EP2057341A1 - Joint adhésif scellé au silicone - Google Patents

Joint adhésif scellé au silicone

Info

Publication number
EP2057341A1
EP2057341A1 EP07786959A EP07786959A EP2057341A1 EP 2057341 A1 EP2057341 A1 EP 2057341A1 EP 07786959 A EP07786959 A EP 07786959A EP 07786959 A EP07786959 A EP 07786959A EP 2057341 A1 EP2057341 A1 EP 2057341A1
Authority
EP
European Patent Office
Prior art keywords
meth
acrylate
adhesive
disc
holder
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Withdrawn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
EP07786959A
Other languages
German (de)
English (en)
Inventor
Uwe Bankwitz
Ulli Müller
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 EP07786959A priority Critical patent/EP2057341A1/fr
Publication of EP2057341A1 publication Critical patent/EP2057341A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • E—FIXED CONSTRUCTIONS
    • E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
    • E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
    • E06B3/00—Window sashes, door leaves, or like elements for closing wall or like openings; Layout of fixed or moving closures, e.g. windows in wall or like openings; Features of rigidly-mounted outer frames relating to the mounting of wing frames
    • E06B3/54—Fixing of glass panes or like plates
    • E06B3/56—Fixing of glass panes or like plates by means of putty, cement, or adhesives only
    • 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
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F13/00—Coverings or linings, e.g. for walls or ceilings
    • E04F13/07—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor
    • E04F13/08—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements
    • E04F13/0885—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements specially adapted for being adhesively fixed to the wall; Fastening means therefor; Fixing by means of plastics materials hardening after application
    • E—FIXED CONSTRUCTIONS
    • E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
    • E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
    • E06B3/00—Window sashes, door leaves, or like elements for closing wall or like openings; Layout of fixed or moving closures, e.g. windows in wall or like openings; Features of rigidly-mounted outer frames relating to the mounting of wing frames
    • E06B3/54—Fixing of glass panes or like plates
    • E06B3/5427—Fixing of glass panes or like plates the panes mounted flush with the surrounding frame or with the surrounding panes
    • 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
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/10—Presence of inorganic materials
    • C09J2400/14—Glass
    • C09J2400/143—Glass in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer
    • 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
    • Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
    • Y10T156/10—Methods of surface bonding and/or assembly therefor
    • 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
    • Y10T428/23—Sheet including cover or casing
    • Y10T428/239—Complete cover or casing

Definitions

  • the present invention relates to the field of wafer bonding.
  • the invention relates to an adhesive bond for fastening a metallic holder to a pane, wherein the holder and the pane are glued together by means of a (meth) acrylate adhesive which is completely encased by a silicone sealant.
  • Metallic brackets for fixing panes, in particular glass panes, to components, for example on facades, are known.
  • clamps are used, in which the disc is attached like a clamp.
  • a disadvantage is that external components are undesirable for aesthetic reasons and that due to the mechanical fastening is a great risk for the occurrence of glass breakage.
  • point-shaped holders are used, wherein the disc is pierced and the corresponding point holder is mechanically screwed to the disc.
  • brackets can be glued to the disc in addition to the clamp or the system with pierced glass.
  • DE 199 39 172 A1 describes a punctiform holder which is adhesively and positively attached to an insulating glass pane by an adhesive.
  • the weight of the insulating glass also by the two spaced discs safely through the punctiform holder can be included, however, is located in the air gap between the spaced glass panes a spacer.
  • the position of the spacers between the two discs defines the positions of the point holders to be attached to the disc.
  • glued point holders come due to their UV
  • Silicone sealants are known for their weathering, UV and temperature resistance and have therefore been used successfully for many years for gluing glass in construction.
  • the disadvantage of silicone sealants is their lower mechanical strength compared to other adhesives. This leads in the case of sticking point holders that the adhesive surfaces, d. H.
