EP2934886A1 - Pièce composite - Google Patents

Pièce composite

Info

Publication number
EP2934886A1
EP2934886A1 EP13821471.3A EP13821471A EP2934886A1 EP 2934886 A1 EP2934886 A1 EP 2934886A1 EP 13821471 A EP13821471 A EP 13821471A EP 2934886 A1 EP2934886 A1 EP 2934886A1
Authority
EP
European Patent Office
Prior art keywords
rubber
polyamide
parts
weight
composite part
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Withdrawn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
EP13821471.3A
Other languages
German (de)
English (en)
Inventor
Thomas FRÜH
Thomas DEDERICHS
Andreas Bischoff
Ulrich Giese
Torsten Thust
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.)
Lanxess Deutschland GmbH
Original Assignee
Lanxess Deutschland 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 Lanxess Deutschland GmbH filed Critical Lanxess Deutschland GmbH
Priority to EP13821471.3A priority Critical patent/EP2934886A1/fr
Publication of EP2934886A1 publication Critical patent/EP2934886A1/fr
Withdrawn legal-status Critical Current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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/16—Making multilayered or multicoloured articles
    • B29C45/1676—Making multilayered or multicoloured articles using a soft material and a rigid material, e.g. making articles with a sealing part
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J107/00—Adhesives based on natural rubber
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
    • C09J109/06—Copolymers with styrene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J145/00—Adhesives based on homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic system; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
    • C09J177/06—Polyamides derived from polyamines and polycarboxylic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2007/00—Use of natural rubber as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2009/00—Use of rubber derived from conjugated dienes, as moulding material
    • B29K2009/06—SB polymers, i.e. butadiene-styrene polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/16—EPM, i.e. ethylene-propylene copolymers; EPDM, i.e. ethylene-propylene-diene copolymers; EPT, i.e. ethylene-propylene terpolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/41—Organometallic coupling reactions
    • C08G2261/418—Ring opening metathesis polymerisation [ROMP]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the invention relates to a composite part which is produced by means of 2-component processing, preferably 2-component injection molding (2K injection molding), from at least one part of at least one polyalkenamer-additized polyamide molding compound and at least one section of at least one elastomer, is made of rubber to be vulcanized or crosslinked with elemental sulfur, or is prepared by processing these components, without an adhesion promoter is used, ie in direct adhesion.
  • the individual parts of the composite part are macroscopic moldings, but not e.g. dispersed particles in a plastic elastomer blend or polyamide fibers in an elastomer matrix. Such blends are therefore not composite parts in the sense of the invention.
  • the invention also provides a process for the preparation of such composite parts and the use of polyalkenamer for improving the adhesion of polyamide-based molded parts with an elastomeric component, obtainable from elemental sulfur to be vulcanized or vulcanized rubber, and the use of polyalkenamer for the reduction of Melting point or softening point of polyamide.
  • Composite parts of rigid thermoplastic as well as rubber-elastic molded parts are usually assembled by gluing, screwing, mechanical clawing or using a bonding agent, since in the vast majority of combinations of thermoplastic and elastomer, a sufficiently strong adhesion can not be achieved.
  • the primer is applied to the component, either thermoplastic or elastomer, which was first manufactured. If the thermoplastic component is first prepared, the adhesion promoter is applied to the surface of the thermoplastic, then the rubber compound to be crosslinked is sprayed on and vulcanized. When the elastomer is first made, the primer is applied to its surface before the thermoplastic is sprayed on. Depending on the material combination, a one-layer or two-layer adhesive system may be used. Conventionally and preferably used adhesion promoters are described in J.
  • adhesion promoters of the Chemlok® or Chemosil® brand (Lord) or the Cilbond® brand (CI L).
  • adhesion promoters in principle the use of environmentally harmful solvents and / or heavy metals is problematic, provided that no water-based adhesion promoters are used. In general, the job of an adhesion promoter is an additional step, which requires an additional operation and thus time and effort.
  • EP 0 142 930 A2 a way is shown how composite parts of polyamides and EPDM elastomers can be produced.
  • a mixture of the crosslinking agent dicumyl peroxide and the coagenz N, N'-m-phenylenedimaleimide is added to the rubber.
  • the addition of the coagenz N, N'-m-phenylenedimaleimide is essential here for high adhesive strengths.
  • the method described in EP 0 142 930 A2 can only be carried out with a peroxidically crosslinked elastomer component. When using a vulcanization with sulfur, there is no liability.
  • 5,132,182 describes that polyamides having an excess of amino end groups have good adhesion to carboxylated EPDM or NBR rubbers. According to US-A 5,132,182 only chemically modified rubbers (carboxylation) can be used. Furthermore, the process described there is reduced to a peroxide crosslinking of the elastomer component. A sulfur vulcanized elastomer shows no adhesion to the polyamide.
  • EP 1 666 535 describes composite parts which are produced from an elastomer component and a polyamide component in direct adhesion.
  • the polyamide component will form coagents for peroxide crosslinking and radical catching stabilizers added.
  • EP 1 666 535 exclusively teaches the crosslinking of the rubber component with an organic peroxide for direct adhesion in combination with a polyamide component.
  • EP 1 533 344 A1 and JP 2003 320 618 A1 describe the use of coagents for the peroxidic crosslinking in the thermoplastic in order to produce a composite part with an elastomer component in direct adhesion.
  • Example 5 of EP 1533 344 A1 teaches not only the coagenz trimethylolpropane trimethacrylate but also the addition of Vestenamer® 8012 / polyoctenamer in polyamide PA612. However, the method has disadvantages.
  • the examples of EP 1 533 344 A1 exclusively show the crosslinking of the rubber component with an organic peroxide for direct adhesion in combination with a polyamide component.
  • sulfur vulcanization is the dominant crosslinking process.
  • the peroxide crosslinking is also sensitive to atmospheric oxygen, which leads to a limitation of the possible vulcanization process.
  • different mixture components can interfere with peroxide crosslinking. in the In contrast, sulfur vulcanization is insensitive to most of the blend ingredients otherwise to be used in the rubber.
  • the crosslinking system of the rubber mixture When connecting a thermoplastic component produced in a first production step with an elastomer component using an adhesion promoter, as mentioned above, or under direct adhesion, the crosslinking system of the rubber mixture has a decisive role for the strength of the adhesive force.
  • This important role of the crosslinking system is not only observed in the bonding of thermoplastic with crosslinking compositions to be crosslinked, but generally in the joining of different substrate materials made in a first manufacturing step, e.g. Metal, glass, etc, with Kauschukmischieux to be crosslinked.
  • brass parts or brass substrates in general, can be bonded directly to rubber compounds to be crosslinked with sulfur.
  • Peroxide-cured rubber blends can not be directly adhered to brass (B. Crowther, "Handbook of Rubber Bonding,” iSmithers Rapra Publishing, 2001, pages 163 to 195.)
  • galvanized metal parts can bond directly to sulfur-compounded rubber blends (F. Röthemeyer, F. Sommer “Rubber Technology”, 2nd revised edition, Carl Hanser Verlag Kunststoff Vienna, 2006, pages 829 to 830).
  • plastics in particular polyamides.
  • plastics such as polyamide are mostly added organic additives to achieve certain properties in the later to be produced from it product. So while the use of organic additives in plastics such as polyamide is quite common, organic additives in metals or glass would be destroyed at the high processing temperatures of metals or glass, be it decomposed under exclusion of air or oxidized by atmospheric oxygen.
  • a solid composite of an elastomer component to a polyamide component means an adhesion strength in a 90 ° peel test based on DIN ISO 813 of at least 3 N / mm, and a tensile strength of the elastomer component of at least 10 MPa and an elongation at break of the elastomer component of at least 300%.
  • a solid composite of a section obtainable from a polyamide molding compound and a section of an elastomer component obtainable from rubber to be vulcanized or crosslinked with elemental sulfur is characterized according to the invention by an adhesive strength in a 90 ° peel test based on DIN ISO 813 of at least 3 N / mm. Adhesive strengths below 3 N / mm are too low for the presence of a solid composite. Low adhesive strengths below 3 N / mm are also referred to as assembly adhesion in industrial practice. A minimum adhesive strength of 3 N / mm has proved to be a criterion for a solid composite of a polyamide section and an elastomer section.
  • JP2010269481 A2 designates adhesive strengths of a composite of a polyamide section and an elastomer section measured with a peel test as follows: ⁇ 3 N / mm: unacceptable,> 3 N / mm and ⁇ 4 N / mm: good,> 4 N / mm: excellent.
  • the tensile stress at break or breaking stress and elongation at break or elongation at break are parameters in the material testing, which are determined in a tensile test (F. Röthemeyer, F. Sommer “Rubber Technology", 2nd revised edition, Carl Hanser Verlag Kunststoff Vienna, 2006, page 494 to 496; The Plastics - Chemistry, Physics, Technology, edited by B.
  • DIN 53504 describes a method for determining the tensile stress-strain properties of vulcanized and thermoplastic rubbers. Shadows that can be determined are tensile strength, breaking stress, breaking elongation, stress at a given strain, elongation at a given strain, yield stress, and yield strength elongation. During the tensile test, the specimens are stretched to the crack at a constant strain rate and the necessary force and change in length are recorded. Tear stress and elongation at break are determined in the context of the present invention by tensile tests according to DIN 53504.
  • the tensile stress o R also referred to as tensile strength, is defined as the quotient of the force F R measured at the moment of tearing and the initial cross section A 0 of the specimen.
  • the tensile strength is given in N / mm 2 or MPa.
  • the elongation at break e R is defined as the quotient of the change in length L R - L 0 measured at the moment of tearing and the original measuring length L 0 of the test specimen. The elongation at break is given in percent.
  • a tensile strength of at least 10 MPa and an elongation at break of at least 300% describes a technically usable elastomer component.
  • Industrially utilizable elastomers are prepared via the crosslinking of rubbers, e.g. obtained via sulfur or peroxide crosslinking. With increasing crosslink density, that is, the number of crosslinks per volume element, the ultimate tensile strength of elastomers is maximized (DL Hertz, Jr., Elastomerics, 1984, Issue 16, pp. 17-21, Science and Technology of Rubber, ed. Erman, FR Eirich, 2nd Edition, Academic Press, San Diego, 1994, pages 339-343). Thus, a technically utilizable elastomer is obtained only in a certain interval of the crosslinking density. If the crosslink density is too low or too high, the tensile stress is less than 10 MPa.
