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EP4504808A1 - Adhésif à base de (méth)acrylate pour liaison d'angle de coin - Google Patents

Adhésif à base de (méth)acrylate pour liaison d'angle de coin

Info

Publication number
EP4504808A1
EP4504808A1 EP23717882.7A EP23717882A EP4504808A1 EP 4504808 A1 EP4504808 A1 EP 4504808A1 EP 23717882 A EP23717882 A EP 23717882A EP 4504808 A1 EP4504808 A1 EP 4504808A1
Authority
EP
European Patent Office
Prior art keywords
weight
component
meth
acrylate
composition according
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.)
Pending
Application number
EP23717882.7A
Other languages
German (de)
English (en)
Inventor
Denise Storrer
Fabien Choffat
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 EP4504808A1 publication Critical patent/EP4504808A1/fr
Pending legal-status Critical Current

Links

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
    • C09J133/00—Adhesives 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/414—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of a copolymer
    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer
    • 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
    • C09J2475/00—Presence of polyurethane

Definitions

  • the invention relates to the field of two-component (meth)acrylate compositions and their use as adhesives.
  • adhesives are widely used, for example to connect metal, wood or plastic elements to one another. Bonding has various advantages over other fasteners such as screws, as the connection without screw holes is aesthetically and mechanically more stable and a better seal is also achieved, for example against heat and moisture.
  • a classic field of application in this area is the bonding of corner brackets in window profiles, which are usually made of aluminum. In such applications, the adhesive used must have high tensile strength and sufficient rigidity to provide the required stability to the manufactured frame. Furthermore, good adhesion is necessary, especially on aluminum or alloys thereof.
  • the adhesive Since, for example, window profiles and similar elements are normally manufactured industrially, the adhesive must also have an open time suitable for an efficient manufacturing process and cure as quickly as possible.
  • Today's such processes primarily use adhesives based on polyurethanes or epoxy resins, as these meet the mechanical requirements and are suitable in terms of adhesion to the substrates used.
  • two-component adhesives are usually used, which harden quickly after mixing the reactive components with one another and enable rapid cycle times.
  • US 2017/204311 discloses a two-component polyurethane-based adhesive.
  • polyurethane-based adhesives have disadvantages.
  • the isocyanates contained therein, especially if they are in the form of monomeric diisocyanates, as is usual with two-component polyurethanes are not harmless to health and require additional, legally required occupational safety measures when used.
  • Epoxy resin-based compositions also have disadvantages. These are primarily due to the comparatively slow curing process, even with two-component epoxy adhesives, if a sufficiently long open time is required at the same time. Although the curing of epoxy adhesives can be accelerated, for example by heating, this is not desirable for industrial processes.
  • Adhesives based on other chemicals are usually not used or only rarely used for such applications. Silicones, for example, have poor paintability or paintability and are often unsuitable in terms of strength and rigidity. Other adhesives on a different basis are often too expensive to be used economically in such processes or they have too high a viscosity to be easily applied into gaps or cavities, for example by injection.
  • US 2007/054975 discloses a radiation-curing, one-component, acrylate-based adhesive that is particularly suitable for bonding optical elements such as camera lenses.
  • optical elements such as camera lenses.
  • US 4,855,002 discloses a one-component, thermally conductive, acrylate-based adhesive containing between 30% by weight and 80% by weight of aluminum powder as a filler. This makes it suitable for bonding and heat dissipation in highly thermally emitting objects such as electrical components, but is also expensive to formulate and limited in terms of mechanical and adhesive properties. Aluminum powder is also not harmless in terms of occupational safety.
  • the object of the present invention is therefore to provide an adhesive for the bonding of corner angles, frames or profiles in window, door, container or vehicle construction that meets the mechanical requirements with regard to tensile strength, elastic modulus and adhesion, a sufficiently long open time and a has sufficiently rapid curing at room temperature and thus enables short cycle times in industrial production, has a sufficiently low viscosity for easy application and is also harmless in terms of occupational safety and toxicology.
  • compositions according to claim 1 solve this problem.
  • the compositions according to claim 1 have excellent adhesion to commonly used materials of corner angles, frames or profiles in window, door, container or vehicle construction, for example aluminum and aluminum alloys such as AIMgs. They surprisingly achieve the required mechanical properties, in particular tensile strength and modulus of elasticity, without any problems, and they can be applied with sufficiently long open times and then harden quickly at room temperature.
  • these compositions can be formulated without the use of volatile and odor-intensive (meth)acrylate monomers such as MMA and have a high level of occupational safety and a favorable EHS profile.
  • compositions are therefore optimally suited for use as adhesives for bonding corner angles, frames or profiles in window, door, container or vehicle construction and, due to their unexpectedly low viscosity, can also be applied by injection, but at the same time despite it not so low in viscosity that they can no longer be mixed homogeneously and they run or splash uncontrollably when applied, especially from a cartridge.
  • the tensile strengths of the compositions according to the invention measured according to EN 53504 are at room temperature (23 ° C) in particular at least 9 MPa, preferably at least 10 MPa, in particular at least 11 MPa or higher, with elastic moduli in particular in the range from 700 MPa to 1700 MPa or higher and elongations at break particularly in the range of at least 2% to 15% or higher.
  • the tensile shear strengths of the compositions according to the invention on AIMgs measured according to ISO 4587/DIN EN 1465 are at room temperature (23° C.) in particular at least 2 MPa, preferably at least 3 MPa, in particular at least 4 MPa or higher.
  • compositions according to the invention according to claim 1 harden quickly after application at room temperature, in particular within 20 to 40 minutes, and have an open time of in particular 5 to 15 minutes, whereby these properties can be influenced and adjusted via formulation measures.