  • the size of the point holder for the removal of all loads must often be dimensioned so that it makes neither economic nor aesthetic sense.
  • Acrylic adhesives have a higher strength than silicone sealants and are therefore better suited to accommodate even large loads.
  • their weatherability is not sufficient, so that their use is not possible, especially in the construction of facades due to the expected now long useful life of the building.
  • Object of the present invention is therefore to provide a glued bracket available, which overcomes the disadvantages of the prior art.
  • an adhesive composite according to claim 1 solves this problem.
  • Such adhesive composites are characterized by high strength and very good weather resistance.
  • this effect can be achieved by the use of a specific combination of acrylate adhesives and silicone sealants.
  • the present invention relates to an adhesive bond comprising a metallic support, a disc and an adhesive assembly, the adhesive assembly comprising a (meth) acrylate adhesive completely encased by a silicone sealant.
  • the present invention therefore relates to an adhesive composite comprising a metallic holder and a pane, characterized in that the holder and the pane are adhesively bonded to one another via a (meth) acrylate adhesive, and wherein the (meth) acrylate adhesive is completely encased by a silicone sealant.
  • the silicone sealant is disposed between the metallic support and the disc. But it can also be arranged entirely or at least partially outside the metallic holder. It is essential that the silicone sealant completely encapsulates the (meth) acrylate adhesive.
  • the arrangement of the adhesive in the adhesive bond allows a resistance of the adhesion of the (Meth) acrylate adhesive against environmental influences, in particular against moisture.
  • the silicone sealant seals the (meth) acrylate adhesive disposed between the disc and the metallic support against the environment such that the (meth) acrylate adhesive does not interfere with environmental conditions, such as This means that the (meth) acrylate adhesive is on the one hand in direct contact with the pane and the metallic holder, and on the other hand at the places where the (meth) acrylate adhesive contacts neither the pane nor the metallic holder, There is no silicone sealant, at least in regions, between the wafer and the (meth) acrylate adhesive and between the metallic holder and the (meth) acrylate adhesive.
  • the silicone sealant is in direct contact with the (meth) acrylate adhesive. In another embodiment, the silicone sealant does not contact the (meth) acrylate adhesive, but there is a gap between the silicone sealant and the (meth) acrylate adhesive. The distance can be filled, for example, with air. Preferably, the silicone sealant is in direct contact with the (meth) acrylate adhesive.
  • metal support throughout the present document is meant a support which is suitable for fastening a panel, preferably a pane, to a support structure, for example a facade, by gluing the metallic support to the pane surface preferably has a flat, ie a flat or curved surface, which serves as a mounting surface, which can be attached to a disk by a positive and non-positive fit is glued.
  • the metallic holder may be point-shaped, oval or angular, in particular rectangular or triangular, four-sided or pentagonal or trapezoidal in the contact area with the pane, or have another shape which is suitable for bonding between the metallic holder and a pane.
  • metal support in the sense of the present invention is understood to mean a frame, such as a window or door frame, which at least partially surrounds a pane, in particular an insulating glass pane, at the front.
  • the metallic holder is preferably a punctiform holder.
  • the systems commonly used in glass construction such as point holder DORMA can be used.
  • the metals and alloys of iron, aluminum, copper, chromium and nickel are particularly preferred metals.
  • Particularly preferred are steel and aluminum and its alloys.
  • Particularly preferred is stainless steel.
  • the cross section through the adhesive and sealant arrangement parallel to the disk surface preferably has the same shape as the cross section through the surface of the metallic holder.
  • Disc surface preferably substantially circular.
  • Embodiment forms the silicone sealant, which completely covers the (meth) acrylate adhesive, a ring around the (meth) acrylate adhesive.
  • Silicone sealant is preferably used in a starch, i. a width, between
  • 0.1 and 20 mm preferably between 0.2 and 10 mm, more preferably between 0.5 and 2 mm arranged around the (meth) acrylate adhesive.
