EP4077559A1 - Agent de prétraitement à base de solvant à adhérence améliorée vis-à-vis de cordons de colle résiduels - Google Patents

Agent de prétraitement à base de solvant à adhérence améliorée vis-à-vis de cordons de colle résiduels

Info

Publication number
EP4077559A1
EP4077559A1 EP20824241.2A EP20824241A EP4077559A1 EP 4077559 A1 EP4077559 A1 EP 4077559A1 EP 20824241 A EP20824241 A EP 20824241A EP 4077559 A1 EP4077559 A1 EP 4077559A1
Authority
EP
European Patent Office
Prior art keywords
weight
pretreatment agent
parts
polyisocyanate
adhesive
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
EP20824241.2A
Other languages
German (de)
English (en)
Inventor
Nicole KUBE
Sven Reimann
Michael Schlumpf
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 EP4077559A1 publication Critical patent/EP4077559A1/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
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
    • 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/227—Catalysts containing metal compounds of antimony, bismuth or arsenic
    • 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
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/285—Nitrogen containing compounds
    • C08G18/2865—Compounds having only one primary or secondary amino group; Ammonia
    • 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
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
    • 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
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
    • 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
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • 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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/775—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur sulfur
    • 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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/776—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur phosphorus
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • 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
    • 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
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • 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
    • 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
    • C09J2475/003—Presence of polyurethane in the primer coating
    • 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
    • C09J2483/00—Presence of polysiloxane

Definitions

  • the invention relates to the field of solvent-based pretreatment agents for bondings, as well as methods for bonding or sealing by means of such pretreatment agents.
  • Solvent-based pretreatment agents in particular as primers or primers, have long been used to improve the adhesion of adhesives, sealants, coatings and coverings to the substrate.
  • adhesion promoter compositions enable robust bonding or coating of substrates without these having to be further pretreated in any other way, for example mechanical pretreatment or other complex processes.
  • the rapid evaporation of the solvents also enables fast working and cycle times for bonds in construction or industry or short drive-away times for automobile window repairs.
  • an adhesive When installing replacement windows, in particular windshields, in vehicles, an adhesive must be used to ensure that the new bond meets the requirements for crash resistance, mechanics and tightness after a short time, typically 30 to 60 minutes, as well as over the entire service period. In addition to the required mechanical properties and the high reactivity of the adhesive, robust adhesion between the adhesive and the substrates involved must also be ensured. This is typically achieved through the use of pretreatment agents (adhesion promoters, activators or primers).
  • Black pre-treatment agents containing soot are primarily used for replacement glazing in vehicles. These generally have advantageous properties such as good adhesion promotion and, in particular, increased UV stability. However, they have the disadvantage that, depending on the design of the flange and the color of the paint used, they remain visible on the vehicle after the replacement window has been glued in, if the application is inaccurate or too wide, which is perceived by the customer as aesthetically disturbing. In addition, the risk of clearly visible soiling on other vehicle parts with black pretreatment agents is significantly increased.
  • the object of the present invention is therefore to provide a solvent-based pretreatment agent for adhesive bonds which enables the applied adhesive to adhere very well both to the flange and to the replacement pane.
  • a solvent-based pretreatment agent for adhesive bonds which enables the applied adhesive to adhere very well both to the flange and to the replacement pane.
  • the adhesive that makes up the residual bead is typically a polyurethane adhesive or an adhesive based on silane-functional polymers.
  • the corresponding pretreatment agent should be able to be used over a wide temperature range.
  • this pretreatment agent should be formulated to be clear, transparent and largely colorless.
  • the pretreatment agent according to the invention forms a clear, transparent and at most light-colored film on the substrate and is therefore not permanently visible on the flange after application. In all embodiments, it causes good to very good adhesion of an adhesive applied thereon to the flange, and in particular it improves the adhesion to residual beads, namely both fresh and aged residual beads. Good adhesion to the flange is also achieved if an accelerated hardening (boosted) adhesive system is used.
  • the pretreatment agent also produces very good adhesion to the other substrates relevant to the replacement glazing, such as glass, ceramics and paints, and thus ensures the full functionality of the bond.
  • the present invention relates to a pretreatment agent for bonds containing i) between 10 and 30 parts by weight of at least one isocyanate group-containing polyurethane polymer PU, obtained from the reaction of at least one poly (meth) acrylate polyol P and at least one polyisocyanate
  • the poly (meth) acrylate polyol P has an OH number of at least 35 and the polyurethane polymer PU has an NCO content of between 2.0 and 25.0% by weight, preferably between 3.0 and 20.0% by weight, in particular between 5.0 and 15.0% by weight, based on the polyurethane polymer PU; ii) 0.1 to 10 parts by weight of at least one organosilane OS; iii) 0 to 10 parts by weight of at least one further polyisocyanate I2; iv) 60 to 90 parts by weight of a solvent L; v) 0 to 15 parts by weight of an industrial carbon black; vi) 0 to 10 parts by weight of a pyrogenic hydrophobic silica.
  • polymer comprises, on the one hand, a group of chemically uniform macromolecules that differ in terms of degree of polymerization, molar mass and chain length by a polyreaction (polymerisation, polyaddition, polycondensation).
  • the term also encompasses derivatives of such a collective of macromolecules from polyreactions, i.e. compounds that have been 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 that is, reactive oligomeric pre-adducts, the functional groups of which are involved in the construction of macromolecules.
  • polyurethane polymer encompasses all polymers which are produced using the so-called polyisocyanate polyaddition process. This also includes polymers that are almost or completely free of urethane groups. Examples of polyurethane polymers are polyether-poly urethanes, polyester-polyurethanes, polyether-polyureas, polyureas, polyester-polyureas, polyisocyanurates and polycarbodiimides.
  • a “monomeric diisocyanate” is an organic compound with two isocyanate groups that are separated from one another by a divalent hydrocarbon radical with 4 to 15 carbon atoms.
  • the “NCO content” refers to the content of isocyanate groups in% by weight based on the entire polymer.
  • silane denotes compounds which on the one hand have at least one, usually two, three or four alkoxy groups or acyloxy groups bonded directly to the silicon atom via Si — O bonds.
  • organosilane denotes silanes, which also contain at least one, sometimes two or three via a Si-C-
  • silane bonds have organic radical bonded directly to the silicon atom.
