WO2017064227A1 - VERFAHREN ZUM SCHWEIßEN DER KUNSTSTOFFE POLYAMID- UND POLY(METH)ACRYLAT - Google Patents

VERFAHREN ZUM SCHWEIßEN DER KUNSTSTOFFE POLYAMID- UND POLY(METH)ACRYLAT Download PDF

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Publication number
WO2017064227A1
WO2017064227A1 PCT/EP2016/074655 EP2016074655W WO2017064227A1 WO 2017064227 A1 WO2017064227 A1 WO 2017064227A1 EP 2016074655 W EP2016074655 W EP 2016074655W WO 2017064227 A1 WO2017064227 A1 WO 2017064227A1
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Prior art keywords
primer
polyamide
welding
plastic
copolymer
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2016/074655
Other languages
German (de)
English (en)
French (fr)
Inventor
Pablo Walter
Norman Friedrich
Lina GONZALEZ
Hendrik Lützen
Thomas Härtig
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.)
Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to JP2018519367A priority Critical patent/JP2019501037A/ja
Priority to CN201680060616.5A priority patent/CN108136683A/zh
Priority to KR1020187013474A priority patent/KR20180070621A/ko
Publication of WO2017064227A1 publication Critical patent/WO2017064227A1/de
Priority to US15/933,906 priority patent/US10894366B2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J5/12Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
    • C08J5/121Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives by heating
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    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D125/00Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
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    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/16Laser beams
    • B29C65/1629Laser beams characterised by the way of heating the interface
    • B29C65/1664Laser beams characterised by the way of heating the interface making use of several radiators
    • B29C65/1667Laser beams characterised by the way of heating the interface making use of several radiators at the same time, i.e. simultaneous laser welding
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/16Laser beams
    • B29C65/1696Laser beams making use of masks
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/18Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated tools
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/18Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated tools
    • B29C65/20Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated tools with direct contact, e.g. using "mirror"
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/38Impulse heating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B29C65/50Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding using adhesive tape, e.g. thermoplastic tape; using threads or the like
    • B29C65/5057Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding using adhesive tape, e.g. thermoplastic tape; using threads or the like positioned between the surfaces to be joined
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/72Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by combined operations or combined techniques, e.g. welding and stitching
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/70General 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
    • B29C66/73General 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
    • B29C66/731General 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 intensive physical properties of the material of the parts to be joined
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING 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
    • B29K2033/00Use of polymers of unsaturated acids or derivatives thereof as moulding material
    • B29K2033/04Polymers of esters
    • B29K2033/08Polymers of acrylic acid esters, e.g. PMA, i.e. polymethylacrylate
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING 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
    • B29K2033/00Use of polymers of unsaturated acids or derivatives thereof as moulding material
    • B29K2033/04Polymers of esters
    • B29K2033/12Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING 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
    • B29K2077/00Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/10Homopolymers or copolymers of methacrylic acid esters
    • C08J2333/12Homopolymers or copolymers of methyl methacrylate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2425/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2425/02Homopolymers or copolymers of hydrocarbons
    • C08J2425/04Homopolymers or copolymers of styrene
    • C08J2425/08Copolymers of styrene

Definitions

  • the present invention relates to a method for welding a polyamide plastic with a poly (meth) acrylate plastic using a primer, wherein the primer synthesized from at least one styrene or styrene derivative and at least one maleic anhydride or maleic anhydride Contains derivative. Moreover, the present invention relates to welded products accordingly.
  • connections such as snapping or screwing, or gluing.
  • plastics can also be welded together. Welding is a joining process for a non-releasable, physical-physical bond of generally similar plastics, e.g. PE with PE or PA with PA. conspecific
  • Thermoplastic plastics are those polymers which do not differ substantially in terms of their molecular structure, their melting temperature, the melt viscosity and their thermal expansion coefficient and, in principle, are miscible with one another. In most cases, plastics of the same type are plastics of identical polymer base or identical plastic.
  • the object of the present invention was thus to find a simple method for welding a polyamide plastic and a poly (meth) acrylate, in particular polymethyl methacrylate plastic.
  • the connection between these different plastics through the weld should be as stable and durable as possible.
  • a primer contains at least one copolymer synthesized from at least one styrene or styrene derivative and at least one maleic anhydride or maleic anhydride derivative ,
  • the first joining partner for welding using a primer is a polyamide plastic.
  • the polyamide plastic is preferably a thermoplastic polyamide.