  • compositions according to the invention according to claim 1 have a low viscosity immediately after mixing the components, in particular a viscosity of at most 80 Pa s, preferably at most 70 Pa s, in particular at most 50 Pa s, particularly preferably at most 40 Pa s or less, measured on a thermostated Anton Paar rheometer with the Rheoplus software and plate-plate (PP25; diameter 25 mm) measuring system at 23 °C and a shear rate of 10 s -1 and a plate distance of 1.5 mm.
  • the viscosity of the composition according to the invention should not be too low in order to ensure a homogeneous mixture and a clean application, especially from a cartridge, when used as adhesives for bonding corner angles, frames or profiles in windows, doors, containers - or vehicle construction.
  • the viscosity measured using the method just mentioned, is at least 15 Pa s, preferably at least 20 Pa s, particularly preferably at least 25 Pa s.
  • Lower viscosities can lead to the one in particular Composition applied to the cartridge runs uncontrolled and, for example, the layer thickness of the adhesive is not sufficiently high for a mechanically sufficient bond.
  • the mixing homogeneity of a mixed two-component composition according to the present invention if one of the two components has a much lower viscosity than the other.
  • the viscosity (as defined above) of the lower viscosity component of the two-component composition is not less than 10% of the viscosity of the higher viscosity components, preferably not less than 20%, based on the viscosity of the higher viscosity component.
  • the present invention relates to a two-component composition for use as a free-radically curing adhesive for bonding corner angles, frames or profiles in window, door, container or vehicle construction, consisting of a component K1, comprising a) at least one (meth)acrylate monomer A ; b) at least one elastomer C with (meth)acrylate end groups, produced from the reaction of at least one diol D, at least one diisocyanate, and a (meth)acrylic acid, a (meth)acrylamide or a (meth)acrylic acid ester, which is a has hydroxyl group; c) at least one radical curing activator; d) preferably at least one radical curing inhibitor; e) at least one filler; f) and, if necessary, other additives; and a component K2, comprising g) at least one initiator for free radical curing; h) preferably at least one filler; i) preferably at least one plasticizer; j) and, if
  • polymer includes, on the one hand, a collective of macromolecules that are chemically uniform but differ in terms of degree of polymerization, molecular weight and chain length, which were produced by a polyreaction (polymerization, polyaddition, polycondensation).
  • the term also includes derivatives of such a collective of macromolecules from polyreactions, i.e. compounds that were obtained through reactions, such as additions or substitutions, of functional groups on given macromolecules and which can be chemically uniform or chemically non-uniform.
  • prepolymers i.e. reactive oligomeric pre-adducts whose functional groups are involved in the construction of macromolecules.
  • polymeric polyol in this document includes any polymer as defined above that has more than one hydroxyl group. Accordingly, the term “polymeric diol” includes any polymer that has exactly two hydroxyl groups.
  • polyurethane polymer includes all polymers that are produced using the so-called diisocyanate polyaddition process. This also includes polymers that are almost or completely free of urethane groups. Examples of polyurethane polymers are polyether polyurethanes, polyester polyurethanes, polyether polyureas, polyureas, polyester polyureas, polyisocyanurates and polycarbodiimides.
  • molecular weight is understood to mean the defined and discrete molar mass (in grams per mole) of a molecule or part of a molecule, also referred to as “residue”. It is called “average molecular weight”. denotes the number average M n of a particular polydisperse oligomeric or polymeric mixture of molecules or residues, which is usually determined using gel permeation chromatography (GPC) against polystyrene as a standard.
  • GPC gel permeation chromatography
  • (meth)acrylate means “methacrylate” or “acrylate”.
  • a dashed line in the formulas in this document represents the bond between a substituent and the associated molecular residue, unless otherwise specified.
  • room temperature A temperature of approx. 23°C is referred to as “room temperature”.
  • any industry norm or standard mentioned in the document unless otherwise stated, refers to the version of the industry norm or standard in effect at the time of filing the patent application.
  • the terms “mass” and “weight” are used interchangeably in this document.
  • a “weight percent” (% by weight) refers to a percentage by mass which, unless otherwise stated, refers to the mass (weight) of the entire composition or, depending on the context, of the entire molecule.
  • the two-component composition according to the invention consists of a first component K1 and a second component K2.
  • Component K1 initially comprises at least one (meth)acrylate monomer A.
  • (Meth)acrylate monomer A can include all (meth)acrylate monomers that are commonly used in (meth)acrylate adhesives.
  • (meth)acrylate monomer A preferably does not comprise methyl methacrylate (MMA), since this is problematic in terms of high vapor pressure, easy flammability, unpleasant odor and health concerns.
  • MMA methyl methacrylate
  • (Meth)acrylate monomer A particularly includes at least one
  • R 2 either represents an isobornyl group, or represents a linear or branched hydroxyalkyl group with 2 to 6 carbon atoms, or represents a radical with 4 to 8 carbon atoms which is either a phenyl group or an aliphatic 5- or 6-ring with at least one ether oxygen included in the ring structure.
  • R 1 in formula (Illa) preferably represents a methyl group.
  • R 2 in formula (Illa) represents a linear or branched hydroxyalkyl group with 2 to 4 carbon atoms.
  • monomers are hydroxypropyl acrylate (HPA), hydroxypropyl methacrylate (HPMA), hydroxybutyl acrylate (HBA) or hydroxybutyl methacrylate (HBMA), preferably hydroxyethyl acrylate (HEA) or hydroxyethyl methacrylate (HEMA), with hydroxyethyl methacrylate (HEMA) being particularly preferred.