  • Such silanes are also known to the person skilled in the art as organoalkoxysilanes or organoacyloxysilanes. “Tetraalkoxysilanes” are therefore not organosilanes according to this definition, but they are classed as silanes.
  • silane group denotes the silicon-containing group bound to the organic residue of the silane bound via the Si-C bond.
  • the silanes, or their alkoxy or acyloxysilane groups have the property of hydrolyzing on contact with moisture. There Organosilanols are formed, i.e.
  • organosilicon compounds containing one or more silanol groups Si-OH groups
  • organosiloxanes i.e. organosilicon compounds containing one or more siloxane groups (Si-O-Si groups).
  • silane-functional or “silane-functional” denotes compounds which have at least one, in particular hydrolyzable, silane group.
  • silane-functional polymers are accordingly polymers which have at least one, in particular hydrolyzable, silane group.
  • “Aminosilanes”, “Hydroxysilanes” or “Mercaptosilanes” are the names of organosilanes whose organic residue has an amino group, a hydroxyl group or a mercapto group.
  • “Primary aminosilanes” are aminosilanes that have a primary amino group, i.e. an NH2 group that is bound to an organic residue.
  • “Secondary aminosilanes” are aminosilanes which have a secondary amino group, i.e. an NH group that is bonded to two organic radicals.
  • a substance or a composition is referred to as “storage-stable” or “storable” if it can be stored at room temperature in a suitable container for a longer period of time, typically at least 3 months, preferably up to 6 months and more, without it changes in their application or usage properties through storage to an extent relevant to their use.
  • storage-stable or “storable” if it can be stored at room temperature in a suitable container for a longer period of time, typically at least 3 months, preferably up to 6 months and more, without it changes in their application or usage properties through storage to an extent relevant to their use.
  • storage at elevated temperatures can be carried out, which simulates longer storage at lower temperatures, such as room temperature.
  • solids content of the pretreatment agent according to the invention is the percentage by mass which would remain after the volatile constituents (primarily the solvent) had theoretically volatilized.
  • solid content in the context of the present invention refers in particular to the percentage of the sum of the masses of the polyurethane polymer PU, the organosilane OS, and any other further contained non-volatile components such as polyisocyanate I2, based on the total mass of the pretreatment agent.
  • a temperature of approx. 23 ° C is referred to as “room temperature”.
  • molecular weight means the molar mass (in grams per mole) of a molecule or part of a molecule, also referred to as “remainder”.
  • Average molecular weight is the number average M n of an oligomeric or polymeric mixture of molecules or residues, which is usually determined using gel permeation chromatography (GPC) against polystyrene as the standard.
  • Pretreatment agents are between 10 and 30 parts by weight of at least one isocyanate group-containing polyurethane polymer PU, obtained from the reaction of at least one poly (meth) acrylate polyol P and at least one polyisocyanate 11, with the proviso that the poly (meth) acrylate polyol P has an OH number of has at least 35 and the polyurethane polymer PU has an NCO content of between 2.0 and 25.0% by weight, preferably between 3.0 and 20.0% by weight, in particular between 5.0 and 15.0% by weight, based on the polyurethane polymer PU, and that the polyurethane polymer PU preferably has a residual content of unreacted polyisocyanate 11 of ⁇ 0.5% by weight, based on the polyurethane polymer PU.
  • the specified 10 to 30 parts by weight relate to the pure isocyanate-group-containing polymer PU, which in the reaction as above described was created. Any solvents or plasticizers, as they are often contained in the polyols to reduce viscosity, unreacted starting materials, by-products or cleavage products are not included in the 10 to 30 parts by weight.
  • Suitable polyurethane polymers PU containing isocyanate groups are polymers which are obtainable by reacting at least one polyol P with at least one polyisocyanate 11, in particular a diisocyanate or a triisocyanate. This reaction can take place in that the polyol P and the polyisocyanate 11 are reacted by conventional methods, for example at temperatures from 50 ° C. to 100 ° C., preferably using a suitable catalyst, the polyisocyanate 11 being metered in this way that its isocyanate groups are present in a stoichiometric excess in relation to the hydroxyl groups of the polyol P.
  • the excess of polyisocyanate 11 is chosen so that in the resulting polyurethane polymer, after the conversion of all hydroxyl groups of the polyol, a content of free isocyanate groups of 2.0 to 25.0% by weight, preferably between 3.0 and 20.0% by weight, in particular between 5.0 and 15.0 % By weight, based on the total polymer, remains.
  • the polyurethane polymer is preferably produced using solvent L, the solvent L not being allowed to contain any isocyanate-reactive groups.
  • polyurethane polymers PU with the above-mentioned content of free isocyanate groups are preferred, which are obtained from the reaction of polyisocyanate 11 with polyol P in an NCOOH ratio (molar ratio of the NCO groups of polyisocyanate 11 to the OH groups of polyol P) of 1.3: 1 to 10: 1 can be obtained.
  • the reaction is preferably carried out with exclusion of moisture at a temperature in the range from 20 to 160 ° C., in particular from 40 to 140 ° C., if appropriate in the presence of suitable catalysts.
  • the NCO / OH ratio is preferably in the range from 1.3 / 1 to 10/1.
  • The, in particular monomeric, polyisocyanate 11 remaining in the reaction mixture after the conversion of the OH groups can be removed, in particular by means of distillation.
  • the NCO / OFI ratio in the reaction is preferably in the range from 3/1 to 10/1, in particular 4/1 to 7/1, and the isocyanate groups obtained After the distillation, the polyurethane polymer PU containing preferably less than 0.5% by weight, particularly preferably at most 0.3% by weight, of monomeric polyisocyanate 11.
  • the NCO / OFI ratio in the implementation is preferably in the range from 1.3 / 1 to 10/1, preferably from 1.5 / 1 to 8/1. Furthermore, in these cases it is preferred not to use a monomeric but rather an oligomeric polyisocyanate 11 or, most preferably, tris (p-isocyanatophenyl) thiophosphate.
  • the polyurethane polymer PU preferably contains, after its formation and any removal of residual, unreacted polyisocyanate 11, at most 0.5% by weight, preferably at most 0.3% by weight, in particular at most 0.2
  • % By weight, particularly preferably less than 0.1% by weight, of unreacted polyisocyanate 11, based on the total weight of the polyurethane polymer PU. This is particularly preferred when using monomeric diisocyanates such as MDI as polyisocyanate 11. Such a low content of polyisocyanate 11, in particular monomeric diisocyanates, has advantages above all with regard to occupational safety and toxicology.
