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WO1997012931A1 - Matiere d'etancheite pour fermetures a etancheite mecanique - Google Patents

Matiere d'etancheite pour fermetures a etancheite mecanique Download PDF

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Publication number
WO1997012931A1
WO1997012931A1 PCT/EP1996/004082 EP9604082W WO9712931A1 WO 1997012931 A1 WO1997012931 A1 WO 1997012931A1 EP 9604082 W EP9604082 W EP 9604082W WO 9712931 A1 WO9712931 A1 WO 9712931A1
Authority
WO
WIPO (PCT)
Prior art keywords
component
weight
sealing
closures
optionally
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.)
Ceased
Application number
PCT/EP1996/004082
Other languages
German (de)
English (en)
Inventor
Peter Nüssen
Doris Osterkamp
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.)
BASF Farben und Fasern AG
PPG Industries Inc
Original Assignee
BASF Lacke und Farben AG
PPG Industries Inc
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 BASF Lacke und Farben AG, PPG Industries Inc filed Critical BASF Lacke und Farben AG
Publication of WO1997012931A1 publication Critical patent/WO1997012931A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C08L23/22—Copolymers of isobutene; Butyl rubber; Homopolymers or copolymers of other iso-olefins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/02—Inorganic compounds
    • C09K2200/0239—Oxides, hydroxides, carbonates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/02—Inorganic compounds
    • C09K2200/0243—Silica-rich compounds, e.g. silicates, cement, glass
    • C09K2200/0252—Clays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0607—Rubber or rubber derivatives
    • C09K2200/061—Butyl rubber
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09K2200/0617—Polyalkenes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09K2200/0617—Polyalkenes
    • C09K2200/062—Polyethylene

