EP2780406A1 - Mélange de caoutchouc et flexible contenant le mélange de caoutchouc - Google Patents

Mélange de caoutchouc et flexible contenant le mélange de caoutchouc

Info

Publication number
EP2780406A1
EP2780406A1 EP12780474.8A EP12780474A EP2780406A1 EP 2780406 A1 EP2780406 A1 EP 2780406A1 EP 12780474 A EP12780474 A EP 12780474A EP 2780406 A1 EP2780406 A1 EP 2780406A1
Authority
EP
European Patent Office
Prior art keywords
phr
rubber
rubber mixture
layer
inner layer
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Withdrawn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
EP12780474.8A
Other languages
German (de)
English (en)
Inventor
Sebastian Seibold
Hauke WESTERBERG
Stefan Kossek
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.)
ContiTech MGW GmbH
Original Assignee
ContiTech MGW 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 ContiTech MGW GmbH filed Critical ContiTech MGW GmbH
Publication of EP2780406A1 publication Critical patent/EP2780406A1/fr
Withdrawn legal-status Critical Current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
    • C08L15/00—Compositions of rubber derivatives
    • C08L15/02—Rubber derivatives containing halogen
    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L11/00—Hoses, i.e. flexible pipes
    • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
    • F16L11/08—Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall
    • F16L11/085—Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall comprising one or more braided layers

