EP2029649A1 - Système de catalysation - Google Patents

Système de catalysation

Info

Publication number
EP2029649A1
EP2029649A1 EP07729481A EP07729481A EP2029649A1 EP 2029649 A1 EP2029649 A1 EP 2029649A1 EP 07729481 A EP07729481 A EP 07729481A EP 07729481 A EP07729481 A EP 07729481A EP 2029649 A1 EP2029649 A1 EP 2029649A1
Authority
EP
European Patent Office
Prior art keywords
component
adhesive
complex
sealant composition
composition according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP07729481A
Other languages
German (de)
English (en)
Inventor
Michael Schlumpf
Martin Konstanzer
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
Priority to EP07729481A priority Critical patent/EP2029649A1/fr
Publication of EP2029649A1 publication Critical patent/EP2029649A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • C08G18/222—Catalysts containing metal compounds metal compounds not provided for in groups C08G18/225 - C08G18/26
    • 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
    • C08G18/26—Catalysts containing metal compounds of lead
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]

Definitions

  • the field of the present invention relates to the field of polyurethane adhesives and sealants.
  • Polyurethanes and adhesives have long been known and are widely used. Classically, a distinction is made in the professional world between one-component and two-component polyurethane adhesives.
  • One-component polyurethane adhesives react under the influence of atmospheric moisture.
  • Known two-component polyurethane adhesives contain as second components a hardener component which essentially contains polyamines and / or polyols. In both cases, isocyanate-containing compounds or prepolymers are used. In order to accelerate the crosslinking, the isocyanate group-containing compounds or prepolymers are added in both types of catalysts.
  • EP-B-0 737 699 discloses amine, tin or mercury catalysts for accelerating moisture-crosslinking polyurethane adhesives and sealants.
  • catalysts for one-component polyurethane adhesives in particular amine catalysts and organotin catalysts, in particular dibutyltin dilaurate apply.
  • a disadvantage of the one-component polyurethane adhesives is that they cure very slowly, typically for days. speed Curing, however, is a major need in the adhesives industry, especially in the automotive industry. In order to achieve a fast reaction, classic two-component polyurethane adhesives with an isocyanate component and a hardener component are therefore often used. However, the two-component polyurethane adhesives have the great disadvantage that the high demands on the mixing quality must be made, since even small mixing errors can lead to a sharp drop in the mechanical values.
  • the object of the present invention is therefore to provide a polyurethane composition which cures quickly, is insensitive to mixing errors, and exhibits good adhesion to painted substrates, in particular to automotive finishes.
  • a two-component adhesive or sealant composition according to claim 1 solves this problem.
  • a major advantage of such a composition is that the accelerator component can be added to any one-component polyurethane adhesive as the first component and that their curing is greatly accelerated, without the usual problems of mixing accuracy occurs in two-component adhesives.
  • these two-component polyurethane compositions have very good adhesion to painted substrates, in particular automotive topcoats.
  • the present invention makes it possible in a simple manner to set the curing for winter and summer climatic conditions with the aim of combining good curing and adhesion. Ways to carry out the invention
  • the present invention relates to a two-component adhesive or sealant composition which consists of a first component K1 and an accelerator component K2.
  • the first component K1 contains at least one isocyanate group-containing prepolymer P, which is prepared from at least one polyisocyanate and at least one polyol.
  • the accelerator component K2 has a content of not more than 1% by weight, in particular not more than 0.1% by weight, based on the weight of the accelerator component K2, of compounds containing isocyanate-reactive groups. Thus, only traces of these compounds are present in the composition. If the content is greater, either the requirements for the quality of the mixing increase or the accelerator component K2 is not stable in storage over a longer period of time.
