EP4355797A1 - Composition de (méth)acrylate présentant une élasticité à basse température améliorée - Google Patents

Composition de (méth)acrylate présentant une élasticité à basse température améliorée

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Publication number
EP4355797A1
EP4355797A1 EP22733392.9A EP22733392A EP4355797A1 EP 4355797 A1 EP4355797 A1 EP 4355797A1 EP 22733392 A EP22733392 A EP 22733392A EP 4355797 A1 EP4355797 A1 EP 4355797A1
Authority
EP
European Patent Office
Prior art keywords
component
weight
meth
group
monomer
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
EP22733392.9A
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 EP4355797A1 publication Critical patent/EP4355797A1/fr
Pending legal-status Critical Current

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1806—C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/282—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing two or more oxygen atoms
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/301—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one oxygen in the alcohol moiety
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
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    • 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
    • C09J11/08—Macromolecular additives
    • 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
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
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    • 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
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    • 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
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
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    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
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    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/53—Core-shell polymer
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    • C09J2433/00—Presence of (meth)acrylic polymer
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    • C09J2475/00—Presence of polyurethane

Definitions

  • the invention relates to the field of two-component (meth)acrylate adhesives, sealants and coatings.
  • (Meth)acrylate compositions have long been used in particular as adhesives or adhesive coatings, since they have good mechanical and optical stability and, above all, allow very good adhesion to many substrates.
  • elastic properties are also important for bonding, sealing and coating, especially in applications that are subject to thermal or mechanical loads.
  • different approaches have been taken.
  • US Pat. No. 3,994,764 describes the addition of non-reactive elastomers, which are stable at room temperature, to the (meth)acrylate composition.
  • WO2008151849 describes elastic (meth)acrylate compositions comprising a first (meth)acrylate monomer selected from a specific list, preferably methyl methacrylate (MMA) and tetrahydrofurfuryl methacrylate (THFMA), and a second (meth)acrylate monomer which is ethylhexyl acrylate (EHA) or diallyl maleate (MADAE ) and additionally an elastomer.
  • MMA methyl methacrylate
  • THFMA tetrahydrofurfuryl methacrylate
  • EHA ethylhexyl acrylate
  • MADAE diallyl maleate
  • the compositions taught in this publication do have improved elastic properties and are particularly suitable for structural and semi-structural applications, such as for bonding glass to PVC and/or aluminum. However, some of these compositions still have insufficient elasticity at low temperatures below zero Celsius, which limits their use.
  • EP 2 272 922 describes (meth)acrylate-based compositions as adhesives, sealants or coatings with improved adhesion on galvanized surfaces, containing (meth)acrylate monomers and at least one metal compound selected from CaO, MgO and Ca(OH) 2 .
  • Polyurethane (meth)acrylates are also taught as optional components of the composition, in addition to other suitable elastomers.
  • US 2019/0233683 discloses pressure-sensitive adhesives for adhesive tapes and films comprising a polymer with poly(meth)acrylate and polyurethane segments in defined ratios. This gives a pressure-sensitive adhesive film which remains transparent in the event of mechanical deformation and shows no turbidity.
  • the object of the present invention is therefore to provide two-component (meth)acrylate compositions which, with optimal elastic properties, are suitable for structural and semi-structural applications and which have adequate elastic properties even at very low temperatures down to -20.degree. Furthermore, these compositions should be able to be formulated without the use of highly volatile and odor-intensive (meth)acrylate monomers such as MMA. Surprisingly, it has now been found that compositions according to claim 1 solve this problem.
  • compositions according to the invention exhibit very good adhesion to a large number of substrates, but in particular to glass, PVC and aluminum.
  • the present invention relates to a two-component composition consisting of a component K1, comprising a) at least one monomer A according to formula (IIIa), where R 1 is either a hydrogen atom or a methyl group, preferably a methyl group;
  • R 2 is either a linear or branched hydroxyalkyl group with 2 to 6 carbon atoms or a radical with 4 to 8
  • R 4 is a linear alkyl radical having more than 12 carbon atoms in the chain and preferably at most 20 carbon atoms in the chain; c) preferably between 10% by weight and 20% by weight, based on component K1, of at least one elastomer C of the formula (I), where R is either a hydrogen atom or a methyl group;
  • X is a polymeric polyol after removal of two OH groups; and Y represents O or NR”, where R” represents a hydrocarbon radical or a hydrogen atom, preferably a hydrogen atom; and d) preferably at least one additive selected from the group consisting of core-shell polymer, activator for free radical curing, inhibitor for free radical curing, filler and adhesion promoter; with the proviso that component K1 contains between 25% by weight and 75% by weight, preferably between 40% by weight and 60% by weight, based on component K1, of the mixture of monomer A and monomer B, and with the proviso that the mass ratio of monomer A to monomer B in component K1 is between 1:1 and 9:1, preferably between 6:4 and 8:2; and a component K2, comprising at least one initiator for free-radical curing.
