WO2009149143A1 - Adhérence de polyamides à des résines époxy - Google Patents

Adhérence de polyamides à des résines époxy Download PDF

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Publication number
WO2009149143A1
WO2009149143A1 PCT/US2009/046064 US2009046064W WO2009149143A1 WO 2009149143 A1 WO2009149143 A1 WO 2009149143A1 US 2009046064 W US2009046064 W US 2009046064W WO 2009149143 A1 WO2009149143 A1 WO 2009149143A1
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WIPO (PCT)
Prior art keywords
polyamide
epoxy resin
adhesion
cured
weight percent
Prior art date
Application number
PCT/US2009/046064
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English (en)
Inventor
Paul J. Kane
Original Assignee
E. I. Du Pont De Nemours And Company
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Filing date
Publication date
Application filed by E. I. Du Pont De Nemours And Company filed Critical E. I. Du Pont De Nemours And Company
Publication of WO2009149143A1 publication Critical patent/WO2009149143A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
    • B29C66/712—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined the composition of one of the parts to be joined being different from the composition of the other part
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/737—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined
    • B29C66/7375—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined uncured, partially cured or fully cured
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/737—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined
    • B29C66/7375—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined uncured, partially cured or fully cured
    • B29C66/73755—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined uncured, partially cured or fully cured the to-be-joined area of at least one of the parts to be joined being fully cured, i.e. fully cross-linked, fully vulcanized
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/739—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/7392—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of at least one of the parts being a thermoplastic
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/739—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/7394—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of at least one of the parts being a thermoset
    • 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
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/68—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts by incorporating or moulding on preformed parts, e.g. inserts or layers, e.g. foam blocks
    • B29C70/70—Completely encapsulating inserts
    • 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
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/68—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts by incorporating or moulding on preformed parts, e.g. inserts or layers, e.g. foam blocks
    • B29C70/74—Moulding material on a relatively small portion of the preformed part, e.g. outsert moulding
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
    • C08J5/121—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives by heating
    • 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
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/10—Joining materials by welding overlapping edges with an insertion of plastic material
    • 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
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • 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
    • B29K2063/00—Use of EP, i.e. epoxy resins or derivatives thereof, 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
    • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, 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
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/24—Condition, form or state of moulded material or of the material to be shaped crosslinked or vulcanised
    • 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
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/24—Condition, form or state of moulded material or of the material to be shaped crosslinked or vulcanised
    • B29K2105/243—Partially cured
    • 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
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/24—Condition, form or state of moulded material or of the material to be shaped crosslinked or vulcanised
    • B29K2105/246—Uncured, e.g. green