  • the tensile strength of crosslinked elastomers is also significantly influenced by the addition of additives or fillers.
  • Fillers are powdery rubber mixture components which are added to the elastomer to achieve certain properties of the vulcanizate (J. Schnetger “Encyclopedia of Rubber Technology” 3rd Edition, Hüthig Verlag Heidelberg, 2004, pages 179 to 180, F. Röthemeyer, F. Sommer “Rubber Technology” , 2nd revised edition, Carl Hanser Verlag Kunststoff Vienna, 2006, pages 231 to 275). While inactive fillers with rather larger particle diameters dilute the matrix, active fillers, especially carbon black or silica with a particle diameter below that of the inactive fillers, have a reinforcing effect on the elastomer.
  • the invention relates to a composite part, which is composed in direct adhesion of at least one polyamide molding compound and at least one section made of at least one elastomer waiving any adhesion promoter, characterized in that the polyamide molding composition to at least 30 wt .-%, preferably at least 45 wt .-%, more preferably at least 55 wt .-% and particularly preferably at least 65 wt .-% of a mixture of a) 60 to 99.9 parts by weight, preferably 75 to 99.8 wt ., Parts and particularly preferably 85 to 99.7 parts by weight and most preferably 88 to 99.5 parts by weight of polyamide and
  • Parts by weight of polyalkenamer wherein the sum of the parts by weight of a) and b) is 100, the elastomeric portion of elemental sulfur crosslinking agent to be vulcanized or vulcanized rubber was prepared, and as Polyalkenamer at least one of Group polybutadiene, polyisoprene, polyoctenamer (Polyoctenylen), polynorbornene (poly-1, 3-cyclopentylenevinylene) and poly-dicyclopentadiene is selected.
  • Polyalkenamer at least one of Group polybutadiene, polyisoprene, polyoctenamer (Polyoctenylen), polynorbornene (poly-1, 3-cyclopentylenevinylene) and poly-dicyclopentadiene is selected.
  • the composite part according to the invention of polyamide section and elastomeric section has a liability that even at high temperature, e.g. 120 ° C, and under the influence of nonpolar media, e.g. Storage in non-polar solvents, especially toluene, is stable.
  • the present invention further relates to a process for producing direct adhesion composite parts composed of at least one part made of at least one polyamide molding compound and at least one part made of at least one elastomer obtainable from rubber to be vulcanized or crosslinked with elemental sulfur as a crosslinking agent , characterized in that waiving any adhesion promoter by at least one molding process of the series extrusion, Flachfolienextrustion, film blowing, extrusion blow molding, coextrusion, calendering, casting, compression molding, injection compression molding, transfer molding, transfer molding or injection molding or its special processes, in particular gas injection technique , Preferably by 2-component injection molding, either the portion of the polyamide molding composition with an elementary sulfur-containing rubber component applied and de n exposes the vulcanization conditions of the rubber, or the portion of crosslinked with elemental sulfur crosslinking agent elastomer applied with a polyamide molding composition and in both cases, the polyamide molding composition to at least 30 wt .-%, preferably at least
  • Parts by weight of polyalkenamer wherein the sum of the parts by weight of a) and b) is 100 and as Polyalkenamer at least one from the group polybutadiene, polyisoprene, polyoctenamer (polyoctenylene), polynorbornene (poly-1, 3-cyclopentylen- vinylene) and polydicyclopentadiene is selected.
  • the polyamide molding compound for the polyamide section is additized with at least one polyalkenamer.
  • polyalkenamer in the sense of the present invention, at least one of the group polybutadiene, polyisoprene, polyoctenamer (polyoctenylene), polynorbornene (poly-1, 3-cyclopentylene-vinylene) and polydicyclopentadiene is used (H.G.
  • polyalkenamers to be used according to the invention can also be prepared by partial hydrogenation of polyalkenylenes, for example or in particular polybutadiene, or by other methods.
  • the polyalkenamer is used in the polyamide molding composition for the polyamide segment individually or in combinations of several polyalkenamers.
  • the polyamide molding composition of the polyamide section 1, 8 trans-polyoctenamer used, for which in the present invention, the abbreviation TOR (1, 8-trans polyoctenamer rubber) is used.
  • the 1, 8-trans-polyoctenamer, [CAS No. 28730-09-8] also referred to as trans-polyoctenylene, which is particularly preferably used according to the invention, is obtained from cyclooctene by ring-opening metathesis polymerization and comprises both macrocyclic and linear polymers.
  • TOR is a low molecular weight specialty rubber with a bimodal molecular weight distribution.
  • the bimodal molecular weight distribution of the TOR is due to the fact that the low molecular weight components are generally in a weight-average molecular weight range of 200 to 6,000 g / mol, the high polymer components in a weight-average molecular weight range of 8,000 to 400,000 g / mol (A. Dräxler, rubber, Rubber, Plastics, 1981, Volume 34, Issue 3, pages 185 to 190).
  • the polyalkenamer to be used according to the invention preferably the 1,8-trans-polyoctenamer, is prepared according to EP 0 508 056 A1.
  • the weight-average molecular weight M w of the 1, 8-trans-polyoctenamer preferably to be used according to the invention is preferably in the range from 80,000 to 120,000 g / mol, particularly preferably at about 90,000 g / mol.
  • the crystallinity content of the preferred use according to the invention 1, 8-trans-Polyoctenamers at room temperature (25 ° C) in the range of 20 to 30%.
  • Particularly preferred according to the invention is 1,8-trans-polyoctenamer rubber having a weight average molecular weight Mw of 90,000 g / mol and a trans / cis double bond ratio of 80:20, ie Vestenamer® 8012.
  • 1, 8-trans polyoctenamer as Vestenamer® 8012, according to the manufacturer, a 1, 8-trans polyoctenamer rubber having a weight average molecular weight Mw of 90,000 g / mol and a trans / cis double bond ratio of 80:20, and Vestenamer® 6213, according to the manufacturer, a 1, 8-trans-Polyoctenamer-Kautschuk with a weight average molecular weight of Mw 1, 1 ⁇ 10 5 g / mol and a trans / cis double bond ratio of 62:38 (Product Information Evonik Industries AG, Marl, Germany; Handbook of Elastomers, edited by AK Bhowmick, HL Stephens, 2nd revised edition, Marcel Dekkers Inc. New York, 2001, pages 698-703).
  • polybutadiene (BR) [CAS No. 9003-17-2] is particularly preferably used as polyalkenamer in the polyamide molding compound of the polyamide section.
  • the polybutadiene is used in the polyamide molding compound for the polyamide section individually or in combinations of several polyalkeneamers.
  • Polybutadiene (BR) in particular comprises two different polybutadiene type classes. The first class has a 1,4-cis content of at least 90% and is produced using Ziegler / Natta transition-metal based catalysts.
  • Low molecular weight polybutadienes may be liquid at room temperature.
  • liquid polybutadienes can be prepared via synthesis, that is, molecular weight build-up, or via degradation of higher molecular weight polybutadiene.
  • liquid polybutadienes can be prepared as described above via Ziegler-Natta polymerization or via anionic polymerization (H.G. Elias, "Macromolecules, Volume 2: Industrial Polymers and Syntheses", Wiley-VCH Verlag GmbH, Weinheim, 2007, p 242 to 245; H.G. Elias, "Macromolecules, Volume 4: Applications of Polymers", Wiley-VCH Verlag GmbH, Weinheim, 2007, pp. 284 to 285).
  • polybutadienes having a number average molecular weight Mn in the range from 800 to 20,000 g / mol, particularly preferably in the range from 1,500 to 15,000 g / mol, very particularly preferably in the range from 2,000 to 9,000 g / mol, and / or with a dynamic viscosity, measured by the cone-plate method according to DIN 53019, at atmospheric pressure and at a temperature of 25 ° C in the range of 100 to 15,000 mPas, more preferably in the range of 300 to 10,000 mPas, most preferably in the range of 500 used up to 5,000 mPas. These are characterized by the fact that they are liquid at room temperature (25 ° C).
  • Such liquid polybutadienes are obtained, for example, from Synthomer Ltd. , Lithene®, especially Lithene® ultra N4-5000, a liquid polybutadiene having a dynamic viscosity at 25 ° C (DIN 53019) of 4,240 mPas with a number average molecular weight Mn in the range of 5,000 g / mol (Manufacturer's information) (see Synthomer Ltd., Lithene® Liquid Polybutadiene, Product Range, Harlow, Essex, UK).
  • Alternative liquid polybutadienes to be used are from the company Evonik Industries AG, Marl, Germany, under the name Polyvest®, in particular Polyvest® 1 10, a liquid polybutadiene having a dynamic viscosity at 25 ° C (DIN 53019) of 650 mPas and a number average Molecular weight Mn in the range of 2,600 g / mol (manufacturer), or by Kuraray Europe GmbH, Hattersheim am Main, Germany, under the name LBR, especially LBR-307, a liquid polybutadiene having a dynamic viscosity at 25 ° C (DIN No.
  • polyisoprene [CAS no. 9003-31 -0] as a polyalkene- mer.
  • the polyisoprene is used in the polyamide molding compound for the polyamide section individually or in the form of a combination of several polyalkenamers.
  • Polyisoprene (IR) is prepared both by means of alkali metal and with the aid of Ziegler / Natta catalysts, preferably with titanium and neodymium catalysts (Houben-Weyl, Methods of Organic Chemistry, Thieme Verlag, Stuttgart, 1987, Volume E 20, pages 822 Ullmann's Encyclopedia of Industrial Chemistry, Vol. A 23, Rubber 3. Synthetic, VCH Verlagsgesellschaft mbH, D-840 69451 Weinheim, 1993, pp. 239-364).
  • Polyisoprene (IR) typically has a 1,4-cis content of at least 70%.
  • Low molecular weight polyisoprene may be liquid at room temperature.
  • liquid polyisoprenes can be prepared via synthesis, ie molecular weight build-up, or via degradation of higher molecular weight polyisoprene Synthetically, liquid polyisoprenes can be prepared as described above via Ziegler-Natta polymerization or via anionic polymerization (H Elias, "Macromolecules, Volume 4: Applications of Polymers", WI LEY-VCH Verlag GmbH, Weinheim, 2007, pp. 284 to 285).
  • These polyisoprenes are characterized by being liquid at room temperature (25 ° C).
  • Such liquid polyisoprenes are, for example, from the company Kuraray Europe GmbH, Hattersheim am Main, Germany, under the name LIR, especially LI R-30, a liquid polyisoprene with a dynamic viscosity at 38 ° C of 70,000 mPas (manufacturer) and with a weight average MW in the range of 28,000 g / mol (manufacturer's information) (see Kuraray Europe GmbH, Kuraray Liquid Rubber, Hattersheim am Main, Germany), or by Royal Elastomers, Belleville, NJ07109, USA, under the name Isolene®, in particular Isolene ® S-40, a liquid polyisoprene with a dynamic viscosity at 38 ° C of 36,000 to 55,000 mPas (manufacturer) and with a weight-average molecular weight Mw in the range of 32,000 g / mol (manufacturer) (see Royal Elastomers, Royal Elastomers Com
  • polynorbornene (CAS No. 25038-76-0) as polyalkenamer.
  • the polynorbornene is used in the polyamide molding compound for the polyamide section individually or in combinations of several polyalkenamers.
  • Polynorbornene is obtained by norbornene ring-opening metathesis polymerization (ROMP) and is used, for example, by Astrotech Advanced Elastomer Products GmbH, Vienna, Austria as Norsorex® with a molecular weight in the range of 3,000,000 g / mol offered.
  • the distribution of cis and trans groups in the polymer prevents its crystallization.
  • the polymer is amorphous with a glass transition temperature around 37 ° C (manufacturer's instructions).
  • polydicyclopentadiene is used as Polyalkenamer.