  • R 2 in formula (Illa) represents a radical with 4 to 8 carbon atoms, which comprises an aliphatic 5- or 6-ring with one or two ether oxygens in the ring structure.
  • R 2 in formula (Illa) represents an isobornyl group.
  • R 2 in formula (Illa) represents an isobornyl group or a hydroxyethyl group or a benzyl group or at least one of the groups (IVa) to (IVc) in formula (IV), where the dashed lines in forms (IV) represent the bond between the oxygen atom and R 2 .
  • IBOA isobornyl acrylate
  • IBOMA isobornyl methacrylate
  • BNA benzyl acrylate
  • BNMA benzyl methacrylate
  • HEMA hydroxyethyl methacrylate
  • THFMA tetrahydrofurfuryl methacrylate
  • glycerol formyl methacrylate (“glycerol formal methacrylate » comprising the structures (IVb) and (IVc) in formula (IV); CAS No. 1620329-57-8), which is available from Evonik under the trade name GLYFOMA.
  • Most preferred monomers according to formula (Illa) are isobornyl methacrylate (IBOMA), benzyl methacrylate (BNMA), tetrahydrofurfuryl methacrylate (THFMA), hydroxyethyl methacrylate (HEMA), and glycerol formyl methacrylate (GLYFOMA).
  • IBOMA isobornyl methacrylate
  • BNMA benzyl methacrylate
  • THFMA tetrahydrofurfuryl methacrylate
  • HEMA hydroxyethyl methacrylate
  • GLYFOMA glycerol formyl methacrylate
  • (Meth)acrylate monomer A includes in particular at least one (meth)acrylate monomer according to formula (IIIb), where R 3 represents either a hydrogen atom or a methyl group, preferably a methyl group; and
  • R 4 represents a linear alkyl radical with more than 12 carbon atoms in the chain and preferably at most 20 carbon atoms in the chain.
  • R 3 in formula (IIIlb) preferably represents a methyl group.
  • R 4 in formula (IIIlb) preferably represents a linear alkyl radical with 13 to 18 carbon atoms in the chain. If there is a mixture of different chain lengths in the residue R 4 , then the average value of the chain lengths is formally used as a measure for the effective chain length in R 4 .
  • Examples of such (meth)acrylate monomers according to formula (IIIb) are lauryl tetradecyl acrylate (LATEA), lauryl tetradecyl methacrylate (LATEMA), stearyl acrylate (STEA), and stearyl methacrylate (STEMA). Most preferred are lauryl tetradecyl methacrylate (LATEMA) and stearyl methacrylate (STEMA).
  • Component K1 preferably contains between 10% by weight and 25% by weight, preferably between 10% by weight and 20% by weight, based on component K1, of (meth)acrylate monomer A.
  • the weight ratio of (meth)acrylate monomers according to formula (Illa) and (meth)acrylate monomers is according to formula (IIIlb) preferably between 1:1 and 9:1, preferably between 6:4 and 8:2. Within these limits it is possible to achieve improved elasticity both at room temperature and at very low temperatures down to -20 °C.
  • Component K1 further contains at least one elastomer e with (meth)acrylate end groups, produced from the reaction of at least one diol D, at least one diisocyanate, and a (meth)acrylic acid, a (meth)acrylamide or a (meth)acrylic acid ester, which has a hydroxyl group.
  • the elastomer C preferably has an average molecular weight of 1,000 to 40,000 g/mol, in particular of 2,000 to 30,000 g/mol, preferably of 3,000 to 20,000 g/mol.
  • Elastomer C is a polyurethane (meth)acrylate. Such compounds can typically be prepared from the reaction of at least one diol D with at least one diisocyanate and a (meth)acrylic acid, a (meth)acrylamide or a (meth)acrylic acid ester which has a hydroxyl group.
  • Elastomer e is preferably produced from a polyoxypropylene diol and at least one diisocyanate and a (meth)acrylic acid ester which has a hydroxyl group.
  • this reaction can be carried out by causing the diol D and the diisocyanate to react using conventional processes, for example at temperatures of 50 ° C to 100 ° C, optionally with the use of suitable catalysts, it being important to ensure that that the NCO groups are present in a stoichiometric excess compared to the OH groups.
  • the isocyanate group-terminated polyurethane polymer resulting from this reaction is then treated with a (meth)acrylic acid, a (meth)acrylamide or with a (meth)acrylic acid ester which has a hydroxyl group, in particular with a hydroxyalkyl (meth)acrylate such as hydroxypropyl acrylate (HPA), hydroxypropyl methacrylate (HPMA), hydroxybutyl acrylate (HBA) or hydroxybutyl methacrylate (HBMA) preferably with hydroxyethyl acrylate (HEA) or hydroxyethyl methacrylate (HEMA), or with a monohydroxypoly(meth)acrylate of a polyol, preferably glycerin or trimethylolpropane, to form a polyurethane (meth) acrylate, implemented.
  • a hydroxyalkyl (meth)acrylate such as hydroxypropyl acrylate (HPA), hydroxypropyl me
  • the diol D can be reacted with the diisocyanate, the OH groups being present in a stoichiometric excess compared to the NCO groups.
  • the hydroxyl-terminated polyurethane polymer resulting from this reaction can be esterified with a (meth)acrylic acid to give the elastomer C of the formula (I).