  • isocyanate-reactive group-containing compounds are examples of compounds containing isocyanate-reactive groups.
  • the accelerator component K2 preferably contains no
  • Compounds with isocyanate-reactive groups and is in particular free of water, free of polyamines, free of polymercaptans and free of polyols.
  • the first component K1 contains at least one isocyanate group-containing prepolymer P, which is prepared from at least one polyisocyanate and at least one polyol. Such a preparation can be carried out in that the polyol and the polyisocyanate with conventional
  • the polyisocyanate is metered so that its isocyanate groups in proportion to the hydroxyl groups of the polyol in stoichiometric excess are present.
  • the excess of polyisocyanate is chosen so that in the resulting polyurethane prepolymer after the reaction of all the hydroxyl groups of the polyol, a content of free isocyanate groups of 0.1 to 5% by weight, preferably 0.25 to 2.5% by weight, particularly preferably 0.3 to 1% by weight, based on the total polymer remains.
  • the polyurethane polymer P can be prepared with the concomitant use of plasticizers, wherein the plasticizers used contain no isocyanate-reactive groups.
  • polyurethane prepolymers having the specified content of free isocyanate groups which are obtained from the reaction of diisocyanates with high molecular weight diols in an NCO / OH ratio of 1.5 / 1 to 2/1.
  • polyols for the preparation of an isocyanate group-containing prepolymer P for example, the following commercially available polyols, or any mixtures thereof, can be used:
  • Polyoxyalkylenpolyole also called polyether polyols or oligoetherols, which are polymerization of ethylene oxide, 1, 2-propylene oxide, 1, 2- or 2,3-butylene oxide, tetrahydrofuran or mixtures thereof, possibly polymerized using a starter molecule having two or more active hydrogen atoms such as Water, ammonia or
  • polyoxyalkylene polyols having a low degree of unsaturation prepared, for example, by means of so-called double metal cyanide complex catalysts (DMC) can be used.
  • DMC double metal cyanide complex catalysts
  • Catalysts), as well as polyoxyalkylene polyols having a higher degree of unsaturation prepared for example with the aid of anionic catalysts such as NaOH, KOH, CsOH or alkali metal alkoxides.
  • polyoxyalkylenediols or polyoxyalkylenetriols are particularly suitable, in particular polyoxypropylenediols or polyoxypropylenetholes.
  • polyoxyalkylenediols or polyoxyalkylenetriols having a degree of unsaturation lower than 0.02 meq / g and having a molecular weight in the range from 10 000 to 30 000 g / mol, and also polyoxypropylenediols and triols having a molecular weight of 400-800 g / mol.
  • molecular weight in the present document denotes the molecular weight average M n .
  • ethylene oxide-terminated (“EO-endcapped", ethylene oxide-endcapped) polyoxypropylene polyols
  • EO-endcapped ethylene oxide-endcapped polyoxypropylene polyols
  • polyoxypropylene-polyoxyethylene polyols obtained, for example, by pure polyoxypropylene polyols, in particular polyoxypropylene diols and triols, after completion of the reaction Polyoxypolyoxylation reaction with ethylene oxide, thereby having primary hydroxyl groups.
  • Styrene-acrylonitrile or acrylonitrile-methyl methacrylate-grafted polyether polyols Styrene-acrylonitrile or acrylonitrile-methyl methacrylate-grafted polyether polyols.
  • Polyesterpolyols also called oligoesterols, prepared, for example, from dihydric to trihydric alcohols, for example 1,2-ethanediol, diethylene glycol, 1,2-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1, 6-hexanediol, neopentyl glycol, glycehn, 1,1,1-thymethylolpropane or mixtures of the abovementioned alcohols with organic dicarboxylic acids or their anhydrides or esters, for example succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, Phthalic acid, isophthalic acid, Terephthalic acid and hexahydrophthalic acid or mixtures of the aforementioned acids, and polyester polyols from lactones such as ⁇
  • Polycarbonate polyols as by reacting, for example, the abovementioned - used to build the polyester polyols - alcohols with