  • the polydicyclopentadiene is used in the polyamide molding composition for the polyamide segment individually or in combinations of several polyalkenamers.
  • Dicyclopentadiene is a by-product of the cracking process in gasoline production. In a purity of 99% it gets in the mixture with norbornene a liquid consistency above -2 ° C to 0 ° C.
  • Polydicyclopentadiene can then be prepared via catalyzed olefin metathesis reactions, for example, a ring-opening metathesis polymerization (ROMP).
  • the polyamide component is characterized in that it contains no coagenz.
  • Coagents are used for the peroxide crosslinking of rubbers and lead to an increased crosslinking yield. Chemically, coagents are polyfunctional compounds that react with polymer radicals and form more stable radicals (F. Röthemeyer, F. Sommer “Rubber Technology”, 2nd revised edition, Carl Hanser Verlag Kunststoff Vienna, 2006, pages 315 to 317, J. Schnetger “Encyclopedia of Rubber Technology” 3rd edition, Wegig Verlag Heidelberg, 2004, pages 82 to 83).
  • the polyamide component is characterized by having no coough of ethylene glycol dimethacrylate (EDMA), trimethylolpropane trimethacrylate (TMPTMA, TRIM), trimethylolpropane triacrylate (TM PTA), 1,6-hexanediol diacrylate (HDDA), 1,6-hexane - diol dimethacrylate (HDDMA), butanediol dimethacrylate, zinc diacrylate, zinc dimethacrylate, triallyl cyanurate (TAC), triallyl isocyanurate (TAIC), diallyl terephthalate, triallyl trimellitate (TATM) or ⁇ , ⁇ '-m-phenylenebismaleimide (MPBM, HVA-2).
  • EDMA ethylene glycol dimethacrylate
  • TMPTMA trimethylolpropane trimethacrylate
  • TM PTA trimethylolpropane triacrylate
  • HDDA 1,6-hexaned
  • the rubbers to be vulcanized or crosslinked with elemental sulfur in the elastomeric part of the composite part according to the invention are elastomers obtainable by a vulcanization process.
  • Vulcanization is a chemical-technical process developed by Charles Goodyear, in which rubber is made resistant to atmospheric and chemical influences as well as to mechanical stress under the influence of time, temperature, pressure and suitable crosslinking chemicals.
  • the sulfur vulcanization is a rubber mixture consisting of raw rubber, sulfur in the form of soluble and / or in the form of insoluble sulfur and / or sulfur donating substances, these include, for example, the well-known in the rubber industry as sulfur donors organic Additives, and in particular Dischwefeldichlorid (S 2 CI 2 ), catalysts, auxiliaries and optionally further fillers heated.
  • the rubber component may be added with at least one vulcanization accelerator suitable for sulfur vulcanization.
  • phr parts per hundred of rubber, ie parts by weight based on 100 parts by weight of rubber
  • accelerators 1, 0 to 2.0 phr sulfur and 1, 0 to 2.5 phr accelerators are used.
  • the so-called "EV” crosslinking system contains 0.3 to 1.0 phr of sulfur and 2.0 to 6.0 phr of accelerator Substituting 0.3 to 0.6 phr of sulfur, 3.0 to 6.0 phr of accelerator and 0 , 0 to 2.0 phr sulfur donors, one speaks of the so-called "low-sulfur EV" crosslinking system.
  • the so-called “sulfur donor crosslinking system” contains no elemental sulfur (0.0 phr), but 0.0 to 2.0 phr of accelerator and 1.0 to 4.0 phr sulfur donors
  • the sulfur donors used in the "sulfur donor crosslinking system” act as vulcanizing agents (F.Röthemeyer, F.R. Summer “Rubber Technology", 2nd revised edition, Carl Hanser Verlag Kunststoff Vienna, 2006, pages 291 to 295).
  • the elastomer component of the composite part according to the invention is a rubber to be vulcanized or crosslinked with elemental sulfur as crosslinking agent in the presence of at least one sulfur crosslinking system of the conventional sulfur crosslinking system, semi-EV crosslinking system, EV crosslinking system or EV low-sulfur crosslinking system used.
  • the crosslinking system in addition to the so-called main accelerators may contain different and possibly also several so-called secondary accelerators.
  • Their type, dosage and combination is matched to the particular application and is also different depending on the type of rubber.
  • the long-chain rubber molecules are cross-linked by sulfur bridges.
  • the plastic properties of the rubber or the rubber mixture are lost, the material is transferred by means of the process of vulcanization of the plastic in an elastic state.
  • the elasticity of a sulfur-crosslinked elastomer component depends on the number of sulfur bridges. The more sulfur bridges are present, the harder the rubber is. The number and length of the sulfur bridges in turn depends on the amount of sulfur added, the nature of the crosslinking system and the duration of vulcanization.
  • double bond-containing rubbers which, from industrial production, have a gel fraction of less than 30%, preferably less than 5%, in particular less than 3%, and according to DIN / ISO 1629 as "R” or as "M”. Rubbers are called.
  • Gel content in the sense of the present invention means the proportion of insoluble but swellable three-dimensionally crosslinked polymeric material.
  • Rubbers to be crosslinked according to the invention for the elastomeric part are rubbers of the series natural rubber (NR), ethylene-propylene-diene rubbers (EPDM), styrene / diolefin rubbers, preferably styrene / butadiene rubber (SBR), in particular E.
  • NR series natural rubber
  • EPDM ethylene-propylene-diene rubbers
  • SBR styrene / diolefin rubbers
  • SBR styrene / butadiene rubber
  • -SBR polybutadiene rubber
  • IR polyisoprene
  • butyl rubber especially isobutene / isoprene rubber (II FR)
  • halobutyl rubber especially chloro- or bromobutyl rubber (XIIR), nitrile rubber (NBR), hydrogenated nitrile rubber (H-NBR ), carboxylated butadiene / acrylonitrile rubber (XNBR) or polychloroprene (CR).
  • XIIR chloro- or bromobutyl rubber
  • NBR nitrile rubber
  • H-NBR hydrogenated nitrile rubber
  • XNBR carboxylated butadiene / acrylonitrile rubber
  • CR polychloroprene
  • Preferred rubber blends are blends of NR as a matrix phase and BR as dispersed Rubber phase with BR contents up to 50 phr and BR as matrix phase and SBR or CR as dispersed rubber phase with SBR or CR fractions up to 50 phr.
  • At least natural rubber (NR) is used for the elastomer section as a rubber to be vulcanized or crosslinked with elemental sulfur.
  • the inventively particularly preferred elemental sulfur to be crosslinked natural rubber (NR) for the elastomeric section in the invention The composite part is chemically a polyisoprene having a cis-1,4-content of> 99% at average molecular weights of 2-10 6 to 3-10 7 g / mol.
  • NR is synthesized biochemically, preferably in the plantation plant Hevea Brasiliensis.
  • Natural rubbers are commercially available, for example, as products from the product series SMR (Standard Malaysian Rubber) from Pacidunia Sdn. Bhd. or from the Standard Vietnamese Rubber (SVR) range from Phu An Imexco. Ltd. (J. Schnetger "Encyclopedia of Rubber Technology” 3rd edition, Wegig Verlag Heidelberg, 2004, pages 331 to 338).
  • EPDM rubber is used in an alternative preferred embodiment for the elastomer section in the composite part according to the invention.
  • EPDM are polymers made by terpolymerizing ethylene and larger proportions of propylene, as well as a few weight percent of a third diene monomer. The diene monomer provides the double bonds for the subsequent vulcanization ready.
  • COD 5-cyclooctadiene
  • DCP exo-dicyclopentadiene
  • EDCP endo-dicyclopentadiene
  • HX 1, 4-hexadiene
  • EN B 5-ethylidene-2-norbornene
  • VNB vinyl norbornene
  • EPDM rubber is prepared in a known manner by polymerization of a mixture of ethene and propene and a diene in the presence of Ziegler-Natta catalyst systems, such as e.g. Vanadium compounds with organoaluminum cocatalysts, or metallocene catalyst systems produced (J.
  • Both E-SBR and S-SBR can be used in the elastomer components for the elastomer section in the composite part according to the invention in ⁇ lverstreckter form.
  • oil-drawn means that oils are mixed into the rubber in the production process.
  • the oils serve as plasticizers.
  • Application find in this case known to those skilled and industrially customary oils. Preference is given to those which contain little to no polyaromatic hydrocarbons. Suitable are TDAE (Treated Distillates Aromatic Extract), MES (Mild Extraction Solvates) and naphthenic oils.
  • TDAE Transmission Distillates Aromatic Extract
  • MES Meld Extraction Solvates
  • naphthenic oils As rubber to be crosslinked with elemental sulfur, polybutadiene (BR) is used in an alternative preferred embodiment for the rubber section in the composite part according to the invention.
  • polyisoprene As rubber to be crosslinked with elemental sulfur, polyisoprene (IR) is used in an alternative preferred embodiment for the rubber section in the composite part according to the invention.
  • Polyisoprene (IR) typically has a 1,4-cis content of at least 70%.
  • the term IR includes both synthetically produced 1,4-cis-polyisoprene and natural rubber, (NR).
  • Synthetically IR is prepared both by lithium and by means of Ziegler / Natta catalysts, preferably with titanium and neodymium catalysts (Houben-Weyl, Methods of Organic Chemistry, Thieme Verlag, Stuttgart, 1987, Volume E 20, pages 822-840 Ullmann's Encyclopedia of Industrial Chemistry, Vol. A 23, Rubber 3. Synthetic, VCH Verlagsgesellschaft mbH, D-69451 Weinheim, 1993, pp. 239-364).
  • natural rubber is used.
  • NBR nitrile rubber
  • J J.
  • H-NBR hydrogenated nitrile rubber
  • butyl rubber in particular isobutene / isoprene rubber, is used in an alternative preferred embodiment for the rubber section in the composite part according to the invention.
  • Butyl rubber is produced via a copolymerization of isorprene and isobutylene (J. Schnetger "Encyclopedia of rubber technology” 3rd edition, Hüthig Verlag Heidelberg, 2004, pages 69 to 71).
  • Halobutyl rubber in particular chlorine (CNR) or bromobutyl rubber (BI IR), is used as the rubber to be crosslinked with elemental sulfur in an alternative preferred embodiment for the rubber section in the composite part according to the invention.
  • Chlorobutyl rubber (CNR) is prepared by introducing chlorine gas into a butyl rubber solution (J. Schnetger “Lexikon der Kautschuktechnik” 3rd Edition, Hüthig Verlag Heidelberg, 2004, page 75) .
  • Brombutyl rubber (BI IR) is prepared by treating butyl rubber in solution with bromine (J. Schnetger “Encyclopedia of Rubber Technology” 3rd edition, Hüthig Verlag Heidelberg, 2004, pages 66 to 67).
  • mercaptans for example n-dodecyl mercaptan, or xanthogen disulphide
  • special accelerator systems in particular thioureas (ETU, DBTU, TBTU, DETU, MTT) can be used (J. Schnetger “Encyclopedia of Rubber Technology” 3rd Edition, Hüthig Verlag Heidelberg, 2004, pages 78 to 81, F. Röthemeyer, F. Summer “Rubber Technology", 2nd revised edition, Carl Hanser Verlag Kunststoff Vienna, 2006, pages 15 to 163).
  • NR natural rubber
  • EPDM ethylene-propylene-diene rubbers
  • styrene / diolefin rubber preferably styrene / butadiene rubber
  • SBR in particular E-SBR, polybutadiene rubber (BR), polyisoprene (IR), butyl rubber, in particular isobutene / isoprene rubber (II FR), halobutyl rubber, in particular chloro- or bromobutyl rubber (XIIR), nitrile rubber (NBR), hydrogenated Nitrile rubber (H-NBR), carboxylated butadiene / acrylonitrile rubber (XNBR) or polychloroprene (CR) or mixtures of two or more of the abovementioned rubbers.
  • BR polybutadiene rubber
  • IR polyisoprene
  • II FR isobutene / isoprene rubber
  • XIIR chloro- or bromobutyl rubber
  • NBR nitrile rubber
  • H-NBR hydrogenated Nitrile rubber
  • XNBR carboxylated butadiene / acrylonitrile rubber
  • CR polych
  • At least one rubber from the group of natural rubber (NR), ethylene-propylene-diene rubber (EPDM), styrene / diolefin rubber (SBR) is particularly preferred as the rubber to be crosslinked with elemental sulfur for the rubber section in the composite part according to the invention.