Definitions

  • the invention relates to sealing compounds for mechanically sealing, in particular thin-lip closures, consisting of polymer mixtures PM, comprising A) at least one metallocene-free polyolefin homopolymer, B) a polypropylene random copolymer, C) optionally a synthetic rubber, D) optionally at least one Filler ⁇ and E) optionally other additives.
  • the sealing element has been made from a synthetic polymer mixture for a long time.
  • polymer blends that are durable and resistant enough and at the same time have the required elasticity are suitable for this.
  • this is mainly polyvinyl chloride used; Polyethylene and mixtures of the aforementioned polymers with polyvinyl acetate and vinyl acetate-ethylene copolymers have also been used. The production of vascular occlusions using such polymer mixtures is described, for example, in DE-AS 20 33 064 and DE-A-30 21 488.
  • compositions are described, preferably consisting of a) at least one polyolefin produced using catalysts from the group of metallocenes, b) at least one polypropylene copolymer, c) at least a synthetic rubber, d) optionally fillers and e) optionally further additives, which are necessary as an inner insert in a sealing element for vessels
  • the polypropylene copolymers b) described in German patent application 195 29 230.8 are preferably mixtures of polypropylene random copolymers and polypropylene homopolymers.
  • the individual components of the polypropylene random copolymer and polypropylene homopolymer have to be carefully and therefore laboriously coordinated with one another in order to avoid malfunctions in the compounding of the mixture components, such as incomplete melting of a mixture component become.
  • Such disturbances lead to loss of properties in the sealing compounds, such as pressure loss or leaks in the vascular occlusions, due to inhomogeneities in the polymer mixture.
  • the sealing compounds for vessel closures according to the invention are accordingly polymer mixtures PM of:
  • the polymer mixtures PM according to the invention preferably contain 15 to 85% by weight, particularly preferably 25 to 60% by weight, of metallocene-free polyolefin A), 15 to 35% by weight, particularly preferably 20 to 30% by weight. % of the polypropylene random copolymer B), 0 to 25% by weight, particularly preferably 5 to 20% by weight, of the synthetic rubber C), 0 to 20% by weight, particularly preferably 5 to 20% by weight. % Fillers D) and 0 to 5% by weight, particularly preferably 0.1 to 5% by weight, further additives E).
  • the data in% by weight relate to the polymer mixture PM in its entirety. Implementation of the invention
  • Polylolefins A) are preferably homopolymers and / or copolymers of ethylene and / or propylene, with the exception of polypropylene random copolymers.
  • LDPE low density polyethylenes
  • LLDPE or VLDPE linear low and linear very low density polyethylene
  • MDPE medium density polyethylene
  • HDPE high density polyethylene
  • copolymers of ethylene can be used as component A) with one or more comonomers, such as, for example, alpha-olefins, vinyl esters, such as vinyl acetate or vinyl propionate, vinyl alkyl ethers, such as vinyl methyl ether, and also unsaturated mono- and dicarboxylic acids, their salts, anhydrides or Esters such as acrylic acid, maleic acid, maleic anhydride or diethyl maleate.
  • comonomers such as, for example, alpha-olefins, vinyl esters, such as vinyl acetate or vinyl propionate, vinyl alkyl ethers, such as vinyl methyl ether, and also unsaturated mono- and dicarboxylic acids, their salts, anhydrides or Esters such as acrylic acid, maleic acid, maleic anhydride or diethyl maleate.
  • polyolefins are commercially available, for example, under the brand names Escorene®, Lupolen®, Lotader®, Laqctene®, Orevac®, Dowlex®, Lucalen®, Primacor®, Surlyn®, Admer®, Novatec®, Sclair® and Stamylan® .
  • the polypropylene random copolymers B) are statistical copolymers of 90 to 99% by weight, preferably 93 to 99% by weight of propylene and 1 to 10% by weight, preferably 1 to 7% by weight. % of further comonomers, in each case based on the total weight of the monomers used.
  • the melt index MFI 230 degrees C / 2.16 kg according to DIN 53 735 of the copolymer B) is in the range between 1 and 10 g / 10 min, preferably between 4 and 15 g / 10 min.
  • Such polypropylenes B) and methods for their production are known. They can be produced, for example, by the polymerization process described in DE-A-37 30 022 using a Ziegler-Natta catalyst.
  • the propylene copolymers B) are, for example, in a gas phase polymerization process at temperatures between 20 and 160
  • the molecular weights of the polymers can be adjusted by generally known measures, for example using molecular weight regulators, such as e.g. Hydrogen.
  • Suitable comonomers for the propylene in the propylene copolymers are, for example, ethylene and alpha-mono-olefins with 4 to 12 carbon atoms, in particular ethylene and alpha-mono-olefins with 4 to 6 carbon atoms, such as butene-1,4-methyl-pentene -1, hexene-1, n-octene-1, n-decene-1 ⁇ and n-dodecene-1.
  • Polypropylene-random copolymers B) composed of 96 to 99% by weight of propylene and 1 to 4% by weight of ethylene, in each case based on the total weight of the monomers used, are particularly suitable, such polypropylene random Copolymers B) generally have a non-uniformity U between 3 and 6 and a melt index MFI (230 degrees C / 2.16 kg according to DIN 53 735) between 5 and 9 g / 10 min.
  • Such polypropylene copolymers B) have a melting range of about 135 to 155 degrees C (determined by DSC).
  • Polypropylene random copolymers B) composed of 90 to 97% by weight of propylene, 2 to 5% by weight of ethylene and 1 to 6% by weight of butene-1, each based on the total weight of the monomers used, are also particularly suitable ren, which is a non-uniformity U between 3 and 6, have a melt index MFI (230 degrees C / 2.16 kg) between 4 and 8 g / 10 min and a melting range between 120 and 140 degrees C (measured by DSC).
  • the polypropylene random copolymers described are available, for example, under the trade name Novolen® 3520 LX from BASF AG.
  • SBS rubber styrene-butadiene-styrene block copolymers
  • SIS rubbers styrene-isoprene-styrene block copolymers
  • Suitable SBS and SIS rubbers are described, for example, in DE-A-16 92 059 and in US Pat. No. 3,779,965.
  • block copolymers of type A-B-A which contain polystyrene as block A and polybutadiene or polyisoprene as block B.
  • Suitable SBS chewing pads consist, for example, of 30 to 60% by weight of polystyrene end segments and correspondingly 40 to 70% by weight of central segments made of polybutadiene or polyisoprene.
  • SBS block copolymers and styrene-butadiene copolymers are available, for example, from Fina under the trade name Finaprene®.