  • Another method for producing the elastomer C is, in a first step, the (meth)acrylic acid, the (meth)acrylamide or the (meth)acrylic acid ester which has a hydroxyl group, in particular hydroxyalkyl (meth)acrylate such as hydroxypropyl acrylate (HPA), hydroxypropyl methacrylate (HPMA), hydroxybutyl acrylate (HBA) or hydroxybutyl methacrylate (HBMA), preferably hydroxyethyl acrylate (HEA) or hydroxyethyl methacrylate (HEMA), or a monohydroxypoly(meth)acrylate of a polyol, preferably glycerin or Trimethylolpropane, with at least one diisocyanate, which is used in an amount that the NCO groups are present in excess of the OH groups.
  • the resulting intermediate product containing an isocyanate group is reacted with at least one diol D to form the elastocyanate
  • the elastomer C by esterifying a (meth)acrylic acid with a diol D, the diol being present in stoichiometric excess. In a subsequent reaction, the partially esterified diol D reacts with a diisocyanate to form the elastomer C.
  • Preferred diols D are polyoxyalkylene diols, also called “polyether diols”, polyester diols, polycarbonate diols and mixtures thereof.
  • the most preferred diols are polyoxyethylene diols, polyoxypropylene diols or polyoxybutylene diols.
  • the polyoxyalkylene diols can have different degrees of unsaturation (measured according to ASTM D-2849-69 and stated in milliequivalents of unsaturation per gram of polyol (mEq/g)).
  • DMC catalysts double metal cyanide complex catalysts
  • anionic catalysts such as NaOH, KOH, CsOH or alkali metal alcoholates.
  • polyoxyalkylene diols with a low degree of unsaturation, especially less than 0.01 mEq/g, is preferred for diols with a molecular weight of >2000 g/mol.
  • diols are available, for example, under the trade name Acclaim® Polyol from Covestro. Acclaim® Polyol 4200 and 12200 N are preferred.
  • diisocyanates are suitable as diisocyanates for the production of elastomer C.
  • diisocyanates 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- are mentioned.
  • HDI 1,6-hexamethylene diisocyanate
  • TMDI 2,2,4- and 2,4,4-trimethyl-1,6-hexamethylene diisocyanate
  • Dodecamethylene diisocyanate, lysine and lysine ester diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane ( isophoronediisocyanate- nat or IPDI), perhydro-2,4'-diphenylmethane diisocyanate and perhydro-4,4'-diphenylmethane diisocyanate, 1,4-diisocyanato-2,2,6-trimethylcyclohexane (TMCDI), 1,3- and 1,4 -Bis-(isocyanatomethyl)cyclohexane, m- and p-xylylene diisocyanate (m- and p-XDI), m- and p-tetramethyl-1,3-xylylene diis
  • the preferred diisocyanate is 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI).
  • elastomer e is a polyurethane (meth)acrylate, in particular producible from the reaction of at least one diol D, in particular a polyoxypropylene diol, with at least one diisocyanate and a (meth)acrylic acid ester which has a hydroxyl group, the diol D reacts with a diisocyanate, in particular isophorone diisocyanate, which is present in stoichiometric excess; and the resulting isocyanate group-terminated polyurethane is reacted with the (meth)acrylic acid ester which has a hydroxyl group, in particular with a hydroxyalkyl (meth)acrylate, preferably with hydroxyethyl acrylate (HEA) or hydroxyethyl methacrylate (HEMA) to form the elastomer C of the formula (I). .
  • diol D in particular a polyoxypropylene diol
  • HEMA hydroxyethyl
  • the OH groups of the diol D react with the isocyanate groups of the monomeric diisocyanate.
  • chain extension reactions in which OH groups and/or isocyanate groups of reaction products react between diol D and monomeric diisocyanate.
  • a measure of the chain elongation reaction is the average molecular weight of the Polymers or the width and distribution of the peaks in the GPC analysis.
  • Another measure is the effective NCO content of the monomer-free polymer in relation to the theoretical NCO content calculated from the reaction of each OH group with a monomeric diisocyanate.
  • a suitable NCO/OH ratio in the reaction of diol D and diisocyanate is, for example, in the range from 1/1 to 10/1, in particular 1.1/1 to 1.25/1.
  • an NCO/OH ratio of at least 3/1 is set.
  • the NCO/OH ratio is preferably in the range from 3/1 to 10/1, particularly preferably 3/1 to 8/1, in particular 4/1 to 7/1, most preferably 5/1 to 7/1.
  • the reaction is preferably carried out with exclusion of moisture at a temperature in the range from 20 to 160 ° C, in particular 40 to 140 ° C, if necessary in the presence of suitable catalysts.
  • any monomeric diisocyanate remaining in the reaction mixture is removed to the desired residual content using a suitable separation process.
  • the preferred separation process in such cases is a distillation process, in particular thin-film distillation or short-path distillation, preferably with the application of vacuum.
  • Particularly preferred is a multi-stage process in which the monomeric diisocyanate is removed in a short-path evaporator at a jacket temperature in the range of 120 to 200 ° C and a pressure of 0.001 to 0.5 mbar.
  • the monomeric diisocyanate removed after the reaction is preferably then reused, i.e. used again for the production of polymer containing isocyanate groups.
  • Diol D can also include other diols, in particular:
  • Polyester diols in particular from the polycondensation of hydroxycarboxylic acids or in particular those which are made from dihydric alcohols, such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1 ,5-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol,
  • dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1 ,5-hexanediol, 1,6-hexanediol, 1,8-o
  • organic dicarbony acids or their anhydrides or esters, such as amber or acid, glutaric acid, obesity
  • Dimer fatty acid-based polyester diols in particular those which have an average molecular weight Mn in the range of 950 to 4,000 g/mol and are amorphous (for example commercially available under the name Priplast® from Croda).
