EP3390562A1 - Article adhésif autoporteur pour collages structuraux - Google Patents

Article adhésif autoporteur pour collages structuraux

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Publication number
EP3390562A1
EP3390562A1 EP16819862.0A EP16819862A EP3390562A1 EP 3390562 A1 EP3390562 A1 EP 3390562A1 EP 16819862 A EP16819862 A EP 16819862A EP 3390562 A1 EP3390562 A1 EP 3390562A1
Authority
EP
European Patent Office
Prior art keywords
silane
polymer
adhesive
groups
functional
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP16819862.0A
Other languages
German (de)
English (en)
Inventor
Rui Xu-Rabl
Matthias GÖSSI
Jürgen Finter
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.)
Sika Technology AG
Original Assignee
Sika Technology AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sika Technology AG filed Critical Sika Technology AG
Publication of EP3390562A1 publication Critical patent/EP3390562A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C09J171/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F36/06—Butadiene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F36/08—Isoprene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions 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; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
    • C09J109/02—Copolymers with acrylonitrile
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins

Definitions

  • the invention is in the field of adhesive bodies, in particular in the form of adhesive tapes, which are in particular so dimensionally stable that they are not
  • the invention relates to a method for producing such adhesives, which consists of a corresponding
  • Composition are formed, as well as a method for bonding substrates, in which the adhesive body between the substrates attached and, preferably, with heating, is cured.
  • Structural adhesives in particular epoxy-based, have long been known in the art and are, for example, under the
  • the adhesive tapes mentioned above have the advantage that they can be applied by hand.
  • the adhesive applied to the substrate is subject to the same requirements in terms of stability as the conventional structural adhesives.
  • the addition of thixotropic agents is also required here.
  • Intrinsic viscosity of the structural adhesive at the application temperature is high, to the detriment of impairing the properties of the structural adhesive
  • EP 2 570 450 A1 describes shape memory materials based on heat-curing structural adhesives and chemically crosslinked silane-functional elastomers.
  • the chemically cross-linked elastomers used in EP 2 570 450 A1 are, in particular, silane-modified polyethylene or polypropylene glycols.
  • these polyglycols have the disadvantage that they are soluble in the cured adhesive and affect its mechanical properties.
  • structural adhesives which, on the one hand, have a sufficiently high viscosity, even at elevated temperatures, so that the adhesive does not run off or drip off the substrate.
  • the adhesives should, if possible, require only small amounts or no thixotropic agents which impair the adhesive properties of the pure adhesive.
  • Such adhesives could become self-supporting adhesive bodies, in particular in the form of
  • Adhesive tapes are processed and so would the use of Avoid supporting substrates and associated compatibility problems.
  • the present application addresses this need.
  • the object of the present invention is therefore to specify a suitable composition for producing a self-supporting adhesive body which can be used for structural bonding, in particular in the form of adhesive tapes, which overcomes the disadvantages of the prior art and can in particular be produced without the use of thixotropic agents.
  • the adhesive body should have properties with those of over
  • Cartridges to be applied structural adhesives are comparable.
  • compositions according to claim 1 can be solved. It has been found, in particular, that self-supporting adhesive bodies, in particular in the form of adhesive tapes, can be produced with the specified compositions, which, in particular with respect to properties such as the impact peel strength and the tensile shear strength, in comparison to
  • the present invention relates in a first aspect a
  • a composition comprising at least one structural adhesive and at least one chemically crosslinked elastomer based on a silane-functional non-polar polymer.
  • the chemically crosslinked elastomer is preferably present as a penetrating polymer network in the structural adhesive.
  • structural adhesive is a curable composition containing crosslinkable organic compounds referred to in the
  • Curing developed a high adhesion (adhesion) and internal strength (cohesion), so that it is suitable for the structural connection of adherends, for example in vehicle construction.
  • polymer on the one hand comprises a collective of chemical
  • Macromolecules from polyreactions i. Compounds obtained by reactions, such as additions or substitutions, of functional groups on given macromolecules which may be chemically uniform or chemically nonuniform.
  • the term also includes so-called prepolymers, that is, reactive oligomeric pre-adducts whose functional groups are involved in the construction of macromolecules.
  • silane denotes compounds which on the one hand at least one, usually two or three, via Si-O bonds, directly to the
  • silanes are the ones having bound organic radical.