Definitions

  • the adhesion of epoxy resins to polyamides is improved by adding a novolac resin to the polyamide.
  • various assemblies contain polymeric parts which made from different polymers. In some of these assemblies it may be desirable to adhere parts made from two different types of polymers to each other. It is well known in the art that most types (chemical compositions) of polymers are incompatible with other polymers, and so good adhesion between two different polymer types is often difficult to obtain. This is the case with the adhe- sion of epoxy resins to polyamides, particularly when the polyamide part is formed first, for example as by melt forming, and then the epoxy portion is cast onto a surface of the polyamide part. Oftentimes poor or no adhesion between the parts is the result. Thus an improved procedure for adhering such parts is desired.
  • This invention concerns an apparatus, comprising:
  • This invention also concerns a process for adhering a first part comprising a polyamide to a second part comprising a cured epoxy resin, comprising:
  • polyamide is polymer in which at least 70 percent of the connecting groups between repeat units are amide groups, preferably at least 80 percent, more preferably at least 90 percent, very preferably at least 95%, and especially preferably essentially all of the connecting groups are amide groups.
  • a “partially aromatic polyamide” is meant a polyamide or blend of polyamides in which at least 5 mole percent of all repeat units in the polyamide or blend of polyamides have an aromatic ring, which means thermoplastic polyamides having all repeat units containing an aromatic ring may be used. However, no more than 90 mole percent of the repeat units, preferably no than 60 mole percent of the repeat units, have an aromatic ring.
  • an aromatic ring is meant a group such as phenyl or phenylene, naphthyl or naphthylylene, biphenyl or biphenylene, or pyridyl or pyridylylene.
  • the aromatic ring is in the main chain of the polymer, i.e., is not a "side group" in the repeat unit.
  • Units in the main chain would include those derived from terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, 1 ,4- diaminobenzene, 1 ,3-diaminobenzene, 1 ,4-bis(aminomethyl)benzene, 1 ,3- bis(aminomethyl)benzene, 4,4'diaminobiphenyl, 4-aminobenzoic acid, and 3- aminobenzoic acid.
  • Repeat units with aromatic side groups include those derived from 3-phenyl-1 ,6-diaminohexane and 2-(4-pyridyl)succinic acid. If more than one polyamide is present (a blend of polyamides) then all repeat units in all polyamides are used in this calculation, whether any particular polyamide has any repeat units containing aromatic groups or not. PAPs are one type of preferred polyamides.
  • nylon-6,6 sometimes also called polyamide-6,6), nylon-6, nylon 6,12, nylon-12, nylon-10, and nylon-6,10.
  • Nylon-6,6 and nylon-6 are preferred polyamides, and nylon-6,6 is especially preferred.
  • a novolac resin is typically meant a usually substantially linear polymer produced by the reaction of an aldehyde, particularly formaldehyde, and a phenol, and during the polymer formation the phenol is present in stoichiometric excess.
  • Novolacs may be thought of as polyphenols (that is polymers which have hydroxyl groups attached directly to aromatic ring car- bon atoms) which are not crosslinked, and herein the term novolac shall mean these types of polymers. Typically they have molecular weights of 200-5000, and glass transition temperatures of 45 to 7O 0 C.
  • epoxy resin is a resinous material which, on average, contains at least two epoxy groups per molecule. Such materials are commercially avail- able and well known in the art, see for instance H. Q. Pham, et al., Encyclopedia of Polymer Science & Technology, 3 rd Ed., Vol. 9, John Wiley & Sons, New York, 2002, p. 678-804. Epoxy resins are cured using compound which have functional groups, such as amino or hydroxyl, which react with epoxy groups. The curing agent has an average of two or more of these functional groups per molecule.
  • Curing conditions for various epoxy resins with any particular curing agent may vary, but typically the (usually liquid) epoxy resin is mixed with the curing agent and then the mixture is usually heated to effect the curing reaction to form the cured epoxy resin.
  • Conditions for any particular epoxy resin/curing agent combination are generally available from their manufacturers. After curing the cured epoxy resin is crosslinked so it usually cannot be reformed, so it is almost always cured in the shape of the desired final part, unless a so-called "stock shape” is being made to be later machined to the final shape. Such curing often takes place in a mold or other similar device, sometimes under superatmospheric pressure.
  • the polyamide composition used herein comprises a novolac resin.
  • the weight percentage of the novolac resin is about 2 to about 20 weight percent, based on the total weight of the polyamide and novolac resin present, more preferably about 5 to about 15 weight percent, and especially preferably about 8 to about 13 weight percent. It is to be understood that any minimum amount may be combined with any maximum amount mentioned above to form a new concentration range.
  • Other materials may be present in the polyamide composition such as fillers, reinforcing agent, antioxidants, stabilizers, tougheners (generally rub- bers or rubbery-like polymers), antioxidants, colorants, flame retardants, crystallization accelerators, etc.