  • Polycarbonate dioli as can be obtained by reacting, for example, the above-mentioned alcohols - used to synthesize the polyester polyols - with dialkyl carbonates, diaryl carbonates or phosgene.
  • Block copolymers bearing two hydroxyl groups which have at least two different blocks with a polyether, polyester and/or polycarbonate structure of the type described above, in particular polyether polyester diol.
  • Polyhydrocarbon diols also called oligohydrocarbonols, such as dihydroxy-functional polyolefins, polyisobutylenes, polyisoprenes; dihydroxy-functional ethylene-propylene, ethylene-butylene or ethylene-propylene-diene copolymers, such as those produced by Kraton Polymers; dihydroxy-functional polymers of dienes, in particular of 1,3-butadiene, which can in particular also be produced from anionic polymerization; dihydroxy-functional copolymers from dienes such as 1,3-butadiene or diene mixtures and vinyl monomers such as styrene, acrylonitrile, vinyl chloride, vinyl acetate, vinyl alcohol, isobutylene and isoprene, for example dihydroxy-functional acrylonitrile/butadiene copolymers, such as those from epoxides or amino alcohols and carboxyl-terminated acrylonitrile/butadiene copolymers (for example commercial
  • the composition preferably additionally contains in component K1 between 0.5% by weight and 5% by weight, based on component K1, of an adhesion promoter, in particular selected from the list of organosilanes, metal (meth)acrylates, preferably metal (meth)acrylates of calcium , magnesium or zinc, polyfunctional (meth)acrylates with more than two (meth)acrylate groups, and (meth)acrylates of the formula (II).
  • an adhesion promoter in particular selected from the list of organosilanes, metal (meth)acrylates, preferably metal (meth)acrylates of calcium , magnesium or zinc, polyfunctional (meth)acrylates with more than two (meth)acrylate groups, and (meth)acrylates of the formula (II).
  • the radical R' represents either a hydrogen atom or a methyl group
  • n represents a value from 1 to 15, in particular from 1 to 5, preferably from 1 to 3.
  • m stands for a value of 1 to 3 and p stands for a value of 3 minus m.
  • Preferred metal (meth)acrylates are metal (meth)acrylates of calcium, magnesium or zinc, which have a hydroxyl group and/or (meth)acrylic acid or (meth)acrylate as a ligand or anion.
  • Particularly preferred metal (meth)acrylates are zinc (meth)acrylates, calcium (meth)acrylates, Zn(OH)(meth)acrylates and magnesium (meth)acrylates.
  • Preferred (meth)acrylates of the formula (II) are 2-methacryloyloxyethyl phosphate, bis(2-methacryloyloxyethyl) phosphate and tris(2-methacryloyloxyethyl) phosphate and mixtures thereof.
  • Preferred organosilanes are epoxy-functional silanes, especially 3-glycidoxypropyltrimethoxysilane.
  • Adhesion promoters are used to improve adhesion on special substrates.
  • the use of phosphorus-containing (meth)acrylates according to formula (II) is specifically for metal surfaces (aluminum, anodized aluminum, etc.). advantageous.
  • Organosilanes improve adhesion to glass and ceramic surfaces.
  • Metal (meth)acrylates are also advantageous for bonding to metal surfaces, for example.
  • the proportion of any adhesion promoter present in component K1 is preferably between 1 and 5% by weight, preferably between 1.5 and 3% by weight, based on component K1.
  • the composition in component K1 can preferably additionally contain at least one core-shell polymer.
  • Core-shell polymers consist of an elastic core polymer (core) and a rigid shell polymer (shell).
  • Particularly suitable core-shell polymers consist of a rigid shell of a rigid thermoplastic polymer which is grafted onto a core made of cross-linked elastic acrylate or butadiene polymer.
  • Particularly suitable core-shell polymers are those which swell in the (meth)acrylate monomer A but do not dissolve in it.
  • Preferred core-shell polymers are so-called MBS polymers, which are commercially available, for example, under the trade name Clearstrength® from Arkema Inc., USA, or Paraloid® from Rohm and Haas, USA.
  • the core-shell polymers are preferably used in an amount of 0.01 to 30% by weight, in particular 5 to 10% by weight, based on component K1.
  • the composition in component K1 additionally contains at least one activator for free radical curing, also referred to as a catalyst.
  • the activator is in particular a tertiary amine, a transition metal salt or a transition metal complex.
  • suitable tertary amines are N,N-dimethylaniline, N,N-diethylaniline, N,N-dimethyl-p-toluidine, N,N-diethyl-p-toluidine, N-methyl-N-hydroxyethyl-p-toluidine, N,N-b/s(2-hydroxyethyl)-p-toluidine and alkoxylated N,N-b/s(hydroxyethyl)-p-toluidine, N-ethoxylated p-toluidine, N-alkylmorpholine and mixtures thereof.
  • Transition metal salts and transition metal complexes are, for example, salts and complexes of cobalt, nickel, copper, manganese or vanadium. Mixtures of such substances can also be used as activators.
  • the most preferred activator is N,N-bis-(2-hydroxyethyl)-para-toluidine.
  • the activator is preferably used in an amount of 0.01 to 2.5% by weight, in particular 0.5 to 2.0% by weight, based on component K1.
  • the composition preferably additionally contains an inhibitor for free radical curing in component K1.
  • an inhibitor for free radical curing in component K1.
  • These are substances that somewhat slow down or moderate the radical mechanisms of curing or inhibit undesirable curing reactions (e.g. UV light or atmospheric oxygen-induced mechanisms), which leads to improved storage stability and/or more controlled, uniform curing.