  • the amide-based thermoplastics include, for example, polyamide 6, a homopolymer of epsilon-caprolactam (polycaprolactam); Polyamide 1 1, a polycondensate of 1 1 -aminoundecanoic acid (poly-1 1 -aminoundecanamide); Polyamide 12, a homopolymer of omega-laurolactam (polylaurolactam); Polyamide 6.6, a homopolycondensate
  • Hexamethylenediamine and adipic acid polyhexamethylene adipamide
  • Polyamide 6.10 Polyamide 6.10, a
  • Polyamide 6.12 is a homopolycondensate of hexamethylenediamine and dodecanedioic acid (Polyhexamethylenedodecanamide) or polyamide 6-3-T, a homopolycondensate of trimethylhexamethylenediamine and terephthalic acid (polytrimethylhexamethylene terephthalamide), poly (p-phenylene terephthalamide) or poly (m-phenylene terephthalamide) of phenylenediamine and terephthalic acid, polyphthalamide PPA from various diamines and terephthalic acid and mixtures thereof.
  • Optically transparent polyamides include microcrystalline polyamides containing linear aliphatic dicarboxylic acids and cycloaliphatic diamines, amorphous polyamides containing linear aliphatic dicarboxylic acids and cycloaliphatic diamines and optionally lactams or aminocarboxylic acids containing amorphous polyamides containing terephthalic acid and cycloaliphatic or branched aliphatic diamines and optionally lactams or aminocarboxylic acids or amorphous polyamides Isophthalic acid and cycloaliphatic or linear or branched aliphatic diamines and optionally lactams or aminocarboxylic acids.
  • Suitable optically transparent polyamides are, for example, amides of dodecanedioic acid and a
  • Preferred polyamides are selected from the group consisting of polyamide 6, polyamide 6.6, polyamide 6.10, polyamide 6.12, polyamide 10.10, polyamide 1 1, polyamide 12, polyamide 10.12, polyphthalamides, optical transparent polyamides or mixtures based on these polyamides.
  • Particularly preferred polyamides are selected from polyamide 6, polyamide 6.6, polyamide 12, polyphthalamides, optically transparent polyamides and mixtures thereof, in particular polyamide 12, polyamide 6, polyamide 6.6 and mixtures thereof.
  • the polyamide plastics may also contain other components, e.g. Fillers, such as glass fibers,
  • the polyamide plastic consists of more than 40 wt .-%, in particular more than 60 wt .-%, preferably more than 70 wt .-%, preferably more than 90 wt .-% of said polyamides, respectively based on the total polyamide plastic (with fillers).
  • the polyamide plastic is more than 90 wt .-%, in particular more than 95 wt .-%, preferably more than 98 wt .-% of said polyamides, each based on the polymer content of the polyamide resin (total Polyamide plastic without fillers).
  • the polyamide plastics have a content of said polyamides of 50-90 wt .-%, in particular 60-80 wt .-%, in each case based on the total polyamide plastic (with fillers).
  • Poly (meth) acrylate is a synthetic, preferably transparent, thermoplastic material.
  • Preferred poly (meth) acrylates are composed of 50 to 100 wt .-%, in particular 70 to 100 wt .-% acrylate and / or methacrylate, wherein the (meth) acrylate units preferably with a C1 to C12 alkyl radical, in particular C1- C4, preferably methyl are esterified.
  • the notation poly (meth) acrylate indicates that the polymer is composed of acrylate and / or methacrylate. Respectively. the notation (meth) acrylate indicates that it may be both an acrylate and a methacrylate. Most preferably, the poly (meth) acrylate is a
  • Polymethyl methacrylate (PMMA, colloquially also acrylic glass or Plexiglas).
  • Preferred polymethyl methacrylates are from 50 to 100% by weight, in particular from 70 to 100% by weight.
  • Polymethylmethacrylats are primarily (meth) acrylic acid, in particular acrylic acid, and their alkyl esters having 1 to 12 carbon atoms, in particular 1 to 4 carbon atoms in the alkyl radical, and acrylic and / or methacrylonitrile, acrylic and / or methacrylamide, styrene and / or maleic anhydride into consideration. Preference is given to thermoplastically and thermoelastically deformable plastics. Preferred thermoplastic polymethyl methacrylate plastics have
  • thermoplastic poly (meth) acrylate, in particular polymethyl methacrylate plastics have a weight average molecular weights (weight average Mw) of less than 2,000,000 g / mol, in particular less than 1,000,000 g / mol, preferably less than 500,000 g / mol.
