EP2294130A1 - Polyvinyl alcohol as co-stabilizer for pvc - Google Patents

Polyvinyl alcohol as co-stabilizer for pvc

Info

Publication number
EP2294130A1
EP2294130A1 EP20090765807 EP09765807A EP2294130A1 EP 2294130 A1 EP2294130 A1 EP 2294130A1 EP 20090765807 EP20090765807 EP 20090765807 EP 09765807 A EP09765807 A EP 09765807A EP 2294130 A1 EP2294130 A1 EP 2294130A1
Authority
EP
European Patent Office
Prior art keywords
polyvinyl alcohol
thermoplastic processable
stabilizer
thermoplastic
mixture according
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Withdrawn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
EP20090765807
Other languages
German (de)
French (fr)
Inventor
Robert W. Fuss
Samuel Michel
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.)
Kuraray Europe GmbH
Original Assignee
Kuraray Europe 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 Kuraray Europe GmbH filed Critical Kuraray Europe GmbH
Priority to EP20090765807 priority Critical patent/EP2294130A1/en
Publication of EP2294130A1 publication Critical patent/EP2294130A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids

Definitions

  • the present invention relates to thermoplastic processable mixtures based on polyvinyl chloride (PVC) which are stabilized with at least one metal ion in combination with polyvinyl alcohol having a low degree of polymerization and a medium degree of hydrolysis.
  • PVC polyvinyl chloride
  • Thermoplastic processable mixtures based on PVC have to be stabilized against heat and/or UV-radiation in order to reduce chemical decomposition.
  • metal ions for example lead or tin salts or the more eco-friendly calcium or zinc compounds.
  • the metal based stabilizers should have a good dispersibility within the polymer matrix without showing agglomeration or incompatibility during the thermoplastic processing of the PVC-mixture. Furthermore, the stabilizers should not migrate to the surface of the processed material in order to prevent so called "plate-out" or "fish eye” disturbances. Therefore, most stabilizers for PVC contain a plurality of components like polyols, beta diketones, phenolic compounds or inorganic stabilizers. See, for example US 5,143,959.
  • PVA polyvinyl alcohol
  • US 5,118,741 discloses the use of partially hydrolyzed PVA during suspension polymerization of PVC in an amount of 0,5 phr at most and the stabilisation of the thus obtained PVC-mixture with metal ions.
  • a co-stabilizing effect of the PVA is not mentioned in this publication.
  • the amounts of PVA added are too low to expect any co-stabilizing effect.
  • DE 272 8 862 discloses a mixture of PVC, and Ca/Zn salts of a ⁇ -diketone with PVA as polyol compound without giving any details of the PVA used.
  • thermoplastic processable mixtures based on polyvinyl chloride containing a stabilizer comprising at least one metal ion and polyvinyl alcohol characterized by the addition of 0,1 to 15 parts of a polyvinyl alcohol having a degree of polymerization of less than 700 and a degree of hydrolysis of 75 to 95 mol% per 100 parts of polyvinyl chloride.
  • the mixtures according to the invention contain preferably 0,1 to 5 parts polyvinyl alcohol per 100 parts PVC.
  • the polyvinyl alcohol used in the present invention has a degree of polymerization of 100 to less than 700, especially 250 to 600 or even more preferred 350 to 250.
  • the degree of hydrolysis of the PVA is preferably between 75 and 90 mol% or more preferred between 80 and 90 mol%.
  • Stabilizer according to the invention is at least one metal ion selected from the group barium, zinc, calcium or tin, especially in the form of the respective organic or inorganic salts.
  • metal soaps i.e. salts of carbon acids comprising 1 to 25 carbon atoms, especially stearates, laureates, maleates, oleates, or terephthalates or metal salts of acetyl acetone, a mercaptane or a ⁇ -diketones are used.
  • a stabilizer mixture derived from zinc and calcium salts, preferably the respective salts of ⁇ -diketones, acetyl acetone or carboxylic acids comprising 1 to 25 carbon atoms, preferable in a mixture of 1 :1 to 1 :4, especially 1 :2 parts.
  • thermoplastic mixture in PVC industry commonly used filling materials for example selected from the group consisting Of TiO 2 , CaCO 3 , ZrO 2 , Kaolin, Talcum, K/AI silicates, feldspar, silicate, barium sulphate, metal powder, graphite, calcium sulphate, ceramic and glass particles or wood may be added to the thermoplastic mixture in about 5 to 20 parts per hundred parts of polyvinyl chloride.
  • plasticizers like epoxidised soybean oil which are also contributing to the thermal stabilisation of the PVC
  • lower concentration may be employed and PVA may be added in amounts of about 0,01 to 10 phr of PVC.
  • Another object of the invention is a process for manufacture of thermoplastic processable mixtures based on polyvinyl chloride comprising at least one metal ion as stabilizer and 0,1 to 15 parts of a polyvinyl alcohol having a degree of polymerization of less than 700 and a degree of hydrolysis of 75 to 95 mol% per 100 parts of polyvinyl chloride by mixing the components at a temperature of at least 120 °C for example in an extruder or a kneader.
  • the mixing may be performed prior to or during a thermoplastic form shaping process at about 180 to 240 °C.
  • thermoplastic form shaping process is usually performed with or in an extruder or calender for example by first melting the components during the feeding process at said temperatures and afterwards form shaping the mixture at elevated pressure.
  • the PVA can be added to the PVC as a powder or in form of a solution.
  • This PVA solution can be prepared with water or with a suitable organic solvent or any mixture thereof (for example aqueous ethanol).
  • the metal salts can be added as dry blend or also in form of a solution.
  • all additives can be added alone or together (as "one pack formulation") to the PVC as dry blend, for example in an extruder, dry mill or kneader.
  • the use of said PVA as co-stabilizer in thermoplastic processable mixtures based on PVC containing at least one metal ion as stabilizer is further an object of the present invention.
  • thermoplastic mixture different metal ions in different concentrations may be used.
  • PVC mixtures for bottles, tubes or profiles may contain 0,3 to 3 phr tin ions.
  • For flexible PVC mixtures like plastisoles Ba- and Zn-ions in a total amount of 1 to 3 phr are used. Ca/Zn mixtures in an total amount of 2-3.5 phr are used for floor coverings.
  • Such mixtures and the amounts of metal ions are known in the PVC industry. In cases where epoxidised vegetable oils are employed it may even possible to reduce the amount of PVA and metal ions according to the invention without imparing thermal stabilization.
  • Thermoplastic processable mixtures according to the invention are especially useful for the production of window or door profiles, films, coatings, sheets, tubes, cables, floorings, bottles, or floor coverings.
  • the obtained mixture was pressed into sheets of 50 x 70 mm with a thickness of about 0,45 mm.
  • the sheets were subsequently heated to 180 °C in an oven and the whiteness of the heated sheets was measured at room temperature using a colorimeter.
  • a differential colorimeter (Model SM-T-H 1 colour computer, Suga Shikenki Co., Ltd) with SC-T(P), SM-T(P),ver8.00 software, mounting a specimen holder window 30 mm in diameter was used to measure the whiteness level.
  • the whiteness values show the co-stabilizing effect of the polyvinyl alcohol used.
  • polyvinyl alcohols according to the invention (E1 to E5) have an improved stabilizing effect as compared to polyvinyl alcohols known from prior art (C 1 to C3).