  • the polyurethane polymer PU is particularly preferably obtained:
  • the poly (meth) acrylate polyol having a mean OH- Has functionality of 3.5 to 4.5 and wherein the molar ratio of isocyanate groups of polyisocyanate 11 to OH groups of poly (meth) acrylate polyol P is between 3/1 and 10/1 and the excess polyisocyanate 11 is removed by distillation after the reaction.
  • Suitable polyols P for the production of the polyurethane polymer PU are exclusively poly (meth) acrylate polyols, although small amounts of other polyols can also be used.
  • the polyols P used to produce the polyurethane polymer PU should consist of at least 90% by weight, preferably at least 95% by weight, most preferably 100% by weight, of poly (meth) acrylate polyols.
  • Poly (meth) acrylate polyols P can be polyacrylate polyols or polymethacrylate polyols. It is essential for the invention that the at least one poly (meth) acrylate polyol P has an OH number of at least 35, preferably at least 40, in particular at least 45, most preferably at least 50.
  • the poly (meth) acrylate polyol P preferably has an OH number of at most 200, in particular at most 180, most preferably at most 150.
  • the parameters OH number, OH functionality and equivalent weight of polyols are related.
  • the OH functionality of a polyol is understood here to mean the mean (average) number of OH groups per polyol molecule. These quantities are defined according to formulas (I) and (II),
  • Equivalence weight M n / OH functionality (II) where the OH number (hydroxyl number) is defined as the amount of potassium hydroxide in milligrams which is equivalent to the amount of acetic acid bound in the acetylation of one gram of polyol, and Mn is the number average molecular weight of the polyol. Both formulas (I) and (II) allow the calculation of the equivalent weight. The values required for the calculation are available experimentally (M n , OH number) or are made known by the manufacturer of the polyols (M n , OH functionality).
  • any small amounts of other polyols such as polyoxyalkylene polyols, polyester polyols and polycarbonate polyols, small amounts of low molecular weight dihydric or polyhydric alcohols such as 1,2-ethanediol, 1,2- and 1,3-propanediol , Neopentyl glycol, diethylene glycol, triethylene glycol, the isomeric dipropylene glycols and tripropylene glycols, the isomeric butanediols, pentanediols, hexanediols, heptanediols, octanediols, nonanediols, decanediols, undecanediols, 1,3- and 1,4-cyclohexaned alcohols, dimethyl alcohol, bisimethanol, hydrogenated bisimethanol, hydrogenated bisimethanol
  • the poly (meth) acrylatolyol P preferably has an average OH functionality of 3.5 to 4.5 and / or an average molecular weight M n , measured with GPC against polystyrene, of 1000 to 4000 g / mol, in particular from 1500 to 3500 g / mol , particularly preferably from 1800 to 2500 g / mol.
  • aliphatic or aromatic polyisocyanates in particular Diisocyanates and triisocyanates, as well as oligomers and polymeric forms of these polyisocyanates, can be used.
  • polyisocyanate 11 suitable as polyisocyanate 11 are commercially available aromatic, aliphatic or cycloaliphatic diisocyanates, in particular 4,4'-
  • Diphenylmethane diisocyanate optionally with proportions of 2,4'- and / or 2,2'-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate or mixtures thereof with 2,6-tolylene diisocyanate (TDI), 1,4-phenylene diisocyanate (PDI) , Naphthalene-1,5-diisocyanate (NDI), 1,6-hexane diisocyanate (HDI), 2, 2 (4), 4-trimethyl-1, 6-hexamethylene diisocyanate (TMDI), cyclohexane-1, 3- or -1 , 4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate or IPDI), perhydro-2,4'- or -4,4'-diphenylmethane diisocyanate (HMDI), 1,3- or
  • MDI is particularly preferred.
  • MDI is particularly preferred, in particular 4,4'-diphenylmethane diisocyanate (4, 4 '-MDI).
  • the 4,4'-MDI is in particular of a quality which contains only small proportions of 2,4'- and / or 2,2'-diphenylmethane diisocyanate and is solid at room temperature.
  • the isocyanate groups of the polyurethane polymer PU are thus derived from diphenylmethane diisocyanate.
  • Suitable diisocyanate oligomers as polyisocyanate 11 are in particular
  • HDI biurets such as Desmodur ® N 100 N or 3200 (from Covestro AG), Tolonate ® HDB or HDB-LV (from Vencorex), or Duranate 24A-100 ® (by Asahi Kasei); HDI isocyanurates such as Desmodur ® N 3300, N 3600 or N 3790 BA (all from Covestro), Tolonate ® HDT, HDT-LV or HDT-LV2 (from Vencorex), Duranate ® TPA-100 or THA-100 (from Asahi Kasei ) or Coronate ® HX
  • HDI uretdiones as Desmodur ® N 3400 (from Covestro); HDI Iminooxadiazindiones as Desmodur ® XP 2410 (of Covestro); HDI allophanates such as Desmodur ® VP LS 2102 (from Covestro); IPDI isocyanurates such as in solution as Desmodur ® Z 4470 (from Covestro) or in solid form as Vestanat ® T1890 / 100 (Evonik Industries); TDI oligomers such as Desmodur ® IL (from Covestro); or mixed isocyanurates based on TDI / HDI such as Desmodur ® HL (from Covestro).
  • polyisocyanate are suitable 11 triisocyanates, especially Methylidyntri-p-phenylentriisocyanat (triphenylmethane triisocyanate, for example, Desmodur ® RE), trimers of HDI (for example, Desmodur ® N-3300 and N-3390), trimer of IPDI, for example, Desmodur ® Z4470BA, and Tris (p-isocyanatophenyl) thiophosphate (for example Desmodur ®
  • Methylidyntri-p-phenylentriisocyanat triphenylmethane triisocyanate
  • trimers of HDI for example, Desmodur ® N-3300 and N-3390
  • trimer of IPDI for example, Desmodur ® Z4470BA
  • Tris (p-isocyanatophenyl) thiophosphate for example Desmodur ®
  • MDI methylenediphenyl diisocyanate
  • PMDI oligomeric or polymeric MDI
  • tris p-isocyanatophenyl thiophosphate
  • polyisocyanate 11 tris (p-isocyanatophenyl) thiophosphate is most preferred.