  • NR natural rubber
  • EPDM ethylene-propylene-diene rubber
  • SBR styrene / diolefin rubber
  • XNBR carboxylated butadiene / acrylonitrile rubber
  • BR polybutadiene
  • natural rubber (NR) is used for the rubber section in the composite part according to the invention as a rubber to be crosslinked with elemental sulfur.
  • EPDM ethylene-propylene-diene rubber
  • polybutadiene is used for the rubber section in the composite part according to the invention as rubber to be crosslinked with elemental sulfur.
  • polyisoprene IR
  • IR polyisoprene
  • carboxylated butadiene / acrylonitrile rubber (XNBR) is used for the rubber section in the composite part according to the invention as rubber to be crosslinked with elemental sulfur.
  • soluble sulfur is meant the only stable form which is common at ordinary temperatures, the yellow cycloocta sulfur, also called S 8 sulfur or ⁇ -sulfur, which consists of typical rhombic crystals and is highly soluble in carbon disulfide. So solve at 25 ° C in 100 g of CS 2 30 g ⁇ -S (keyword "sulfur” of Online Römpp Chemie Lexikon, August 2004, Georg Thieme Verlag Stuttgart).
  • stearic acid or 2-ethylhexanoic acid in an amount of 0.1 to 7 parts by weight, preferably 0.25 to 7 parts by weight, preferably 0.5 to 5 parts by weight, based on 100% by weight.
  • stearic acid or 2-ethylhexanoic acid in an amount of 0.1 to 7 parts by weight, preferably 0.25 to 7 parts by weight, preferably 0.5 to 5 parts by weight, based on 100% by weight.
  • zinc stearate can be used in a preferred embodiment.
  • an amount of 0.25 to 5 parts by weight, preferably 1 to 3 parts by weight, based in each case on 100 parts by weight of the rubber of the elastomeric section, is usually used.
  • the zinc salt of 2-ethylhexanoic acid can also be used.
  • the crosslinking in the elastomer section of the composite part according to the invention can also be carried out as mixed sulfur-peroxide crosslinking.
  • the elastomer component for the elastomer section in the inventive composite part contains at least one further component of the series fillers, mastics, plasticizers, processing agents, aging, UV or antiozonants, tackifiers, pigments or dyes, blowing agents, Flame retardants, mold release agents, reinforcements or adhesion systems.
  • the elastomer component for the elastomeric component in the composite part according to the invention preference is given to using at least one filler of the series silicic acid, carbon black, silicates, oxides or organic fillers.
  • Silica or "silica” (Ullmann's Encyclopedia of Industrial Chemistry, VCH Verlagsgesellschaft mbH, D-69451 Weinheim, 1993, "Silica", pp. 635-645), is described in particular as fumed silica (ibid., Pp. 635-642) or as
  • the precipitated silicic acids have a specific surface area of from 5 to 1000 m 2 / g, determined by BET, preferably a specific surface area of from 20 to 400 m 2 / g They are obtained by treatment of waterglass with inorganic acids, sulfuric acid being preferably used.
  • the silicic acids may optionally also be used as mixed oxides with other metal oxides, such as Al, Mg, Ca, Ba, Zn, Zr, Ti.
  • Silicic acids having specific surface areas of from 5 to 1000 m 2 / g, more preferably from 20 to 400 m 2 / g, in each case determined by BET, are preferably used according to the invention.
  • the carbon blacks to be used in one embodiment as fillers in the elastomer component for the elastomer section in the composite part according to the invention are also known to the person skilled in the art (see keywords "carbon” or “carbon black” in Ullmann's Encyclopedia of Industrial Chemistry, VCH Verlagsgesellschaft mbH, D-69451) Weinheim, 1993, vol A 5 pp. 95-158).
  • N 1 10, N 15, N 121 are classified as N 1 10, N 15, N 121 according to the new ASTM nomenclature (ASTM D 1765 and D 2516), N 125, N 212, N 220, N 231, N 234, N 242, N 293, N 299, S 315, N 326, N 330, N 332, N 339, N 343, N 347, N 351, N 375 , N 472, N 539, N 550, N 582, N 630, N642, N 650, N 660, N 683, N 754, N 762, N 765, N 772, N 774, N 787, N 907, N 908 N 990, N 991 S 3 etc.
  • Faktis also known as oil rubber, is a rubber-like material that is made by crosslinking unsaturated mineral and vegetable oils, in Europe, especially rapeseed (Rüb-) and castor oil as well as soybean oil in America, see also http://de.wikipedia.org/wiki/Faktis.
  • UV and antiozonants in the elastomer component is preferably at least one aging, UV and antiozonants of the series UV stabilizers, in particular carbon black - if not already used as a filler - or titanium dioxide, ozone protective waxes, hydroperoxides decomposing additives (tris-nonylphenyl-phosphite), heavy metal stabilizers, substituted phenols, diarylamines, substituted p-phenylenediamines, heterocyclic mercapto compounds, paraffin waxes, microcrystalline waxes or paraphenylenediamines (F. Römemeyer, F. Sommer “Rubber Technology", 2nd revised edition, Carl Hanser Verlag Kunststoff Vienna, 2006, pages 338 to 344).
  • UV and antiozonants of the series UV stabilizers in particular carbon black - if not already used as a filler - or titanium dioxide, ozone protective waxes, hydroperoxides decomposing additives (tris-nonyl
  • At least one tackifier resin of the series of natural resin, hydrocarbon resin or phenol resin is preferably used (F.R. Röthemeyer, F. Sommer “Kautschuktechnologie”, 2nd revised edition , Carl Hanser Verlag Kunststoff Vienna, 2006, pages 345 to 346).
  • additional pigments and dyes in the elastomer component of the elastomeric portion in the composite part is preferably at least one pigment or dye of the series titania - if not already used as a UV protective agent - lithopone, zinc oxide, iron oxide, ultramarine blue, chromium oxide, Antimonsulfide or organic dyes used (F. Röthemeyer, F. Sommer “rubber technology”, 2nd revised edition, Carl Hanser Verlag Kunststoff Vienna, 2006, page 345).
  • At least one mold release agent of the series is preferably used saturated and partially unsaturated fatty and oleic acids or their derivatives, in particular fatty acid esters, fatty acid salts, fatty alcohols, fatty acid amides.
  • the mold release agents it is possible to use products based on low molecular weight silicone compounds, products based on fluoropolymers and products based on phenolic resins.
  • At least one strength support in the form of glass-based fibers is preferably used aliphatic or aromatic polyamides (Nylon®, Aramid®), made of polyesters or of natural fiber products. Both staple fibers and continuous fibers can be used (J. Schnetger “Encyclopedia of Rubber Technology” 3rd edition, Hüthig Verlag Heidelberg, 2004, pages 498 and 528).
  • An exemplary list of conventional reinforcements in the rubber industry can be found e.g. in F. Röthemeyer, F. Sommer “Rubber Technology”, 2nd revised edition, Carl Hanser Verlag Kunststoff Vienna, 2006, pages 823-827.
  • foamed vulcanizates are foamed vulcanizates, cellular rubber or sponge rubber (J. Schnetger “Lexikon der Kautschuktechnik” 3rd edition, Hüthig Verlag Heidelberg, 2004, pages 322-323 and 618).
  • foamed vulcanizates are produced by means of blowing agents.
  • the elastomer component of the elastomer component to be crosslinked with sulfur in the composite part of at least one rubber, sulfur and optionally further constituents is preferably processed by means of the process of so-called mixture processing by means of an internal mixer or a rolling mill to form a vulcanizable rubber mixture and thus prepared for the actual shaping process.
  • mixture processing by means of an internal mixer or a rolling mill to form a vulcanizable rubber mixture and thus prepared for the actual shaping process.
  • the components of the rubber compounds are intimately mixed.
  • the mixture preparation can be carried out batchwise by means of an internal mixer or rolling mill or continuously by means of an extruder (J. Schnetger "Encyclopedia of Rubber Technology” 3rd edition, Hüthig Verlag Heidelberg, 2004, pages 275 and 315 to 318).
  • polyamides For the preparation of polyamides, a variety of procedures have become known, depending on the desired end product different monomer units, various chain regulators to set a desired molecular weight or monomers with reactive groups are used for later intended post-treatments.
  • the technically relevant processes for the preparation of the polyamides to be used according to the invention are preferably via the polycondensation in the melt or via the polyaddition of corresponding lactams.
  • the polyaddition reactions of lactams include hydrolytic, alkaline, activated anionic and cationic lactam polymerizations.
  • Preferred polyamides to be used according to the invention are partially crystalline, aliphatic polyamides which can be prepared starting from diamines and dicarboxylic acids and / or lactams with at least 5 ring members or corresponding amino acids.
  • the identification of the polyamides in the context of the present invention corresponds to international standard, wherein the first digit (s) indicate the C atom number of the starting diamines and the last digit (n) the C atom number of the dicarboxylic acid. If only one number is mentioned, this means that it has been assumed that an ⁇ , ⁇ -aminocarboxylic acid or the lactam derived therefrom; Incidentally, reference is made to H.
  • the semicrystalline polyamides which have a melting enthalpy in the range of 4 to 25 J / g, measured by the DSC method according to ISO 1 1357 during the 2nd heating and integration of the melting peak and of the amorphous polyamides with a melting enthalpy of less as 4 J / g, measured by the DSC method according to ISO 1 1357 at the 2nd heating and integration of the melting peak.
  • Suitable starting materials for preparing the polyamide-based portion of the composite part are preferably aliphatic and / or aromatic dicarboxylic acids, particularly preferably adipic acid, 2,2,4-trimethyladipic acid, 2,4,4-trimethyladipic acid, azelaic acid, sebacic acid, isophthalic acid, terephthalic acid , aliphatic and / or aromatic diamines, particularly preferably tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1, 9-nonanediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, the isomers diamino-dicyclohexylmethane, diaminodicyclohexylpropane, bis-aminomethyl-cyclohexane , Phenylenediamines, xylylenediamines, aminocarboxylic acids, in particular aminocaproic acid, or the corresponding lactam
  • PA-6 polyamide 6
  • PA-66 polyamide 66
  • caprolactam as comonomer-containing copolyamides, very particularly preferably to random, partially crystalline, aliphatic copolyamides, in particular PA 6/66.
  • ⁇ -caprolactam (CAS number 105-60-2) is preferably used inter alia for the production of polyamide. From cyclohexanone, cyclohexanone oxime is first prepared by reaction with the hydrogen sulfate or the hydrochloride of the hydroxylamine. This is converted into ⁇ -caprolactam by a Beckmann rearrangement.
  • Hexamethylenediamine adipate (CAS number 3323-53-3) is the reaction product of adipic acid and hexamethylenediamine. It is also used inter alia as an intermediate in the production of polyamide 66.
  • the common name AH salt is derived from the initial letters of the starting substances.
  • Semicrystalline PA6 and / or PA66 to be used according to the invention is available, for example, under the name Durethan® from Lanxess Deutschland GmbH, Cologne, Germany. Of course, mixtures of these polyamides can be used, wherein the mixing ratio is arbitrary. It may also contain portions of recycled polyamide molding compounds and / or fiber recyclates in the polyamide component.
  • polyamide combinations are known to the person skilled in the art. Preferred polyamide combinations are PA6 / PA66, PA12 / PA1012, PA12 / 1212, PA612 / PA12, PA613 / PA12, PA1014 / PA12 or PA610 / PA12 and corresponding combinations with PA1 1, particularly preferably PA6 / PA66. In case of doubt, compatible combinations can be determined by routine tests.