  • the surface of the metallic support is preferably arranged coplanar with the surface of the disc, ie the distance between the metallic support and the disc is essentially the same everywhere.
  • the distance between the metallic holder and the disc, and thus also the thickness of the adhesive assembly less than 1 cm, preferably between 0.1 and 0.6 cm.
  • the surface of the metallic support on the side of the bond, ie the mounting surface preferably has a diameter of 1 to 25 cm, preferably 2 to 15 cm, more preferably 5 to 10 cm and the surface is preferably between 0.5 and 2000 cm 2 , preferably between 10 and 1000 cm 2 , even more preferably between 50 and 100 cm 2 .
  • a pane which is to be fastened to a supporting structure may comprise a plurality of adhesive composites according to the invention. At least one metallic holder is glued to a pane.
  • more than one, in particular more than two, more preferably more than three, most preferably four or more than four metallic supports are glued to a single pane via the adhesive arrangement according to the invention.
  • Mounts are glued to a single disc, the smaller the respective diameter of the mounting surface of the metallic support can be selected.
  • Disc throughout the present document is understood to mean a flat or curved plate of glass or substantially transparent plastic, which may be single-layer or multi-layer plates, in particular also sheets with foils between the glass plates, such as automotive safety glass panes
  • a Ceramic coating preferably glass panes with ceramic coating.
  • panes of multilayer boards such as insulating glass panes, in particular double and multiple insulating glass panes, as are customary in window and door construction.
  • the disc is made of glass.
  • (meth) acrylate adhesive as used herein and throughout this document is meant an adhesive which comprises at least one organic (meth) acrylate in the uncured state.
  • Organic (meth) acrylate means a monomer or oligomer which is at least has an ester group of acrylic acid or methacrylic acid and thus has at least one polymerizable double bond.
  • Suitable organic (meth) acrylates are the (meth) acrylate monomers or oligomers known to the person skilled in the art.
  • the (meth) acrylate monomers in particular have one, two or three (meth) acrylate groups.
  • Particularly suitable are (meth) acrylates of the formula (I) or (II)
  • R 1 is H or CH 3 and where R 2 is a branched or unbranched organic radical which has in particular 1 to 30, preferably 4 to 10, carbon atoms and which preferably has at least one heteroatom, in particular at least one O.
  • R 2 may have cyclic moieties of saturated, unsaturated or aromatic character.
  • (meth) acrylate monomers of the formula (I) are hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2- Phenoxyethyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, tert-butyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, dihydrodicyclopentadienyl acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, polypropylene glycol mono (meth) acrylate
  • R 3 in formula (II) is a divalent organic radical which has in particular 2 to 100 carbon atoms, and preferably at least one heteroatom, in particular at least one O has.
  • R 3 can be cyclic
  • (meth) acrylate monomers of the formula (II) which are mentioned are ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di-
  • Bisphenol A di (meth) acrylate polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate.
  • Monomers such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, suitable for use. However, in these cases, it is preferred that at least one monofunctional or difunctional (meth) acrylate monomer is present.
  • Methyl (meth) acrylate or tetrahydrofurfuryl (meth) acrylate and their mixtures with other (meth) acrylates have proved to be particularly suitable as organic (meth) acrylate.
  • Particularly preferred is tetrahydrofurfuryl methacrylate or methyl methacrylate.
  • the composition according to the invention comprises at least two (meth) acrylate monomers of the formula (I) and / or formula (II). At least one of them is preferably tetrahydrofurfuryl methacrylate or tetrahydrofurfuryl acrylate or methyl (meth) acrylate.
  • (meth) acrylate oligomers are the partial oligomerization of the monomers which are suitable as (meth) acrylate monomer. However, these oligomers must still have at least one (meth) acrylate group.
  • the total by weight of all organic (meth) acrylates is more than 30% by weight, preferably between 40 and 90% by weight, based on the (meth) acrylate adhesive.
