0.05 parts by weight to 2 parts by weight with respect to 100 parts of the halogen containing polymer, in particular from 0.3 parts by weight to 1 parts by weight with respect to 100 parts of the halogen containing polymer, in particular from 0.3 parts by weight to 0.5 parts by weight with respect to 100 parts of the halogen containing polymer, e.g. if the second component includes the lead salt, or from 0.7 parts by weight to 0.9 parts by weight with respect to 100 parts of the halogen containing polymer, e.g. if the second component consists of the fatty acid zinc salt (and hence does not include a lead salt).
According to an embodiment, the lead salt content is from 0.05 parts by weight to 2.5 parts by weight with respect to 100 parts of the halogen containing polymer, in particular from 0.8 parts by weight to 1.2 parts by weight with respect to 100 parts of the halogen containing polymer.
In accordance with an embodiment, the first component comprises or consists of calcium hydroxide. According to an embodiment, the calcium hydroxide content is from 0.01 parts by weight to 2 parts by weight with respect to 100 parts of the halogen-containing polymer.
According to an embodiment, the calcium hydroxide content is from 0.1 parts by weight to 1 parts by weight with respect to 100 parts of the halogen- containing polymer.
According to a further embodiment, the calcium hydroxide content is from 0.2 parts by weight to 0.5 parts by weight with respect to 100 parts of the halogen-containing polymer.
According to an embodiment, the fatty acid zinc salt is zinc stearate. According to an embodiment, the zinc stearate content is from 0.05 parts by weight to 2 parts by weight with respect to 100 parts of the halogen-containing polymer.
According to an embodiment, the zinc stearate content is from 0.3 parts by weight to 2 parts by weight with respect to 100 parts of the halogen- containing polymer.
According to a further embodiment, the zinc stearate content is from 0.6 parts by weight to 1 parts by weight with respect to 100 parts of the halogen- containing polymer, e.g. 0.8 parts by weight with respect to 100 parts of the halogen-containing polymer, e.g . in a lead stearate free composition.
According to an embodiment, the lead salt is lead stearate. According to an embodiment, the lead stearate content is from 0.05 parts by weight to 2.5 parts by weight with respect to 100 parts of the halogen-containing polymer.
According to a further embodiment, the lead stearate content is from 0.5 parts by weight to 2.5 parts by weight with respect to 100 parts of the halogen- containing polymer. According to a still further embodiment, the lead stearate content is from 0.8 parts by weight to 1.2 parts by weight with respect to 100 parts of the halogen-containing polymer, e.g. 1 part by weight with respect to 100 parts of the halogen-containing polymer. According to a further embodiment, the second component consists of lead stearate and zinc stearate (in the following the composition is referred to as zinc and lead stearate containing composition) wherein the zinc stearate content is from 0.05 parts by weight to 2 parts by weight with respect to 100 parts of the halogen-containing polymer.
According to a further embodiment, in the zinc and lead stearate containing composition the zinc stearate content is from 0.1 parts by weight to 1 parts by weight with respect to 100 parts of the halogen-containing polymer.
According to a further embodiment, in the zinc and lead stearate containing composition the zinc stearate content is from 0.3 parts by weight to 0.5 parts by weight with respect to 100 parts of the halogen-containing polymer, e.g. e.g . 0.4 parts by weight with respect to 100 parts of the halogen-containing polymer.
According to an embodiment, the composition is substantially free from isocyanurate.
According to an embodiment, the term "substantially free from isocyanurate" in particular means that the isocyanurate content is below 0.1 parts by weight with respect to 100 parts of the halogen containing polymer. For example, according to a further embodiment, the term "substantially free from
isocyanurate" in particular means that the isocyanurate content is below 0.05, below 0.01, or below 0.005 parts by weight with respect to 100 parts of the halogen containing polymer. According to an embodiment, the composition is (absolutely) free of isocyanurate.
According to an embodiment, the composition is a thermoplastic composition. According to another embodiment, the composition is a thermosetting composition. According to other embodiments, the composition comprises the halogen containing polymer and, additionally, a polymer which does not contain a halogen.
Examples for the halogen containing polymer are chlorine containing polymers, in particular of vinyl chloride as well as of vinylidene chloride, vinyl resins comprising vinyl chloride units in their structure, as copolymers of vinyl chloride and vinyl ester of aliphatic acids. Further examples are those described in EP 2 110 405 Al which are incorporated herein by reference.