  • silanes are the ones having bound organic radical.
  • silane group denotes the silicon-containing group bonded to the silane-bonded organic group via the Si-C bond
  • Organosilanols ie, organosilicon compounds containing one or more silanol groups (Si-OH groups) and, by subsequent condensation reactions, organosiloxanes, ie, organosilicon compounds containing one or more siloxane groups (Si-O-Si groups).
  • silane-functional refers to compounds which have silane groups.
  • silane-functional polymers are accordingly polymers which have at least one silane group.
  • silanes silanes whose organic radical has an amino group, a mercapto group or a hydroxy group
  • secondary aminosilanes aminosilanes aminosilanes are called which are secondary aminosilanes
  • the term "pervasive polymer network” is used in accordance with the definition of a “semi-interpenetrating polymer network” (SIPN) according to IUPAC Compendium of Chemical Terminology, 2nd Edition (1997). Accordingly, the SIPN comprises at least one network and at least one linear or
  • the elastomer forms the network while the polymer is part of the structural adhesive.
  • chemically crosslinked elastomer is meant an elastomer which is crosslinked via covalent chemical bonds the crosslinking of a thermoplastic elastomers on physical
  • a chemically crosslinked elastomer differs from a thermoplastic elastomer in that it swells in a suitable solvent but is not dissolved. On the other hand, a thermoplastic elastomer dissolves completely in a suitable solvent.
  • the presence of a chemically crosslinked elastomer can be determined, for example, on the basis of ASTM D 2765.
  • the structural adhesive is in particular a
  • thermosetting structural adhesive which is preferably a
  • Curing temperature in the range of 120 ° C to 220 ° C, in particular 160 ° C to 200 ° C, having. Is it the structural adhesive is a thermosetting
  • the structural adhesive is a thermosetting epoxy resin composition comprising at least one epoxy resin and at least one epoxy resin curing agent which is activated by elevated temperature.
  • the epoxy resin has, on average, more than one epoxide group per molecule and, in particular, is an epoxy liquid resin or a mixture of an epoxy liquid resin with a solid epoxy resin.
  • epoxy liquid resin is well known to the epoxy expert and is in the
  • the glass transition temperature T g of solid resins is above room temperature (23 ° C).
  • Preferred liquid epoxy resins, which can be used in particular together with a solid epoxy resin, have the formula (I).
  • the substituents R 1 and R 2 are again, independently of one another, either H or CH 3 .
  • the index r stands for a value of 0 to 1.
  • r stands for a value of ⁇ 0.2.
  • liquid epoxy resins include diglycidyl ethers of bisphenol A (DGEBA), bisphenol F and bisphenol A F.
  • DGEBA diglycidyl ethers of bisphenol A
  • a / F refers to a mixture of acetone with
  • Formaldehyde which is used as starting material in its preparation.
  • liquid epoxy resins are, for example, under the trade names Araldite ® GY 250, Araldite ® PY 304, Araldite ® GY 282 from Huntsman International LLC, or DER ® 331 or DER ® 330 from Dow Chemical Company, or under the trade name Epikote TM 828 or Epikote TM 862 from Momentive
  • Preferred solid epoxy resins have the formula (II).
  • substituents R 1 and R 2 are each independently either H or CH 3. Furthermore, the index s stands for a value of> 1,
  • Preferred solid epoxy resins have a glass transition temperature T g in the range of 23 ° C to 95 ° C, in particular from 30 ° C to 80 ° C, preferably from 35 ° C to 75 ° C, on.
  • Such solid epoxy resins are, for example
  • the epoxy resin which is used as one of the starting compounds in structural adhesive can also be a solid epoxy resin.
  • radical X is a hydrogen atom or a methyl group.
  • radical Y is -CH 2 - or a radical of the formula (IV).
  • the index z stands for a value from 0 to 7, in particular for a value of> 3.
  • Epoxy resins are sold under the trade names EPN or ECN and Tactix ® 556 from Huntsman International, LLC, or through the product series DEN TM from Dow Chemical Company, are commercially available.
  • the epoxy resin is an epoxy liquid resin of formula (I).
  • the thermosetting resin is an epoxy liquid resin of formula (I).
  • Epoxy resin composition both at least one liquid epoxy resin of the formula (I) and at least one solid epoxy resin of the formula (II).