  • the (meth) acrylate adhesive may optionally contain further constituents.
  • additional ingredients are core-shell polymers,
  • suitable catalysts are, in particular, tertiary amines, for example N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-diethylaniline, N, N-diethyltoluidine, N, N-bis (2-hydroxyethyl) -p Toluidine, N-ethoxylated p-toluidines, N-alkylmorpholines or mixtures thereof.
  • transition metal salts or complexes in particular the metals cobalt, manganese, vanadium and copper, are suitable as catalysts.
  • adhesion promoters are alkoxysilanes, (meth) acrylates containing phosphorus atoms, or metal (meth) acrylates.
  • Hydroquinones in particular hydroquinone and methylhydroquinones, or t-butyl-p-cresol are particularly suitable as polymerization inhibitors.
  • Catalysts in particular core-shell polymers and liquid rubbers.
  • Core-shell polymer consist of an elastic core polymer and a rigid shell polymer.
  • Particularly suitable core-shell polymers consist of a core of crosslinked elastic acrylate or butadiene polymer which is surrounded by a rigid shell of a rigid thermoplastic polymer.
  • Particularly suitable core-shell polymers are those which swell in the organic (meth) acrylate but do not dissolve.
  • Preferred core-shell polymers are so-called MBS polymers, which are commercially available under the trade names Clearstrength TM from Atofina or Paraloid TM from Rohm and Haas.
  • the core-shell polymers are preferably used in an amount of 5 to 40% by weight based on the composition.
  • liquid rubbers in particular butadiene / acrylonitrile copolymer-based liquid rubbers or polyurethane-based liquid rubbers are suitable.
  • the liquid rubbers preferably have unsaturated double bonds.
  • liquid rubbers are (meth) acrylate-terminated polyurethane polymers.
  • Such polymers can be prepared from polyols and polyisocyanates to form isocyanate-functional polyurethane prepolymers and subsequent reaction with hydroxyalkyl (meth) acrylates.
  • Preferred isocyanate-functional polyurethane prepolymers are the reaction product of a polyisocyanate, in particular a diisocyanate and a polyol in the ratio of isocyanate group equivalents to hydroxyl group equivalents of greater than 1.
  • adducts of the type NCO-xx-NHCO-O-yy -O-OCONH-xx-OCN also be understood as a polyurethane prepolymer in this context, where xx is a diisocyanate without NCO groups and yy is a diol without OH groups.
  • any polyol HO-R- (OH) q with q> 1 can be used for this, where R stands for a polymer skeleton with heteroatoms in the skeleton or as side chains.
  • Preferred polyols are polyols which are selected from among
  • polyoxyalkylene polyols also called “polyether polyols", polyester polyols, polycarbonate polyols and mixtures thereof.
  • Preferred polyols are diols.
  • the most preferred diols are polyoxyethylene diols or polyoxypropylene diols or polyoxybutylene diols.
  • the polyoxyalkylene polyols may or may not have a low degree of unsaturation (measured to ASTM D-2849-69 and expressed in milliequivalents of unsaturation per gram of polyol (mEq / g)) prepared, for example, by so-called double metal cyanide complex catalysts (DMC catalysts) a higher degree of unsaturation, prepared for example with the aid of anionic catalysts such as NaOH, KOH, CsOH or alkali alcoholates.
  • DMC catalysts double metal cyanide complex catalysts
  • low degree of unsaturation polyoxyalkylene polyols particularly less than 0.01 meq / g, is preferred for polyols having a molecular weight of> 2000.
  • any polyisocyanates having two or more isocyanate groups can be used.