  • a partially aromatic polyamide may also be used whose dicarboxylic acid moiety results from 5 to 100 mol% of aromatic dicarboxylic acid having 8 to 22 carbon atoms and which preferably has a crystallite melting point T m of at least 250 according to ISO 1 1357-3 ° C, more preferably of at least 260 ° C and particularly preferably of at least 270 ° C.
  • Suitable types are preferably PA66 / 6T, PA6 / 6T, PA6T / MPMDT (MPMD stands for 2-methylpentamethylenediamine), PA9T, PA10T, PA1 1T, PA12T, PA14T and copolycondensates of these last types with an aliphatic diamine and an aliphatic dicarboxylic acid or with an ⁇ -aminocarboxylic acid or a lactam.
  • the partly aromatic polyamide can also be used as a blend with another, preferably aliphatic polyamide, more preferably with PA6, PA66, PA1 1 or PA12.
  • Another suitable polyamide class are transparent polyamides; these are amorphous in most cases, but can also be microcrystalline. They can be used either alone or in a mixture with aliphatic and / or partially aromatic polyamides, preferably PA6, PA66, PA1 1 or PA12. To achieve good adhesion, the level of transparency is not important; It is crucial here that the glass transition point T g , measured according to ISO 1 1357-3, at least 1 10 ° C, preferably at least 120 ° C, more preferably at least 130 ° C and particularly preferably at least 140 ° C.
  • Preferred transparent polyamides are: the polyamide from 1, 12-dodecanedioic acid and 4,4'-diaminodicyclohexylmethane (PAPACM12), in particular starting from a 4,4'-diaminodicyclohexyl methane having a trans, trans isomer content of from 35 to 65%;
  • PAPACM12 4,4'-diaminodicyclohexylmethane
  • copolyamide from a mixture of terephthalic acid / isophthalic acid and 1: 6-hexamethylenediamine, optionally mixed with 4,4'-diaminodicyclohexylmethane,
  • copolyamide from terephthalic acid and / or isophthalic acid, 3,3'-dimethyl-
  • polyamide from 1, 12-dodecanedioic acid and 4,4'-diaminodicyclohexylmethane (at low trans, trans isomer content),
  • another dicarboxylic acid e.g. Terephthalic acid and / or 2,6-naphthalenedicarboxylic acid
  • copolyamide from a mixture of bis (4-amino-cyclohexyl) methane and bis (4-amino-3-methyl-cyclohexyl) methane and aliphatic dicarboxylic acids having 8 to 14 carbon atoms, and
  • Polyamides or copolyamides from a mixture containing 1, 14-tetradecanedioic acid and an aromatic, arylaliphatic or cycloaliphatic diamine are examples. These examples can be varied as far as possible by the addition of further components, preferably caprolactam, laurolactam or diamine / dicarboxylic acid combinations, or by partial or complete replacement of starting components by other components.
  • Lactams or ⁇ -aminocarboxylic acids which are used as polyamide-forming monomers contain 4 to 19 and in particular 6 to 12 carbon atoms. Particular preference is given to using ⁇ -caprolactam, ⁇ -aminocaproic acid, capryllactam, ⁇ -aminocaprylic acid, laurolactam, ⁇ -aminododecanoic acid and / or ⁇ -aminoundecanoic acid.
  • Combinations of diamine and dicarboxylic acid are, for example, hexamethylenediamine / adipic acid, hexamethylenediamine / dodecanedioic acid, octamethylenediamine / sebacic acid, decamethylenediamine / sebacic acid, decamethylenediamine / dodecanedioic acid, dodecamethylenediamine / dodecanedioic acid and dodecamethylenediamine / 2,6-naphthalenedicarboxylic acid.
  • Polyamide molding compositions for the purposes of this invention are preparations of polyamides for the production of the polyamide component in the composite according to the invention, which have been made to improve the processing properties or to modify the performance properties.
  • ABS ABS
  • polyphenylene ethers acrylonitrile-butadiene-styrene
  • phase morphology primarily depends on the volume fractions of the individual polymers and on the melt viscosities. If the other polymer has a significantly higher melt viscosity than the polyamide, the polyamide forms the matrix even if it is less than 50 volume percent of the thermoplastic moiety, for example, about 40 volume percent. This is especially relevant for blends with polyphenylene ether; b) fibrous reinforcing materials, in particular round or flat glass fibers, carbon fibers, aramid fibers, stainless steel fibers or potassium titanate whiskers; c) fillers, especially talc, mica, silicate, quartz.
  • the polyalkenamer to be used according to the invention is incorporated in various ways into the polyamide or into the polyamide component of the polyamide section for the composite part.
  • the polyalkenamer is added either during the compounding of the polyamide molding compounds together with the other additives to the polyamide, or as a masterbatch added to the polyamide during compounding, or as a mixture with the polyamide molding compound, which is mostly used as granules, via a metering funnel supplied to the injection unit.
  • the Polyalkenamer-containing polyamide molding composition in the form of a granular mixture (dry blend, dry blend, see The Plastics - Chemistry, Physics, Technology, edited by B. Carlowitz, Carl Hanser Verlag Kunststoff Vienna, 1990, p 266) from a polyalkenamer-containing polyamide molding composition and a further non-polyalkenamer-containing polyamide molding composition prepared and thus obtained a polyamide molding composition having an adjusted Polyalkenamer concentration.
  • Particularly preferred according to the invention is the addition of polyalkenamer to the polyamide via a metering funnel in the injection unit or during compounding together with the other additives, more preferably during compounding together with the other additives.
  • Injection-compression molding is a special process of injection molding for producing high-precision plastic parts without distortion.
  • the molten plastic is injected into the tool only under reduced closing force, which leads to an easy opening of the tool halves.
  • the full closing force is applied and thus the molded part is finally molded (Ullmann's Encyclopedia of Industrial Chemistry, 7th Edition, Vol. 28, Plastics Processing, Wiley-VCH Verlag, Weinheim, 201 1, p. 187).
  • the procedure is analogous in that the rubber mixture is injected into a tool heated to vulcanization temperature. When the tool is closed, shaping and vulcanization are carried out (F.R. Röthemeyer, F.
  • injection molding - often referred to as injection molding or injection molding - is a primary molding process that is mainly used in plastics processing. With this method, economically directly usable moldings can be produced in large numbers without post-processing.
  • the respective polymeric material is plasticized in an injection unit with an injection molding machine and injected into an injection mold.
  • the cavity, the cavity, of the tool determines the shape of the finished part.
  • parts of a few tenths of a gram can be produced up to the larger kilogram range by injection molding (Ullmann's Encyclopedia of Industrial Chemistry, 7th Edition, Vol. 28, Plastics Processing, Wiley-VCH Verlag, Weinheim, 201 1, pp. 181 to 189 ).
  • multi-component injection molding several components are joined by injection molding to form a composite part.
  • 2-component injection molding two components are injection-molded to form a composite part.
  • a polyamide component and an elastomer component are preferably combined in the 2-component injection molding process to form a composite part.
  • the 2-component injection molding process can be operated both in a one-step process and in a two-step process (F. Johannaber, W. Michaeli, Handbook Injection Molding, 2nd Edition, Carl Hanser Verlag Kunststoff, 2004, page 506 bis 523; Handbuch Kunststoff-Veritatistechnik, edited by GW Ehrenstein, Carl Hanser Verlag Kunststoff Vienna, 1990, pages 517 to 540).
  • the rigid, thermoplastic molding is first produced from the polyamide molding composition containing polyalkenes to be used according to the invention, in particular by one of the abovementioned processing methods, preferably by injection molding.
  • This thermoplastic molding can be stored as needed.
  • thermoplastic molding with the elastomer component by means of one of the above processing methods, preferably by injection molding, applied and exposed to the vulcanization conditions of the rubber.
  • the production can also be carried out with a machine (single-stage process), which preferably has a turning plate or a turntable, and / or via appropriate tool technology, preferably by means of slides, which release delayed areas of the cavity for the second component.
  • a machine single-stage process
  • a machine which has a turning plate, a turntable or a tool that has one or more slides, usually in a first cycle a preform of the poly- amid component in a cavity of the tool, the first station, manufactured.
  • the preform After a rotary movement of the tool, or by means of Umsetztechnik, the preform is placed in a second, geometrically modified spray-finished station (for example by means of the rotation technique by a rotation of 180 ° or 120 ° in three-cavity tools or by means of a gate valve technique, so-called core Baking process) and, in a second cycle, the rubber composition for the elastomeric section, obtainable from elemental sulfur to be vulcanized or vulcanized rubber injected. After reaching the demolding stability of the elastomer component can be removed from the mold.
  • a second, geometrically modified spray-finished station for example by means of the rotation technique by a rotation of 180 ° or 120 ° in three-cavity tools or by means of a gate valve technique, so-called core Baking process
  • the rubber composition for the elastomeric section obtainable from elemental sulfur to be vulcanized or vulcanized rubber injected.
  • the melt temperatures of the polyamide to be used according to the invention as a thermoplastic component are preferably in the range from 1 80 to 340 ° C., more preferably in the range from 200 to 300 ° C.
  • the mold temperatures of the thermoplastic temperature ranges are preferably in the range from 20 to 200 ° C., more preferably in the range from 60 to 180 ° C.
  • Preferred melt temperatures of the rubber mixture for the elastomer section, obtainable from rubber to be vulcanized or crosslinked with elemental sulfur, in the plasticizing cylinder are in the range from 20 to 150.degree. C., preferably in the range from 60 to 100.degree.
  • Preferred vulcanization temperatures of the elastomer component are in the range of 120 to 220 ° C, preferably in the range of 140 to 200 ° C.
  • an annealing takes place after the removal of the elastomer component from the tool cavity.
  • annealing means that a solid is heated to a temperature below the melting temperature. This happens over a long period of time - from a few minutes to a few days -.
  • the increased mobility of the atoms can thus compensate for structural defects and improve the crystal structure in the near and distant order. In this way, the process of melting and (extremely) slow cooling to adjust the crystal structure can be avoided.
  • An annealing in the context of the present invention is preferably carried out at a temperature in the range of 120 to 220 ° C, preferably at a temperature in the range of 140 to 200 ° C.
  • the holding pressure phase is preferably in the range from 0 to 3000 bar with holding pressure times of 0 seconds until the tool is opened.
  • the composite part of a polyamide section and an elastomer section in the so-called reverse 2-component injection molding (2K injection molding) is made, ie in the order first the soft component, then the hard component in which the polyamide section is in turn made from the polyalkenamer-containing polyamide molding compound to be used according to the invention and the elastomer section from the rubber to be crosslinked in the presence of free sulfur.
  • the rubber mixture for the elastomer portion obtainable from rubber to be vulcanized or crosslinked with elemental sulfur, is injection-molded and vulcanized, after which the polyalkenamer-containing polyamide molding composition to be used according to the invention is sprayed on.