  • the proportion of epoxy resin is preferably 2 to 95 wt .-%
  • the curing agent for epoxy resins is a compound selected from the group consisting of dicyandiamide, guanamines, guanidines, aminoguanidines and their derivatives; Substituted ureas, in particular 3- (3-chloro-4-methylphenyl) -1, 1-dimethylurea (chlorotoluron), or phenyldimethylureas, in particular p-chlorophenyl-N, N-dimethylurea (monuron), 3-phenyl- 1, 1 -dimethylurea (Fenuron), 3,4-dichlorophenyl-N, N-dimethylurea (diuron), as well as imidazoles and amine complexes.
  • the curing agent for epoxy resins is a compound selected from the group consisting of dicyandiamide, guanamines, guanidines, aminoguanidines and their derivatives; Substituted ureas, in particular 3- (3-
  • a hardener for epoxy resins is dicyandiamide
  • the proportion of the curing agent for epoxy resins is preferably 0.05 to 10 wt .-%, in particular 0.1 to 8 wt .-%, preferably 0.2 to 6 wt .-%, based on the total weight of the structural adhesive.
  • the term "hardener” also includes catalysts and catalytically active compounds In this context, it is clear to the person skilled in the art that when using a catalyst or a catalytically active compound as a hardener for epoxy resins, the proportion of the curing agent in the whole
  • Structural adhesive is in the lower range of the specified value range.
  • the epoxy resin composition may contain at least one
  • Impact modifier include.
  • an “impact modifier” is meant addition of an organic polymer to an epoxy resin matrix which, even at low levels, ie, typically between 0.1 and 20% by weight, relative to the structural adhesive causes a significant increase in toughness, and thus in is able to absorb higher impact or impact stress before the matrix breaks or breaks.
  • Suitable impact modifiers are, in particular, reactive liquid rubbers based on nitrile rubber or derivatives of polyetherpolyol-polyurethanes, core-shell polymers and similar systems known to the person skilled in the art.
  • the structural adhesive may contain other ingredients, such as
  • the structural adhesive may additionally contain at least one filler.
  • these are preferably mica, talc, kaolin, wollastonite, feldspar, syenite, chlorite, bentonite, montmorillonite, calcium carbonate (precipitated or ground), dolomite, quartz, silicic acids (pyrogenic or precipitated), cristobalite, calcium oxide, aluminum hydroxide, magnesium oxide, Ceramic hollow spheres, glass hollow spheres, organic hollow spheres, glass spheres, color pigments.
  • Filler means both the organically coated and the uncoated commercially available and known in the art forms.
  • Another example is functionalized alumoxanes, as z. As described in US 6,322,890 and the contents of which are hereby incorporated by reference.
  • the proportion of the filler, if one is included in the structural adhesive is usually 1 to 60 wt .-%, in particular 5 to 50 wt .-%, and particularly preferably 10 to 35 wt .-%, by weight of the entire structural adhesive.
  • the structural adhesive may also contain thixotropic agents, such as
  • Toughness modifiers reactive diluents and other ingredients known to those skilled in the art, but the addition of particular thixotropic agents is not required. As a result, the
  • composition according to the invention preferably no thixotropic agent.
  • the structural adhesive is a one-part, thermosetting epoxy resin composition.
  • the proportion of the structural adhesive is preferably 50 to 85% by weight, especially 60 to 85% by weight, and most preferably about 65 to 80% by weight, based on the total composition.
  • the composition according to the invention has a chemically crosslinked elastomer based on a silane-functional, nonpolar polymer.
  • the non-polarity refers to the backbone or to the base polymer of the silane-functional polymer prior to its functionalization with silane groups.
  • the non-polarity of the silane-functional polymer is essential for the present invention, as it is incompatible with the cured structural adhesive and it should thereby come to a phase separation in the curing of the structural adhesive. Only in this way can suitable systems be formulated as self-supporting adhesive bodies, which have sufficient mechanical strengths. That it comes in a specific case to a phase separation, can be easily determined by DMA (Dynamic Mechanical Analysis).
  • the silane-functional nonpolar polymer is dissolved in the structural adhesive before curing and largely homogeneously distributed.
  • the structural adhesive is an epoxy resin composition
  • curing of the epoxy resin results in secondary hydroxyl groups which are incompatible with the non-polar backbone of the silane-functional nonpolar polymer.