  • Dialkyl carbonates, diaryl carbonates or phosgene are accessible. Polyacrylate and polymethacrylate polyols.
  • Polyhydrocarbons also called Oligohydrocarbonole, such as polyhydroxy-functional ethylene-propylene, ethylene-butylene or ethylene-propylene-diene copolymers, as described for example by the
  • Polyhydroxy Acrylonithl / polybutadiene copolymers as from epoxides or aminoalcohols and carboxyl Acrylonithl / polybutadiene copolymers can be prepared (commercially available under the name of Hycar ® CTBN from Noveon), for example.
  • polystyrene resin have an average molecular weight of 250-30,000 g / mol, in particular of 10,000-30,000 g / mol, and an average OH functionality in the range of 1.6-3.
  • Preferred polyols are polyoxyalkylene polyols. Further preferred polyols are diols. Particular preference is given to polyoxyalkylenediols, in particular those having a degree of unsaturation of less than 0.02 meq / g and a molecular weight in the range from 40,000 to 30,000 g / mol, in particular
  • small amounts of low molecular weight di- or polyhydric alcohols such as 1, 2-ethanediol, 1, 2- and 1, 3-propanediol, neopentyl glycol, diethylene glycol, th-ethylene glycol, the isomeric dipropylene glycols and tripropylene glycols, the isomeric butanediols, pentanediols, hexanediols, heptanediols, octanediols, nonanediols, decanediols, undecanediols, 1, 3- and 1, 4-cyclohexanedimethanol, hydrogenated bisphenol A, dimeric fatty alcohols, 1, 1, 1 -Thmethylolethan, 1, 1, 1 -Th - Methylolpropane, glycerol, pentaerythritol, sugar alcohols such as
  • polyisocyanates for the preparation of an isocyanate group-containing prepolymer P for example, the following commercially available polyisocyanates can be used:
  • the accelerator component K2 contains at least one catalyst C, which catalyzes the reaction of isocyanate groups.
  • This catalyst C is a lead complex or a zinc complex or an iron (III) complex.
  • lead complex or “zinc complex” or “iron (III) complex” is meant coordination compounds of lead or zinc or iron (III) as the central atom and ligands which are coordinately bonded to lead or zinc or iron (III) may be of organic or inorganic nature, and depending on the nature and charge of the particular ligands, the complex is a neutral complex or a complex anion or cation.
  • Lead and zinc and iron (III) complexes which are particularly suitable for Atoms to the lead, zinc or iron (III) bound organic ligands.
  • the organic ligands particularly preferably contain at least 2 oxygen atoms.As particularly suitable such ligands, organic carboxylates have proven.
  • tetravalent zinc or lead complexes or hexavalent iron (III) complexes are particularly suitable.
  • the most preferred zinc and lead complexes are so-called metal soaps of zinc or lead, which are zinc or lead complexes of fatty acid carboxylates or naphthenates.
  • the most preferred complexes are the acetylacetonato-iron (III) complexes.
  • Examples of particularly suitable zinc complexes are zinc octoate, zinc neodecanoate, zinc 2-ethylhexanoate or zinc naphthenate.
  • Examples of particularly suitable lead complexes are lead octoate,
  • iron (III) complexes examples include iron (III) octoate, iron (III) neodecanoate or iron (III) acetylacetonate.
  • Such zinc and lead and iron (III) complexes are commercially available, for example, from ABCR GmbH & Co (Germany), Alfa Aersar GmBH & Co (Germany), Shepherd Chemical Company (USA) or Gelest Inc. (USA). It can be quite beneficial lead and / or zinc and / or
  • Iron (III) complexes mixed with each other used may also be advantageous under certain conditions to use lead and / or zinc and / or iron (III) complexes mixed with amine complexes.
  • the accelerator component K2 preferably also contains a liquid carrier, in particular a plasticizer or solvent.
  • the accelerator component K2 additionally contains thixotropic agents.
  • a thixotropic agent may be inorganic in nature, such as fumed silica, for example, commercially available as Aerosil® from Degussa AG (Germany), or organic such as, for example, urea-based thixotropic agents.
  • a preferred organic thixotropic agent is a urea-based thixotropic agent in a vehicle. Suitable urea derivatives in a carrier are, in particular, reaction products of an aromatic monomeric diisocyanate with an aliphatic amine compound.