  • the production can be carried out in a machine (single-stage process), which preferably has a turning plate or a turntable, and / or via appropriate tool technology, preferably by means of slides, the delayed regions of the Release cavity for the second component.
  • the corresponding injection molding parameters can be taken from the (conventional) 2K injection molding process (cylinder temperatures,
  • the method of injection molding of polyamide is characterized in that the raw material, ie the molding composition according to the invention, preferably in granular form, is melted (plasticized) in a heated cylindrical cavity and sprayed as a spray mass under pressure into a tempered cavity. After cooling (solidification) of the mass, the injection molded part is removed from the mold.
  • An injection molding machine to be used for this purpose consists of a closing unit, the injection unit, the drive and the controller.
  • the clamping unit includes fixed and movable clamping plates for the tool, a face plate as well as columns and drive of the moving tool clamping plate (toggle joint or hydraulic clamping unit).
  • An injection unit comprises the electrically heatable cylinder, the drive of the screw (motor, gearbox) and optionally the hydraulics for moving the screw and injection unit.
  • the task of the injection unit is to melt the powder or the granules, to dose, to inject and to press (because of contraction). The problem of melt backflow within the screw (leakage flow) is solved by backflow stops.
  • the method of injection molding for the production of molded rubber parts is characterized in that the raw material, ie the rubber mixture to be crosslinked, is plasticized in a heated cylindrical cavity and sprayed as a spray mass under pressure in a cavity tempered to vulcanization temperature. After exiting vulcanizing the mass, the injection molded part is removed from the mold. Cylinders and screws of the injection molding machine are designed in a manner known to those skilled in the rubber processing and the tool can be heated to vulcanization temperature.
  • the vulcanization times of the rubber component depend, apart from the rubber mixture, on the vulcanization temperatures and on the geometry of the rubber component to be produced. They are preferably between 15 s and 15 min; Lower temperatures and thicker rubber parts require longer vulcanization times (F.
  • fatty and oleic acids and their derivatives are preferably used as mold release agents (also referred to as lubricants or mold release agents).
  • mold release agents also referred to as lubricants or mold release agents.
  • Fatty acid salts, fatty alcohols, fatty acid amides which are preferably used as a mixture component, into consideration and further applicable to the mold surface products, in particular products based on low molecular weight silicone compounds, products based on fluorophor lymeren and products based on phenolic resins.
  • the mold release agents are used as the mixing component preferably in amounts of about 0.1 to 10 phr, particularly preferably 0.5 to 5 phr, based on 100 phr of the elastomer (s) in the rubber component.
  • the present invention relates to a composite part in direct adhesion of at least one section produced from at least one polyamide molding at least 30% by weight of a mixture of a) 60 to 99.9 parts by weight of polyamide and b) 0 to 1 to 40 parts by weight of polyalkenamer, characterized in that the polyamide molding composition comprises wherein the sum of the parts by weight of a) and b) is 100 and as polyalkenamer at least 1, 8-trans polyoctenamer, as polyamide PA6 and for the elastomer portion at least one of the series NR to be crosslinked with elemental sulfur as a crosslinking agent, EPDM, NBR, CR, BR, SBR, XNBR is used.
  • the present invention relates to a composite part in direct adhesion of at least one section made of at least one polyamide molding compound and at least one elastomeric section, characterized in that the polyamide molding composition to at least 30 wt .-% of a mixture of a) 60 to 99.9 wt Parts polyamide and b) 0, 1 to 40 parts by weight of polyalkenamer, wherein the sum of the parts by weight of a) and b) is 100 and as Polyalkenamer at least one polybutadiene having a number average molecular weight Mn in the range of 800 to 20,000 g / mol and / or with a dynamic viscosity, measured by the cone-plate method according to DIN 53019 at atmospheric pressure and at a temperature of 25 ° C in the range of 100 to 15,000 mPas is used, and as a polyamide PA66 and for the elastomeric portion at least one elemental sulfur crosslinking agent to be crosslinked rubber NR, EPDM
  • the present invention relates to a composite part in direct adhesion of at least one section made of at least one polyamide molding composition and at least one elastomeric fragment, characterized in that the polyamide molding composition comprises at least 30 wt .-% of a mixture of a) 60 to 99, 9 parts by weight of polyamide and b) 0, 1 to 40 parts by weight of polyalkenamer contains, wherein the sum of the parts by weight of a) and b) is 100 and as polyalkenamer at least 1, 8-trans polyoctenamer, as polyamide PA66 and for the elastomer portion at least one with elemental sulfur as the crosslinking agent to be crosslinked rubber NR, EPDM, NBR, CR, BR, SBR, XNBR series.
  • the present invention relates to a composite part in direct adhesion of at least one section made of at least one polyamide molding compound and at least one elastomeric section, characterized in that the polyamide molding composition to at least 30 wt .-% of a mixture of a) 60 to 99.9 wt Parts polyamide and b) 0, 1 to 40 parts by weight of polyalkenamer, wherein the sum of the parts by weight of a) and b) is 100 and as Polyalkenamer at least one polybutadiene having a number average molecular weight Mn in the range of 800 to 20,000 g / mol and / or with a dynamic viscosity, measured by the cone-plate method according to DIN 53019 at atmospheric pressure and at a temperature of 25 ° C in the range of 100 to 15,000 mPas is used, and as polyamide PA66 and is used for the elastomeric portion with elemental sulfur crosslinking agent to be crosslinked rubber NR.
  • the polyamide molding composition to at
  • the present invention relates to a composite part in direct adhesion of at least one section made of at least one polyamide molding composition and at least one elastomeric fragment, characterized in that the polyamide molding composition comprises at least 30 wt .-% of a mixture of a) 60 to 99, 9 parts by weight of polyamide and b) 0, 1 to 40 parts by weight of polyalkenamer, wherein the sum of the parts by weight of a) and b) is 100 and as Polyalkenamer at least 1, 8-trans polyoctenamer, as Polyamide PA66 and for the elastomer section with elemental sulfur crosslinking agent to be crosslinked rubber NR is used.
  • the polyamide molding composition comprises at least 30 wt .-% of a mixture of a) 60 to 99, 9 parts by weight of polyamide and b) 0, 1 to 40 parts by weight of polyalkenamer, wherein the sum of the parts by weight of a) and b) is 100 and as Polyalkenamer at least 1, 8-
  • the present invention relates to a composite part in direct adhesion of at least one section produced from at least one polyamide molding at least 30% by weight of a mixture of a) 60 to 99.9 parts by weight of polyamide and b) 0 to 1 to 40 parts by weight of polyalkenamer in which the sum of the parts by weight of a) and b) is 100 and as polyalkenamer at least one polybutadiene having a number average molecular weight Mn in the range of 800 to 20,000 g / mol and / or with a dynamic viscosity, measured with the cone Plate method according to DIN 53019 at atmospheric pressure and at a temperature of 25 ° C in the range of 100 to 15,000 mPas is used, and as the polyamide PA6 and for the elastomeric portion with elemental sulfur crosslinking agent to be crosslinked rubber NR is used.
  • the present invention relates to a composite part in direct adhesion of at least one section made of at least one polyamide molding compound and at least one elastomeric section, characterized in that the polyamide molding composition to at least 30 wt .-% of a mixture of a) 60 to 99.9 wt Parts polyamide and b) 0, 1 to 40 parts by wt.
  • Polyalkenamer contains, wherein the sum of the parts by wt. Of a) and b) is 100 and as Polyalkenamer at least 1, 8-trans polyoctenamer, as polyamide PA6 and for the elastomeric portion with elemental sulfur crosslinking agent to be crosslinked rubber NR is used.
  • the present invention relates to a composite part in direct adhesion of at least one section made of at least one polyamide molding compound and at least one elastomeric section, characterized in that the polyamide molding composition to at least 30 wt .-% of a mixture of a) 60 to 99.9 wt Parts polyamide and b) 0, 1 to 40 parts by wt.
  • Polyalkenamer contains, wherein the sum of the wt.
  • a) and b) is 100 and as Polyalkename mer at least one polybutadiene having a number average molecular weight Mn in the range of 800 to 20,000 g / mol and / or with a dynamic viscosity, measured by the cone-plate method according to DIN 53019 at normal pressure and at a temperature of 25 ° C in the range of 100 to 15,000 mPas is used, and is used as the polyamide PA6 and for the elastomeric portion with elemental sulfur crosslinking agent to be crosslinked rubber CR.
  • the present invention relates to a composite part in direct adhesion of at least one section made of at least one polyamide molding compound and at least one elastomeric section, characterized in that the polyamide molding composition to at least 30 wt .-% of a mixture of a) 60 to 99.9 wt Parts polyamide and b) 0, 1 to 40 parts by weight of polyalkenamer, wherein the sum of the parts by weight of a) and b) is 100 and as Polyalkenamer at least one polybutadiene having a number average molecular weight Mn in the range of 800 to 20,000 g / mol and / or with a dynamic viscosity, measured by the cone-plate method according to DIN 53019 at atmospheric pressure and at a temperature of 25 ° C in the range of 100 to 15,000 mPas is used, and as polyamide PA66 and for the elastomer section with elemental sulfur as crosslinking agent to be crosslinked rubber BR is used.
  • the present invention relates to a composite part in direct adhesion of at least one section made of at least one polyamide molding composition and at least one elastomeric fragment, characterized in that the polyamide molding composition comprises at least 30 wt .-% of a mixture of a) 60 to 99, 9 parts by weight of polyamide and b) 0, 1 to 40 parts by weight of polyalkenamer contains, wherein the sum of the parts by weight of a) and b) is 100 and is used as Polyalkenamer at least 1, 8-trans polyoctenamer, as polyamide PA66 and for the elastomeric portion with elemental sulfur crosslinking agent to be crosslinked rubber BR.
  • the polyamide molding composition comprises at least 30 wt .-% of a mixture of a) 60 to 99, 9 parts by weight of polyamide and b) 0, 1 to 40 parts by weight of polyalkenamer contains, wherein the sum of the parts by weight of a) and b) is 100 and is used as Polyalkenamer at
  • the present invention relates to a composite part in direct adhesion of at least one section made of at least one polyamide molding compound and at least one elastomeric section, characterized in that the polyamide molding composition to at least 30 wt .-% of a mixture of a) 60 to 99.9 wt Parts polyamide and b) 0, 1 to 40 parts by weight of polyalkenamer, wherein the sum of the parts by weight of a) and b) is 100 and as Polyalkenamer at least one polybutadiene having a number average molecular weight Mn in the range of 800 to 20,000 g / mol and / or with a dynamic viscosity, measured by the cone-plate method according to DIN 53019 at normal pressure and at a temperature of 25 ° C in the range of 100 to 15,000 mPas is used, and as polyamide PA6 and for the elastomer section with elemental sulfur as crosslinking agent to be crosslinked rubber BR is used.