  • TDI 2,4- and 2,6-toluylene diisocyanate
  • MDI 4,4'-diphenylmethane diisocyanate
  • IPDI isophorone diisocyanate
  • HMDI perhydro-2,4'- and -4,4'-diphenylmethane diisocyanate
  • TCDI 1,4-diisocyanato-2,2,6-trimethylcyclohexane
  • XDI 1,4-diisocyanato-2,2,6-trimethylcyclohexane
  • XDI m- and p- Xylylenediisocyanat
  • TMXDI 4-tetramethyl-xylylenediisocyanat
  • TMXDI 1, 3, and 1, 4-bis (isocyanatomethyl) cyclohexane, any oligomers or polymers of the above isocyanates and any mixtures of mentioned isocyanates with each other.
  • Preferred polyisocyanates are MDI, TDI, HDI, IPDI and mixtures thereof. Most preferred are IPDI and HDI and their mixture.
  • the isocyanate-terminated prepolymers prepared from the polyols and polyisocyanates are reacted with (meth) acrylic acid esters which have hydroxyl groups.
  • Preferred (meth) acrylic acid esters which have hydroxyl groups are hydroxyethyl (meth) acrylate or hydroxypropyl (meth) acrylate.
  • the two reactants are reacted together in a manner known per se, typically in a stoichiometric excess of the (meth) acrylic acid ester having hydroxyl groups.
  • the preferred (meth) acrylate-terminated polyurethane polymer is the reaction product of an IPDI / polypropylene glycol polyurethane prepolymer or an HDI / polypropylene glycol polyurethane prepolymer with hydroxyethyl (meth) acrylate or with hydroxypropyl (meth) acrylate.
  • the preparation of the polyurethane prepolymer and / or of the (meth) acrylate-terminated polyurethane polymer can be carried out in the presence of the organic (meth) acrylate as long as it has no NCO-active groups.
  • the liquid rubbers are preferably used in an amount of 5 to 40% by weight, based on the (meth) acrylate adhesive.
  • the (meth) acrylate adhesive can basically be produced by the methods and apparatus known to the person skilled in the art. In particular, however, the following manufacturing method has proved to be advantageous:
  • the organic (meth) acrylate is initially charged in a reaction vessel.
  • the optionally present liquid rubber and / or core-shell polymer is stirred.
  • other raw materials such as activators, adhesion promoters, additives, etc. are stirred. After a homogeneous composition is obtained, it is optionally deaerated and packaged.
  • the (meth) acrylate adhesive can be cured thermally, by radiation or by chemical generation of radicals.
  • the curing takes place by chemical radical production.
  • the (meth) acrylate adhesive is a free-radically curing two-component (meth) acrylate adhesive, which consists of a first component K1 and a second component K2.
  • the raw materials used are distributed to the two components so that a sufficient storage stability is ensured.
  • a preferred such two-component (meth) acrylate adhesive is described as follows: The first component K1 forms that described above
  • the second component K2 contains a radical generator.
  • This radical generator is in particular a peroxide or a perester.
  • peroxide in addition to hydrogen peroxide, especially organic peroxides or hydroperoxides are mentioned.
  • the usable organic peroxides or hydroperoxides depend on the fields of application, temperatures and the chemical compatibility with other raw materials.
  • Dibenzoyl peroxide has proven to be particularly preferred as peroxide. Cumene hydroperoxide and isopropyl cumene hydroperoxide are particularly preferred as hydroperoxides.
  • dibenzoyl peroxide is preferred.
  • Component K2 may contain other ingredients. In particular, these are in the acting as component K1 (meth) acrylate adhesive previously mentioned additional ingredients, under the condition that these additional ingredients do not interfere with other ingredients such.
  • the radical generator react at least during storage time to a significant extent.
  • components K1 and K2 preferably have comparable viscosities.
  • the volume ratio of component K1 and K2 preferably have comparable viscosities.
  • K2 between 20: 1 and 1: 2, preferably in about 10: 1.
  • the components K1 and K2 are mixed for curing.
  • the resulting mixture is preferably pasty and preferably thixotropic.
  • Components K1 and K2 are stored in separate containers prior to mixing.