  • Preferred additives are fillers and reinforcing agents such as clays, glass fibers, milled glass, carbon fiber, carbon black, aramid fibers, wollastonite, mica, talc, and other minerals. Minerals or other fillers may be present as very small particles, for examples as so-called nano particles, whose average particle size is typically about 1 to about 500 nm.
  • Preferred fillers and reinforcing agents are glass fiber, talc, clays and mica, and glass fiber is especially preferred.
  • the filler(s) and/or reinforcing agent(s) be present as about 10 to about 60 weight percent of the total composition, more preferably about 20 to about 50 weight percent. More than one filler and/or reinforcing agent may be present, and these weight per- cents refer to the total of these materials.
  • a toughener usually a rubber or rubber-like polymer which improves the toughness of the polyamide composition.
  • Useful tougheners for polyamides are well known in the art, see for instance U.S. Patent 4,174,358 and 5,112,908, both of which are hereby included by reference.
  • the toughener has attached to it functional group which may react with the polyamide end groups, which are typically amino and and/or carboxyl.
  • Such functional groups include epoxy, carboxylic anhydride, and carboxyl.
  • the toughener is present at a concentration of about 3 weight percent to about 20 weight percent, based on the total composition, more preferably about 6 weight percent to about 15 weight percent.
  • the polyamide composition may be made by techniques usually used for making similar compositions from thermoplastics, including polyamides. Most commonly the composition may be made by melt mixing the ingredients in an apparatus such as a single or twin screw extruder, or a kneader. The polyamide is heated above its melting point in the apparatus and mixed with the other ingredients. If for instance a twin screw extruder is used all or some of the ingredients may be added at the rear of the extruder, and then ingredients not added at the rear such as reinforcing agent or plasticizers may be "side fed" along the length of the extruder. It is preferred to add the novolac resin at the rear of the extruder.
  • the polyamide composition may be formed into shaped parts by typical thermoplastic forming techniques, particularly melt forming techniques such as injection molding, extrusion, compression molding, etc. Injection molding is a preferred forming method. These methods are well known in the art.
  • the polyamide part After the polyamide part is formed it is brought into contact with the un- cured or partially cured epoxy resin and the curing of the epoxy resin is com- pleted, usually by heating. Since it will usually be desired to form the epoxy resin into a particular shape it will usually be placed in a mold or similar device.
  • the PAP part may form part of that mold (surface) so that part of the interior surface of that mold is the PAP part, and the epoxy resin contacts that surface while curing.
  • the PAP part may be completely or partially over- molded by the epoxy rein. If the PAP part is completely overmolded, it becomes encapsulated inside the epoxy resin.
  • the epoxy resin is cured while in contact with the PAP part and an assembly is formed containing both the PAP part and the epoxy part.
  • adhesion Although the adhesion may supplemented by mechanical fasteners, in- terlocking of the parts, or other devices to hold the parts together in the desired configuration. Indeed the adhesion may be used to temporarily hold the parts together until stronger means of attachment, such as mechanical means, can be applied.
  • Other factors may affect the adhesion level.
  • the PAP part surface finish for example matte or glossy, may affect the adhesion.
  • the surface morphology may be affected by molding conditions, for example higher mold temperatures often give smoother (glossier) surfaces.
  • An- other factor is the cleanliness of the PAP composition surface when brought into contact with the epoxy resin. It is well known that dirty surfaces often don't adhere as well as clean surfaces.
  • cleaning of the PAP composition surface may improve adhesion.
  • the surface may be wiped with an isopropanol containing cloth or wipe, or dipped in isopropanol, and then dried.
  • a cured or partially cured (cured enough so the part retains its shape) epoxy part is first made by standard epoxy resin molding methods. This epoxy part is then overmolded or partially overmolded with a PAP composition, for example by injection molding. The epoxy part may be cleaned or not as described above for the PAP part. The epoxy part may be completely overmolded so it is encapsulated in the PAP composition, or only part of the surface of the epoxy part is contacted with the PAP composition during the molding process. Again, these two parts are held together by adhesion, although the adhesion may supplemented by mechanical fasteners, interlocking of the parts, or other devices to hold the parts together in the desired configuration.
  • adhesion may be used to temporarily hold the parts together until stronger means of attachment, such as mechanical means, can be applied.
  • Typical uses for such an apparatus include automotive parts such as ignition components, and other electrical and electronic parts for automotive and nonautomotive uses.
  • Adhesion Procedure A Tensile bars prepared according ASTM Method D638, Type 1 bars, 0.16 cm (1/16") thick are made. These bars are cut in half perpendicular to their long axis, and the two halves form a set which will be tested together.
  • a silicone rubber "frame” is made by cutting out a piece 19.05 mm square from a sheet 1.8 mm thick.