Landscapes

  • 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

Use of a polyvinyl alcohol having a degree of polymerization of less than 700 and a degree of hydrolysis of 75 to 95 mol% as co-stabilizer for thermoplastic processable PVC mixtures in combination with metal ions.

Description

Description
Polyvinyl alcohol as co-stabilizer for PVC
Field of the invention
[0001] The present invention relates to thermoplastic processable mixtures based on polyvinyl chloride (PVC) which are stabilized with at least one metal ion in combination with polyvinyl alcohol having a low degree of polymerization and a medium degree of hydrolysis.
Prior Art
[0002] Thermoplastic processable mixtures based on PVC have to be stabilized against heat and/or UV-radiation in order to reduce chemical decomposition. Especially useful for this purpose are metal ions, for example lead or tin salts or the more eco-friendly calcium or zinc compounds. The metal based stabilizers should have a good dispersibility within the polymer matrix without showing agglomeration or incompatibility during the thermoplastic processing of the PVC-mixture. Furthermore, the stabilizers should not migrate to the surface of the processed material in order to prevent so called "plate-out" or "fish eye" disturbances. Therefore, most stabilizers for PVC contain a plurality of components like polyols, beta diketones, phenolic compounds or inorganic stabilizers. See, for example US 5,143,959.
[0003] The use of polyvinyl alcohol (PVA) in metal-based stabilizer mixtures for PVC is known. For example, US 5,118,741 discloses the use of partially hydrolyzed PVA during suspension polymerization of PVC in an amount of 0,5 phr at most and the stabilisation of the thus obtained PVC-mixture with metal ions. A co-stabilizing effect of the PVA is not mentioned in this publication. Furthermore, the amounts of PVA added are too low to expect any co-stabilizing effect.
[0004] DE 272 8 862 discloses a mixture of PVC, and Ca/Zn salts of a β-diketone with PVA as polyol compound without giving any details of the PVA used.
[0005] The thermal stability of PVC-mixtures containing PVA as co-stabilizer was further analysed by lkeda et. al. in "Polymers and Polymer Composites", p 649 to 662, vol. 11 no. 8, 2003. In this paper, PVA having a high (>98 Mol%) or a low degree (<40 Mol%) of saponification in combination with high or low degree of polymerisation can be used as co-stabilizer for Zn-stabilized PVC mixtures.
[0006] The known PVA-containing stabilizer mixtures for PVC still have deficiencies in view of thermal stability and/or processability during the extrusion of PVC-mixtures.
[0007] Surprisingly, it was found that partially saponified polyvinyl alcohols having a low degree of polymerization and a medium degree of hydrolysis improve the thermal stability of PVC mixtures stabilized with metal ions and show sufficient compatibility with the polymer matrix.
[0008] Therefore, one aspect of the invention are thermoplastic processable mixtures based on polyvinyl chloride containing a stabilizer comprising at least one metal ion and polyvinyl alcohol, characterized by the addition of 0,1 to 15 parts of a polyvinyl alcohol having a degree of polymerization of less than 700 and a degree of hydrolysis of 75 to 95 mol% per 100 parts of polyvinyl chloride.
[0009] The mixtures according to the invention contain preferably 0,1 to 5 parts polyvinyl alcohol per 100 parts PVC. Preferably 0,1 to 1 phr, preferably 0,1 to 0,5 phr.
[0010] Preferably, the polyvinyl alcohol used in the present invention has a degree of polymerization of 100 to less than 700, especially 250 to 600 or even more preferred 350 to 250.
[0011] Furthermore, the degree of hydrolysis of the PVA is preferably between 75 and 90 mol% or more preferred between 80 and 90 mol%.
[0012] Stabilizer according to the invention is at least one metal ion selected from the group barium, zinc, calcium or tin, especially in the form of the respective organic or inorganic salts. Preferable "metal soaps", i.e. salts of carbon acids comprising 1 to 25 carbon atoms, especially stearates, laureates, maleates, oleates, or terephthalates or metal salts of acetyl acetone, a mercaptane or a β-diketones are used.