  • polymer includes, on the one hand, a group of macromolecules that are chemically the same but differ in terms of degree of polymerisation, molar mass and chain length and which were produced by a polyreaction (polymerisation, polyaddition, polycondensation).
  • the term also includes derivatives of such a collective of macromolecules from polyreactions, i.e. compounds which are obtained by reactions, such as additions or substitutions, of functional groups on given macromolecules and which can be chemically uniform or chemically heterogeneous.
  • prepolymers ie reactive oligomeric pre-adducts whose functional groups are involved in the construction of macromolecules.
  • polymeric polyol includes any polymer as defined above, which 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 those polymers that are almost or entirely free of urethane groups. Examples of polyurethane polymers are polyether-poly urethanes, polyester-polyurethanes, polyether-polyureas, polyureas, polyester-polyureas, polyisocyanurates and polycarbodiimides.
  • molecular weight means the defined and discrete molar mass (in grams per mole) of a molecule or part of a molecule, also referred to as the "remainder”.
  • the “average molecular weight” is the number average M n of a particular polydisperse oligomeric or polymeric mixture of molecules or radicals, which is usually determined by means of gel permeation chromatography (GPC) against polystyrene as the standard.
  • (meth)acrylate means "methacrylate” or "acrylate”.
  • a dashed line in the formulas in this document represents the bond between a substituent and the associated moiety, unless otherwise specified.
  • room temperature A temperature of approx. 23°C is referred to as "room temperature”.
  • weight percent means a mass percentage which, unless otherwise noted, is by mass (weight) of the entire composition, or the entire molecule as the context requires.
  • 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 monomer A according to formula (purple), where R 1 is either a hydrogen atom or a methyl group, preferably a methyl group; R 2 is either a linear or branched hydroxyalkyl group of 2 to 6 carbon atoms or a radical of 4 to 8 carbon atoms comprising either a phenyl group or a 5- or 6-membered aliphatic ring having at least one ether oxygen in the ring structure.
  • R 1 is either a hydrogen atom or a methyl group, preferably a methyl group
  • R 2 is either a linear or branched hydroxyalkyl group of 2 to 6 carbon atoms or a radical of 4 to 8 carbon atoms comprising either a phenyl group or a 5- or 6-membered aliphatic ring having at least one ether oxygen in the ring structure.
  • R 1 in formula (lila) preferably represents a methyl group.
  • R 2 in formula (IIIa) represents a linear or branched hydroxyalkyl group having 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 (IIIa) is a radical having 4 to 8 carbon atoms and comprising an aliphatic 5- or 6-membered ring having one or two ether oxygens in the ring structure.
  • R 2 in formula (IIIa) is a hydroxyethyl group or a benzyl group or is at least one of the groups (IVa) to (IVc) in formula (IV),
  • Most preferred monomers A are benzyl methacrylate (BNMA), tetrahydrofurfuryl methacrylate (THFMA), hydroxyethyl methacrylate (HEMA) and glycerol formyl methacrylate (GLYFOMA).
  • BNMA benzyl methacrylate
  • THFMA tetrahydrofurfuryl methacrylate
  • HEMA hydroxyethyl methacrylate
  • GLYFOMA glycerol formyl methacrylate
  • the component K1 further comprises at least one monomer B according to formula (IIIb), where R 3 is either a hydrogen atom or a methyl group, preferably a methyl group; and
  • R 4 is a linear alkyl radical having more than 12 carbon atoms in the chain and preferably not more than 20 carbon atoms in the chain.
  • R 3 in formula (IIIb) preferably represents a methyl group.
  • R 4 in formula (IIIb) preferably represents a linear alkyl radical having 13 to 18 carbon atoms in the chain. If there is a mixture of different chain lengths in the R 4 radical, the average value of the chain lengths is formally used as a measure of the effective chain length in R 4 .