According to an embodiment, the composition according to embodiments of the herein disclosed subject-matter comprises, in addition to the halogen- containing polymer and the stabilizer composition according to the first aspect (or one or more embodiments thereof), further additives, e.g . one or more of the following additives:
• zeolite, dawsonite and layer lattice compounds
· Catena-p2,2',2"-nitrilotrisethanol-perchlorato (-triflato)-sodium or
lithium intracomplexes respectively lithium or sodium perchlorates (triflates) in dissolved or supported form
• fatty acid calcium salts (calcium soaps)
• polyols und sugar alcohols and/or 1,4-Dihydropyridine derivatives (DHP) · linear oder cyclic β-Diketones bzw. β-ketoester and their calcium,
magnesium or zinc salts
• phosphoric acid ester (phosphites) und sterically hindered amines
• glycidol compounds and epoxidized fatty acid esters
• antioxidants, UV absorbers und optical brighteners
· pigments and biocides
• fillers and propellants
• lubricants and plasticisers
• flame retardants and smoke reducers
• impact modifier e.g . on the basis of acrylate or CPE or mixtures thereof · processing aids e.g. melt flow enhancers
For example, such additives may be those disclosed in EP 2 110 405 Al which is incorporated herein by reference. In the following, examples of a composition according to embodiments of the herein disclosed subject matter have been prepared and investigated, wherein details of the examples are provided in table 1 below.
Table 1 exemplary compositions (No. 1 and 2) according to embodiments without isocyanurate (THEIC) and of comparison examples (No. 3 and 4) with isocyanurate.
As generally in this document (unless explicitly specified otherwise), in table 1 the given numbers specify the weight of the respective component in parts by weight with respect to 100 parts of the halogen containing polymer (PVC K- value 68 in the present examples). For example, the amount of 0.3 calcium hydroxide in table 1 means that per 100 parts by weight of the halogen containing polymer 0.3 parts by weight of calcium hydroxide are added .
In accordance with an embodiment, the compositions have been prepared in a heating / cooling mixer comination FML 10/KM23 of the firm Reimelt Henschel at a temperature of 120 °C/ 35°C.
Each of the compositions 1 to 4 has been plasticized on a laboratory rolling mill Polymix 150P of the firm Swabenthan for 5 minutes at 200 degrees Celsius. The thus obtained foils have been used for further investigations.
In order to characterize the obtained compositions, colorimetry has been performed on the foils according to the CIE L*a*b* (color space) system with a device of the firm Datacolor, model Check II plus lav/usav. The light type used was D65/10.
The results of the colorimetry are given in table 2, wherein the b* value refers to the CIE L*a*b* color space:
Table 2 : colorimetry results for the investigated compositions In the CIE L*a*b* system the b* value is a measure for the yellow-blue axis. The lower the b* value, the more blue is the color. For a good stabilization, a low b* value is advantageous.
As can be taken from table 2, the compositions No. 1 and 2, which implement embodiments of the herein disclosed subject matter and which do not contain isocyanurate, show a lower b* value than the comparison compositions containing isocyanurate.
Nevertheless it is noted that in some applications even a moderately lesser stabilization of the halogen containing polymer (compared to a comparision composition containing isocyanurate) may be sufficient. Anyway, compositions according to embodiments of the herein disclosed subject matter provide a much higher cost efficiency than similar compositions with isocyanurate. Sufficient stabilization of the halogen containing polymers according to embodiments of the herein disclosed subject matter is achieved by the advantageous combination of calcium hydroxide and zinc stearate (and optionally lead stearate).
According to embodiments of the second aspect, the stabilizer composition is adapted for providing the functionality of one or more of the embodiments disclosed herein and/or for providing the functionality as required by one or more of the herein disclosed embodiments, in particular of the embodiments of the first aspect described above and of the third aspect described below.
According to an embodiment of a third aspect of the herein disclosed subject- matter, there is provided a use of a stabilizer composition according to the first aspect or an embodiment thereof, for stabilizing a halogen-containing polymer. For example, the use of a stabilizing composition according to the first aspect or an embodiment thereof results, according to a respective embodiment, in a composition according to the second aspect or an embodiment thereof. According to an embodiment, the halogen containing polymer is a chlorine containing polymer, in particular polyvinyl chloride as mentioned above.