  • the polyurethane polymer PU containing isocyanate groups is preferably prepared in the presence of a catalyst which can catalyze the reaction of the polyisocyanate I with the polyol P. It is preferably a metal catalyst, in particular a bismuth, tin or zirconium catalyst.
  • Suitable metal catalysts which are very well known to those skilled in the field of polyurethane chemistry are, for example, compounds of titanium, bismuth, zirconium or tin, in particular organotin compounds, organobismutates, organotitanates or
  • Organozirconates these metal catalysts in particular having ligands with alkoxy groups, sulfonate groups, carboxyl groups, dialkyl phosphate groups, dialkyl pyrophosphate groups and diketonate groups.
  • Tin, bismuth and zirconium catalysts are particularly preferred. Compared to other catalysts, for example titanates, these have the advantage that no possibly undesirable discoloration occurs in the composition.
  • Suitable catalysts are catalysts for accelerating the reaction of isocyanate groups, in particular organotin (IV) compounds such as, in particular, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, di-butyltin diacetylacetonate, dimethyltin dilaurate, dioctyltin diacetone, or dioctyltin diacetone (IV), or dioctyltin diacetone (IV) or dioctyltin diacetone (IV) butyltin diacetate, dioctyltin diacetate (IV) or ), in particular with ligands selected from alcoholates, carboxylates, 1,3-diketonates, oxinate, 1,3-ketoesterates and 1,3-ketoamidates, or compounds containing tertiary amino groups such as in particular 2,2'-dimorpholinodiethylether
  • a bismuth catalyst in particular a bismuth carboxylate, is particularly preferably used in the production of the polyurethane polymer PU.
  • the catalyst which usually remains in the polyurethane polymer PU and thus in the composition after the reaction, can also take on the role of a hydrolysis or crosslinking catalyst for organosilanes OS. This can be advantageous during and after the application of the adhesion promoter composition, since a substantial acceleration or improvement of the adhesion promoter effect can be achieved.
  • the organosilane OS is in an amount of 0.1 to 10 parts by weight, in particular 0.5 to 9 parts by weight, preferably 1 to 8 parts by weight, in particular 2.5 to 7 parts by weight per 10 to 30 parts by weight of the
  • Organosilane OS enables good adhesion on glass and ceramic substrates and, depending on the organic residue, on many others Substrates. In addition, if they are an organic radical with a functional group that can react with isocyanate groups (such as amino, hydroxyl or mercapto groups), organosilanes OS can react with the polyurethane polymer PU and thus build up a particularly good adhesive bond.
  • organosilanes OS examples include hydroxysilanes, epoxysilanes, alkylsilanes, isocyanatosilanes, acrylatosilanes, mercaptosilanes or aminosilanes.
  • organosilicon compounds selected from the group comprising octyltrimethoxysilane, dodecyltrimethoxysilane, hexadecyltrimethoxysilane, methyloctyldimethoxysilane; 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane; 3-methacryloxypropyltrialkoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane;
  • Isocyanuratosilane compounds such as 1,3,5-N-tris (3-trimethoxysilylpropyl) isocyanuratosilane, 1,3,5-N-tris (3-methyldimethoxysilylpropyl) isocyanuratosilane, 1,3,5-N-tris (3-triethoxysilylpropyl) isocyanuratosilane , 1,3,5-N-tris (3-methyl-diethoxysilylpropyl) isocyanuratosilane;
  • the organosilicon compounds mentioned are also suitable, their
  • organosilicon compounds split off acetic acid during hydrolysis.
  • Hydroxysilanes are also suitable.
  • organosilicon compounds selected from the group comprising bis [3- (trimethoxysilyl) propyl] amine, bis [3-
  • (triethoxysilyl) propyl] amine 4,4, 15,15-tetraethoxy-3, 16-dioxa-8,9, 10,11-tetrathia-4-15-disilaoctadecane (bis (triethoxysilylpropyl) polysulfide or bis- ( triethoxysilylpropyl) tetrasulfane), bis (triethoxysilylpropyl) disulfide.
  • the organosilane OS is preferably an aminosilane of the formula (III).
  • the radical R 1 here stands for an alkyl group with 1 to 8 carbon atoms, in particular for a methyl or an ethyl group.
  • the radical R 2 represents an alkyl group with 1 to 12 carbon atoms, in particular an alkyl group with 2 to 8 carbon atoms, preferably a methyl, ethyl or isopropyl group, most preferably a methyl or ethyl group .
  • R 9 here independently represents a divalent, linear or branched, optionally cyclic, alkylene group with 1 to 20 carbon atoms, optionally with aromatic components, and optionally with one or more heteroatoms, in particular nitrogen atoms.
  • suitable organosilanes of the formula (III) are, for example, the organosilanes selected from the group comprising bis [3- (trimethoxysilyl) propyl] amine and bis [3- (triethoxysilyl) propyl] amine.
  • Suitable hydroxysilanes are, for example, those as described in EP2805985 (in particular p. 2, line 51 to p. 3, line 28) and WO 2013/174891 (in particular p. 6, line 11 to p. 8, Line 5) and WO 2013/174892 (in particular page 6, line 6 to page 7, line 6).
  • Suitable mercaptosilanes are, for example, 3-
  • Organosilane OS that have at least one hydrolyzable alkoxylsilane group and are selected from the group consisting of aminosilanes, hydroxysilanes, epoxysilanes, mercaptosilanes, isocyanuratosilanes, reaction products of amines and epoxysilanes, reaction products of aminosilanes and epoxides, reaction products of aminosilanes and epoxysilanes, reaction products of aminosilanes and epoxysilanes, are particularly preferred and aminosilanes, reaction products of isocyanates and hydroxysilanes, tetraalkoxy titanates, dialkoxy-bis-acetylacetonato-titanates, and mixtures, hydrolysates, partial hydro
  • the pretreatment agent according to the invention can also contain additional polyisocyanates. If necessary, these are added after the synthesis of the
  • Polyurethane polymer PU added in the final formulation of the pretreatment agent together with the organosilane OS and the solvent L or can already be present during the synthesis of polyurethane polymer PU. In the context of this description they are referred to as polyisocyanates 12.