  • Examples of such monomers B 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 contains between 25% by weight and 75% by weight, preferably between 40% by weight and 60% by weight, based on component K1, of the mixture of monomer A and monomer B.
  • the mass ratio of monomer A to monomer B in component K1 should be set to 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.
  • the two-component composition contains no other monomers than the monomers A and B described above.
  • Component K1 also preferably contains between 10% by weight and 20% by weight, based on component K1, of at least one elastomer C of the formula (I), where R is either a hydrogen atom or a methyl group;
  • X is a polymeric polyol after removal of two OH groups; and Y is O or NR”, where R” is a hydrocarbon radical or a hydrogen atom, preferably a hydrogen atom.
  • the elastomer C of the formula (I) preferably has an average molecular weight of from 000 to 40000 g/mol, in particular from 0000 to 30000 g/mol, preferably from 0000 to 20000 g/mol.
  • the radical X represents a polymeric polyol after removal of two OH groups, this polymeric polyol being in particular a polyalkylene polyol, a polyoxyalkylene polyol or a polyurethane polyol; a polyhydroxy functional ethylene-propylene, ethylene-butylene or ethylene propylene diene copolymer; a polyhydroxy-functional copolymer of dienes such as 1,3-butanediene or diene mixtures and vinyl monomers such as styrene, acrylonitrile or isobutylene; a polyhydroxy functional polybutadiene polyol; a polyhydroxy functional acrylonitrile/butadiene copolymer; or a polysiloxane polyol.
  • Polyhydroxy-terminated acrylonitrile/butadiene copolymers are typically prepared from carboxyl-terminated acrylonitrile/butadiene copolymers, which are commercially available, for example, under the name Hycar® CTBN from Emerald Performance Materials, LLC, USA, and epoxides or amino alcohols.
  • Suitable elastomers C of the formula (I) are commercially available, for example, from Kraton Polymers, USA, or under the trade names Hycar® VTB and Hycar® VTBNX from Emerald Performance Materials, LLC, USA.
  • the polymeric polyol is a polymeric diol PD.
  • the elastomer C of the formula (I) is preferably 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.
  • this reaction can be carried out by reacting the diol D and the diisocyanate using customary methods, for example at temperatures of from 50° C. to 100° C., optionally with the use of suitable catalysts, care being taken to ensure that that the NCO groups are present in stoichiometric excess compared to the OH groups.
  • isocyanate-terminated polyurethane polymer is then 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 glycerol or trimethylolpropane, to give a polyurethane (meth)acrylate.
  • HPA hydroxypropyl acrylate
  • HPMA Hydroxypropyl methacrylate
  • HBA Hydroxybutyl acrylate
  • the diol D can be reacted with the diisocyanate, the OH groups being present in a stoichiometric excess over 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, (meth)acrylic acid, (meth)acrylamide or (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 glycerol or trimethylolpropane, with at least one diisocyanate which is used in such 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 give the elasto
  • the elastomer C of the formula (I) by esterifying a (meth)acrylic acid with a diol D, the diol being present in a stoichiometric excess. In a subsequent reaction, the partially esterified diol D reacts with a diisocyanate to form the elastomer C of the formula (I).
  • 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 varying degrees of unsaturation (measured according to ASTM D-2849-69 and reported in milliequivalents of unsaturation per gram of polyol (mEq/g)).
  • Those with one low degree of unsaturation are produced, for example, using so-called double metal cyanide complex catalysts (DMC catalysts), those with a higher degree of unsaturation are produced, for example, using anionic catalysts such as NaOH, KOH, CsOH or alkali metal alcoholates.
  • polyoxyalkylene diols with a low degree of unsaturation in particular less than 0.01 mEq/g, is preferred for diols with a molecular weight of >2000 g/mol.
  • Elastomer C is most preferably a polyurethane (meth)acrylate, in particular preparable from the reaction of at least one diol D, in particular a polyoxypropylene diol, with at least one diisocyanate and a (meth)acrylic ester which has a hydroxyl group, where the diol D reacts with a diisocyanate, in particular isophorone diisocyanate, which is present in a stoichiometric excess; and the resulting polyurethane terminated with isocyanate groups is reacted with the (meth)acrylic ester which has a hydroxyl group, in particular with a hydroxyalkyl (meth)acrylate, preferably with hydroxyethyl acrylate (HEA) or hydroxyethyl methacrylate (HEMA) to give elastomer C of the formula (I).