According to a further embodiment, the halogen containing polymer is stabilized against at least one of heat, moisture, radiation, oxidative stress, mechanical stress, aging, thermal cycling .
According to a further embodiment, the halogen containing polymer is stabilized in terms of waterproofing, oxidation resistance, wear resistance. According to embodiments of the third aspect, the stabilizer composition is adapted for providing the functionality of one or more of the embodiments disclosed herein and/or for providing the functionality as required by one or more of the herein disclosed embodiments, in particular of the embodiments of the first aspect and the second aspect described above.
According to a fourth aspect of the herein disclosed subject-matter, there is provided an article, in particular an extruded or a molded article manufactured from or containing a composition according to the second aspect or an embodiment thereof. The article may be e.g . a window profile. Further examples of an article are e.g . cables, wallpapers, floorings, foils, housings, etc., e.g. articles as described in EP 2 110 405 Al .
According to an embodiment, the article further comprises a protective layer on the composition. According to an embodiment, the protective layer forms an outer surface of the article. The protective layer may be configured for protecting the composition according to embodiments of the herein disclosed subject matter from environmental influences. For example, according to an embodiment, a window frame is manufactured from the composition according to one or more embodiments of the herein disclosed subject matter and provided thereon with a protecting layer. According to such an embodiment, a window frame is produced with the composition according to one or more embodiments of the herein disclosed subject matter and a further
composition, e.g . an even more stabilized composition, is provided thereon. This embodiment has the advantage of being cost-efficient and providing nevertheless a good stabilization of the article. Providing a halogen-containing polymer with a polymer composition according to one or more embodiments of the herein disclosed subject matter is advantageous in many applications, e.g . in an application where the polymer is subjected to decomposition, in particular decomposition due to aging or thermal cycling. Using a stabilizer composition according to one or more embodiments of the herein disclosed subject matter provides a cost efficient stabilizer for halogen containing polymers such as PVC. It is noted that the herein disclosed aspects and embodiments are only a limited selection of possible embodiments of the herein disclosed subject matter. It should be noted that any substance disclosed herein is not limited to the purpose as described in some embodiments. Rather, the herein disclosed subject matter may be implemented in various ways and with various modifications while still providing the specified functionality.
It should be noted that the term "comprising" does not exclude other elements or steps and that "a" or "an" does not exclude a plurality. For example, a reference to a polymer or does not exclude an embodiment where "the" polymer is replaced by two or more polymers. Furthermore, according to an embodiment the term "comprising" stands for "comprising inter alea".
According to further embodiment, the term "comprising" stands for "consisting of". Hence each use of the term "comprising" discloses two embodiments, one with "comprising" in the sense of "comprising inter alea" and one with
"comprising" in the sense of "consisting of". Further, elements, components, weight ratios or contents by weight described in association with different embodiments or examples may be combined. Further, it should be noted that any other combination of embodiment is possible and is considered to be disclosed with this application. For example, if an embodiment describes the first component as being calcium hydroxide with content of 0.3 parts by weight per 100 parts of the halogen containing polymer and a further embodiment describes the second component as being zinc stearate with a content of 0.8 parts by weight per 100 parts of the halogen containing polymer, a composition comprising calcium hydroxide with a content of 0.3 parts by weight per 100 parts of the halogen containing polymer and zinc stearate with a content of 0.8 parts by weight per 100 parts of the halogen containing polymer is also disclosed by this application.
In order to recapitulate some of the above described embodiments of the present invention one can state: Disclosed is a stabilizer composition for a halogen containing polymer, the stabilizer composition comprising : as a first component at least one of alkaline earth oxide, alkaline earth hydroxide, and calcinated dolomite; and, as a second component, at least one of a fatty acid zinc salt and a lead salt. An exemplary stabilizer composition comprises calcium hydroxide; zinc stearate and/or lead stearate. According to an embodiment, the stabilizer composition or, in another embodiment, a composition comprising the stabilizer
composition is substantially free from isocyanurate.

Claims

C l a i m s
1. Stabilizer composition for a halogen containing polymer, the stabilizer composition comprising :
as a first component at least one of alkaline earth oxide, alkaline earth hydroxide, and calcinated dolomite; and
as a second component at least one of a fatty acid zinc salt and a lead salt.