  • polyisocyanates 12 has the advantage that the processability and in particular also the open time of the pretreatment agent are improved. Furthermore, the adhesion to certain substrates is further improved.
  • the polyisocyanate 12 is preferably used in an amount of 1 to 10 parts by weight, preferably 2 to 8 parts by weight, in particular 3 to 7 Parts by weight per 10 to 30 parts by weight of the isocyanate group-containing polyurethane polymer PU contained in the pretreatment agent.
  • polyisocyanates which can be used for polyisocyanate 11 can be used as polyisocyanates I2.
  • polyisocyanate I2 can be identical to polyisocyanate II.
  • an excess of polyisocyanate 11 can be used in the synthesis of polyurethane polymer PU, in which case unreacted polyisocyanate 11 can remain in the reaction mixture as polyisocyanate I2.
  • the polyisocyanate I2 is preferably selected from the group consisting of methylenediphenyl diisocyanate (MDI), oligomeric or polymeric MDI (PMDI), tris (p-isocyanatophenyl) thiophosphate and oligomeric or polymeric hexamethylene-1,6-diisocyanate (PHDI), and is with in an amount of 1 to 10 parts by weight per 10 to 30 parts by weight of polyurethane polymer PU in the pretreatment agent.
  • MDI methylenediphenyl diisocyanate
  • PMDI oligomeric or polymeric MDI
  • PTDI tris
  • organosilane OS as described above;
  • the pretreatment agent consists of these four components, with any unreacted polyisocyanate 11 present from the synthesis of the polyurethane polymer PU being regarded as polyisocyanate I2 and / or catalyst is also included in the weight of the polyurethane polymer PU.
  • composition is the organosilane OS an aminotrialkoxysilane and / or the polyisocyanate 11 tris (p-isocyanatophenyl) thiophosphate and / or the polyisocyanate I2 tris (p-isocyanatophenyl) thiophosphate.
  • Solvent L is the organosilane OS an aminotrialkoxysilane and / or the polyisocyanate 11 tris (p-isocyanatophenyl) thiophosphate and / or the polyisocyanate I2 tris (p-isocyanatophenyl) thiophosphate.
  • the pretreatment agent according to the invention comprises at least one solvent L.
  • Suitable solvents L are all solvents which sufficiently dissolve or at least disperse the constituents of the binder composition so that a stable solution or dispersion is formed.
  • the solvents L should not have any functional groups that are reactive toward isocyanates or alkoxysilanes, such as hydroxyl groups. Thus, for example, alcohols are not suitable.
  • the solvent L has a comparatively high volatility, that is to say a comparatively low boiling point and / or vapor pressure, so that the solvent L evaporates or volatilizes rapidly after the adhesion promoter according to the invention has been used.
  • low-volatility or high-boiling solvents can also be used, but these may then have to be removed using a “wipe-off process (wiping off or sucking up the solvent after the binder has set on the substrate).
  • Suitable solvents L are, for example, esters of linear or branched Ci to C ⁇ carboxylic acids, in particular mono- or diacids, which have been esterified with fatty alcohols or linear or branched Ci to C ⁇ monoalcohols, as well as esters of low molecular weight alcohols, in particular Ci to C6 alcohols, which have been esterified with fatty acids and cyclic such esters. Examples of these are methyl laurate, ethyl laurate, methyl myrstin and lauryl acetate.
  • esters are also esters of carbonic acid or monocarboxylic acids or polycarboxylic acids.
  • the dialkyl carbonates are to be mentioned in particular as esters of carbonic acid.
  • Esters of carboxylic acids with polyethylene glycols or polypropylene glycols are also suitable.
  • esters are organic phosphonates and phosphates.
  • Cyclic esters i.e. lactones, are also suitable.
  • Further suitable as solvent L are linear or branched ether compounds with one or two ether functions bridging C2 to C12 alkyl radicals.
  • ethers are, in particular, alkoxy-terminated polyols, in particular alkoxy-terminated polyoxyalkylene polyols, including alkoxy-terminated polyether polyols. examples for this are
  • Polypropylene glycol dialkyl ether or polyethylene glycol dialkyl ether are examples of these are tetraglyme (tetraethylene glycol dimethyl ether), pentaglyme (pentaethylene glycol dimethyl ether), hexaglyme (hexaethylene glycol dimethyl ether), polyethylene glycol dimethyl ether, for example as sold commercially by Clariant under the names of polyglycol ether, polyglycol ether, polypropylene glycol ether, polypropylene glycol dimethyl glycol, polyglycol DME 250utylene glycol, propylene glycol ether, polypropylene glycol, propylene glycol, diethylene glycol, propylene glycol, propylene glycol, diethylene glycol ether, propylene glycol dimethyl ether, propylene glycol - monoacetate and polypropylene glycol monomethyl ether monoacetate.
  • Poly Propylene glycol diethers have the advantage over the corresponding polyethylene glycol diethers that they are typically still liquid due to better dissolution behavior and higher molecular weights.
  • solvent L also suitable as solvent L are ketones with linear or branched C 1 to C 12 alkyl radicals and amides, in particular fatty acid amides or cyclic amides, ie lactams.
  • the pretreatment agent can also, as solvent L, be a carrier agent which is liquid at room temperature and has a boiling point of greater than 250 ° C. at standard pressure or a vapor pressure of less than 0.1 mbar at 20 ° C.
  • solvent L a carrier agent which is liquid at room temperature and has a boiling point of greater than 250 ° C. at standard pressure or a vapor pressure of less than 0.1 mbar at 20 ° C.
  • VOC refers to volatile organic compounds.
  • Suitable carriers for low-VOC or VOC-free compositions are on the one hand plasticizers with a boiling point of greater than 250 ° C at standard pressure or a vapor pressure of less than 0.1 mbar at 20 ° C.
  • the plasticizers are selected from the group consisting of esters of phthalic acids, esters of aliphatic dicarboxylic acids and fatty acid esters and organic esters of phosphoric acids. As an ester of
  • Phthalic acids are particularly the dialkyl phthalates, preferably the diesters of phthalic acid and Cs-Ci6 alcohols, in particular dioctyl phthalate (DOP), diisononyl phthalate (DINP) and diisodecyl phthalate (DIDP).