  • Component K1 preferably contains between 0.001% by weight and 0.5% by weight, preferably between 0.01% by weight and 0.25% by weight, based on component K1, of at least one inhibitor for free radical curing, in particular an alkylated phenol, preferably 2, 6-Di-tert-butyl-p-cresol.
  • component K1 additionally contains at least one filler. There must be enough filler included so that the composition has a filler content of at least 50% by weight after mixing the components.
  • chalks natural, ground or precipitated calcium carbonates (chalks), which may be coated with fatty acids, in particular stearates, montmorillonites, bentonites, barium sulfate (BaSC, also called barite or barite), calcined kaolins, quartz powder, aluminum oxides, aluminum hydroxides, silicas , in particular fumed silicas, modified castor oil derivatives and polymer powders or polymer fibers.
  • Calcium carbonates, in particular ground and optionally coated calcium carbonates are preferred.
  • the most preferred filler is calcium carbonate.
  • the filler is preferably obtained in an amount of between 50% by weight and 85% by weight, preferably between 55% by weight and 80% by weight, in particular between 60% by weight and 75% by weight on component K1.
  • the second component K2 of the two-component summary includes at least one initiator for radical hardening.
  • the initiator is a radical generator that forms reactive radicals, which trigger the radical curing mechanism of the monomers in component K1.
  • Molecules which, under the influence of heat or electromagnetic radiation, form radicals which then lead to the polymerization of the composition are particularly suitable as such radical generators.
  • Radical formers include, in particular, thermally activated radical formers and photoinitiators.
  • thermally activatable radical formers are those which are still sufficiently stable at room temperature but already form radicals at slightly elevated temperatures.
  • a radical generator is a peroxide, a perester or a hydroperoxide.
  • Organic peroxides are preferred.
  • Dibenzoyl peroxide is most preferred.
  • Photoinitiators are radical formers that form radicals under the influence of electromagnetic radiation.
  • One is particularly suitable Photoinitiator, which forms radicals when irradiated with electromagnetic radiation with a wavelength of 230 nm to 400 nm and is liquid at room temperature.
  • the photoinitiator is particularly preferably selected from the group consisting of a-hydroxyketones, phenylglyoxylates, monoacylphosphines, diacylphosphines, phosphine oxides and mixtures thereof, in particular 1-hydroxycyclohexylphenyl ketone, benzophenone, 2-hydroxy-2-methyl 1-phenyl-propanone, methyl-phenyl-glycoxylate, oxy-phenyl-acetic acid 2-[2-oxo-2-phenyl-acetoxy-ethoxy]ethyl ester, oxy-phenyl-acetic acid 2-[2-hydroxy-ethoxy]ethyl ester , diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide and mixtures thereof.
  • Such photoinitiators are commercially available, for example, from the IRGACURE® and DAROC
  • Component K2 of the two-component composition preferably contains between 5% by weight and 75% by weight, in particular between 10% by weight and 50% by weight, based on component K2, of the at least one initiator for free radical curing, which is this is in particular a thermally activatable radical generator, preferably a peroxide, a hydroperoxide or a perester, most preferably dibenzoyl peroxide, or it is a photoinitiator, in particular a photoinitiator, which when irradiated with electromagnetic radiation with a wavelength of 230 nm up to 400 nm forms radicals.
  • a thermally activatable radical generator preferably a peroxide, a hydroperoxide or a perester, most preferably dibenzoyl peroxide, or it is a photoinitiator, in particular a photoinitiator, which when irradiated with electromagnetic radiation with a wavelength of 230 nm up to 400 nm forms radicals.
  • the most preferred initiator in component K2 is dibenzoyl peroxide. This is preferably used dispersed in a plasticizer or other inert carrier.
  • Component K2 of the composition according to the invention preferably additionally contains at least one additive selected from the group consisting of plasticizer, filler, thixotope additive and dye, in particular all of these additives. All non-reactive substances that are liquid at room temperature and are usually used in this function in (meth)acrylate compositions are suitable as plasticizers. Oleochemical plasticizers such as castor oil are preferred.
  • fillers as described for component K1 are suitable as fillers.
  • Non-reactive organic dyes and pigments are suitable as dyes. All such additives commonly used in (meth)acrylate compositions are suitable as thixotropy additives.
  • the composition may optionally contain additional components in one or both components K1 and K2.
  • additional components are toughness modifiers, dyes, pigments, inhibitors, UV and heat stabilizers, metal oxides, antistatic agents, flame retardants, biocides, plasticizers, waxes, leveling agents, adhesion promoters, thixotropic agents and other common raw materials and additives known to those skilled in the art.
  • component K1 of the composition comprises between 10% by weight and 20% by weight of (meth)acrylate monomer A, in particular hydroxyethyl methacrylate and/or benzyl methacrylate; b) between 5% by weight and 15% by weight of elastomer C; c) between 0.5% by weight and 2.5% by weight of the free radical curing activator, in particular a tertiary aromatic amine; d) between 0.001% by weight and 0.5% by weight of the free radical curing inhibitor, in particular an alkylated phenol; e) between 50% by weight and 80% by weight of filler, in particular chalk; f) and optionally further additives, in particular between 0.5% by weight and 5% by weight of at least one adhesion promoter; contains.
  • component K2 of the composition comprises between 5% by weight and 50% by weight of the initiator for radical curing, in particular dibenzoyl peroxide; h) between 10% by weight and 75% by weight of filler, in particular chalk; i) between 10% by weight and 40% by weight of plasticizers, in particular oleochemical plasticizers; j) and optionally further additives, in particular thixotropic agents and pigments.