  • a 6.2x10 mm section (6.2 mm dimension is parallel to the edge from which it is cut) is cut from this piece along one of the edges so that one has a piece resembling the letter "u" when the cutout is on the top portion of the piece.
  • the frame is then positioned at the narrower ends of a set of test pieces (see above) between the two pieces, so that the open part of the "u” is along an edge of and parallel to the long axis of both bars.
  • the open center part of the frame forms and the surfaces of the two bars form a containers into which the epoxy resin will be poured.
  • the assembly of the testing array shall be done using cotton gloves to protect the cleaned surfaces.
  • the testing array is preheated in aluminum pans (as secondary catch basins) to 12O 0 C for 2 hours.
  • the assembly should be supported so that the epoxy resin may be easily poured into cavity formed by the silicone frame.
  • the epoxy resin While preheating the testing array the epoxy resin is heated for 1 hour in a convection oven, then subjected to a vacuum at room temperature to remove gases.
  • the hardener (curing agent) is also be subjected separately to vacuum at the same time.
  • the epoxy resin and hardener are then mixed in the proper proportions. Remove gases under vacuum and place in a convection oven at 6O 0 C for 30 min.
  • the epoxy resin/hardener mixture and the testing arrays are then removed from their respective ovens and the epoxy mixture is then placed into each of the cavities formed by the silicone rubber frames by injecting the epoxy mixture into the cavities using a 10 ml syringe with a 16 gauge needle. Fill to the top of the cavities. Inject up to 5 assemblies at a time. Record the times these are done.
  • Each set of 5 (or less) is then cured in a convection oven at 9O 0 C for 150 minutes and then at 13O 0 C (second oven) for 150 minutes (these curing times and temperatures may be varied according to the epoxy resin and hardener used).
  • the arrays are allowed to cool to ambient temperature.
  • the clamps, mending plates and outer silicone pieces are removed, and the silicone rubber frame is removed by gently pulling it from between the two bars.
  • An array is then placed in a tensile testing machine and then tab ends of the array are clamped to the draw bars of the machines and the tabs are pulled apart at a rate of 0.51 cm/min (0.027min). The maximum amount of force before breaking apart of the array, and the elongation at break, are recorded. All testing is done a standard laboratory atmosphere (ASTM D618) unless otherwise noted.
  • This adhesion test which is basically a so-called lap-shear adhesion test, may or may not simulate actual use conditions, but is particularly useful for comparing the adhesion of various polymer compositions to epoxy resins.
  • Color Concentrate - A carbon black containing color concentrate in a polymer binder.
  • Lubricant A - Licomont® CaV102 lubricant available from Clariant Intl., Ltd., 4132 Muttenz, Switzerland.
  • Novolac A - A novolac resin with a number average molecular weight of about 1000 and a glass transition temperature of about 8O 0 C.
  • Polymer A A PAP copolymer made from terephthalic acid, 1 ,6- hexandiamine, and 2-methyl-1 ,5-pentanediamine, in which the molar ration of 1 ,6-hexanediamine to 2-methyl-1 ,5-pentaediamine was 1 :1.
  • the PAP had a melting point of 300 0 C.
  • Polymer B An ethylene/1 -octene copolymer grafted with 1.8 weight percent maleic anhydride.
  • the PAP had a melting point of 31O 0 C.
  • Stabilizer A - A stabilizer containing 1 part of CuI and 4 part of Kl. In the Examples unless otherwise noted all parts shown are parts by weight.
  • compositions are shown in Table 1.
  • compositions were injection molded on a 6-oz. barrel capacity machine. Melt temperatures were 325 0 C, and the mold temperature was 16O 0 C. The compositions were then tested per Adhesion Testing Procedure A. The results are shown in Table 3.
  • the PAP compositions were prepared in the same manner as in Examples 1-3 except. Compositions are shown in Table 2. Melt and mold temperatures are shown in Table 3. Table 2
  • compositions were injection molded on a Nissei FN4000 molding machine. Polymer melt and mold surface temperatures are given in Table 3. The compositions were then tested for adhesion per Adhesion Testing Procedure A. The results are shown in Table 3.
  • Epoxy resin was TCG2129A from Kyocera Chemical Corp. (Kawaguchi-city, 332-853 Japan) and the hardener (curing agent) was TCG2129B from Kyo- cera used in 100 parts epoxy resin to 28 parts hardener.
  • the resin is reported to be 90% diglycidyl ether of bisphenol-A, and that hardener is described as 99% methyltetrahydrophthalic acid anhydride and ⁇ 1 % 2-ethyl-4- methylimidazole.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Composite Materials (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Manufacturing & Machinery (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Selon la présente invention, l’adhérence de compositions de polyamide à des résines époxy durcies est améliorée lorsque la composition contient des quantités relativement faibles de résines novolaques. De préférence, la résine époxy est durcie en contact avec une partie de composition de polyamide préformée, ou bien la composition de polyamide est moulée pendant que le polyamide est en contact avec la résine époxy durcie ou partiellement durcie. De tels assemblages sont utiles dans un appareil électrique.
PCT/US2009/046064 2008-06-03 2009-06-03 Adhérence de polyamides à des résines époxy WO2009149143A1 (fr)