  • Support material may be a plasticizer, in particular a phthalate or an adipate, preferably a diisodecyl phthalate (DIDP) or dioctyl adipate (DOA).
  • the carrier may also be a blocked polyurethane prepolymer. The preparation of such preferred urea derivatives and carrier materials are described in detail in the patent application EP 1 152 019 A1.
  • the support material is advantageously a blocked polyurethane prepolymer, in particular obtained by reacting a trifunctional polyether polyol with IPDI and subsequent blocking of the terminal isocyanate groups with caprolactam.
  • plasticizer and / or thixotropic agent in the accelerator component K2 is particularly advantageous if the component K1 is pasty, because then the dosing and / or mixing can be done easier.
  • the components K1 and K2 can also have further components. However, in order to ensure storage stability of the two components before mixing them, it is important that, in the absence of moisture, such additional components in the components do not react with other components of the same component. Thus, the additional constituents of the component K1 must not react with the isocyanate group-containing prepolymer P, while the additional constituents of the accelerator component K2 do not react with the catalyst C.
  • components K1 and K2 are - plasticizers, for example esters of organic carboxylic acids or their anhydrides, such as phthalates, for example dioctyl phthalate, diisononyl phthalate or diisodecyl phthalate, adipates, for example dioctyl adipate, azelates and sebacates, polyols, for example polyoxyalkylene polyols or polyester polyols, organic Phosphoric and sulfonic acid esters or polybutenes; - solvents;
  • plasticizers for example esters of organic carboxylic acids or their anhydrides, such as phthalates, for example dioctyl phthalate, diisononyl phthalate or diisodecyl phthalate, adipates, for example dioctyl adipate, azelates and sebacates, polyols, for example polyoxyalkylene polyols or polyester polyols,
  • inorganic and organic fillers for example ground or precipitated calcium carbonates, which are optionally coated with stearates, in particular finely divided coated calcium carbonate, Russian, in particular industrially produced Russian (hereinafter referred to as "soot"), kaolins, aluminum oxides, silicic acids, in particular finely divided silicic acids from pyrolysis processes, PVC powder or hollow spheres.
  • Preferred fillers are carbon black, calcium carbonates, in particular finely divided coated calcium carbonates, finely divided silicas from pyrolysis processes, and combinations of these fillers.
  • Fibers such as polyethylene; - pigments; for example, titanium dioxide;
  • Catalysts for example metal catalysts in the form of organotin compounds such as dibutyltin dilaurate and dibutyltin diacetylacetonate, bismuth organic compounds or bismuth complexes; Amino group-containing compounds, for example 1, 4-diazabicyclo [2.2.2] octane and 2,2'-dimorpholinodiethyl ether;
  • Rheology modifiers such as thickeners, for example urea compounds, polyamide waxes, bentonites or pyrogenic silicas;
  • Adhesion promoters for example epoxysilanes, (meth) acrylsilanes, anhydridosilanes or adducts of the abovementioned silanes with primary aminosilanes, and urea silanes;
  • Desiccants for example vinylthmethoxysilane, ⁇ -functional silanes, such as N- (silylmethyl) -O-methyl-carbamates, in particular N- (methyldimethoxysilylmethyl) -O-methyl-carbamate, (methacryloxymethyl) silanes, methoxymethylsilanes, N- Phenyl, N-cyclohexyl and N-alkylsilanes, orthoformic acid esters, calcium oxide or molecular sieves;
  • N- (silylmethyl) -O-methyl-carbamates in particular N- (methyldimethoxysilylmethyl) -O-methyl-carbamate, (methacryloxymethyl) silanes, methoxymethylsilanes, N- Phenyl, N-cyclohexyl and N-alkylsilanes, orthoformic acid esters, calcium oxide or molecular sieves;
  • surfactants such as wetting agents, leveling agents, deaerators or defoamers
  • Biocides such as algicides, fungicides or fungal growth inhibiting substances; and other commonly used in moisture-curing compositions substances.
  • these additional ingredients should preferably contain no or at most traces of water. It may therefore be useful to dry certain constituents chemically or physically before mixing into the components.
  • the component K1 and optionally the component K2 contains filler, in particular carbon black.