Definitions

  • Rubber mixture and hose containing the rubber mixture Rubber mixture and hose containing the rubber mixture
  • the invention relates to a rubber mixture and a hose, which has at least the following layer structure:
  • the hose is a two-layer hose without embedded
  • Reinforcing layer thus formed exclusively of an inner layer and an outer layer.
  • a reinforcement layer which is formed in one or more layers between the inner layer and the outer layer, is present.
  • further layers may be present.
  • FKM mixtures also referred to as FPM mixtures
  • polyols polyols
  • Quaternary ammonium salts such as, for example, in DE 43 11 549 AI or in EP 1 096
  • the inner layer should act as a barrier against aggressive media, such as. Acids or fuels, so that in this case the tear resistance, in particular the
  • Tear propagation resistance which plays an important role.
  • a common method for increasing the tear propagation resistance is the targeted
  • the rubber mixture containing at least one fluororubber additionally contains at least one active filler, i. a filler which shows a significant interaction with the polymers used contains.
  • active fillers for example, active carbon blacks, magnesium carbonate, active precipitated silica, fumed silica, condensed silica, calcium and aluminum silicates, fibers (short and long fibers, glass, carbon, aramid fibers), whiskers (alumina, silicon carbide ), Mica, zinc oxide, core / shell fillers and others.
  • active carbon black has been found to be advantageous in terms of tear properties. Whether soot is referred to as active or inactive depends essentially on its specific surface area. As active usually all carbon blacks are called, which has an iodine value, according to ASTM D 1510, which also as
  • Iodine absorption number is between 60 and 300 g / kg and a DBP number, between 60 and 150 cm 3 / 100g.
  • the DBP number according to ASTM D 2414 determines the specific absorption volume of a carbon black or a light filler by means of dibutyl phthalate. This means that preference is given to using and using carbon blacks with the identifier N-lxx, N-2xx or else N-3xx as active carbon blacks.
  • the identification of the carbon blacks follows the classification table of ASTM D 1765-06.
  • the silicas used in the rubber industry are generally precipitated silicas, which are characterized in particular according to their surface. Again, there is a direct correlation between active silica and the surface.
  • the nitrogen surface area (BET) according to DIN 66131 and DIN 66132 as a measure of the inner and outer filler surface in m 2 / g
  • the CTAB surface according to ASTM D 3765 as a measure of the outer surface, often as the rubber surface, in m 2 / g.
  • silicas are used in the rubber mixture, they preferably have a nitrogen surface area (BET) between 50 and 400 m 2 / g and a CTAB surface area between 100 and 300 m 2 / g.
  • BET nitrogen surface area
  • the total amount of active fillers is preferably 2 to 70 phr, more preferably 5 to 60 phr and most preferably 10 to 50 phr.
  • the term phr (parts per hundred parts of rubber by weight) used in this document is the quantity used in the rubber industry for mixture formulations. The dosage of the parts by weight of the individual substances is always based on 100 parts by weight of the total mass of all the rubbers present in the mixture.
  • the rubber mixture contains no or only small amounts of inactive fillers, ie the total amount of inactive fillers is between 0 and 20 phr, preferably between 0 and 10 phr, very particularly preferably between 0 and 5 phr. It is particularly preferred if the rubber mixture is free from inactive fillers, ie the total amount is 0 phr.
  • Inactive fillers include, in particular, chalk, kieselguhr, clay gel, asphalt, hard rubber dust, inorganic and organic pigments, glass beads, limestone (CaCO 3 ), silicic acid (inactive), carbon black (inactive), wood flour, nut shell meal, kaolin, feldspar and talc.
  • Rubber compounds serve primarily as a processing aid and cause the necessary green stickiness of the rubber mixtures. Furthermore, the resins can influence certain vulcanizate properties, such as hardness, modulus and swelling behavior.
  • the use of at least one resin shows an additional improvement in the elongation at break properties of the rubber composition.
  • Resins used in the rubber industry are e.g. Hydrocarbon resins, such as.
  • Petroleum resins terpene resins and coal tar resins, or natural resins, such as.
  • Rosin and tall resin or epoxy resins, melamine resins, polyester resins,
  • Polyurethane resins acrylic resins, fluorine resins or vinyl ester resins, ketone resins, phenolic resins.
  • coal tar resins such as coumarone-indene resins have a positive influence on the elongation at break properties.
  • any fluorororubber known to a person skilled in the art can be used.
  • the copolymers as bespw.
  • the fluororubber used in the fluororubber mixture is preferably a co-polymer or ter-polymer, wherein the fluorine content is
  • the fluororubber may be used singly or in admixture with at least one further fluororubber, such as fluorosilicone, polytetrafluoroethylene (PTFE) or
  • FEP Perfluoroethylene propylene
  • the total amount of fluororubber is suitably 50 to 100 phr, preferably 70 to 100 phr, more preferably 90 to 100 phr.
  • the rubber mixture may contain at least one further rubber.