  • DOP dioctyl phthalate
  • DINP diisononyl phthalate
  • DIDP diisodecyl phthalate
  • Esters of aliphatic dicarboxylic acids are, in particular, the esters of adipic acid or sebacic acid, such as, for example, dioctyl adipate (DOA) and diisodecyl adipate (DIDA).
  • DOA dioctyl adipate
  • DIDA diisodecyl adipate
  • polyesters such as, for example, polyesters of adipic acid or sebacic acid with diols, such as, for example, hexanediol or butanediol, with the proviso that these polyesters are liquid at room temperature.
  • diols such as, for example, hexanediol or butanediol
  • the proviso applies that they must be liquid (flowable) at 23 ° C., preferably at 10 ° C., in particular at 5 ° C.
  • the solvent L is selected from the group consisting of carboxylic acid esters, in particular methyl acetate, ethyl acetate, butyl acetate, isopropyl acetate, 1-methoxy-2-propyl acetate and 3-methoxy-n-butyl acetate, ketones, especially acetone, butanone , Methyl ethyl ketone and methyl isobutyl ketone, acetals, especially ethylal, and aromatic hydrocarbons, especially toluene and ethylbenzene, and mixtures of these solvents.
  • carboxylic acid esters in particular methyl acetate, ethyl acetate, butyl acetate, isopropyl acetate, 1-methoxy-2-propyl acetate and 3-methoxy-n-butyl acetate
  • ketones especially acetone, butanone , Methyl ethyl ketone and methyl
  • the amount of solvent L1 in the binder composition is between 60 and 90 parts by weight, preferably 65 to 80 parts by weight per 10 to 30 parts by weight of the isocyanate group-containing polyurethane polymer PU
  • constituents of the pretreatment agent are insoluble or insoluble in solvent L, for surfactants, in particular in the form of emulsifiers and / or co-emulsifiers, to be constituents of the pretreatment agent.
  • surfactants in particular in the form of emulsifiers and / or co-emulsifiers
  • Such substances are known to those skilled in the art of solvent-based adhesion promoter compositions.
  • the pretreatment agent according to the invention can also contain further additives. These include, in particular, organotitanates, carbon black, silicas, in particular pyrogenic hydrophobic silicas, UV markers, and other additives that are customary for pretreatment agents. Organotitanates can be added as adhesion-promoting additives. Organotitanates here have at least one substituent bonded to the titanium atom via an oxygen-titanium bond.
  • Particularly suitable for this are compounds in which all of the substituents bonded to the titanium are selected from the group consisting of alkoxy group, sulfonate group, carboxylate group, dialkyl phosphate group, dialkyl pyrophosphate group and acetylacetonate group, it being possible for all substituents to be identical or different from one another.
  • Carboxylates of fatty acids have proven particularly suitable as carboxylate groups. Decanoate is the preferred carboxylate.
  • Organotitanium compounds which are suitable as organotitanates in the pretreatment agent according to the invention are commercially available, for example from Kenrich Petrochemicals or DuPont.
  • suitable organo-titanium compounds are, for example, Ken-React ® KR TTS, KR 7, KR 9S, KR 12 KR 26S, KR 33DS, KR 38S, KR 39DS, KR44, KR 134S, KR 138S, KR 158FS, KR212, KR 238S, KR 262ES, KR 138D, KR 158D, KR238T, KR 238M, KR238A, KR238J, KR262A, LICA 38J, KR 55, LICA 01, LICA 09, LICA 12, LICA 38, LICA 44, LICA 97, LICA 99, KR OPPR, KR OPP2 from Kenrich Petrochemicals or Tyzor ® ET, IBAY, TBT, TOT T
  • Tyzor® TBT, Tyzor® OGT and, particularly preferred, Tyzor® IBAY are particularly preferred.
  • organotitanium compounds hydrolyze under the influence of water and form OH groups bonded to the Ti atom. Such hydrolyzed or partially hydrolyzed organotitanium compounds can then in turn condense and form condensation products which have Ti-O-Ti bonds.
  • silanes and / or titanates are mixed in the adhesion promoter, mixed condensation products are also possible which have Si-O-Ti bonds. A small proportion of such condensation products is possible, especially if they are soluble, emulsifiable or dispersible.
  • Organotitanates if present, are usually used in the same amounts as the organosilane OS.
  • the pretreatment agent can furthermore preferably contain at least one drying agent. This increases the storage stability of the composition by binding any water present and thus inhibiting the undesired, premature hydrolysis and condensation of alkoxysilanes in the container.
  • Suitable drying agents are, for example, reactive silanes such as tetramethoxysilane, vinyltrimethoxysilane, ⁇ -functional silanes such as N- (silylmethyl) -O-methyl-carbamate, in particular N- (methyldiethoxysilylmethyl) -O-methyl-carbamate, (methacryloxymethyl) silanes, ethoxymethylsilanes , N-phenyl-, N-cyclohexyl- and N-alkylsilanes, orthoformic acid esters, calcium oxide or molecular sieves, and isocyanates.
  • reactive silanes such as tetramethoxysilane, vinyltrimethoxysilane
  • ⁇ -functional silanes such as N- (silylmethyl) -O-methyl-carbamate, in particular N- (methyldiethoxysilylmethyl) -O-methyl-carbamate, (methacryloxymethyl) silanes, ethoxymethyl
  • the amount of drying agent in the pretreatment agent is between 0 and 3% by weight, preferably between 0.5 and 2% by weight, based on the total pretreatment agent.
  • the pretreatment agent contains a filler.
  • the filler can be inorganic or organic. It is particularly advantageous if the filler has a particle diameter of less than 100 micrometers, in particular less than 1 micrometer. Carbon black, chalk, in particular coated chalk, and different forms of silicon dioxide, such as quartz powder, colloidal or pyrogenic silicas, preferably pyrogenic silicas, most preferably pyrogenic hydrophobic silicas, are particularly preferred. The most preferred filler is considered to be Carbon black. This leads to a particularly good UV resistance of the bond, which is advantageous, for example, for window and automobile glass bonds.
  • Preferred amounts of filler, in particular carbon black are 0 to 30% by weight, in particular 5 to 20% by weight, preferably 7 to 15% by weight, based on the total flaft promoter composition.