[0013] Especially useful is a stabilizer mixture derived from zinc and calcium salts, preferably the respective salts of β-diketones, acetyl acetone or carboxylic acids comprising 1 to 25 carbon atoms, preferable in a mixture of 1 :1 to 1 :4, especially 1 :2 parts. [0014] Furthermore, in PVC industry commonly used filling materials for example selected from the group consisting Of TiO2, CaCO3, ZrO2, Kaolin, Talcum, K/AI silicates, feldspar, silicate, barium sulphate, metal powder, graphite, calcium sulphate, ceramic and glass particles or wood may be added to the thermoplastic mixture in about 5 to 20 parts per hundred parts of polyvinyl chloride.
[0015] The addition of common plasticizers known to the PVC processing industry like dioctyl phthalate, diisononyl phthalate, or their hydrated derivates, dioctyl therephthalate, alkyladipates, alkylbenzoates, epoxidised alkyl ester or epoxidised vegetable oils like epoxidised soybean or linseed oil, each in 0,1 to 100 parts per 100 parts PVC is possible.
[0016] In the case of plasticizers like epoxidised soybean oil which are also contributing to the thermal stabilisation of the PVC, lower concentration may be employed and PVA may be added in amounts of about 0,01 to 10 phr of PVC.
[0017] Another object of the invention is a process for manufacture of thermoplastic processable mixtures based on polyvinyl chloride comprising at least one metal ion as stabilizer and 0,1 to 15 parts of a polyvinyl alcohol having a degree of polymerization of less than 700 and a degree of hydrolysis of 75 to 95 mol% per 100 parts of polyvinyl chloride by mixing the components at a temperature of at least 120 °C for example in an extruder or a kneader. Preferably, the mixing may be performed prior to or during a thermoplastic form shaping process at about 180 to 240 °C.
[0018] The optional thermoplastic form shaping process is usually performed with or in an extruder or calender for example by first melting the components during the feeding process at said temperatures and afterwards form shaping the mixture at elevated pressure.
[0019] The PVA can be added to the PVC as a powder or in form of a solution. This PVA solution can be prepared with water or with a suitable organic solvent or any mixture thereof (for example aqueous ethanol). The metal salts can be added as dry blend or also in form of a solution. Alternatively, all additives can be added alone or together (as "one pack formulation") to the PVC as dry blend, for example in an extruder, dry mill or kneader. [0020] The use of said PVA as co-stabilizer in thermoplastic processable mixtures based on PVC containing at least one metal ion as stabilizer is further an object of the present invention.
[0021] Depending on the intended use of the thermoplastic mixture, different metal ions in different concentrations may be used.
[0022] Typically, PVC mixtures for bottles, tubes or profiles may contain 0,3 to 3 phr tin ions. For flexible PVC mixtures, like plastisoles Ba- and Zn-ions in a total amount of 1 to 3 phr are used. Ca/Zn mixtures in an total amount of 2-3.5 phr are used for floor coverings. Such mixtures and the amounts of metal ions are known in the PVC industry. In cases where epoxidised vegetable oils are employed it may even possible to reduce the amount of PVA and metal ions according to the invention without imparing thermal stabilization.
Industrial Applicability
[0023] Thermoplastic processable mixtures according to the invention are especially useful for the production of window or door profiles, films, coatings, sheets, tubes, cables, floorings, bottles, or floor coverings.
Examples
[0024] Samples comprising the components according to table 1 were prepared by the following steps:
• 1 % of PVA was dissolved in water.
• PVC was added to the solution, and then dried at 50°C for 8 hrs
• To the PVC/PVA mixture, DOP (Dioctyl phthalate), Zn-stearate and Ca-stearate were added and dry blended
• 60 g of the resulting mixture was milled using an open roll at 160°C for 5 min.
[0025] The obtained mixture was pressed into sheets of 50 x 70 mm with a thickness of about 0,45 mm. The sheets were subsequently heated to 180 °C in an oven and the whiteness of the heated sheets was measured at room temperature using a colorimeter.
[0026] A differential colorimeter (Model SM-T-H 1 colour computer, Suga Shikenki Co., Ltd) with SC-T(P), SM-T(P),ver8.00 software, mounting a specimen holder window 30 mm in diameter was used to measure the whiteness level. [0027] The whiteness values show the co-stabilizing effect of the polyvinyl alcohol used. [0028]
Table 1
[0029] As can be seen from table 1 , polyvinyl alcohols according to the invention (E1 to E5) have an improved stabilizing effect as compared to polyvinyl alcohols known from prior art (C 1 to C3).