  • the present invention relates to a composite part in direct adhesion of at least one section made of at least one polyamide molding composition and at least one elastomeric fragment, characterized in that the polyamide molding composition comprises at least 30 wt .-% of a mixture of a) 60 to 99, 9 parts by weight of polyamide and b) 0, 1 to 40 parts by weight of polyalkenamer, wherein the sum of the parts by weight of a) and b) is 100 and as Polyalkename mer at least 1, 8-trans polyoctenamer , as polyamide PA6 and for the elastomeric fragment with elemental sulfur as crosslinking agent to be crosslinked rubber BR is used.
  • the polyamide molding composition comprises at least 30 wt .-% of a mixture of a) 60 to 99, 9 parts by weight of polyamide and b) 0, 1 to 40 parts by weight of polyalkenamer, wherein the sum of the parts by weight of a) and b) is 100 and as Polyalkename mer at
  • the present invention relates to a composite part in direct adhesion of at least one section made of at least one polyamide molding composition and at least one elastomeric section, characterized in that the polyamide molding composition to at least 30 wt .-% is a mixture of a) 60 to 99.9 parts by weight of polyamide and b) 0.1 to 40 parts by weight of polyalkenamer, wherein the sum of the parts by weight of a) and b) is 100 and as Polyalkenamer at least one polybutadiene having a number-average molecular weight Mn in the range from 800 to 20,000 g / mol and / or having a dynamic viscosity, measured by the cone-plate method according to DIN 53019 at normal pressure and at a temperature of 25 ° C.
  • the present invention relates to a composite part in direct adhesion of at least one section made of at least one polyamide molding compound and at least one elastomeric section, characterized in that the polyamide molding composition to at least 30 wt .-% of a mixture of a) 60 to 99.9 wt Parts polyamide and b) contains 0.1 to 40 parts by weight of polyalkenamer, wherein the sum of the parts by weight of a) and b) is 100 and as Polyalkenamer at least 1, 8-trans polyoctenamer, as polyamide PA66 and for the elastomeric portion with elemental sulfur crosslinking agent rubber SBR is used as the crosslinking agent.
  • the present invention relates to a composite part in direct adhesion of at least one section made of at least one polyamide molding compound and at least one elastomeric section, characterized in that the polyamide molding composition to at least 30 wt .-% of a mixture of a) 60 to 99.9 wt Parts polyamide and b) 0.1 to 40 parts by weight of polyalkenamer, wherein the sum of the parts by weight of a) and b) is 100 and as Polyalkenamer at least one polybutadiene having a number average molecular weight Mn in the range of 800 to 20,000 g / mol and / or with a dynamic viscosity, measured by the cone-plate method according to DIN 53019 at atmospheric pressure and at a temperature of 25 ° C in the range of 100 to 15,000 mPas is used, and as Polyamide PA6 and for the elastomer section with elemental sulfur as crosslinking agent to be crosslinked rubber SBR is used.
  • the present invention relates to a composite part in direct adhesion of at least one section made of at least one polyamide molding composition and at least one elastomeric fragment, characterized in that the polyamide molding composition comprises at least 30 wt .-% of a mixture of a) 60 to 99, 9 parts by weight of polyamide and b) 0.1 to 40 parts by weight of polyalkenamer, wherein the sum of the parts by weight of a) and b) is 100 and as Polyalkename mer at least 1, 8-trans polyoctenamer , is used as polyamide PA6 and for the elastomeric portion with elemental sulfur crosslinking rubber SBR to be crosslinked.
  • the polyamide molding composition comprises at least 30 wt .-% of a mixture of a) 60 to 99, 9 parts by weight of polyamide and b) 0.1 to 40 parts by weight of polyalkenamer, wherein the sum of the parts by weight of a) and b) is 100 and as Polyalkename mer at least 1,
  • the present invention relates to a composite part in direct adhesion of at least one section made of at least one polyamide molding composition and at least one elastomeric fragment, characterized in that the polyamide molding composition comprises at least 30 wt .-% of a mixture of a) 60 to 99, 9 parts by weight of polyamide and b) 0.1 to 40 parts by weight of polyalkenamer, wherein the sum of the parts by weight of a) and b) is 100 and as Polyalkename mer at least one polybutadiene having a number average molecular weight Mn in the range of 800 to 20,000 g / mol and / or with a dynamic viscosity, measured by the cone-plate method according to DIN 53019 at normal pressure and at a temperature of 25 ° C in the range of 100 to 15,000 mPas is used, and is used as the polyamide PA66 and for the elastomer section with elemental sulfur as a crosslinking agent to be crosslinked rubber XN
  • the present invention relates to a composite part in direct adhesion of at least one section made of at least one polyamide molding compound and at least one elastomeric section, characterized in that the polyamide molding composition to at least 30 wt .-% of a mixture of a) 60 to 99.9 wt . Parts of polyamide as well b) 0.1 to 40 parts by wt.
  • Polyalkenamer contains, wherein the sum of the parts by wt. of a) and b) is 100 and as Polyalkenamer at least 1, 8-trans polyoctenamer, as polyamide PA66 and for the elastomer section Rubber XNBR to be crosslinked with elemental sulfur as crosslinking agent is used.
  • the present invention relates to a composite part in direct adhesion of at least one section made of at least one polyamide molding composition and at least one elastomeric component, characterized in that the polyamide molding composition comprises at least 30 wt .-% of a mixture of a) 60 to 99, 9 parts by weight of polyamide and b) 0.1 to 40 parts by weight of polyalkenamer, wherein the sum of the parts by weight of a) and b) is 100 and as Polyalkenamer at least one polybutadiene having a number average molecular weight Mn im Range of 800 to 20,000 g / mol and / or with a dynamic viscosity, measured by the cone-plate method according to DIN 53019 at atmospheric pressure and at a temperature of 25 ° C in the range of 100 to 15,000 mPas used, and as polyamide PA6 and for the elastomer portion with elemental sulfur crosslinking agent to be crosslinked rubber XNBR is used.
  • the polyamide molding composition comprises at least
  • the present invention relates to a composite part in direct adhesion of at least one section made of at least one polyamide molding composition and at least one elastomeric fragment, characterized in that the polyamide molding composition comprises at least 30 wt .-% of a mixture of a) 60 to 99, 9 parts by weight of polyamide and b) 0.1 to 40 parts by wt.
  • Polyalkenamer contains, wherein the sum of the wt. Parts of a) and b) is 100 and polyalkenamer at least 1, 8-trans polyoctenamer, as Polyamide PA6 and for the elastomer section with elemental sulfur crosslinking agent to be crosslinked rubber XNBR is used.
  • the present invention relates to a composite part in direct adhesion, which consists of at least one part made of mini- at least one polyamide molding composition and at least one component prepared from at least one rubber to be vulcanized with elemental sulfur as a crosslinking agent without any adhesion promoter, characterized in that the polyamide molding composition contains at least 30% by weight, preferably at least 45% by weight, more preferably at least 55 wt .-% and particularly preferably at least 65 wt .-% consists of the mixture of the following components: a) 60 to 99.9 parts by weight, preferably 75 to 99.8 parts by weight and especially preferably 85 to 99.7 parts by weight and very particularly preferably 88 to 99.5 parts by weight of polyamide and b) 0, 1 to 40 parts by weight, preferably 0.2 to 25 parts by weight, particularly preferably 0.3 to 15 parts by weight, very particularly preferably 0.5 to 12 parts by weight of polyalkene mer, preferably 1, 8-trans-polyoctena
  • the present invention further relates to the use of polyalkenamer in the polyamide component for increasing the composite adhesion of a composite part of at least one piece made of a polyamide molding compound and at least one piece made of an elastomer obtainable from elemental sulfur vulcanized rubber to be vulcanized by at least one molding process of the series extrusion, pressing method, injection compression molding, transfer molding, transfer molding or injection molding or its special process, in particular gas injection technique, preferably by 2-component injection molding (2-K injection molding) was obtained.
  • compositions of the polyamide components are summarized in Table 1.
  • Component B 30 30 - - 30 30 - 30 30 30 30 30 30 30 30
  • Component A1 linear polyamide 6 (Durethan® B29, Lanxess Germany
  • Component A2 linear polyamide 66 (Radipol® A45H, Radici Chimica SpA
  • Component B chopped CS fiber CS 7928 coated, Lanxess
  • Component C1 heat stabilizer Cul / KBr mixture (molar ratio 1/4) in
  • Component C2 mold release agent montan wax (ester of montanic acid with multifunctional alcohols) Licowax® E of Clariant Products Germany GmbH, Gersthofen
  • Component C3 nucleating agent talc Mistron®, Imerys Tale Europe,
  • polyamide component 7 after compounding and granulation by dry blending, the composition of Table 1 and a polyamide molding composition Durethan® BKV30 H2.0 901510 from LANXESS Deutschland GmbH, Cologne, obtained from the compounding and granulation, were obtained in equal parts by weight (1: 1) made a dry blend. Since Durethan® BKV30 H2.0 901510 does not contain a polyalkenamer, Polyamide Component 7's Dry Blend has a content of 5% polyalkeneer Lithene® ultra N4-5000. In the case of the polyamide components 1 to 6 and 8 to 1 1, no production of a dry blend took place.
  • the polyamide molding compositions were dried for 4 hours in a dry air dryer at 80 ° C, before they were then processed by injection molding.
  • compositions of the rubber mixtures of the vulcanization-resulting elastomer components are summarized in Table 2.
  • the specification of the rubber mixture constituents of the elastomer components is given in parts by mass based on 100 parts by mass of rubber.
  • N550 Corax® N550 industrial carbon black from Orion Engineered Carbons
  • PEG-4000 plasticizer from Carl Roth GmbH & Co. KG, Düsseldorf Sunpar® 2280 Paraffinic process oil from Schill & Seilacher
  • S-80 polymer-bound elemental sulfur Rhenogran® S-80 as a vulcanizing agent of Rhein Chemie Rheinau GmbH, Mannheim
  • ZDT-50 polymer bound vulcanization accelerator
  • Rhenogran® ZDT-50 from Rhein Chemie Rheinau GmbH, Mannheim
  • MBTS-70 Polymer bonded vulcanization accelerator
  • TBBS vulcanization accelerator Vulkacit NZ of LANXESS
  • Rhenogran® TBzTD-70 from Rhein Chemie Rheinau GmbH, Mannheim
  • MBS vulcanization accelerator Vulkacit-MOZ / LG
  • MBTS Vulcanization accelerator Vulkacit-DM / C of LANXESS
  • DPG Vulcanization accelerator Ekaland® DPG C from Safic-Alcan GmbH, Bad Kreuznach
  • the rubber compounds were prepared by means of a laboratory internal mixer Werner & Pfleiderer GK 5E.
  • Elastomer component ABCD o R > 10 MPa + + + + +
  • a "+” sign in Table 6 indicates a composite test specimen comprising a polyamide component and an elastomeric component which has been found to have an adhesion of> 3 N / mm in the peel test
  • a "-" character in Table 6 indicates a composite specimen of a polyamide component and an elastomer component in which an adhesion of ⁇ 3 N / mm was determined in the peel test.
  • a "*" character in Table 6 indicates that the preparation of such a composite specimen is outstanding from a polyamide component and an elastomer component.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
  • Sealing Material Composition (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)