  • Silane-functional nonpolar polymers typically include silane-functional hydrocarbon polymers, typically one
  • Liquid rubber i.e., a rubbery polymer having a liquid consistency at 23 ° C
  • polyesters are not a nonpolar polymer in the sense of the present invention.
  • Suitable silane-functional non-polar polymers are, for example, those based on saturated or unsaturated polymers and polyethers.
  • polyethers it should be borne in mind that only those in the context of the present invention should be considered as "non-polar polymers" in which the ratio of the
  • Polyethylene glycols or polypropylene glycols are within the scope of
  • Polyethylene glycols or polypropylene glycols not as a silane-functional nonpolar polymer The same applies to copolymers with polyethylene oxide and polypropylene oxide units.
  • Polymers are, for example, those based on polyisoprene, polybutadiene and butadiene / acrylonitrile copolymers.
  • the liquid rubbers mentioned have in particular a molecular weight in the range from 1000 to 10000 g / mol, preferably about 1500 to 5000 g / mol, particularly preferably about 2000 to 5000 g / mol.
  • the liquid rubbers have an equivalent weight (i.e., an equivalent weight)
  • the chemically crosslinked elastomer is preferably present as a penetrating polymer network in the structural adhesive.
  • the chemically crosslinked elastomer based on a silane-functional non-polar polymer can be incorporated into the composition by mixing a silane-functional polymer with the structural adhesive and then crosslinking in the mixture to form a penetrating polymer network in the structural adhesive.
  • the proportion of the chemically crosslinked elastomer based on a silane-functional non-polar polymer is preferably from 15 to 50% by weight, in particular from 15 to 40% by weight, and particularly preferably from 20 to 35% by weight, based in each case on the total Composition.
  • silane-functional non-polar polymer are particularly suitable
  • the radicals R 1 , R 2 and R 3 are alkyl groups,
  • radicals R 1 , R 2 and R 3 may also be the same or different.
  • Particularly suitable radicals R 1 , R 2 and R 3 are methyl or ethyl groups and -OC 2 H 4 OC 2 H 4 OCH 3 groups.
  • the silane groups are -R 4 -Si (OEt) 3 or -R 4 -Si (OMe) x (OC 2 H 4 OC 2 H 4 OCH 3 ) 3-x, where x is 0 to 2 can accept.
  • the radical R 4 is a linear or branched divalent hydrocarbon radical having 1 to 12 C atoms, which optionally cyclic and / or aromatic moieties, and optionally one or more
  • R 4 is a linear or branched alkylene group having 1 to 6 C atoms, preferably methylene or 2-hydroxy-1, 3-propylene.
  • the silane-functional nonpolar polymer is a silane-functional polymer P1 obtainable by reacting a silane having at least one epoxy-reactive group with a nonpolar polymer having terminal
  • EBN functionalized butyl rubbers
  • the silane which is at least one opposite epoxy groups
  • Group is, in particular, a mercaptosilane, a hydroxysilane or or an aminosilane, preferably an aminosilane.
  • suitable aminosilanes are primary aminosilanes such as 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane; secondary Aminosilanes such as N-butyl-3-aminopropyltrinnethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane; Michael-like addition products of primary aminosilanes such as 3-aminopropyltrimethoxysilane or 3-aminopropyldimethoxymethylsilane to Michael acceptors such as acrylonitrile, (meth) acrylic acid esters, (meth) acrylic acid amides, maleic and fumaric diesters, citraconic diesters and itaconic diesters, for example N- (3-trimethoxysilyl-propyl) -amino-succinic acid dimethyl and diethyl ester; and analogs of said aminosilanes with ethoxy
  • Methyloxyethoxyethoxy groups (-O-C2H-O-C2H -OCH 3 ) in place of
  • the silane functional nonpolar polymer is a silane functional polymer P2 obtainable by the reaction of an epoxysilane with a nonpolar polymer having terminal epoxide-reactive functional groups.
  • Epoxysilanes suitable for such reactions are not subject to any limitations except for the requirement that they contain an epoxy group and a silane group linked together via a linker.
  • glycidoxypropylsilanes as typically made from glycidol and 3-chloropropylsilanes, have been found to be particularly useful because of low commercial availability.