Claims

Claims
1. Thermoplastic processable mixture based on polyvinyl chloride containing a stabilizer comprising at least one metal ion and polyvinyl alcohol, characterized by the addition of 0,1 to 15 parts of a polyvinyl alcohol having a degree of polymerization of less than 700 and a degree of hydrolysis of 75 to 95 mol% per 100 parts of polyvinyl chloride.
2. Thermoplastic processable mixture according to claim 1 , characterized in that the polyvinyl alcohol has a degree of hydrolysis of 80 to 90 mol%.
3. Thermoplastic processable mixture according to claim 1 or 2, characterized in that as stabilizer at least one metal ion selected from the group barium, zinc, calcium or tin is used.
4. Thermoplastic processable mixture according to any of the claims 1 to 3, characterized in that as stabilizer a mixture of zinc and calcium salts of a carboxylic acid comprising 1 to 25 carbon atoms, of acetyl acetone or a β-diketone is used.
5. Thermoplastic processable mixture according to one of the claims 1 to 4 characterized in that the mixture contains 5 to 20 parts per 100 parts of polyvinyl chloride of a filler material selected from the group consisting Of TiO2, CaCO3, ZrO2, Kaolin, Talcum, K/AI silicates, feldspar, silicate, barium sulphate, metal powder, graphite, calcium sulphate, ceramic and glass particles or wood.
6. Thermoplastic processable mixture according to any of the claims 1 to 5 characterized in that the polyvinyl alcohol has a degree of polymerization of 100 to less than 700.
7. Thermoplastic processable mixture according to any of the claims 1 to 6 characterized in that the polyvinyl alcohol has a hydrolysis of 75 to 90 mol%.
8. Process for the production of the thermoplastic processable mixtures according to one of the claims 1 to 7 by mixing the components at a temperature of least 120 °C.
9. Process according to claim 8 characterized in that the mixing is obtained during thermoplastic form shaping process at 180 to 240 °C
10. Use of the thermoplastic processable mixture according to any of the claims 1 to 8 for the production of window or door profiles, films, coatings, sheets, tubes, cables, floorings, bottles, or floor coverings.
EP20090765807 2008-06-16 2009-06-15 Polyvinyl alcohol as co-stabilizer for pvc Withdrawn EP2294130A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP20090765807 EP2294130A1 (en) 2008-06-16 2009-06-15 Polyvinyl alcohol as co-stabilizer for pvc