  • Particularly preferred thermoplastic poly (meth) acrylate, in particular polymethyl methacrylate plastics have weight average molecular weights (weight average Mw) of 50,000 g / mol to 250,000 g / mol, z. B. about 100000 g / mol to about 180000 g / mol for injection molding.
  • the poly (meth) acrylate, especially the polymethyl methacrylate plastics may also contain other components, e.g. Fillers, such as glass fibers, pigments, dyes, rheology aids, mold release agents or stabilizers.
  • the poly (meth) acrylate, in particular the polymethyl methacrylate plastic to more than 90 wt .-%, in particular more than 95 wt .-%, preferably more than 98 wt .-% of said poly (meth) acrylates, in particular the said polymethyl methacrylates, in each case based on the polymer content of
  • Poly (meth) acrylate plastic total poly (meth) acrylate plastic without fillers.
  • the polymethyl methacrylate plastic to more than 90 wt .-%, in particular more than 95 wt .-%, preferably more than 98 wt .-% of said poly (meth) acrylate, in particular the polymethyl methacrylate, respectively on the whole
  • the primer contains at least one copolymer which is known as copolymerized monomers contain at least one styrene or styrene derivative and at least one maleic anhydride or maleic anhydride derivative.
  • the primer is a welding aid, which is preferably applied as a pretreatment layer on at least one of the surfaces to be welded of the substrates in the region of the joining zone.
  • the primer is not to be understood as an adhesive, cleaning agent or the like, but the primer is a tool for welding, whereby the joining partners in the joining zone (or welding zone) are made compatible with each other and so in the joining zone during joining a material and non-positive connection arises between the substrates to be welded.
  • the experiments have shown that by using an appropriate primer containing a copolymer of the invention, the plastics polyamide and poly (meth) acrylate could be compatibilized during welding in the joint seam and thus a stable and durable connection can be achieved. Without the use of an appropriate primer, little or no strength of the welded joint could be achieved.
  • the bonded substrates preferably have a tensile strength of more than 2 MPa, in particular more than 4 MPa. Tensile strength is determined by means of a tensile speed of 5 mm / s according to the experimental procedure described in the experiments.
  • the at least one copolymer in the primer is synthesized at least from the monomers styrene and maleic anhydride.
  • the monomers styrene or styrene derivative such as alpha- methylstyrene
  • maleic anhydride or maleic anhydride derivative the styrene or styrene derivative
  • Copolymer also contain other monomers in copolymerized form. Preferably contains
  • Copolymer Monomers selected from the group of acrylates and methacrylates (together (meth) acrylates), in particular (meth) acrylates having an alkyl radical having 1 to 12 carbon atoms, preferably 1 to 4 carbon atoms, preferably methyl (meth) acrylate.
  • functional monomers with functionalities such as epoxide or
  • Isocyanate groups carboxyl or amine groups, but also alkoxysilane, are used.
  • the copolymer consists of copolymerized styrene and maleic anhydride. In another particular embodiment, the copolymer consists of copolymerized styrene, maleic anhydride and methyl methacrylate. In these variants, the monomers can be used in different molar ratios.
  • the molar ratio of styrene to maleic anhydride is 1: 0.01 to 1: 2, preferably 1: 0.05 to 1: 1, more preferably 1: 0.1 to 1: 0.3.
  • Copolymer with copolymerized acrylate and / or methacrylates, in particular methyl acrylate and / or methyl methacrylate is the molar ratio of styrene to (meth) acrylate
  • the copolymers can be synthesized from the monomers in a known manner.
  • the copolymers may be grafted in a polymer-analogous reaction.
  • Particularly preferred reactants for grafting are alcohols, thiols, amines, isocyanates, anhydrides,
  • Carboxylic acids in particular alcohols, preferably alcohols having 1 to 6 carbon atoms, such as methanol and isobutanol.
  • alcohols preferably alcohols having 1 to 6 carbon atoms, such as methanol and isobutanol.
  • maleic anhydride units in the polymer with the reactants in particular be esterified by alcohols.
  • the maleic anhydride groups react or esterify only partially, in particular less than 70% of the maleic anhydride groups.
  • maleic anhydride groups are not reacted and continue to be present as anhydride groups.
  • the maleic anhydride groups are not reacted and continue to be present as anhydride groups.
  • Maleic anhydride groups are also partially hydrolyzed. Complete reaction of the maleic anhydride groups can lead to a reduction in the strength of the resulting weld joint.