Abstract

L'invention concerne une pièce composite qui est fabriquée au moyen d'un procédé de fabrication à 2 constituants, de préférence de moulage par injection à 2 constituants, à partir d'un élément composé d'au moins une matière moulable en polyamide à laquelle on a ajouté du polyalcénamère et d'au moins un élément composé d'au moins un élastomère, pouvant être obtenu à partir de caoutchouc à vulcaniser ou à réticuler avec du soufre élémentaire ou qui, après sa fabrication, est composée de ces constituants, sans qu'un agent adhésif soit utilisé. Les éléments individuels de la pièce composite sont des pièces moulées macroscopiques mais ne sont toutefois pas par exemple des particules dispersées dans un mélange plastique-élastomère ou des fibres de polyamide dans une matrice élastomère et par conséquent des tels mélanges ne sont pas des pièces composites au sens de l'invention. L'invention concerne également un procédé de fabrication de telles pièces composites, l'utilisation de polyalcénamère pour améliorer l'adhérence de pièces moulées à base de polyamide avec un composant élastomère, pouvant être obtenu à partir de caoutchouc à vulcaniser ou à réticuler avec du soufre élémentaire, et l'utilisation de polyalcénamère pour réduire le point de fusion ou le point de ramollissement du polyamide.
EP13821471.3A 2012-12-21 2013-12-20 Pièce composite Withdrawn EP2934886A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP13821471.3A EP2934886A1 (fr) 2012-12-21 2013-12-20 Pièce composite

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP12198791.1A EP2746046A1 (fr) 2012-12-21 2012-12-21 Pièce composite
PCT/EP2013/077760 WO2014096392A1 (fr) 2012-12-21 2013-12-20 Pièce composite
EP13821471.3A EP2934886A1 (fr) 2012-12-21 2013-12-20 Pièce composite

Publications (1)

Publication Number Publication Date
EP2934886A1 true EP2934886A1 (fr) 2015-10-28

Family

ID=47561192

Family Applications (2)

Application Number Title Priority Date Filing Date
EP12198791.1A Withdrawn EP2746046A1 (fr) 2012-12-21 2012-12-21 Pièce composite
EP13821471.3A Withdrawn EP2934886A1 (fr) 2012-12-21 2013-12-20 Pièce composite

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP12198791.1A Withdrawn EP2746046A1 (fr) 2012-12-21 2012-12-21 Pièce composite

Country Status (7)

Country Link
US (1) US20150306854A1 (fr)
EP (2) EP2746046A1 (fr)
JP (1) JP6430957B2 (fr)
KR (1) KR20150099745A (fr)
CN (1) CN104870188B (fr)
BR (1) BR112015014916A2 (fr)
WO (1) WO2014096392A1 (fr)

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Also Published As

Publication number Publication date
US20150306854A1 (en) 2015-10-29
EP2746046A1 (fr) 2014-06-25
JP6430957B2 (ja) 2018-11-28
CN104870188A (zh) 2015-08-26
JP2016508082A (ja) 2016-03-17
KR20150099745A (ko) 2015-09-01
CN104870188B (zh) 2017-11-14
BR112015014916A2 (pt) 2017-07-11
WO2014096392A1 (fr) 2014-06-26

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