  • a polyurethane (meth)acrylate in particular preparable from the reaction of at least one dio
  • component K1 contains tetrahydrofurfuryl methacrylate (THFMA) as monomer A, lauryl tetradecyl methacrylate (LATEMA) and/or stearyl methacrylate (STEMA) and in particular no other monomers as monomer B, and a polyurethane (meth)acrylate as elastomer C.
  • THFMA tetrahydrofurfuryl methacrylate
  • LATEMA lauryl tetradecyl methacrylate
  • STEMA stearyl methacrylate
  • component K1 contains glycerol formyl methacrylate (GLYFOMA) as monomer A, lauryl tetradecyl methacrylate (LATEMA) and/or stearyl methacrylate (STEMA) and in particular no other monomers as monomer B, and a polyurethane (meth)acrylate as elastomer C.
  • GLYFOMA glycerol formyl methacrylate
  • LATEMA lauryl tetradecyl methacrylate
  • STEMA stearyl methacrylate
  • component K1 contains hydroxyethyl methacrylate (HEMA) as monomer A, lauryl tetradecyl methacrylate (LATEMA) and/or stearyl methacrylate (STEMA) and in particular no other monomers as monomer B, and a polyurethane (meth)acrylate as elastomer C.
  • HEMA hydroxyethyl methacrylate
  • LATEMA lauryl tetradecyl methacrylate
  • STEMA stearyl methacrylate
  • elastomer C a polyurethane (meth)acrylate
  • component K1 contains benzyl methacrylate (BNMA) as monomer A, lauryl tetradecyl methacrylate (LATEMA) and/or stearyl methacrylate (STEMA) as monomer B and, in particular, no other monomers, and elastomer C, a polyurethane (meth)acrylate.
  • the composition preferably additionally contains between 0.5% by weight and 5% by weight, based on component K1, of an adhesion promoter, in particular an organosilane, and/or a metal (meth)acrylate or a (meth)acrylate Formula (II).
  • the radical R' is either a hydrogen atom or a
  • Methyl group n is from 1 to 15, in particular from 1 to 5, preferably from 1 to 3.
  • m is from 1 to 3 and p is from 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)acrylate, calcium (meth)acrylate, Zn(OH) (meth)acrylate and magnesium (meth)acrylate.
  • 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
  • phosphorus-containing (meth)acrylates according to formula (II) is particularly suitable for metal surfaces (aluminum, anodized aluminum, etc.). advantageous.
  • Organosilanes improve adhesion on glass and ceramic surfaces.
  • Metal (meth)acrylates are also advantageous for bonding to metal surfaces, for example.
  • any adhesion promoter present in component K1 is preferably between 1 and 3% by weight, based on component
  • composition can preferably additionally contain at least one core-shell polymer in component K1.
  • Core-shell polymers consist of an elastic core polymer (core) and a rigid shell polymer (shell).
  • Particularly useful core-shell polymers consist of a rigid shell of rigid thermoplastic polymer grafted onto a core of crosslinked elastic acrylate or butadiene polymer.
  • Particularly suitable core-shell polymers are those which swell in monomer A and/or in comonomer B but do not dissolve therein.
  • 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 from 0.01 to 30% by weight, in particular from 5 to 20% by weight, based on component K1.
  • the composition in component K1 can additionally preferably contain 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 tertiary 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,Nb/s(2-hydroxyethyl)-p-toluidine as well as alkoxylated N,Nb/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 an activator be used. The most preferred activator is N,N-bis-(2-hydroxyethyl)-para-toluidine.
  • the activator is preferably used in an amount of from 0.01 to 2.5% by weight, in particular from 0.5 to 2.5% by weight, based on component K1.
  • composition preferably additionally contains an inhibitor for free-radical curing in component K1.
  • inhibitors for free-radical curing are substances that somewhat slow down or moderate the free-radical mechanisms of curing or inhibit undesirable curing reactions (for example mechanisms induced by UV light or atmospheric oxygen), which leads to improved storage stability and/or more controlled, more uniform curing.
  • Component K1 preferably contains between 0.001% by weight and 0.5% by weight, based on component K1, of at least one inhibitor for free-radical curing, in particular an alkylated phenol, preferably 2,6-di-fe/. butyl-p-cresol.
  • component K1 can preferably additionally contain at least one filler.