  • copolymers which have a maleic anhydride content of greater than or equal to 0.1% by weight, in particular greater than or equal to 0.5% by weight, preferably greater than or equal to 4% by weight, particularly preferably greater than or equal to 8% by weight. based on the copolymer.
  • the copolymers advantageously contain a maleic anhydride content of 0.1-50% by weight, in particular 0.5-40% by weight, preferably 4-30% by weight, particularly preferably 8-26% by weight. based on the copolymer.
  • Maleic anhydride content has particularly good strengths of the welded connection.
  • copolymers which have a glass transition temperature Tg (by means of DSC at a heating rate of 10 K / min under nitrogen, in particular in accordance with DIN EN ISO 1 1357-1: 2010-3 and DIN EN ISO 1 1357-2: 2014-). 07 determined) of greater than 30 ° C, in particular greater than 80 ° C, more preferably greater than 100 ° C.
  • copolymers having a corresponding glass transition temperature improve the mechanical properties of the weld at elevated temperatures.
  • the copolymers have a weight-average molecular weight Mw of greater than or equal to 5000 g / mol, in particular greater than or equal to 50,000 g / mol, preferably greater than or equal to 100,000 g / mol.
  • the copolymers preferably have a weight-average molecular weight M w in the range from 5000 to 200 000 g / mol, in particular from 50 000 to 100 000 g / mol, preferably from 100 000. 500000 g / mol.
  • Copolymers having a corresponding weight average molecular weight have a positive effect on the brittleness and strength of the resulting compound.
  • the weight average molecular weight can be determined by GPC against a polystyrene standard.
  • the primer may preferably contain at least one further polymer.
  • the at least one further polymer or copolymer is preferably compatible with at least one of the two plastics to be welded and with the primer copolymer.
  • the primer comprises at least one polyamide polymer and / or a poly (meth) acrylate, in particular polymethyl methacrylate polymer, preferably in each case those specified above.
  • the primer contains at least one polymethyl methacrylate polymer.
  • a polymer is preferably used, which to a, in particular to be joined plastics and in particular also to the abovementioned first inventive polymer a weighted square distance of the Hansen parameters (R a ) 2 of less than 22 MPa, in particular less than 17 MPa, preferably of less than 15 MPa, more preferably of less than 12 MPa.
  • the weighted quadratic distance of the Hansen parameters (R a ) 2 is determined according to the following formula:
  • ⁇ D is the Hansen parameter for the dispersion forces
  • is the Hansen parameter for the polarity
  • is the Hansen parameter for the hydrogen bonds.
  • the determination of the values of the individual Hansen parameters ⁇ D, ⁇ and ⁇ H for the respective plastics or polymers is carried out according to the book "Hansen Solubility Parameters: A User 's Handbook" by Charles M. Hansen (second edition: Taylor & Francis Group; 2007; ISBN-10 0-8493-7248-8).
  • the Hansen parameters can preferably be taken from the supplied database with the HSPIP program (4th Edition 4.1.07), or, if not available, with the included "DIY” functionality of the program, preferably using the supplied neural network as described in the help.
  • the HSPIP program is available through the company Steven Abbott TCNF Ltd.
  • the at least one poly (meth) acrylate, in particular polymethyl methacrylate polymer in the primer has weight-average molar masses (weight average Mw) of greater than 50,000, in particular greater than 100,000 g / mol.
  • the poly (meth) acrylate, in particular polymethyl methacrylate polymers in the primer on a weight average molecular weight (weight average Mw) of less than 2,000,000 g / mol, in particular less than 1,000,000 g / mol, preferably less than 500,000 g / mol.
  • Polymethyl methacrylate polymers in the primer have weight average molecular weights (weight average Mw) of 50,000 to 250,000 g / mol.
  • the content of the further polymer, in particular of the polymethyl methacrylate polymer, on the primer is preferably 1-40% by weight, in particular 5-30% by weight, particularly preferably 10-20% by weight, in each case based on the total weight of the primer ,
  • Polymer, in particular of the polymethyl methacrylate polymer, at the polymer content of the primer is preferably 5 to 70 wt .-%, in particular 20 to 60 wt .-%, particularly preferably 30 to 50 wt .-%, in each case based on the total polymer content of the primer (primer without solvent and without fillers).
  • the primer may also contain a solvent, in particular an organic solvent.
  • the primer contains a solvent content of 10 to 90 wt .-%, in particular 50 to 85 wt .-%, particularly preferably 60 to 80 wt .-%, each based on the total weight of the primer.