  • the initiator for radical curing in particular dibenzoyl peroxide
  • filler in particular chalk
  • filler in particular chalk
  • plasticizers in particular oleochemical plasticizers
  • j) and optionally further additives in particular thixotropic agents and pigments.
  • a two-component composition consisting of a component K1 as just described and a component K2 as just described, which have a volume ratio K1:K2 of 1:1 to 10:1.
  • the composition according to the invention is always a two-component composition, the two components K1 and K2 of which are stored separately from one another until application.
  • the first component K1 contains in particular those ingredients of the composition described which have radically polymerizable groups.
  • the second component K2 contains in particular the radical formers, also called initiators.
  • other components in particular those which impair the storage stability of the composition by reacting with one another, can also be stored separately.
  • component K1 usually has the components monomers, elastomers, activators, inhibitors, adhesion promoters and fillers and component K2 has the components initiators, optionally pigments, plasticizers and fillers.
  • the volume mixing ratio of K1 to K2 is in particular in the range from 1:1 to 10:1. In certain cases it can be advantageous to color the two components K1 and K2 differently. This allows the mixing quality to be checked when mixing the components and mixing errors can be identified at an early stage. This measure can also be used to qualitatively check whether the intended mixing ratio has been adhered to.
  • a further aspect of the invention relates to a pack which consists of a packaging and a packaged item.
  • the packaging has two separate chambers.
  • the packaged goods are a two-component radically curing composition consisting of a first component K1 and a second component K2, as just described.
  • the components K1 is present in one chamber and the component K2 is present in the other chamber of the packaging.
  • the packaging in particular forms a unit in which the two chambers are held together or tied directly to one another.
  • the separation between the chambers can be, for example, a film or a breakable layer or one or two closures that seal an opening.
  • the packaging is a double cartridge.
  • Another packaging option is a multi-chamber tubular bag or a multi-chamber tubular bag with an adapter, as disclosed, for example, in WO 01/44074 A1.
  • the two components K1 and K2 are preferably mixed using a static mixer, which can be placed on the packaging with two chambers that is preferably used for this process.
  • the two components K1 and K2 are typically stored separately from each other in barrels or hobbocks and are pressed out and mixed during application, for example using gear pumps.
  • the composition can be applied to a substrate by hand or in an automated process using a robot.
  • the composition according to the invention is low-viscosity, both with regard to the two components K1 and K2 and, and particularly advantageously, with regard to the mixture of these two components. This means that the composition according to the invention can be applied easily by machine or by hand.
  • the freshly mixed mixture of the two components has a viscosity of at most 70 Pa s, in particular at most 50 Pa s, particularly preferably at most 40 Pa s, measured by the method described above.
  • Such low-viscosity compositions with a viscosity of at most 70 Pa s or less are particularly suitable for bonding corner angles, frames or profiles in window, door, container or vehicle construction, especially if the composition is sprayed or injected into cavities or gaps shall be.
  • the invention further includes the use of a composition as described above as an adhesive or sealant or for producing coatings, in particular as a structural adhesive.
  • a composition as described above as an adhesive or sealant or for producing coatings, in particular as a structural adhesive.
  • Particular preference is given to using a two-component composition according to the invention as a free-radically curing adhesive, in particular for bonding corner angles, frames or profiles in window, door, container or vehicle construction.
  • the substrate onto whose surface the mixed composition is applied may have been treated in advance with suitable pretreatment agents or cleaners.
  • suitable pretreatment agents or cleaners particularly suitable is the pretreatment or cleaning of the substrates with Sika®Cleaner P or Sika® ADPrep, which are commercially available from Sika Nurse AG.
  • compositions according to the invention have proven to be particularly advantageous because they can be applied without a primer on numerous substrates, in particular on plastics such as PVC and metals such as aluminum or alloys, without loss of adhesion .
  • the invention further comprises a method of bonding substrates S1 and S2 comprising the steps i) applying a composition according to the previous description to a substrate S1; ii) contacting the applied composition with a second substrate S2 within the open time; or i') applying a composition according to the previous description to a substrate S1; ii') applying a composition according to the previous description to a substrate S2; iii') joining the two substrates S1 and S2 applied with composition within the open time; wherein the second substrate S2 consists of the same or a different material as the substrate S1.
  • a step I) of at least partially mixing the two components takes place.
  • the present invention includes a cured composition which was obtained from a previously described composition through a curing process.
  • the composition is characterized by the fact that it does not exhibit any viscoelastic behavior and that there is therefore no, or almost no, plastic deformation of the composition under pressure.
  • the invention also includes articles which have been glued or sealed using a method described above.
  • These articles are preferably a building, in particular a building or civil engineering structure, or an industrial good or a consumer good, in particular a window, a household machine, a tool or a means of transport, in particular a vehicle on water or on land, preferably an automobile, a bus, a truck, a train or a ship.
  • Such articles are also preferred as attachments for industrial goods or means of transport, in particular modular parts that are used as modules on the production line in particular be glued on or glued in.
  • These prefabricated add-on parts are used in particular in the construction of means of transport.
  • such attachments are driver's cabs of trucks or locomotives or sliding roofs of automobiles.
  • These items are preferably windows and doors, such as those used in buildings.
  • the elastomer C1 was prepared as follows:
  • IPDI isophorone diisocyanate
  • HEMA hydroxyethyl methacrylate
  • compositions were prepared:
  • component K1 to be tested the components listed in Table 2 were mixed together in the amounts indicated in a dissolver at a maximum temperature of 80 ° C and stirred in until a macroscopically homogeneous paste was obtained.