  • Glycidoxypropylsilane are 3-glycidoxypropyltrimethoxysilane (eg available as Silquest ® A-187 of
  • 3-glycidoxypropyltriethoxysilane obtainable, for example available as CoatOSil ® 2287 from Momentive
  • transesterification products of 3-glycidoxypropyltrimethoxysilane with diethylene glycol monomethyl ether for example as Dynasylan ® GLYEO from Evonik
  • 3-glycidoxypropylmethyldiethoxysilane eg
  • Araldite ® DY 1158 available from Huntsman available as Araldite ® DY 1158 available from Huntsman.
  • Nonpolar polymers which have terminal epoxide-reactive functional groups can be used in particular nonpolar polymers having terminal hydroxyl, amino, mercapto or carboxy functions, the use of carboxy functions being relatively unfavorable and therefore less preferred than the other variants because of the high reaction temperatures required for reaction with epoxides.
  • carboxy functions being relatively unfavorable and therefore less preferred than the other variants because of the high reaction temperatures required for reaction with epoxides.
  • non-polar polymers are amino-terminated butadiene / acrylonitrile copolymers (ATBN) and hydroxy-terminated butadiene / acrylonitrile copolymers (OH-HTBN).
  • ATBN amino-terminated butadiene / acrylonitrile copolymers
  • OH-HTBN hydroxy-terminated butadiene / acrylonitrile copolymers
  • An amino-terminated butadiene / acrylonitrile copolymer is available, for example, under the tradename Hypro TM 1300X16 ATBN from Emerald Performance Materials.
  • terminal to epoxides have reactive functional groups and are based on polyethers, amino-terminated poly (tetramethylene) glycols are, for example Jeffann ine THF ® 170 from Huntsman.
  • the silane-functional non-polar polymer is a silane-functional polymer P3 obtainable by reacting a silane having at least one isocyanate-reactive group with a non-polar polymer having terminal
  • This reaction is preferably also carried out in a stoichiometric ratio of the isocyanate-reactive groups to the isocyanate groups of about 1: 1 and a slight excess of isocyanate-reactive groups, so that the resulting silane-functional polymer P3 is completely free of isocyanate groups.
  • Suitable silanes which have at least one isocyanate-reactive group are the same compounds which have been described above for the reaction with epoxy-terminated nonpolar polymers have been mentioned since amino, hydroxy and mercapto functions react with both epoxy groups and isocyanate groups.
  • Suitable nonpolar polymers containing isocyanate groups for preparing a silane-functional polymer P3 are, in particular, nonpolar polymers obtainable by reacting non-polar polyols or polyamines according to the above provisos with at least one polyisocyanate, in particular a diisocyanate.
  • the preparation of these non-polar polymers can be carried out by the polyol and the polyisocyanate by conventional methods, for example at temperatures of 50 ° C to 100 ° C,
  • Isocyanate groups in relation to the hydroxyl groups or amine groups of the polyol or polyamine in the stoichiometric excess of about 2: 1 or more are present.
  • Polyisocyanates is functionalized and it does not come to the formation of long-chain polyurethane polymers.
  • Commercially available polyisocyanates, in particular diisocyanates can be used as polyisocyanates.
  • suitable diisocyanates are 1, 6-hexamethylene diisocyanate (HDI), 2-methylpentamethylene-1,5-diisocyanate, 2,2,4- and 2,4,4-trimethyl-1,6-hexamethylene diisocyanate (TMDI), 1, 12 -Dodeca- methylene diisocyanate, lysine and Lysinesterdiisocyanat, cyclohexane-1, 3-diisocyanate, cyclohexane-1, 4-diisocyanate, 1 -lsocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate or IPDI), Perhydro -2,4'-diphenylmethane
  • Particularly suitable polyisocyanates are HDI, TMDI, IPDI, TDI and MDI, in particular IPDI.
  • Embodiment of the non-polar polymer to a butyl rubber in particular based on polybutadiene or a butadiene / acrylonitrile copolymer.
  • Such rubbers may in particular be functionalized with amino groups, hydroxy groups or mercapto groups.
  • a polyether, preferably a hydroxy-terminated polyether, and most preferably a hydroxy-terminated poly (tetramethylene) glycol may be used as the non-polar polymer in the third embodiment.
  • a commercially available poly (tetramethylene) glycol for example PolyTHF ® 2000 from BASF.