  • Particularly suitable here are natural, ground or precipitated calcium carbonates (chalks), which are optionally coated with fatty acids, in particular stearates, montmorillonites, bentonites, barium sulfate (BaS04, also called barite or heavy spar), calcined kaolins, quartz flour, aluminum oxides, aluminum hydroxides, Silicic acids, in particular pyrogenic silicic acids, modified castor oil derivatives and polymer powder or polymer fibers. Calcium carbonates are preferred, and coated calcium carbonates are most preferred.
  • the filler is usually used in an amount of from 0.01 to 35% by weight, in particular from 5 to 30% by weight, preferably 15 to 25% by weight, based on component K1.
  • the second component K2 of the two-component combination comprises at least one initiator for free-radical curing.
  • a free radical generator that forms reactive free radicals, which trigger the free radical curing mechanism of the monomers in component K1.
  • Molecules which form free radicals under the influence of heat or electromagnetic radiation, which then lead to the polymerization of the composition are particularly suitable as such free radical generators.
  • thermally activatable free radical generators and photoinitiators are regarded as free radical generators.
  • Thermally activatable free radical formers are particularly preferred which are still sufficiently stable at room temperature but already form free radicals at slightly elevated temperatures.
  • a radical former is a peroxide, a perester or a hydroperoxide.
  • Organic peroxides are preferred. Most preferred is dibenzoyl peroxide.
  • Photoinitiators are free radical generators that form free radicals under the influence of electromagnetic radiation.
  • a photoinitiator which forms free radicals when irradiated with electromagnetic radiation with a wavelength of 230 nm to 400 nm and is liquid at room temperature is particularly suitable.
  • 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-phe - nyl-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.
  • Photoinitiators of this type are commercially available, for example, from the
  • Component K2 of the two-component composition preferably contains between 5% by weight and 75% by weight, based on component K2, of the at least one initiator for free-radical curing, it being in particular a thermally activatable radical former, 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 to 400 nm forms radicals, acts.
  • a thermally activatable radical former preferably a peroxide, a hydroperoxide or a perester, most preferably dibenzoyl peroxide
  • a photoinitiator in particular a photoinitiator, which, when irradiated with electromagnetic radiation with a wavelength of 230 nm to 400 nm forms radicals, acts.
  • the most preferred initiator in component K2 is dibenzoyl peroxide. This is preferably used in dispersed form in a plasticizer.
  • Component K2 of the composition according to the invention preferably additionally contains at least one additive selected from the group consisting of plasticizer, filler, thixotropic additive and dye, in particular all of these additives.
  • fillers as described for component K1 are suitable as fillers.
  • Non-reactive organic dyes and pigments are suitable as dyes.
  • thixotropic additives all are commonly in
  • composition can optionally also contain further components in one or both components.
  • 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, spacers and other common raw materials and additives known to those skilled in the art.
  • the composition according to the invention is a two-component composition, with its two components K1 and K2 are stored separately from each other until application.
  • the first component K1 contains in particular those ingredients of the composition described which have radically polymerizable groups.
  • the second component K2 includes, in particular, the free-radical generators, 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 contains monomers, elastomers, core-shell polymers, catalysts, adhesion promoters, pigments and fillers
  • component K2 contains free-radical initiators, pigments and fillers.
  • the mixing ratio of K1 to K2 is in particular in the range from 1:1 to 10:1.
  • a further aspect of the invention relates to a pack which consists of a pack and a packaged item.
  • the packaging here 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.
  • Component K1 is in one chamber and component K2 is in the other chamber of the packaging.
  • the package forms a unit in which the two compartments are held together or bonded directly to one another.
  • the separation between the chambers can be, for example, a foil or a frangible layer or one or two closures which a seal the opening.
  • the packaging represents a double cartridge.
  • cartridge packs are state of the art for two-component compositions and are disclosed, for example, in WO2008151849.
  • 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 with the aid of a static mixer which can be placed on the packaging with two chambers preferably used for this method.
  • the two components K1 and K2 are typically stored separately from one another in barrels or hobbocks and are pressed out and mixed during application, for example by means of gear pumps.
  • the composition can be applied to a substrate by hand or in an automated process using a robot.
  • the invention also includes the use of a composition as described above as an adhesive or sealant or for the production of coatings.
  • the invention includes the use of the composition for bonding materials with different linear thermal expansion coefficients, preferably for bonding glass and ceramic substrates with plastics and/or metals.