  • Any filler present is preferably contained in the pretreatment agent in an amount of 0.1 to 15 parts by weight, in particular 0.5 to 10 parts by weight per 10 to 30 parts by weight of the isocyanate group-containing polyurethane polymer PU.
  • a preferred amount of carbon black in the composition is in particular 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight per 10 to 30 parts by weight of the isocyanate group-containing polyurethane polymer
  • a preferred amount of pyrogenic hydrophobic silica in the composition is in particular 0.1 to 10 parts by weight, preferably 0.5 to 7.5 parts by weight per 10 to 30 parts by weight of the isocyanate group-containing polyurethane polymer PU.
  • fillers are also particularly suitable for mechanical reinforcement of the pretreatment agent. Furthermore, thicker-layered applications can be realized using fillers.
  • a particularly preferred embodiment of the pretreatment agent according to this invention is free from fillers, in particular free from carbon black and pyrogenic hydrophobic silica. This enables clear, transparent and largely colorless pretreatment agents to be produced in a simple manner, which have the advantage, in particular over soot-containing pretreatment agents, that they leave no visible traces after use.
  • the pretreatment agent is a primer, it can be advantageous if at least one organic film former is also used. This can be, for example, an epoxy resin or poly (meth) acrylate.
  • the composition can also have other components.
  • these are pigments, dyes, UV markers, fluorescent indicators, leveling additives, biocides, in particular algicides or fungicides, thixotropic agents, flame retardants and stabilizers.
  • the pretreatment agent according to the invention particularly preferably contains a UV marker. This is a substance that becomes visible under UV light. The use of such a substance has the advantage that, after the application of transparent pretreatment agents, it is possible to check exactly where the composition has been applied and / or where the adhesive is to be applied.
  • the pretreatment agents according to the invention can be used in many ways. In a particularly preferred embodiment, they represent a primer or an adhesion promoter undercoat.
  • the present invention relates to a method for gluing or for sealing.
  • This method comprises the following steps: i) application of a pretreatment agent as described above to a substrate S1 to be bonded or sealed; ii) Preferably flashing off the applied pretreatment agent, so that a film is formed from the pretreatment agent on the substrate S1; iii) application of an adhesive or sealant to the film which was formed from the pretreatment agent and which is located on the substrate S1; iv) Contacting the adhesive or sealant with a second substrate S2, with the second substrate optionally also beforehand has been treated with the same or a different pretreatment agent.
  • any commercially available adhesive or sealant can be used as the adhesive or sealant in the above-mentioned process.
  • the selection depends, among other things, on the open time and the mechanical requirements of the bond formed. It has been shown that this method is particularly suitable for polyurethane adhesives or sealants, in particular for polyurethane adhesives which contain at least one polyurethane prepolymer having isocyanate groups.
  • Polyurethane adhesives cure under the influence of humidity on a crosslinking reaction of the isocyanate groups and are widely available commercially, in particular under the name Sikaflex ®, SikaTack ® or SikaBond ® Sika Switzerland AG.
  • the adhesion promoter composition is also particularly suitable for silane-terminated
  • Adhesion promoter composition film i.e. "wet on wet" is possible without this resulting in noticeable disadvantages in the adhesion or the mechanics of the cured sealant or adhesive.
  • a suitable and preferred flash-off time for step ii) is between 1 and 20 minutes, preferably between 2 and 15 minutes, in particular between 3 and 10 minutes, the temperature at which the flashing off takes place surprisingly does not play a major role.
  • the substrate S1 can be identical to or different from substrate S2.
  • Suitable substrates S1 or S2 are, for example, inorganic substrates such as glass, glass ceramic, concrete, mortar, brick, brick, plaster of paris and natural stones such as granite or marble; Metals or alloys such as aluminum, steel, non-ferrous metals, galvanized metals; organic substrates such as wood, plastics such as PVC, polycarbonates, PMMA, polyester, epoxy resins; coated substrates such as powder-coated metals or alloys; as well as paints and varnishes.
  • Particularly preferred substrates S1 or S2 are glass, glass ceramic, aluminum and lacquers, in particular in the form of automotive lacquer.
  • the substrates can be additionally treated before the pretreatment or the adhesive or sealant is applied.
  • additional pretreatments include, in particular, physical and / or chemical cleaning processes, for example grinding, sandblasting, brushing or the like, or treatment with cleaners or solvents.
  • the substrate S1 comprises the residual bead of a previously partially removed, old cured adhesive, metal or lacquered metal
  • substrate S2 comprises glass, metal, lacquered metal or ceramic.
  • the described adhesive or sealant is a polyurethane adhesive which contains at least one isocyanate-containing polyurethane prepolymer or an adhesive based on silane-functional polymers.
  • the present invention thus relates to an article for the production of which a method as described above has been used.
  • this is an article that is a building, an industrial good or a means of transport.
  • it represents a building or a part thereof.
  • the article is in particular a means of transport, in particular an automobile, bus, truck, rail vehicle, ship or aircraft.
  • the polyols in Table 1 were used as polyol P for the production of the exemplary isocyanate-containing polyurethane polymers PU.
  • Desmcdur RFE 88.5 parts by weight of Desmcdur RFE were placed in a vessel and then 11.5 parts by weight of Arufcn UH-2041 were added with stirring. The mixture was heated to 60 ° C. and allowed to react for 8 hours. The reaction was terminated when the measurement of the free NCO groups remained stable.
  • Desmodur RFE 82 parts by weight of Desmodur RFE were placed in a vessel and then 18 parts by weight of Desmophen 670 BA (80% by weight in butyl acetate) were added with stirring. The mixture was heated to 60 ° C. and allowed to react for 8 hours. The reaction was terminated when the measurement of the free NCO groups remained stable.
  • Preparation of the pretreatment agent C7 (not according to the invention) 65 parts by weight of Desmodur RFE were placed in a vessel and then 35 parts by weight of Baycoll AD 2047 were added with stirring. The mixture was heated to 60 ° C. and allowed to react for 8 hours. The reaction was terminated when the measurement of the free NCO groups remained stable. 38.05 parts by weight of the reaction mixture obtained were 61.95
  • the volatile constituents in particular most of the monomeric 4,4'-diphenylmethane diisocyanate, were then removed by distillation in a short-path evaporator (jacket temperature 180 ° C., pressure 0.1 to 0.005 mbar, condensation temperature 47 ° C.).