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP08104424A EP2135896A1 (en) 2008-06-16 2008-06-16 Polyvinyl alcohol as co-stabilizer for PVC
EP20090765807 EP2294130A1 (en) 2008-06-16 2009-06-15 Polyvinyl alcohol as co-stabilizer for pvc
PCT/EP2009/057325 WO2009153227A1 (en) 2008-06-16 2009-06-15 Polyvinyl alcohol as co-stabilizer for pvc

Publications (1)

Publication Number Publication Date
EP2294130A1 true EP2294130A1 (en) 2011-03-16

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EP20090765807 Withdrawn EP2294130A1 (en) 2008-06-16 2009-06-15 Polyvinyl alcohol as co-stabilizer for pvc

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Country Status (3)

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EP (2) EP2135896A1 (en)
RU (1) RU2500698C2 (en)
WO (1) WO2009153227A1 (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007033970A1 (en) * 2007-07-19 2009-01-22 Kuraray Europe Gmbh Use of tempered polyvinyl alcohols as stabilizer additive of PVC
TW201137016A (en) * 2010-02-01 2011-11-01 Kuraray Co Thermal stabilizer for polyvinylchloride, polyvinylchloride resin composition and manufacturing method thereof
FR2974101B1 (en) 2011-04-18 2015-01-16 Arkema France HALOGEN-CONTAINING POLYMER COMPOSITION WITH TIN-BASED STABILIZER AND CO-STABILIZING
CN103804818A (en) * 2014-01-20 2014-05-21 苏州新区华士达工程塑胶有限公司 Novel polyvinyl chloride plastic formula
CN106543477B (en) * 2016-10-14 2018-12-18 新亚电子有限公司 A kind of molecular sieve carried tin type composite calcium zinc heat stabilizer and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2176343B1 (en) * 2007-07-19 2011-02-16 Kuraray Co., Ltd. Carboxy-modified polyvinyl alcohol as co-stabilizer for pvc
EP2176342B1 (en) * 2007-07-19 2013-07-10 Kuraray Europe GmbH Polyvinyl alcohol as co-stabilizer for pvc

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FR2356674A1 (en) 1976-06-28 1978-01-27 Rhone Poulenc Ind STABILIZED COMPOSITIONS BASED ON VINYL CHLORIDE POLYMER
DE3018940A1 (en) * 1980-05-17 1981-11-26 Hoechst Ag, 6000 Frankfurt USE OF A VINYL CHLORIDE Graft COPOLYMERISATE IN PLASTISOL PROCESSING
GB2207923B (en) * 1987-08-14 1991-02-27 Nippon Synthetic Chem Ind Halogen-containing thermoplastic resin composition
PT91654B (en) 1988-09-08 1995-05-31 Shinetsu Chemical Co VINYL CHLORIDE BASED RESIN PREPARATION PROCESS
FR2661182B1 (en) 1990-04-20 1992-07-03 Rhone Poulenc Chimie STABILIZED HALOGEN POLYMER COMPOSITIONS.
JP3339257B2 (en) * 1995-06-20 2002-10-28 信越化学工業株式会社 Vinyl chloride resin composition

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Publication number Priority date Publication date Assignee Title
EP2176343B1 (en) * 2007-07-19 2011-02-16 Kuraray Co., Ltd. Carboxy-modified polyvinyl alcohol as co-stabilizer for pvc
EP2176342B1 (en) * 2007-07-19 2013-07-10 Kuraray Europe GmbH Polyvinyl alcohol as co-stabilizer for pvc

Non-Patent Citations (1)

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Title
See also references of WO2009153227A1 *

Also Published As

Publication number Publication date
RU2500698C2 (en) 2013-12-10
WO2009153227A1 (en) 2009-12-23
RU2011101402A (en) 2012-07-27
EP2135896A1 (en) 2009-12-23

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