  • Proportion of filler preferably carbon black, from 5 to 35 wt .-%, in particular of
  • the dosage of the catalyst C in the accelerator component K2 is preferably such that the catalyst C in an amount of 0.01-0.3 wt .-%, in particular 0.04 - 0.1 wt .-%, of metal, i. lead, zinc or iron (III), based on the weight of the adhesive or sealant composition.
  • the component K1 is pasty and stable.
  • Accelerator component K1 is also preferably pasty.
  • Both components K1 and K2 are storage-stable separately from each other, that is, they can, in particular with the exclusion of moisture, in a suitable packaging or arrangement, such as a keg, a bag or a cartridge over a period of several months to a Be kept for a period of one year or more without altering their application properties or their properties after curing to a level relevant to their use.
  • a suitable packaging or arrangement such as a keg, a bag or a cartridge over a period of several months to a Be kept for a period of one year or more without altering their application properties or their properties after curing to a level relevant to their use.
  • the storage stability is determined by measuring the viscosity, the Auspressmenge or the Auspresskraft.
  • the components K1 and K2 are in the two-component
  • Composition preferably formulated such that the volume ratio of the first component K1 to the accelerator component K2 is a value of 100: 1 to 1: 1, in particular 100: 1 to 10: 1, preferably 100: 1 to 20: 1.
  • accelerator components K2 for example a summer and a winter accelerator component K2, which differ from one another in the concentration of the catalyst C, can be added to an existing component K1 in a fixed mixing ratio K1 / K2.
  • an accelerator component K2 with a given concentration of catalyst C different amounts to an existing component K1, i. with variation of the mixing ratio K1 / K2, admix.
  • the mixing of the two components is preferably carried out by a method for mixing a previously described two-component adhesive or sealant composition in which the accelerator component K2 of the component K1 is mixed immediately before application or during application.
  • the admixing takes place, in particular, by adding the accelerator components K2 to the component K1 before the component K1 enters a static mixer.
  • the components K1 and K2 are mixed quasi-homogeneously after mixing, that is, they are completely homogeneously mixed except for small domains.
  • Such a mixing is referred to as quasi homogeneous, in particular, if, in the case where the two components are differently colored, for example black and white or red and white, a homogeneous mixed color without streaks or stripes is present after the mixing.
  • the great advantage of the present two-component adhesive or sealant composition lies in the fact that due to the fact that primarily a catalyst C and not an isocyanate-reactive component of an isocyanate component is added, complete mixing is not necessary. Because on the one hand, the catalyst C is a small molecule which can easily diffuse into the isocyanate component K1, and on the other hand, the catalyst C merely accelerates the reaction of the isocyanate groups but is otherwise not involved in the crosslinking reaction. If the two components are mixed at least to a certain extent, the components of the accelerator component K2 which are not completely mixed in cause no, or only slight, reduction in the mechanics of the cured composition.
  • the second component consists essentially of an isocyanate-reactive constituent, in particular a polyol and / or a polyamine, namely, the NCO-reactive compounds with the polyisocyanate of the isocyanate must react with each other via an addition reaction, while in the case of the present composition, the curing takes place after the application of the composition via the moisture in the air, the composition according to the invention is thus "moisture-curing".
  • Skin-forming time thus represents a measure of the curing rate.
  • a skin-forming time of up to 4 hours, preferably up to 2 hours, at 23 ° C and 50% relative humidity is desirable.
  • the composition has a high mechanical strength in the cured state with a high elasticity, as well as good adhesion properties. This makes it suitable for a variety of