  • Suitable solvents are all common solvents, such as, for example, water, alcohols, ketones, such as methyl isobutyl ketone (MIBK) or cyclohexanone (CH), ethers, such as diethyl ether or tetrahydrofuran (THF), esters, such as ethyl acetate, or carbonates, such as dimethyl or dipropyl carbonate , or mixtures thereof.
  • MIBK methyl isobutyl ketone
  • CH cyclohexanone
  • ethers such as diethyl ether or tetrahydrofuran (THF)
  • esters such as ethyl acetate
  • carbonates such as dimethyl or dipropyl carbonate , or mixtures thereof.
  • the primer contains organic solvents.
  • Particularly preferred solvents are solvents having a vapor pressure at 20 ° C. of from 1 to 600 hPa, in particular from 2 to 200 hPa, particularly preferably from 5 to 20 hPa.
  • the primer contains a solvent selected from tetrahydrofuran, Mehylisobutylketon, cyclohexanone and mixtures thereof, more preferably, the primer contains tetrahydrofuran or a mixture of Mehylisobutylketon and cyclohexanone. If a mixture of Mehylisobutylketon and cyclohexanone is used as a solvent, this mixture preferably contains 10-50 wt .-%, in particular 20-35 wt .-% cyclohexanone, each based on the total mixture of solvent.
  • the total polymer content of the primer is preferably 10-90% by weight, in particular 15-50% by weight, particularly preferably 20-40 Wt .-%, each based on the total weight of the primer.
  • the total polymer content corresponds to the content of all polymers used in the primer, in particular the
  • Copolymers of the invention and the other polymers described above.
  • the primer is in the form of an aqueous
  • the copolymer according to the invention or, if present, the further polymers are emulsified or dispersed in water.
  • the total polymer content of the primer is preferably 5-90% by weight, in particular 10-70% by weight, particularly preferably 20-55% by weight, in each case based on the total weight of the primer.
  • the polymer component consists essentially only of the copolymer according to the invention and the optionally present above-mentioned further polymer, in particular only of the copolymer according to the invention.
  • the term "substantially from” is understood according to the invention when the
  • Polymer component to more than 95 wt .-%, preferably more than 97 wt .-%, most preferably more than 99 wt .-% of the copolymer according to the invention and optionally present above further polymer, in particular only from the inventive copolymer.
  • the primer may contain further components, such as, for example, fillers, (fluorescence) dyes and pigments, rheological aids defoaming agents,
  • the primer is preferably substantially free of other components, particularly substantially free of any other components.
  • the term "substantially free of” is understood according to the invention when the primer less than 5 wt .-%, preferably less than 1 wt .-%, most preferably less than 0.1 wt .-% of the respective substances, in particular do not contain the respective substances.
  • a primer is used, wherein the primer contains at least one copolymer synthesized from at least one styrene or styrene derivative and at least one maleic anhydride or maleic anhydride derivative.
  • the primer is used in this method as an aid for the welding of the two plastics polyamide and poly (meth) acrylate by respective melting.
  • a compatibility between the two joining partners can be produced, whereby a stable and durable cohesive connection between the two plastics can be produced.
  • the primer can be applied by a variety of methods on the surface of one or both joining partners. For example, the application can be carried out by a metering device, by a needle and dosing robot, by injection molding, by extrusion, by film application, by application as a hotmelt, by spraying, by brushing or by dipping.
  • the primer When applying the primer can be applied either only on one surface or on both surfaces of the substrates to be welded.
  • the primer is only applied to one surface, in particular the polyamide surface.
  • the foil In the case of welding by means of a foil, the foil is placed between the substrates.
  • the primer is preferably dried after application to one or both surfaces until the solvent has evaporated so far that a non-sticky, dimensionally stable primer layer is formed.
  • the primer is weldable after a few seconds and up to several weeks.
  • the primer is dried after application for at least one hour, preferably for at least 12 hours.
  • the application is preferably carried out on one or both surfaces of the substrates to be welded in such a way that the primer has a layer thickness of 1 ⁇ to 5000 ⁇ , in particular 10-3000 ⁇ , preferably 50-1000 ⁇ , particularly preferably 100-500 ⁇ . If a solvent was included in the primer, the layer thickness refers to the solvent-dried primer.
  • the substrates to be welded can be joined to one another using a customary welding method.
  • the welding of plastics is generally carried out by a local plasticization of the joining partners in the joining plane and the joining under pressure.
  • the process parameters are to be selected such that a pronounced
  • Crushing the melt leads to an optimal connection of the joining partners in the joining plane.