  • Nitrile rubber hydrogenated nitrile rubber, hydrogenated acrylonitrile-butadiene rubber, chloroprene rubber, butyl rubber, halobutyl rubber or ethylene-propylene-diene rubber have been found to be particularly suitable for use in the field of hoses.
  • the rubber composition also contains other additives such as the crosslinking system comprising a crosslinking agent and an accelerator. Depending on the type of
  • Rubber mixture which may be varied in a multi-layered hose, the mixture ingredients also include a processing aid and / or a plasticizer and / or an anti-aging agent and optionally further
  • Processing aids may in particular be carnauba waxes, pentaerythrityl tetrastearates, soaps, fatty acid esters, phosphoric acid esters, boric acid esters, acid amides, aliphatic and olefinic waxes and aliphatic and olefinic amines or mixtures thereof.
  • the crosslinking can be bisphenolic, peroxidic or bisaminic. Also mixed forms of these types of crosslinking are possible.
  • the tube has an inner layer as a barrier layer to aggressive medium, which is composed of a rubber mixture containing at least one fluororubber and at least one active filler. Furthermore, the hose has an outer layer of a crosslinked rubber compound. Regarding the composition of the rubber mixture, especially with regard to
  • Fluororubbers the active fillers and further constituents, apply the statements made above on the rubber mixture according to the invention.
  • the tube according to the invention can be extruded or wound and in the simplest case consists of two layers, namely an outer layer and an inner layer. But it is also possible that additional layers are present. These may be intermediate layers and / or strength layers.
  • FKM fluororubber
  • ACM acrylate rubber
  • AEM ethylene-acrylate rubber
  • EPM ethylene-propylene rubber (interpolymer)
  • EPDM ethylene-propylene-diene rubber (interpolymer)
  • VMQ silicone rubber
  • the rubber component of the rubber mixture is preferably FKM, ACM, AEM, EPM, EPDM or VMQ or a blend of the aforementioned rubber components with at least one further rubber component, for example an AEM / EPDM blend. In most cases, however, waste-free rubber mixtures are used.
  • the outer layer Since the outer layer has different requirements than the inner layer, it is not necessary here to use the fluorinated rubber mixture of the inner layer. Frequently the FKM standard mixtures according to the state of the art are sufficient here. If the outer layer also has contact with an acidic medium or if it is extremely thermally or dynamically loaded, then the same solution is then available as for the
  • Rubber mixtures based on ACM and / or AEM are crosslinked in particular diaminisch.
  • Rubber compounds based on EPM, EPDM and VMQ are in turn preferably crosslinked peroxide.
  • the reinforcement layer is formed from a woven, knitted or knitted fabric, in particular based on a textile material.
  • the relevant materials may include polyamide (PA), polyimide (PI), aramid, in particular para-aramid or meta-aramid, polyvinyl acetal (PVA), polyetheretherketone (PEEK), polyester, in particular polyethylene terephthalate (PET) or polyethylene 2,6-naphthalate (PEN), polysulfone (PSU), polyoxadiazole (POD), polyphenylene or polyphenylene derivative, in particular
  • Polyphenylene sulfide PPS
  • glass fibers PPS
  • hybrid concepts i. Mixed forms of the mentioned, can be used, for example, for example in the form of a Mischzwirns from m- and p-aramid or from PPS and PA.
  • the PPS as a high performance material contributes to a high strength, while the PA in addition to the
  • Reinforcement contribution also contributes via its adhesive activability to improved adhesion to the surrounding elastomeric material.
  • the intermediate layer also has the meaning of an adhesive layer between the inner layer and the strengthening layer.
  • the rubber component of the rubber composition is preferably ACM or AEM or a blend of the foregoing
  • Rubber components with at least one further rubber component for example again an AEM / EPDM blend. Usually, however, will
  • waste-free rubber mixtures used, with diaminisch cross-linked AEM is of particular importance.
  • the hose according to the invention is used in particular for air-carrying hoses, such as, for example, charge air hoses, soot particle filter hoses, control hoses, but also for fuel hoses or oil hoses, such as turbo charger cooling hoses.
  • air-carrying hoses such as, for example, charge air hoses, soot particle filter hoses, control hoses, but also for fuel hoses or oil hoses, such as turbo charger cooling hoses.
  • mixtures characterized in this case are mixtures according to the invention, while the mixtures marked with "V" are comparative mixtures, the mixing composition being shown in the upper part of the tables, while the respective corresponding physical properties are illustrated in the lower part of the tables all mixing examples contained in the table are as indicated
  • FPM phr 100 100 100 100 Carbon black, N220 phr 0 - 15 25
  • the single FIGURE shows a hose 1, which is designed as a manifold hose.
  • the tube has the following layer structure with the following example
  • Inner layer 2 peroxide-crosslinked fluororubber mixture containing at least one fluororubber and at least one active filler
  • Interlayer 3 diaminically crosslinked and waste-free
  • Outer layer 5 diaminically crosslinked and waste-free