  • synthetic rubber C) ethylene-propylene copolymers EPM can be used, which are amorphous and which are crosslinked, for example, with the help of peroxides.
  • Terpolymers of ethylene, propylene and a diene EPDM can also be used as synthetic rubber C), the EPDM types being able to be crosslinked both peroxidically and with sulfur accelerator systems.
  • EPM and EPDM types see, for example, Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, volume 13, pages 619 to 621, Verlag Chemie, Weinheim, New York, 1977.
  • Preferred synthetic rubbers C) are butyl rubber.
  • schuke used which preferably consist of copolymers of 95 to 99.5 mol% isobutene and 0.5 to 5 mol% isoprene.
  • Such butyl rubbers C) are obtained, for example, by cationic copolymerization of isobutene and isoprene in methyl chloride as the solvent and with aluminum chloride as the catalyst at -100 ° C.
  • the butyl rubbers C) generally have a double bond content of about 0.5 to 3 mol%, which is suitable for peroxidic or sulfur-induced crosslinking.
  • the weight-average molecular weights Mw of the uncrosslinked butyl rubber C) are approximately 150,000 to 400,000 daltons with a non-uniformity U of approximately 3.
  • U non-uniformity
  • the polymer mixtures according to the invention also contain fillers D), with preference
  • inorganic fillers D include inorganic types: titanium dioxide types, such as titanium dioxide, barium sulfate, silicates, such as magnesium or aluminum silicates, quartz sands, talc, kaolin, mica, amorphous and pyrogenic silicas, calcium carbonate, diatomaceous earth . Titanium dioxide and fillers of the talcum type are preferably used.
  • additives E) are present in the polymer mixtures PM according to the invention. These include internal and external lubricants, anti-blocking agents, stabilizers, antioxidants, pigments, crystallization aids and the like. These additives are used in the manufacturing, processing, packaging and application. agile amounts in the form of powder, powder, pearls or incorporated directly into one of the mixture components. More details on the amounts usually used and examples of suitable additives can be found, for example, in Gachter-Müller, Kunststoffadditive, Carl-Hanser Verlag.
  • the polymer mixtures PM according to the invention contain up to 0.5% by weight, based on the polymer mixture, of lubricants and up to 0.2% by weight of antiblocking agents and, if appropriate, antioxidants and other processing stabilizers.
  • Suitable lubricants are fatty acids, such as stearic and oleic acids, silicone oils, such as polydimethylsiloxane and polymethylsiloxane.
  • Other examples are waxes and
  • Silicas to achieve certain flow behavior.
  • Primary and secondary fatty acid amides such as erucasaureamide or oleic acid amide, are preferably used as lubricants.
  • the antioxidants and processing stabilizers primarily serve to protect against daylight and UV light and against heat. Accordingly, UV light and heat stabilizers are used in particular.
  • sterically hindered amines are used as UV stabilizers.
  • Sterically hindered phenols for example, are used as heat stabilizers.
  • Phenol derivatives are preferably used as antioxidants.
  • the polymer mixtures PM used in accordance with the present invention are first produced by mechanical
  • the closure to be coated with the sealing compound is understood to mean all parts of the packaging material which are connected to the body of the packaging, such as, for example, crown caps for beer, fruit juice and lemonade bottles, metallic closures for bottles and glasses, and others Metallic closures for cans, buckets, fibers and other containers which are common in the packaging industry. In addition to crown caps, aluminum twist locks, cam twist locks and CRIMP closures.
  • the present invention also relates to packaging containers with a metallic closure, the closure containing sealing compounds as a constituent part, which are composed of the polymer mixtures PM according to the invention.
  • closures have the particular advantage that, compared to the usual polyvinyl chloride sealants, the sealants are halogen-free, have no plasticizer migration and have good resistance to solvents and chemicals, good resistance under the conditions of pasteurization and the like Have sterilization and good adhesion to the substrates coated with adhesive lacquers. Furthermore, the components of the polymer mixture PM which form the sealing compounds can be mixed homogeneously in the thermoplastic state without problems and easily available. From an environmental point of view, the sealing compounds according to the invention are particularly advantageous since they contain no harmful substances, in particular no halogen-containing constituents and no low-molecular constituents containing ester groups, and the sealing compounds enable a largely solvent-free process for the manufacture of closures of packaging containers.
  • a mechanical sealant PMI is made from the following components by mechanical mixing and extrusion:
  • HDPE high-density polyethylene
  • Phenol 0.220 parts lubricant (amide wax) 0.100 parts UV stabilizer (sterically hindered
  • Example 2 Crown cork production and properties of the crown corks containing the sealing compounds containing the polymer mixtures PM / coated according to the invention as bottle closures
  • crown cork punch type PTC27 from Sacmi, Imola, Italy, metal sheets coated with adhesive on one side are processed into crown corks.
  • ready-to-use crown caps are produced on a PM1200 and PM250 system from Sacmi, Imola, Italy, for the introduction of the polymer mixture PMI that makes up the sealant.
  • the crown caps show good adhesion between adhesive varnish and sealant in laboratory tests.
  • the sealing compounds have a pressure maintenance of at least 8 bar.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Closures For Containers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une matière d'étanchéité pour fermetures à étanchéité mécanique, formée de mélanges polymères comprenant: A) au moins une polyoléfine exempte de métallocène, B) un copolymère statistique de polypropylène, C) éventuellement, un caoutchouc synthétique, D) éventuellement, des charges, et E) éventuellement d'autres adjuvants. L'invention concerne également des procédés de fabrication de fermetures à étanchéité mécanique utilisant le mélange polymère précité (PM) selon l'invention, comme garniture intérieure sur la surface de fermeture, ainsi que les fermetures elles-mêmes à étanchéité mécanique.
PCT/EP1996/004082 1995-10-04 1996-09-18 Matiere d'etancheite pour fermetures a etancheite mecanique Ceased WO1997012931A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1995136923 DE19536923A1 (de) 1995-10-04 1995-10-04 Dichtungsmassen für mechanisch dichtende Verschlüsse
DE19536923.8 1995-10-04