  • the composition is particularly suitable for bonding materials whose linear thermal expansion coefficients are in a ratio of >2:1 to one another.
  • the linear thermal expansion coefficients of the substrates to be bonded are in a ratio of >3:1 to one another if the substrates to be bonded are glass or a ceramic substrate and a metal; and in a ratio of >8:1 when the substrates to be bonded are glass or a ceramic substrate and a plastic.
  • the linear thermal expansion coefficients are in a ratio of ⁇ 10000:1, preferably in a ratio of ⁇ 100:1, to one another.
  • the invention most preferably includes the use of a composition as described above as an adhesive or sealant in window construction, where glass is bonded to plastics and/or metals, in particular to polyvinyl chloride (PVC) and/or to aluminum.
  • PVC polyvinyl chloride
  • the term aluminum is also to be understood here as alloys of aluminum, in particular with copper, magnesium, silicon, manganese and/or zinc.
  • the aluminum can be subjected to a surface treatment before the composition is applied. Typically, after mechanical (grinding, brushing, blasting, etc.) and/or chemical (pickling, etching, etc.) removal of the aluminum oxide layer, the aluminum is oxidized in a controlled manner, for example by electrolytic aluminum oxidation (ELOXAL ).
  • ELOXAL electrolytic aluminum oxidation
  • Another surface treatment method is the so-called enamelling, in which other inorganic layers, mainly made of oxides and silicates, are applied to the aluminum.
  • composition according to the invention as a sealant for hem flange bonding.
  • the substrate to the surface of which the mixed composition is applied may have been previously treated with suitable pre-treatment agents or cleaners.
  • suitable pre-treatment agents or cleaners The pretreatment or cleaning of the substrates with Sika® Cleaner P or Sika® ADPrep, which are commercially available from Sika Surrey AG, is particularly suitable.
  • compositions according to the invention have proven to be particularly advantageous because they can be applied without a primer to numerous substrates, in particular to glass, PVC and aluminum, without loss of adhesion.
  • the invention also includes a method of bonding substrates S1 and S2, comprising the steps i) applying a composition as described above to a substrate S1; ii) contacting the applied composition with a second substrate S2 within the open time; or i') applying a composition as described above to a substrate S1; ii') applying a composition as described above 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 than the substrate S1.
  • Step i), or i′) and ii′ is preceded by a step I) of at least partially mixing the two components.
  • the invention also includes a method of sealing or of
  • step i) a step I) of at least partially mixing the two components takes place.
  • the present invention comprises a cured composition, which was obtained from a previously described composition by a curing process.
  • the composition is distinguished by the fact that it exhibits no 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 bonded or sealed using a method described above.
  • These articles are preferably a building, in particular a structural or civil engineering structure, or an industrial good or a consumer good, in particular a window, a household appliance, 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 preferably also add-on parts of industrial goods or means of transport, in particular also module parts, which are used as modules on the production line and are in particular glued on or in place.
  • these prefabricated add-on parts are used in the construction of means of transport.
  • such add-on parts are driver's cabs of trucks or locomotives or sunroofs of automobiles.
  • These items are preferably windows and doors as used in buildings.
  • Table 1 Monomers used. 1 monomer A according to the present invention. 2 Monomer B according to the present invention.
  • compositions were made: As component K1 to be tested in each case, the constituents listed in Tables 2 and 3 were mixed with one another in the stated amounts in a dissolver at a maximum temperature of 80° C. and stirred in until a macroscopically homogeneous paste was obtained.
  • component K2 46.5% by weight of dibenzoyl peroxide (20%) in plasticizer, 50% by weight of chalk, 3% by weight of a thixotropic agent and 0.5% by weight of a pigment were mixed together in a dissolver.
  • This component K2 was used in the same way as the respective component K1 from Tables 2 and 3 for all tests.
  • 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 during use.
  • the tensile strength (Tensile Strength, “TS”) and the elongation at break (Elongation at Break, “Elong.”) were determined according to DIN EN 53504 (tensile speed: 200 mm/min) on films with a layer thickness of 2 mm, which were exposed for 7 days cured in standard climate (23 ⁇ 1 °C, 50 ⁇ 5% relative humidity). The measurements were carried out on test specimens that had been stored at a room temperature of 23 °C ( «RT») and also on test specimens of the same composition that were stored at -20°C for 24 hours after curing and measured directly from the cold room were ( «- 20»)
  • Elongation at break is a direct measure of the elasticity of a measured sample. Samples which have an elongation at break of at least 100% in the "RT" measurement and at the same time have an elongation at break of at least 20% in the "-20" measurement are considered to be effective according to the invention.