  • Suitable applications are, for example, the bonding of components in construction or civil engineering and in the manufacture or repair of industrial goods or consumer goods, in particular windows, household machines or means of transport, such as vehicles by water or land, preferably automobiles, buses, trucks, trains or Ships; the sealing of joints, seams or cavities in industrial production or repair, or in civil engineering.
  • Elastic bonding in vehicle construction for example, the sticking of parts, such as plastic covers, moldings, flanges, bumpers, cabs or other attachments to the painted Body of a means of transport, or the gluing of windows into the body.
  • parts such as plastic covers, moldings, flanges, bumpers, cabs or other attachments to the painted Body of a means of transport, or the gluing of windows into the body.
  • vehicles to be mentioned for example, automobiles, trucks, buses, rail vehicles and ships.
  • Composition used as an elastic adhesive or sealant used as an elastic adhesive or sealant.
  • the composition typically has an elongation at break of at least 200% and, as an elastic sealant, at least 500% at room temperature.
  • the mixed components are applied to an adherend surface S1.
  • the application is usually carried out by means of a nozzle in the form of a so-called triangular or round bead.
  • the application is preferably carried out by means of a suitable device on the substrate. Suitable methods for application are, for example, the application of commercially available cartridges, which are operated manually or by means of compressed air, or from a barrel or hobbock by means of a feed pump or an extruder, optionally by means of an application robot.
  • a sealant or adhesive with good application properties has a high stability and a short string. This means that after the application it remains in the applied form, ie it does not flow apart, and does not draw any or only a very short thread after the application device has been set down, so that the substrate is not contaminated.
  • Joining part surface S1 is contacted in a further step, the thus mixed and applied mixed components with a second adherend surface S2 and under the influence of water, in particular in the form of
  • the joining part surfaces S1 and S2 may be of different types. They may be the same or different from each other in shape and / or material.
  • Suitable joint surfaces S1 or S2 are, for example, surfaces of inorganic substrates, such as glass, glass ceramic, concrete, mortar, brick, brick, gypsum and natural stones, such as granite or marble; of metals or alloys, such as aluminum, steel, non-ferrous metals, galvanized metals; of organic substrates, such as wood, of plastics, such as PVC, polycarbonates, PMMA, polyesters, epoxy resins; of coated substrates, such as powder-coated metals or alloys; and of paints and varnishes, in particular automotive finishes. If necessary, the substrates can be applied before applying the adhesive or
  • Sealant be pretreated.
  • Such pretreatments include, in particular, physical and / or chemical cleaning methods, for example grinding, sandblasting, brushing or the like, or treatment with cleaners or solvents or the application of an adhesion promoter, a primer solution or a primer.
  • the inventive composition is particularly suitable for the sealing and / or bonding of automotive topcoat substrates.
  • a glued or sealed article is obtained via a previously described adhesive or sealant application method.
  • Such an article may be a building, in particular a building of civil engineering, or it may be a means of transport, such as a vehicle on water or land, in particular an automobile, a bus, a truck, a train or a ship, or an attachment of it.
  • the bonded article is on the one hand a disc of a means of transport, on the other hand a means of transport or a
  • Attachment for a means of transport is preferably a
  • Road vehicle or a rail vehicle in particular an automobile or a bus or truck.
  • a glass pane printed with glass-ceramic such as, for example, as a front, side or rear window, is used as the pane
  • Automobiles is used, preferably.
  • vitrifying vehicles both in Castverglasung, ie in the vehicle manufacturing, as well as in the repair glazing, ie for example when replacing damaged by stone chips, a high curing rate and good adhesion of significant advantage.