Abstract

L'invention concerne un mélange de caoutchouc qui contient au moins un caoutchouc fluoré et au moins une charge active. Le mélange de caoutchouc se distingue par une résistance améliorée à la poursuite d'une déchirure sans que les autres propriétés physiques, en particulier la résistance à la traction, en soient influencées défavorablement. L'invention concerne en outre un flexible (1), qui présente au moins la structure en couches suivante : - une couche intérieure (2) comme couche barrière vis-à-vis de fluides agressifs, qui contient au moins un caoutchouc fluoré et au moins une charge active ; et - une couche extérieure (5) en un mélange de caoutchouc réticulé.
EP12780474.8A 2011-11-14 2012-10-25 Mélange de caoutchouc et flexible contenant le mélange de caoutchouc Withdrawn EP2780406A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102011055316A DE102011055316A1 (de) 2011-11-14 2011-11-14 Kautschukmischung und Schlauch enthaltend die Kautschukmischung
PCT/EP2012/071102 WO2013072168A1 (fr) 2011-11-14 2012-10-25 Mélange de caoutchouc et flexible contenant le mélange de caoutchouc

Publications (1)

Publication Number Publication Date
EP2780406A1 true EP2780406A1 (fr) 2014-09-24

Family

ID=47115894

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12780474.8A Withdrawn EP2780406A1 (fr) 2011-11-14 2012-10-25 Mélange de caoutchouc et flexible contenant le mélange de caoutchouc

Country Status (4)

Country Link
EP (1) EP2780406A1 (fr)
JP (1) JP2015504454A (fr)
DE (1) DE102011055316A1 (fr)
WO (1) WO2013072168A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013103759A1 (de) 2013-04-15 2014-10-16 Contitech Mgw Gmbh Kautschukmischung und Schlauch enthaltend die Kautschukmischung
JP5892276B1 (ja) * 2014-03-05 2016-03-23 ダイキン工業株式会社 フッ素ゴム組成物及びフッ素ゴム成形品
JP2016070332A (ja) * 2014-09-29 2016-05-09 住友理工株式会社 耐熱ホース
DE102014223979A1 (de) 2014-11-25 2016-05-25 Contitech Mgw Gmbh Kautschukmischung und Schlauch enthaltend die Kautschukmischung
DE102016205557A1 (de) 2016-04-04 2017-10-05 Contitech Mgw Gmbh Polymermischung und Schlauch, insbesondere Ladeluftschlauch, enthaltend die Polymermischung
DE102017223546A1 (de) * 2017-12-21 2019-06-27 Contitech Ag Barriereschicht für Schläuche
DE102017223538A1 (de) * 2017-12-21 2019-06-27 Contitech Luftfedersysteme Gmbh Artikel, insbesondere ein Luftfederbalg, ein Metall-Gummi-Element oder ein Schwingungsdämpfer

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2587107A1 (fr) * 2010-08-25 2013-05-01 Daikin Industries, Ltd. Tuyau souple

Family Cites Families (12)

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JP2706814B2 (ja) * 1989-05-29 1998-01-28 東海ゴム工業株式会社 ゴム積層体
JPH04212844A (ja) * 1990-10-19 1992-08-04 Sumitomo Rubber Ind Ltd 免震積層体用ゴム組成物
JP2737527B2 (ja) 1992-04-08 1998-04-08 豊田合成株式会社 複層ゴムホース及びその製造方法
JP3584086B2 (ja) * 1995-07-05 2004-11-04 三井化学株式会社 ゴム組成物
JPH10267169A (ja) * 1997-03-25 1998-10-09 Tokai Rubber Ind Ltd 耐摩耗性ホース
DE19718504A1 (de) * 1997-05-02 1998-11-05 Huels Chemische Werke Ag Verbund aus einer Formmasse auf Basis von Polyamid einerseits und vulkanisierbaren Fluor-Elastomeren andererseits
JP3077689B2 (ja) * 1998-03-31 2000-08-14 東海ゴム工業株式会社 耐熱ホース
JP2001002834A (ja) * 1999-06-24 2001-01-09 Nippon Zeon Co Ltd ホース用ゴム組成物およびホース
US6340511B1 (en) 1999-10-27 2002-01-22 Tokai Rubber Industries, Ltd. Fuel hose
EP1396670B1 (fr) 2002-09-06 2004-12-29 ContiTech Schlauch GmbH Tuyau flexible
JP4906569B2 (ja) * 2007-04-13 2012-03-28 倉敷化工株式会社 燃料ホース及びその製造方法
EP2404963B1 (fr) * 2010-07-07 2014-12-10 Continental Reifen Deutschland GmbH Composition de caoutchouc

Patent Citations (1)

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Publication number Priority date Publication date Assignee Title
EP2587107A1 (fr) * 2010-08-25 2013-05-01 Daikin Industries, Ltd. Tuyau souple

Also Published As

Publication number Publication date
DE102011055316A1 (de) 2013-05-16
WO2013072168A1 (fr) 2013-05-23
JP2015504454A (ja) 2015-02-12

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