  • Table 2 Components K1 (E1 to E2) according to the invention and reference components K1 (R1 to R6). All figures in percent by weight, based on the respective component K1.
  • tabel components K1 (R7 to R11). All numbers in percent by weight based on the respective component K1.

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Abstract

L'invention concerne une composition à deux constituants constituée d'un constituant K1 comprenant a) au moins un monomère A selon la formule (IIIa), dans laquelle R1 représente soit un atome d'hydrogène, soit un groupe méthyle, de préférence un groupe méthyle ; R2 représente soit un groupe hydroxyalkyle linéaire ou ramifié comprenant de 2 à 6 atomes de carbone soit un groupe comprenant de 4 à 8 atomes de carbone, ledit groupe comprenant soit un groupe phényle soit un cycle aliphatique à 5 ou 6 chaînons comprenant au moins un oxygène d'éther dans la structure cyclique ; b) au moins un monomère B selon la formule (IIIb), dans laquelle R3 représente soit un atome d'hydrogène, soit un groupe méthyle, de préférence un groupe méthyle ; R4 représente un groupe alkyle linéaire comprenant plus de 12 atomes de carbone dans la chaîne et de préférence au maximum 20 atomes de carbone dans la chaîne ; c) de préférence entre 10 % en poids et 20 % en poids, par rapport au constituant K1, d'au moins un élastomère C de formule (I), dans laquelle R représente soit un atome d'hydrogène, soit un groupe méthyle ; X représente un polyol polymère après élimination de deux groupes OH ; et Y représente O ou NR", dans laquelle R" représente un groupe hydrocarboné ou un atome d'hydrogène, de préférence un atome d'hydrogène ; et d) de préférence au moins un additif choisi dans le groupe constitué par un polymère cœur-écorce, un activateur pour un procédé de durcissement radicalaire, un inhibiteur pour un procédé de durcissement radicalaire, une charge et un adhésif ; à condition que le constituant K1 contienne entre 25 % en poids et 75 % en poids, de préférence entre 40 % en poids et 60 % en poids, par rapport au constituant K1, du mélange de monomère A et de monomère B, et à condition que le rapport du monomère A au monomère B dans le constituant K1 s'inscrive dans la plage entre 1:1 et 9:1, de préférence entre 6:4 et 8:2 ; et d'un constituant K2 comprenant au moins un initiateur pour un procédé de durcissement radicalaire. De telles compositions sont appropriées pour des procédés d'adhérence et d'étanchéité et pour la production de revêtements. Les compositions selon l'invention présentent une élasticité élevée à température ambiante mais sont simultanément suffisamment élastiques même à des températures très basses jusqu'à -20 °C et peuvent être formulées sans monomères volatils qui ont une odeur très désagréable tels que le MMA.
EP22733392.9A 2021-06-15 2022-06-10 Composition de (méth)acrylate présentant une élasticité à basse température améliorée Pending EP4355797A1 (fr)

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AU (1) AU2022292055A1 (fr)
BR (1) BR112023023908A2 (fr)
CA (1) CA3221511A1 (fr)
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WO2025217796A1 (fr) * 2024-04-16 2025-10-23 Henkel Ag & Co. Kgaa Compositions adhésives structurales acryliques à deux composants, articles et ensembles associés
FR3163074A1 (fr) * 2024-06-07 2025-12-12 Bostik Sa Composition bicomposante
EP4660268A1 (fr) 2024-06-07 2025-12-10 Sika Technology AG Composition de (méth)acrylate à élasticité et adhérence à basse température améliorées sur des substrats en pvc
EP4663891A1 (fr) * 2024-06-12 2025-12-17 Sika Technology AG Elément composite pour vitrage isolant
EP4682180A1 (fr) 2024-07-18 2026-01-21 Sika Technology AG Adhésif thermoconducteur à base de (méth)acrylate

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KR20240021772A (ko) 2024-02-19
BR112023023908A2 (pt) 2024-02-06
WO2022263325A1 (fr) 2022-12-22
US20240279456A1 (en) 2024-08-22
CA3221511A1 (fr) 2022-12-22
MX2023013869A (es) 2023-12-08
CN117500854A (zh) 2024-02-02

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