  • Preparation Klebstoffbasisformulierunq It has a first prepolymer P (P1) prepared as follows: 590 g of polyol Acclaim ® 4200 N (Bayer), 1180 g of polyol Caradol MD34- ® 02 (Shell) and 230 g of isophorone diisocyanate (IPDI; Vestanat ® IPDI, Degussa) were reacted by known method at 80 ° C to form an NCO-terminated prepolymer. The reaction product had a titrimetrically determined content of free isocyanate groups of 2.12 wt .-%.
  • a second prepolymer P (P2) was prepared as follows:
  • Desmodur ® 44 MC L, Bayer Desmodur ® 44 MC L, Bayer
  • 500 g of diisodecyl phthalate (DIDP; Palatinol ® Z, BASF) were reacted at 80 ° C to give an NCO-terminated polyurethane polymer having a content of free isocyanate groups of 2.07% and a
  • prepolymer P1 and P2 139.5 g of prepolymer was mixed with 73.0 g of diisodecyl phthalate, processed, and 47.0 g of carbon black and 71.3 g of calcium carbonate in a vacuum mixer under exclusion of moisture to form a lump-free, homogeneous paste (DIDP Palatinol ® Z, BASF).
  • the component K1 prepared in this way was immediately filled into moisture-proof aluminum cartridges.
  • component K2 the catalyst specified in Table 1 was mixed in the amount indicated there with the indicated solvent.
  • Components K1 and K2 were each mixed in a ratio of 360 g K1 to 6 g K2 (60: 1).
  • compositions were applied as a round bead immediately after mixing on float glass (Rocholl, Schönbrunn, Germany) ("glass”) and on the following paint sheets:
  • RK8046 1 Clear Coat DuPont RK8046, Color Silver, (ACT Laboratories)
  • RK8046 Clear Coat DuPont RK8013, Color Silver, (ACT Laboratories)
  • FF98-0001 Topcoat BASF FF98-0001 (BASF Coatings AG)
  • the glass was before applying the mixed adhesive with
  • the paint panels were pretreated or pretreated by wiping with heptane and flashed off for 10 minutes.
  • the cured bead was cut in each case at one end just above the surface of the plate (adhesive surface).
  • the cut end of the caterpillar was held by hand and then gently and slowly, peeling in the direction of the other caterpillar end, pulled from the platelet surface. If the adhesion was so strong that the end of the caterpillar threatened to break off while pulling, a cut was made perpendicular to the caterpillar pulling direction up to the bare surface of the plate by means of a cutter and the caterpillar was detached a little way. Such cuts were repeated, if necessary, when moving on at a distance of 2 to 3 mm. In this way, the entire caterpillar was pulled or cut from the plate.
  • the skin formation time was determined as a measure of the curing rate.
  • Skinning time (t Hss ) is the time from mixing to the moment when the touch of the pipette no longer tears any thread from the composition.
  • compositions 1 to 8 cure at an accelerated rate.
  • catalysts C act less accelerating compared to dibutyltin dilaurate.
  • the component K1 used in the preceding examples was modified such that, during its preparation, the amount of catalyst indicated in Table 3 was finally mixed in and was stored in sealed aluminum cartridges with the exclusion of moisture. After storage of these sealed cartridges after 2 days at room temperature (“APK1”), respectively 7 days at 60 ° C ⁇ "APK2 '), respectively 2 days at 70 ° C ⁇ " APK3'), the squeezing force (APK) became follows determined:
  • a cartridge filled with adhesive was opened after conditioning for 12 hours at 23 ° C and screwed on a nozzle of 5 mm. And with a "Zwick 1 120" press-out device, the force is determined to squeeze out the adhesive at a squeezing speed of 60 mm / min. The value stated is an average after 140 ml squeezing.
  • the following adhesive compositions were prepared by applying the mixed compositions of Examples 1, 2 and 3 to the glass region or to the ceramic-coated edge region (both pretreated with Sika® activator, Sika Sau GmbH AG) of an automobile windshield (original windshield of a Ford Fiesta) was applied as a triangular bead on which the painted automotive topcoat sheets RK8046, RK8013 and FF98-0001 (cleaned with heptane) were then pressed (contacted). After 7 days curing, the liability was assessed. All test specimens showed perfect adhesion. When the sheet was peeled off by means of round tongs, all samples, i. on both glass and glass-ceramic, a cohesive break in the adhesive can be detected.