  • component K2 20% by weight of paste containing dibenzoyl peroxide (with 50% by weight of peroxide in an inert carrier), 26.5% by weight of castor oil as a plasticizer, 50.5% by weight of chalk, 2.5% by weight of thixotropic agent and 0.5% by weight of a pigment mixed together in a dissolver.
  • This component K2 was used in all experiments in the same way as the respective component K1 from Table 2.
  • the components K1 and K2 produced were filled into the separate chambers of coaxial cartridges and used in a volume ratio K1:K2 of 10:1.
  • the tensile strength and the elongation at break as well as the modulus of elasticity in the range 0.025-0.05% elongation (modulus of elasticity) were determined according to DIN EN 53504 (tensile speed: 200 mm/min) on films with a layer thickness of 2 mm, which were previously exposed for 7 days Standard climate (23 ⁇ 1 °C, 50 ⁇ 5% relative humidity).
  • the adhesion of the adhesive was tested by measuring the lap shear strength.
  • the lap shear strength was determined based on ISO 4587/DIN EN 1465 on a Zwick/Roell Z010 tractor, each on untreated AIMgs substrates (adhesive surface: 15x45 mm; layer thickness: 1.6 mm; measuring speed: 10 mm/min; temperature: 23°C ).
  • the bonded substrates were cured after application of the adhesive for 7 days in a standard climate (23 ⁇ 1 °C, 50 ⁇ 5% relative humidity).
  • the viscosity was measured on a thermostatized Anton Paar rheometer with the Rheoplus software and plate-plate (PP25; diameter 25 mm) measuring system. The viscosity was always measured at 23 °C and a shear rate of 10 s -1 and a plate distance of 1.5 mm.
  • Table 2 Components K1 (E1 and E2) according to the invention. All numbers in percent by weight, based on the respective component K1.
  • compositions according to the invention are mechanically and adhesively suitable for bonding corner brackets, frames or profiles in window, door, container or vehicle construction.
  • the compositions have an exceptionally low viscosity, particularly in the mixture of their respective components, which also makes them suitable for application by injection without special application devices.
  • composition E2 based on benzyl methacrylate (BNMA) has particularly good mechanical properties as well as particularly good adhesion and particularly low viscosity in the mixture of the two components K1 and K2.
  • Examples V1 and V2 have viscosities that are too low to be suitable, for example, as cartridge-applied adhesives for bonding corner angles, frames or profiles in window, door, container or vehicle construction.
  • the difference in viscosity between the respective components K1 and K2 was too large, so that a homogeneous mixture could not be achieved using the coaxial cartridge.

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Abstract

La présente invention concerne une composition à deux composants destinée à être utilisée en tant qu'adhésif à durcissement radicalaire pour la liaison d'angles de coin, de cadres ou de profils pour la construction de fenêtres, de portes, de conteneurs ou de véhicules, constituée d'un composant K1, comprenant a) au moins un monomère (méth)acrylate A ; b) au moins un élastomère C ayant des groupes terminaux (méth)acrylate, préparé à partir de la réaction d'au moins un diol D, d'au moins un diisocyanate, et également d'un acide (méth)acrylique, d'un (méth)acrylamide ou d'un ester (méth)acrylique qui contient un groupe hydroxyle ; c) au moins un activateur de durcissement radicalaire ; d) de préférence au moins un inhibiteur de durcissement radicalaire ; e) au moins une charge ; f) et éventuellement d'autres additifs ; et également un composant K2, comprenant g) au moins un initiateur de durcissement radicalaire ; h) de préférence au moins une charge ; i) de préférence au moins un plastifiant ; J) et également éventuellement d'autres additifs ; caractérisée en ce que la composition contient au moins 50 % en poids, de préférence entre 60 % en poids et 75 % en poids de charge, sur la base du mélange des composants K1 et K2. De telles compositions sont appropriées en tant qu'adhésif à durcissement radicalaire, en particulier pour la liaison d'angles de coin, de cadres ou de profils dans la construction de fenêtres, de portes, de conteneurs ou de véhicules. Les compositions selon l'invention présentent de bonnes propriétés mécaniques et une bonne adhérence à des substrats utilisés dans ces applications, et ont également une faible viscosité et peuvent être formulées sans monomères volatils et fortement malodorants tels que le MMA.
EP23717882.7A 2022-04-07 2023-04-05 Adhésif à base de (méth)acrylate pour liaison d'angle de coin Pending EP4504808A1 (fr)

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EP22167081 2022-04-07
PCT/EP2023/058913 WO2023194422A1 (fr) 2022-04-07 2023-04-05 Adhésif à base de (méth)acrylate pour liaison d'angle de coin

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US4855002A (en) 1983-01-18 1989-08-08 Loctite Corporation Process of bonding surfaces employing/anaerobic aluminum filled compositions
ES2231282T3 (es) 1999-12-17 2005-05-16 Sika Schweiz Ag Adaptador, disposicion y procedimiento para retirar sustancias de bolsas tubulares multicamara, uso del adaptador y envase bolsa tubular.
AU2003303316A1 (en) 2003-11-24 2005-06-08 Samsung Electronics Co., Ltd Uv-hardenable adhesive composition, optical reading head using said composition and optical recording/reproducing device comprising said reading head
ATE447596T1 (de) * 2004-03-09 2009-11-15 Henkel Corp Wärmeleitfähige zweikomponentige klebstoffzusammensetzung
EP2003153A1 (fr) 2007-06-14 2008-12-17 Sika Technology AG Composition (méth)acrylate élastique
US10793758B2 (en) 2014-06-03 2020-10-06 The Yokohama Rubber Co., Ltd. Two-pack type urethane-based adhesive composition

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