  • the heating can be done by convection, contact heating, radiation or friction.
  • the different energy input for plasticizing can be done in a variety of ways and has led to various processes for welding plastics. Suitable welding methods are, for example:
  • Heating element welding [HE] hot plate welding
  • Ultrasonic Welding (Ultrasonic welding) Heating by friction, a transverse wave in the ultrasonic range leads to a warming in the boundary layer, one-step process
  • Vibration welding (Friction welding: Linear, Orbital, Spin, Angle)
  • Laser welding contour, simultaneous, quasi-simultaneous, mask
  • the above-mentioned welding methods may be combined, such as infrared welding with vibration welding.
  • Welding method selected from heating element welding, thermal contact or
  • Heat impulse welding hot gas or hot gas welding, microwave or
  • Induction welding Laser stump or laser transmission welding, infrared welding, ultrasonic welding, and combinations thereof, in particular selected from
  • Particularly preferred is a method for materially joining the two plastics using the primer, comprising the following steps.
  • Bonding the first joining zone to the second joining zone in particular by using conventional welding methods of plastics such as, for example, infrared welding, heating element welding, hot gas welding, vibration welding, ultrasonic welding.
  • plastics such as, for example, infrared welding, heating element welding, hot gas welding, vibration welding, ultrasonic welding.
  • Convection heating welding by hot gas
  • radiation heating beam welding
  • heating by friction welding by movement
  • a primer is used which is selected and adapted to the process such that application to a heated and / or hot joining zone having a temperature which is lower than the decomposition temperature of the polymers in the primer has no effect on the internal chemical crosslinking of the primer has.
  • preheating by means of irradiation, in particular
  • Infrared radiation or laser radiation may be used to preheat the first joining zone.
  • a heating element or a heated tool may be used to preheat the first joining zone.
  • a preheating in an oven or a heated room is conceivable. It is conceivable preheating the entire plastic and thus also said joining zone. Alternatively or additionally, however, it is also possible to preheat only the joining zone itself.
  • Preheating to the plastic in particular to the preheating first joining zone, in particular the heat-emitting region of the heating device or the heat-releasing region of the heating device or to be preheated effective surface of the heater or the opposite of the first joining zone region of the heater in a range of 0.5 mm to 100 mm, preferably in the range of 1 mm to 60 mm.
  • heating takes place through and / or upon contacting, in particular of the first joining zone, by the heating element of the heating device.
  • the thickness of the melt layer in a preferred embodiment is preferably in the range of 0.05 mm to 6 mm, particularly preferably in the range of 0.1 mm to 5 mm.
  • Such a melt layer can lead to better adhesion and / or diffusion and / or interaction of the molecules and, in conjunction with some flow, to a better bonding layer. If the boundary layer of the first plastic is in the molten state, interactions with the primer can occur, including chemical bonds.
  • the melt layer may in particular be dependent on the Component geometry and the respective component design.
  • Process parameters set and / or selected so that there is no deformation of the components are preferably provided by suitable measures and / or method steps. It is particularly conceivable to preheat the primer to the
  • thermoplastic primer To reduce temperature difference between the preferably thermoplastic primer and the first joining zone. This can counteract, for example, the rapid cooling of the first joining zone between the process steps.
  • a step is preferably carried out before the step of preheating the first joining zone
  • Pretreatment of the first joint zone Pretreatment of the first joint zone.
  • a pretreatment of the second joining zone can also be carried out.
  • a possible pre-treatment for example, the cleaning by means of a solvent or an example, alkaline plastic cleaner conceivable.
  • a mechanical pre-treatment can be used, in particular by means of scratching, sanding, brushing or blasting.
  • Possible chemical pretreatments are in particular the pickling or the use of reactive gases.
  • the use of a thermal, chemical or / and physical pretreatment may prove useful, in particular by means of gas flame or plasma arc.
  • an electrical pretreatment for example, the cleaning by means of a solvent or an example, alkaline plastic cleaner conceivable.
  • a mechanical pre-treatment can be used, in particular by means of scratching, sanding, brushing or blasting.
  • Possible chemical pretreatments are in particular the pickling or the use of reactive gases.
  • the use of a thermal, chemical or / and physical pretreatment may prove useful, in particular by means
  • Joining zone of an electric corona discharge is exposed so that arise on the corresponding surface polar molecules.
  • Another possibility is the plasma treatment, preferably using a plasma nozzle for the pretreatment of the joining zone, in particular in order to achieve activation and / or purification of the corresponding surface. Nevertheless, coating by means of plasma can prove to be expedient.