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

Abstract

La présente invention concerne une composition de matière d'étanchéité ou adhésive à deux composants, ladite composition comprenant un premier composant (K1) contenant un prépolymère P comportant les groupes d'isocyanate, et un composant activateur (K2). Le composant activateur (K2) comporte un catalyseur qui catalyse la réaction des groupes d'isocyanate, et qui est un complexe de plomb – zinc ou de fer (III), ainsi que maximum 1 % en poids de composés comportant des groupes réactifs d'isocyanate. On obtient en particulier des matières adhésives dotées d'une vitesse élevée de durcissement et d'une bonne adhérence, pouvant s'adapter facilement aux conditions ambiantes.
EP07729481A 2006-05-24 2007-05-24 Système de catalysation Withdrawn EP2029649A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP07729481A EP2029649A1 (fr) 2006-05-24 2007-05-24 Système de catalysation

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP20060114497 EP1860131A1 (fr) 2006-05-24 2006-05-24 Système de catalyse
PCT/EP2007/055051 WO2007135187A1 (fr) 2006-05-24 2007-05-24 Système de catalysation
EP07729481A EP2029649A1 (fr) 2006-05-24 2007-05-24 Système de catalysation

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EP2029649A1 true EP2029649A1 (fr) 2009-03-04

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EP20060114497 Withdrawn EP1860131A1 (fr) 2006-05-24 2006-05-24 Système de catalyse
EP07729481A Withdrawn EP2029649A1 (fr) 2006-05-24 2007-05-24 Système de catalysation

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US (1) US20090092840A1 (fr)
EP (2) EP1860131A1 (fr)
CN (1) CN101443375A (fr)
AU (1) AU2007253269A1 (fr)
BR (1) BRPI0710898A2 (fr)
CA (1) CA2648707A1 (fr)
MX (1) MX2008013725A (fr)
WO (1) WO2007135187A1 (fr)

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EP2155460B1 (fr) * 2007-05-23 2022-11-30 Huntsman International LLC Adhésifs, systèmes de réaction et procédés de production de composites lignocellulosiques
CA2773877C (fr) 2009-10-05 2015-06-02 Construction Research & Technology Gmbh Formulation de polyurethane a resistance crue elevee et apte a etre distribuee au moyen d'un pistolet a calfeutrer
EP2322571A1 (fr) 2009-11-06 2011-05-18 Sika Technology AG Composition adhésive ou d'étanchéité à deux composants comprenant un composant accélérant
KR20120094069A (ko) * 2009-12-18 2012-08-23 아크조 노벨 케미칼즈 인터내셔널 비.브이. 기재에 대한 건축용 조성물의 접착성을 향상시키는 방법 및 첨가제
EA025752B1 (ru) 2011-06-10 2017-01-30 Акцо Нобель Кемикалз Интернэшнл Б.В. Способ и добавка для повышения адгезии композиций к основам
EP2604617A1 (fr) * 2011-12-12 2013-06-19 Sika Technology AG Composés à base de complexes de fer (III) comme catalyseurs de compositions de polyuréthane
JP6101147B2 (ja) * 2012-07-31 2017-03-22 日東電工株式会社 樹脂組成物
JP6023897B2 (ja) * 2012-12-20 2016-11-09 ブルースター・シリコーンズ・フランス・エスアエス 室温におけるエラストマーへの加硫に適したオルガノポリシロキサン組成物及び新規のオルガノポリシロキサン重縮合触媒
JP6134006B2 (ja) * 2012-12-20 2017-05-24 ブルースター・シリコーンズ・フランス・エスアエス 水中用途、特に海洋用途を目的とする防汚特性を有する物品
WO2014096567A1 (fr) * 2012-12-20 2014-06-26 Bluestar Silicones France Sas Composition organopolysiloxanique vulcanisable a température ambiante en élastomère et nouveaux catalyseurs de polycondensation d'organopolysiloxanes
FR2999980A1 (fr) * 2012-12-20 2014-06-27 Bluestar Silicones France Article presentant des proprietes antisalissures et destine a etre utilise dans des applications aquatiques en particulier marines
AU2016376643B2 (en) * 2015-12-21 2021-07-01 Sika Technology Ag Sealant for floor joints with a high resistance to fuels
FR3063915B1 (fr) * 2017-03-14 2021-04-02 Bostik Sa Composition thixotrope utilisable comme agent anti-coulure pour des mastics

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Publication number Publication date
BRPI0710898A2 (pt) 2011-08-23
CA2648707A1 (fr) 2007-11-29
AU2007253269A1 (en) 2007-11-29
EP1860131A1 (fr) 2007-11-28
WO2007135187A1 (fr) 2007-11-29
US20090092840A1 (en) 2009-04-09
MX2008013725A (es) 2008-11-14
CN101443375A (zh) 2009-05-27

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