Publications (1)

Publication Number Publication Date
WO1997012931A1 true WO1997012931A1 (fr) 1997-04-10

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ID=7773977

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1996/004082 Ceased WO1997012931A1 (fr) 1995-10-04 1996-09-18 Matiere d'etancheite pour fermetures a etancheite mecanique

Country Status (2)

Country Link
DE (1) DE19536923A1 (fr)
WO (1) WO1997012931A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2023436151A1 (en) * 2023-03-11 2025-09-25 Actega Gmbh Butene (co)polymer-based sealing material for container closures

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0160448A2 (fr) * 1984-04-27 1985-11-06 American Colloid Company Composition d'argile gonflable à l'eau
EP0339831A2 (fr) * 1988-04-15 1989-11-02 W.R. Grace & Co.-Conn. Capsules pour la fermeture de récipient et compositions pour former les joints pour celles-ci
DE4229923A1 (de) * 1992-09-08 1994-03-10 Basf Lacke & Farben Verfahren zur Herstellung von Verschlüssen von Verpackungsbehältern
WO1995000599A2 (fr) * 1993-06-21 1995-01-05 Shell Oil Company Fermetures en plastique et garnitures de fermeture

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0160448A2 (fr) * 1984-04-27 1985-11-06 American Colloid Company Composition d'argile gonflable à l'eau
EP0339831A2 (fr) * 1988-04-15 1989-11-02 W.R. Grace & Co.-Conn. Capsules pour la fermeture de récipient et compositions pour former les joints pour celles-ci
DE4229923A1 (de) * 1992-09-08 1994-03-10 Basf Lacke & Farben Verfahren zur Herstellung von Verschlüssen von Verpackungsbehältern
WO1995000599A2 (fr) * 1993-06-21 1995-01-05 Shell Oil Company Fermetures en plastique et garnitures de fermeture

Also Published As

Publication number Publication date
DE19536923A1 (de) 1997-04-10

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