  • the poly (meth) acrylate urethane polymer thus obtained had an NCO content of 4.8% by weight, a viscosity of 50.7 Pa s at 60 ° C. and a content of monomeric 4,4′-diphenylmethane diisocyanate of 0.12% by weight .
  • the pretreatment agents C1 to C10 were placed in tightly closing glass bottles and used for the adhesion tests after storage for 1 day at room temperature.
  • the pretreatment agents produced were then each applied to an air side and a tin side of a float glass substrate and to the ceramic substrates mentioned below using cellulose cloth ( Tela® , Tela-Kimberly Switzerland GmbH) soaked therewith.
  • SikaTack ® Drive is a one-component moisture-curing polyurethane adhesive which Polyurethane prepolymers with isocyanate groups, but does not contain any adhesion promoters and is commercially available from Sikatician AG.
  • SikaTack ® Drive is an adhesive that is used specifically for bonding vehicle windshields.
  • the adhesive was stored in a standard climatic room (23 ° C, 50% rel. Humidity) (“7d NC”), as well as after a subsequent water storage (“7d H2O”) in water at 23 ° C for 7 days, as well as after a subsequent heat storage of one day at 80 ° C in the oven (“1d 80 ° C”), as well as after a subsequent cataplasm storage (“7d KPL”) of 7 days at 70 ° C, 100% rel. Air humidity, tested for adhesion.
  • the adhesion of the adhesive was tested using a "bead test".
  • the bead is cut at the end just above the adhesive surface.
  • the incised end of the caterpillar is held in place with round pliers and pulled from the ground. This is done by carefully rolling the bead onto the tip of the pliers and placing a cut perpendicular to the bead pulling direction down to the bare surface.
  • the bead removal speed should be selected so that a cut must be made approx. Every 3 seconds.
  • the test route must be at least 8 cm.
  • the adhesive remaining on the substrate after the bead has been peeled off is assessed (cohesive break). The assessment of the adhesive properties is carried out by visually determining the cohesive part of the adhesive surface.
  • the respective pretreatment agent was applied to the respective residual bead substrate (or automotive paint substrate) as described above for the adhesion tests in a standard climate and flashed off.
  • the adhesive was applied in the form of a triangular bead approx. 8 mm wide and approx. 10 mm high to strips of silicone-coated release paper.
  • the triangular beads applied to the release paper were then turned over and placed on the residual adhesive bead remaining on the glass body in such a way that the release paper was on top and the composition was in contact with the residual adhesive bead.
  • Table 5 Adhesion tests on float glass and ceramic substrates.
  • Table 7 Adhesion tests on float glass and ceramic substrates.
  • Table 8 Adhesion tests on adhesive beads and automotive paint.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne un agent de prétraitement destiné à des actions de collage, contenant i) entre 10 et 30 parties en poids d'au moins un polymère de polyuréthane PU contenant des groupes isocyanate, obtenu par réaction d'au moins un poly(méth)acrylate polyol P et d'au moins un polyisocyanate I1, à condition que le poly(méth)acrylate polyol P présente un indice d'OH d'au moins 35, et le polymère de polyuréthane PU présente une teneur en NCO comprise entre 2,0 et 25,0 % en poids par rapport au polymère de polyuréthane PU ; ii) de 0,1 à 10 parties en poids d'au moins un organosilane OS ; iii) de 0 à 10 parties en poids d'au moins un autre polyisocyanate I2 ; iv) de 60 à 90 parties en poids d'un solvant L ; v) de 0 à parties en poids de noir de carbone ; vi) de 0 à 10 parties en poids d'une silice hydrophobe pyrogène. L'agent de prétraitement, selon l'invention, présente des propriétés particulièrement bonnes pour permettre une parfaite adhérence d'un adhésif sur de nombreux substrats, en particulier le verre, la céramique, la peinture et d'anciens cordons de colle résiduels. En outre, l'agent de prétraitement peut être formulé pour être transparent et quasiment incolore.
EP20824241.2A 2019-12-17 2020-12-15 Agent de prétraitement à base de solvant à adhérence améliorée vis-à-vis de cordons de colle résiduels Pending EP4077559A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP19216864 2019-12-17
PCT/EP2020/086214 WO2021122593A1 (fr) 2019-12-17 2020-12-15 Agent de prétraitement à base de solvant à adhérence améliorée vis-à-vis de cordons de colle résiduels

Publications (1)

Publication Number Publication Date
EP4077559A1 true EP4077559A1 (fr) 2022-10-26

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Country Status (4)

Country Link
US (1) US20220348793A1 (fr)
EP (1) EP4077559A1 (fr)
CN (1) CN114729223A (fr)
WO (1) WO2021122593A1 (fr)

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1760100A1 (fr) * 2005-09-01 2007-03-07 Sika Technology AG Produits d'addition contenant des groupes d'isocyanate et composés ayant une forte adhésion sur des substrats revêtus
CN101405316B (zh) * 2006-01-26 2012-03-14 Sika技术股份公司 具有良好的粘附性的含有硅烷官能的聚合物和氨基硅烷-加合物的湿固化组合物
JP5776387B2 (ja) * 2011-07-12 2015-09-09 オート化学工業株式会社 建築用シーリング材または塗膜防水材の下地処理用１液湿気硬化型プライマー
WO2013174891A2 (fr) 2012-05-23 2013-11-28 Sika Technology Ag Polymère contenant des groupes silane
CN104321359B (zh) 2012-05-23 2016-12-14 Sika技术股份公司 含硅烷基团的聚合物
EP2805985A1 (fr) 2013-05-22 2014-11-26 Sika Technology AG Hydroxysilane et polymère contenant des groupes silanes
DE102013218976A1 (de) * 2013-09-20 2015-04-16 Evonik Industries Ag Hydroxylgruppenhaltiges Silikon-Polyester-Acrylat-Bindemittel
AU2016328372B2 (en) * 2015-09-23 2021-01-14 Sika Technology Ag Two-component composition
EP3406644A1 (fr) * 2017-05-23 2018-11-28 Sika Technology Ag Apprêt à base de solvant à temps de prise long et à adhérence améliorée

Also Published As

Publication number Publication date
CN114729223A (zh) 2022-07-08
US20220348793A1 (en) 2022-11-03
WO2021122593A1 (fr) 2021-06-24

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