  • a pretreatment of flaming the joining zone to increase the surface tension of suitable plastics is the irradiation by means of UV rays, electron beams, radioactive rays or by means of laser.
  • the pretreatment can take place in the form of a coating, in particular by means of a coating or a bonding agent.
  • a pretreatment of the first plastic or the joining zones of the first plastic at a greater time interval before preheating is also conceivable.
  • the order of the primer is conceivable in different ways.
  • the application is conceivable by means of an automated application aid, in particular by means of a dosing robot.
  • the same can be equipped with a needle and / or a height sensor in order to carry out complex dosages.
  • the order of the primer can be made by injection molding, by the primer in a Injection molding machine plasticized and injected into the mold containing the first plastic with the first joining zone under pressure.
  • a film application is conceivable, wherein in a first step by means of film blowing or flat film extrusion first a film of the primer is produced.
  • the film can be cut into any shape, for example by means of a cutting or punching process, and applied to the first joining zone in a further step after said preheating.
  • the use of films / plates having a thickness in the range of 1 ⁇ - 5000 ⁇ has proved to be useful.
  • Further conceivable application possibilities are extrusion welding, in which the primer is present in the form of a welding wire or can be melted in an extruder and applied in melt to the first joining zone.
  • the provision of the primer in the form of a welding wire is possible to allow application by hot air welding.
  • Another possibility is the application of the primer by means of a spray process.
  • a pretreatment and / or preheating and / or locally different temperature of the injection mold is possible.
  • other, known in the art and suitable for the specific application order types are conceivable.
  • a further advantage is the further heating or heating of the first joining zone during the application of the primer, in particular in order to avoid a temperature drop of the first joining zone between the preheating and the application of the primer.
  • This may be done by the preheating step described above, which may be continued during the job for the sake of simplicity.
  • additional heating is possible, in particular by means of a further method step.
  • it may prove to be expedient to carry out a simultaneous heating of the first joining zone, for example by simultaneous irradiation of the first joining zone with radiation, forced convection, contact heating during the order in order to avoid a temperature drop of the first joining zone after preheating.
  • Connecting layer is arranged with a thickness in the range of 1 ⁇ to 5 mm, preferably in the range of 10 ⁇ to 3 mm on the first joining zone.
  • the thickness of the connecting layer is to be understood as the material thickness of the connecting layer on the first joining zone.
  • Another advantage is the application of the primer by means of a metering device to the first joining zone with relative movement between the first joining zone and the metering device, wherein by means of a heater, the first joining zone, on which the primer is applied, under relative movement between the first joining zone and heater, before the order the primer is preheated, wherein the order of the primer via the metering device takes place in the preheated state of the first joining zone. It has proved to be particularly advantageous that the heater in the
  • the heating device of the metering device preferably leads in a defined and constant distance.
  • the primer by means of a metering device to the first joining zone with relative movement of metering device and first joining zone in the range of 10 mm / min to 100 m / min, preferably in the range of 10 mm / min to 30 m / min is applied, wherein by means of a heating device said joining zone, on which the primer is applied, is preheated with relative movement of the heating device and the first joining zone before application of the primer, wherein the heating device of the metering device or a nozzle of the
  • a coating unit consisting of metering device and heater.
  • a coating unit can be understood in particular to be a unit which provides a firm connection between heating device and metering device, so that the heating device of the metering device leads in preferably a defined and constant distance during the relative movement to ensure that the first joining zone immediately before the application the primer is preheated.
  • Metering device can be understood as two completely separate or separated modules, however, enter the same or substantially the same relative movement with respect to the plastic to ensure that the job site of the primer is preheated immediately prior to the application of the primer.
  • the heating device and the metering device assume a substantially identical primary relative movement or basic direction with respect to the plastic, however, at least one of the two mentioned devices experiences additional relative movement with respect to the plastic in addition to the said primary relative movement.
  • the heating device and / or the metering device may undergo one or more secondary relative movements in addition to the primary relative movement, in which, for example, the application of the primer can take place.
  • the Heating device and / or the metering enter or experience a circular relative to the primary relative movement or meandering secondary relative movement.
  • the plastic on one side or the heater and metering device or both devices can be moved together as a coating unit on the other side. It is possible that the heating device and metering device or both devices together as a coating unit on one side or the plastic resting on the other side or be moved in each case with the moving part in a different direction.