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US61/130,727 2008-06-03

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012532620A (ja) * 2009-07-16 2012-12-20 グラクソ グループ リミテッド 改良型抗血清アルブミン結合単一可変ドメイン

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4174358A (en) * 1975-05-23 1979-11-13 E. I. Du Pont De Nemours And Company Tough thermoplastic nylon compositions
EP0059136A2 (fr) * 1981-02-23 1982-09-01 Ato Chimie Procédé pour l'enduction de substrats métalliques à l'aide de matières plastiques et complexes métal-plastique ainsi obtenus
EP0592941A2 (fr) * 1992-10-12 1994-04-20 Kishimoto Sangyo Co., Ltd. Composition de polyamide et utilisation
US5965668A (en) * 1996-04-16 1999-10-12 Elf Atochem S.A. Polyamide injection mouldings which include an impact strength modifier that has a particular distribution in the polyamide
WO2004104102A1 (fr) * 2003-05-21 2004-12-02 E.I. Dupont De Nemours And Company Articles elabores a partir de compositions de resine de polyamide et possedant des proprietes ameliorees de barriere de permeance aux fluides

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4174358A (en) * 1975-05-23 1979-11-13 E. I. Du Pont De Nemours And Company Tough thermoplastic nylon compositions
US4174358B1 (fr) * 1975-05-23 1992-08-04 Du Pont
EP0059136A2 (fr) * 1981-02-23 1982-09-01 Ato Chimie Procédé pour l'enduction de substrats métalliques à l'aide de matières plastiques et complexes métal-plastique ainsi obtenus
EP0592941A2 (fr) * 1992-10-12 1994-04-20 Kishimoto Sangyo Co., Ltd. Composition de polyamide et utilisation
US5965668A (en) * 1996-04-16 1999-10-12 Elf Atochem S.A. Polyamide injection mouldings which include an impact strength modifier that has a particular distribution in the polyamide
WO2004104102A1 (fr) * 2003-05-21 2004-12-02 E.I. Dupont De Nemours And Company Articles elabores a partir de compositions de resine de polyamide et possedant des proprietes ameliorees de barriere de permeance aux fluides

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012532620A (ja) * 2009-07-16 2012-12-20 グラクソ グループ リミテッド 改良型抗血清アルブミン結合単一可変ドメイン

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