2. Stabilizer composition according to claim 1, wherein
the first component comprises or consists of calcium hydroxide.
3. Stabilizer composition according to claim 1 or 2, wherein
the second component comprises or consists of at least one of zinc stearate and lead stearate.
4. Stabilizer composition according to any one of the preceding claims, wherein
the weight ratio of the first component to the second component is from
0.01 : 2 to 2 : 0.05, in particular from 0.2 : 1 to 0.5 : 0.6 and is in particular 0.3 : 0.8.
5. Stabilizer composition according to any one of the preceding claims, wherein
the weight ratio of the fatty acid zinc salt to the lead salt is from
0.05 : 2.5 to 2 : 0.05, in particular from 0.3 : 1.2 to 0.5 : 0.8 and is in particular 0.4 : 1.
6. Stabilizer composition according to any one of the preceding claims, the stabilizer composition being substantially free from isocyanurate.
7. Composition comprising :
a halogen containing polymer; and
a stabilizer composition according to any one of the preceding claims.
8. Composition according to claim 7, wherein the halogen containing polymer is a chlorine containing polymer, in particular polyvinyl chloride.
9. Composition according to any one of claims 7 or 8, wherein
the content of the first component is from 0.01 parts by weight to 2 parts by weight with respect to 100 parts of the halogen containing polymer, in particular the content of the first component is from 0.2 parts by weight to 0.5 parts by weight with respect to 100 parts of the halogen containing polymer.
10. Composition according to any one of claims 7 to 9, wherein
the content of the second component is from 0.05 parts by weight to 4 parts by weight with respect to 100 parts of the halogen containing polymer, in particular from 0.05 parts by weight to 2.5 parts by weight with respect to 100 parts of the halogen containing polymer, in particular from 0.3 parts by weight to 1.5 parts by weight with respect to 100 parts of the halogen containing polymer.
11. Composition according to any one of claims 7 to 10, wherein
the fatty acid zinc salt content is from 0.05 parts by weight to 2 parts by weight with respect to 100 parts of the halogen containing polymer, in particular from 0.3 parts by weight to 1 parts by weight with respect to 100 parts of the halogen containing polymer.
12. Composition according to any one of claims 7 to 11, wherein the lead salt content is from 0.05 parts by weight to 2.5 parts by weight with respect to
100 parts of the halogen containing polymer, in particular from 0.8 parts by weight to 1.2 parts by weight with respect to 100 parts of the halogen containing polymer.
13. Composition according to any one claims 7 to 12, the composition being substantially free from isocyanurate.
14. Use of a stabilizer composition as defined in any one of claims 1 to 6 for stabilizing a halogen containing polymer, in particular polyvinyl chloride, wherein the halogen containing polymer is stabilized in particular against at least one of heat, moisture, radiation, oxidative stress, mechanical stress, aging, thermal cycling and/or in terms of waterproofing, oxidation resistance, wear resistance.
15. Article, in particular extruded article, the article comprising the
composition according to any one of claims 7 to 13.
EP14709895.8A 2014-02-24 2014-02-24 Stabilizer composition Withdrawn EP3110880A1 (en)

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USRE27121E (en) * 1969-11-06 1971-04-27 Stabilized vinyl resin molding composition
DE19818441C2 (en) 1998-04-24 2001-11-15 Baerlocher Gmbh Stabilizer combination for halogen-containing thermoplastic resin composition
US6773631B2 (en) * 2001-05-18 2004-08-10 Hammond Group, Inc. Liquid overbased mixed metal stabilizer composition of calcium, barium and zinc for stabilizing halogen-containing polymers
DE10356529A1 (en) 2003-12-04 2005-07-07 Cognis Deutschland Gmbh & Co. Kg Use of compositions containing isocyanurates and magnesium (hydr) oxides for the stabilization of halogen-containing organic plastics
DE102008018872A1 (en) 2008-04-14 2009-10-15 Ika Innovative Kunststoffaufbereitung Gmbh & Co. Kg Stabilizer system for halogen-containing polymers
DE102009045701A1 (en) * 2009-10-14 2011-04-21 Ika Innovative Kunststoffaufbereitung Gmbh & Co. Kg Stabilizer combinations for halogen-containing polymers
US20110275747A1 (en) * 2010-05-06 2011-11-10 Peter Hacker Stabilizer systems for polymers containing halogen

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