  • a primary relative movement takes place at a speed in a range of 10 mm / min to 100 m / min, preferably in the range of 10 mm / min to 30 m / min, so that, for example, in particular by suitable design of the heater as possible give short residence times of the plastic within the heating surface of the heater, in particular in a range of 1 -60 s.
  • This can be understood as meaning the area or the space around the heating device which has an influence on the temperature in the sense of a temperature increase, that is, a preheating of the first joining zone of the first plastic. For example, too high heating and plastic damage or
  • a bus interface in particular a Profibus, or a real-time Ethernet interface.
  • a pretreatment of the second joining zone can be carried out before the step of contacting the second joining zone with the primer layer.
  • all of the above-described techniques for a pretreatment are conceivable.
  • pretreatment of the second plastic or the joining zones of the second plastic at a greater time interval before contacting For example, it is conceivable that the pre-treatment already in the context of the manufacturing process of the second plastic
  • the pretreatment of the second plastic may also include the application of the primer to the second joining zone. In this case, preferably also a preheating the second joining zone before applying the primer conceivable.
  • the above statements are also preferred at this point.
  • Heating element welding and / or thermal contact welding and / or heat pulse welding by friction, in particular ultrasonic, friction / vibration or high-frequency welding;
  • Microwave or induction welding by convection, such as hot gas or hot gas welding; by means of radiation, for example infrared, laser stump or
  • a further subject of this invention are articles or products produced according to the process of the invention.
  • the subject of this invention is the use of a primer according to the invention for the welding of a polyamide plastic with a poly (meth) acrylate plastic.
  • PA polyamide
  • PA 6 polycaprolactam, Durethan BKV30
  • PA 6.6 poly (N, N'-hexamethylene adipamide); Ultramid A3K
  • PMMA poly (methyl methacrylate)
  • Peroxide Luperox A75 (75% by weight dibenzoyl peroxide, 25% by weight water)
  • MIBK methyl isobutyl ketone
  • Copolymer SM1 styrene-maleic anhydride copolymer with 15 wt .-% MAH and Mw 170000 g / mol
  • Copolymer SM2 styrene-maleic anhydride copolymer with 8 wt .-% MAH and Mw 250,000 g / mol
  • Copolymer SM3 styrene-maleic anhydride copolymer with 26 wt .-% MAH and Mw 180000 g / mol
  • Copolymer SM4 styrene-maleic anhydride copolymer; Mw 180000 g / mol, partially esterified with isobutyl / methyl
  • IR infrared welding
  • IR-VIB infrared / vibration welding
  • US ultrasonic welding
  • the composition of the primers can be taken from the following table in g.
  • the primers were added to the surface (130 mm ⁇ 3 mm) at room temperature
  • the primer was dried for 24 hours at room temperature with solvent. After drying, the thickness of the primer was about 0.2 mm.
  • the pre-dried plastic components were welded with a geometry of 130 mm x 68 mm x 3 mm on impact with the 130 mm x 3 mm surface.
  • the tensile strength was determined at room temperature at a pulling speed of 5 mm / s.
  • the PA plastic substrate was coated with the primer 7.
  • the plastics PA 6.6 and PMMA 2 were connected by manual heating element welding at a temperature of about 280 ° C with a heating time of 15 seconds for the PMMA and 45 seconds for the PA 6.6.
  • the samples were then stored at a temperature for a period of time and then after further storage at room temperature for 24 hours the tensile strength test

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Laminated Bodies (AREA)
PCT/EP2016/074655 2015-10-16 2016-10-14 VERFAHREN ZUM SCHWEIßEN DER KUNSTSTOFFE POLYAMID- UND POLY(METH)ACRYLAT Ceased WO2017064227A1 (de)

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JP2018519367A JP2019501037A (ja) 2015-10-16 2016-10-14 ポリアミドプラスチックとポリ(メタ)アクリレートプラスチックとを溶接する方法
CN201680060616.5A CN108136683A (zh) 2015-10-16 2016-10-14 焊接聚酰胺和聚(甲基)丙烯酸酯塑料的方法
KR1020187013474A KR20180070621A (ko) 2015-10-16 2016-10-14 폴리아미드 및 폴리(메트)아크릴레이트 플라스틱의 용접 방법
US15/933,906 US10894366B2 (en) 2015-10-16 2018-03-23 Method for welding polyamide and poly(meth)acrylate plastics

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US20180208726A1 (en) 2018-07-26
EP3156211A1 (de) 2017-04-19
CN108136683A (zh) 2018-06-08
KR20180070621A (ko) 2018-06-26
EP3156211B1 (de) 2018-09-26

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