  • the silane-functional non-polar polymer is a silane-functional polymer P4 which is obtainable by reacting an isocyanatosilane with a non-polar polymer having isocyanate-reactive functional end groups, in particular
  • isocyanatosilanes of the formulas (V) or (VI) are isocyanatomethyltrimethoxysilane, isocyanatomethyldimethoxymethylsilane 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyldimethoxymethylsilane, and their analogs having ethoxy or isopropoxy groups instead of the methoxy groups on the silicon.
  • the nonpolar polymer preferably has amino groups as isocyanate-reactive functional end groups.
  • Suitable amino-containing non-polar polymers are, in particular, the abovementioned polymers based on poly (tetramethylene) glycol, e.g.
  • silane-functional non-polar polymer can be prepared by a hydrosilylation reaction of nonpolar polymers and in particular
  • Polyethers are prepared according to the above specifications, for example, with vinyl or allyl-terminated poly (tetramethylene) glycols.
  • Polymer obtained by reacting carboxy-functional non-polar polymers with aminosilanes obtained by reacting carboxy-functional non-polar polymers with aminosilanes.
  • composition according to the invention is particularly preferably obtainable by
  • the described procedure has the advantage over the preparation of the silane-functional nonpolar polymer in the structural adhesive in situ that the formation of a penetrating polymer network can be more easily ensured.
  • the structural adhesive is mixed with the silane-functional nonpolar polymer, preferably giving a homogeneous mixture.
  • Structural adhesive as an epoxy resin epoxy resin
  • the mixing is carried out at a temperature above the glass transition temperature Tg of
  • Epoxy resin composition this may be mixed with the silane-functional non-polar polymer prior to the addition of the curing agent for epoxy resins.
  • the temperature can be adjusted during mixing to or even beyond the curing temperature of the thermosetting epoxy resin composition, without causing the curing of the
  • Structural adhesive comes. At higher temperatures, more efficient mixing is usually achieved.
  • the elastomer formed in this way is in particular a penetrating polymer network
  • Polymer proceeds by reaction of the contained silane groups with water.
  • the water required for crosslinking is present in particular in the form of atmospheric moisture, which passes through diffusion processes in the composition.
  • the composition may contain a catalyst.
  • Catalysts are, in particular, organotin compounds, for example dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetylacetonate and dioctyltin diacetylacetonate; Titanates and zirconates, for example
  • Nitrogen compounds in particular tertiary amines, for example N, N-dimethylbenzylamine, ⁇ , ⁇ -dimethylcyclohexylamine and 1, 4-diazabicyclo [2.2.2] octane, and amidines and guanidines, for example 1, 8-diazabicyclo [5.4.0] undec-7 -en and 1,1,3,3-tetramethylguanidine; such as
  • composition of the invention an aminosilane, preferably a
  • Suitable aminosilanes include the aforementioned aminosilanes.
  • a particularly suitable aminosilane is N- (2-aminoethyl) -3-aminopropyltrimethoxysilane
  • A-1 is available from Momentive for example, under the trade name Silquest ® 120th
  • the present invention relates to a process for producing an adhesive body from a composition as described above comprising the steps of: reacting a silane with a nonpolar polymer, wherein either the silane or the nonpolar polymer is resistant to epoxides having reactive groups, and the other component has epoxide groups; or reacting a silane with a non-polar polymer, wherein either the silane or the nonpolar polymer has isocyanate-reactive groups, and the other one
  • the shaping takes place in such a way that the adhesive body receives a planar shape, in particular a band or a strip, and thus represents an adhesive tape.
  • the shaping preferably takes place by means of glazing.
  • the crosslinking of the silane-functional nonpolar polymer takes place via the reaction of
  • Silane groups with water in the form of humidity Silane groups with water in the form of humidity.
  • Another aspect of the present invention relates to adhesives made from a composition as described above.
  • Such adhesive bodies are preferably in the form of a band or strip and preferably have a thickness in the range of 0.1 to 5 mm, in particular 0.5 to 3 mm.
  • Such adhesives are in particular self-supporting and in particular constitute adhesive tapes.
  • the adhesives produced from the process according to the invention can be used, in particular, for structural bonding and for reinforcing
  • Metal structures are used, especially in vehicle construction.
  • Another aspect of the present invention finally concerns a
  • a method of joining two substrates comprising the steps
  • composition of the adhesive body preferably by
  • the method of bonding may also be carried out omitting the first step in the event that the shaping of the adhesive body has been carried out according to the described method for producing the adhesive body on a first substrate.
  • the first substrate is preferably a metal substrate, in particular electrolytically galvanized, hot-dip galvanized, and subsequently phosphated steel sheet, oiled steel sheet and various,
  • thermoplastic substrate for example a polyamide, polyester,
  • Polyurethane polyolefin, polysulfone, polyvinyl chloride, in particular a
  • High temperature resistant thermoplastic substrate such as a polyamide, poly (butylene) terephthalate, polyphenylene ether, polysulfone or polyethersulfone, preferably a polyamide, in particular PA 6, PA 6,6, PA 1, PA 12, PA 6,10, PA 6,12 or a mixture of them.
  • the second substrate is preferably likewise a metal substrate, in particular electrolytically galvanized, hot-dip galvanized, and subsequently phosphated steel sheet, oiled steel sheet as well
  • Hypro TM 1300X16 ATBN amine-terminated butadiene-acrylonitrile copolymer; Mw about 3600 g / mol;
  • Silyl TM SAX400 trimethoxysilane-terminated polypropylene glycol having an average functionality of 3 and a Mw of about 24,000 g / mol, from Kaneka
  • Impact peel strength was determined using ISO 1 1343 with measurements taken at 23 ° C.
  • Tensile shear strength was determined from EN1465 on a 2 mm thick 5 x 25 mm strip attached to an acetone-cleaned HDG (H380) steel strip of 0.8 mm thickness.
  • the gel content was determined according to ASTM 2765 according to Method A. To this end, two containers of 100 mesh polyamide fabric, each containing 0.3 g of ground sample material, were stored in an excess of methyl ethyl ketone (MEK) for at least 40 hours at room temperature. Subsequently, the containers were washed with MEK and dried for at least 5 hours at room temperature. Thereafter, further drying was carried out in vacuo at 50 ° C for at least 18 hours. The non-soluble weight fraction remaining in the container corresponds to the gel content or the gel fraction.
  • MEK methyl ethyl ketone
  • Adhesive tapes were made with the finished blends by placing them in a thickness of 5 mm on PTFE molds and 0.3 mm thick directly on the steel substrate of the test specimens and leaving them at 23 ° C for 7 days at room temperature in air, wherein the silane groups crosslinked with moisture.
  • the adhesive tape thus prepared was tested for gel content.
  • silane-functional polymer two different silane-terminated polyethers based on polypropylene glycol (MS Polymer TM S303H and Silyl TM SAX400) were used in combination with a catalyst for silane crosslinking.
  • compositions of the individual formulations and the mechanical properties are given in the following Table 1.
  • Poly (tetramethylene ether) glycol ( "S-PTMEG") was prepared. To this end a hydroxysilane by reaction of 3-aminopropyltriethoxysilane with L-lactide was first prepared addition, an isocyanate-functional poly (tetramethylene ether) glycol by reacting PolyTHF ® 2000 with Vestanat was. ® IPDI in the ratio 1:. 2 the hydroxysilane was then reacted at 80 ° C with the isocyanate-functional poly (tetramethylene ether) glycol with an OH / NCO ratio of 1 .1 / 1 to S- PTMEG.
  • the S-PTMEG was in the following with the aid of a centrifugal M ischers with liquid epoxy resin, hardener, catalyst for the silane crosslinking (Tyzor ® ibay) and optionally aminosilane (Silquest ® A-1 120) are mixed and further driven as described for Example. 1
  • a centrifugal M ischers with liquid epoxy resin, hardener, catalyst for the silane crosslinking (Tyzor ® ibay) and optionally aminosilane (Silquest ® A-1 120) are mixed and further driven as described for Example. 1
  • the exact compositions of the materials studied and the particular physical properties are given in Table 2 below.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

La présente invention concerne une composition contenant au moins un adhésif structural et au moins un élastomère à réticulation chimique à base d'un polymère non polaire à fonction silane, ledit élastomère se présentant sous forme de réseau polymère pénétrant dans l'adhésif structural. Il est possible, à l'aide de telles compositions, de fabriquer des articles adhésifs autoporteurs, en particulier sous forme de rubans adhésifs, qui peuvent être utilisés pour des collages structuraux et pour le renforcement de structures métalliques.
EP16819862.0A 2015-12-17 2016-12-16 Article adhésif autoporteur pour collages structuraux Withdrawn EP3390562A1 (fr)

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