  • Suitable is a (meth) acrylate adhesive which cures by radiation. Curing takes place in particular by UV radiation with the aid of a UV lamp.
  • silicone sealant as used herein and throughout this document is meant a sealant comprising at least one polydiorganosiloxane and at least one crosslinking agent.
  • Such sealants are also referred to as silicone rubbers which contain as base polymers polydiorganosiloxanes having at least two reactive groups.
  • a reactive group are preferably H, OH, alkoxy or vinyl groups in question, which are preferably located at the chain ends, but may also be incorporated into the chain.
  • RTV room temperature vulcanizing
  • RTV-1 single-component
  • RTV-2 two-component
  • RTV-1 the room temperature vulcanizing rubbers consist of one Component, ie the crosslinker is contained in the rubber and is already active at atmospheric humidity.
  • RTV-2 the room temperature vulcanizing rubbers consist of two components; networking only starts when the two components mix together.
  • silicic acid esters eg ethyl silicate
  • organotin compounds are used as crosslinking component in two-component rubbers.
  • RTV-1 the one-component system
  • RTV-1 has proven in which the silicone sealant at room temperature under the
  • Suitable crosslinkers or crosslinking agents are polyfunctional, organosilicon compounds which at room temperature with OH groups, such. Silanol groups of the polymers or the OH groups of water, can react. Polyfunctional means that at least three reactive groups are present in the crosslinker molecule.
  • curing of the RTV-1 rubbers may be acidic, e.g. B. in the presence of carboxysilanes, basic, z. B. by means of aminosilanes or neutral, z. B. by oximo or alkoxy-containing compounds occur.
  • at least one carboxysilane, at least one oximosilane, or at least one alkoxysilane is used as crosslinking agent.
  • Neutral crosslinking silicone sealants which contain at least one ketoximo or at least one alkoxysilane have proven particularly suitable.
  • Neutral-crosslinking silicone sealants which release a neutral cleavage product during crosslinking, are used primarily when a reaction or incompatibility with the substrate is to be avoided.
  • crosslinker is preferably an organosilane and / or its partial hydrolyzate of the general formula R 4 x Si (OR 5 ) 4 x
  • R 4 independently of one another is H or unsubstituted or substituted alkyl and / or alkenyl and / or aryl radicals, preferably methyl, and where R 5 is independently H and / or unsubstituted and / or substituted alkyl, acyl, and / or silyl radicals, and where x is either 0 or 1.
  • the substituents R 4 and R 5 may contain homo atoms or heteroatoms such as, for example, N or O. Suitable substituents are, for example, epoxy, amines, esters or oximes, preferably amines or oximes. More preferably, the organosilane is an alkoxysilane
  • alkoxysilanes are particularly suitable methoxy or ethoxysilanes.
  • the following compounds can be used, for example: methyltrimethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, tetraethoxysilane, phenyltriethoxysilane, tetrakis (2-methoxyethoxy) silane, tetrakis (2-butoxyethoxy) silane, N-1 - (triethoxysilyl) ethylpyrrolidone (2 ), N-2- (triethoxysilyl) ethylpyrrolidone- (2), N-1 - (triethoxysilyl) ethyl-N-methylacetamide, N-2- (triethoxysilyl) -ethyl-N-methylacetamide, N-1- (triethoxysilyl ) ethyl succinimide, N-2- (trie
  • Suitable oximosilanes are aldoximo or ketoximosilanes, preferably methyl isobutyl ketoximosilanes or methyl ethyl ketoximosilanes.
  • the amount of organosilanes of the general formula (III) to be used depends on the content of silicon-bonded hydroxyl or alkoxy groups of the polydiorganosiloxane of the general formula (IV) and is easy to adapt by the skilled person to the respective conditions.
  • the alkoxysilane of the general formula (III) is preferably present in amounts of between 0.1 and 10% by weight, particularly preferably 1 to 5% by weight, based on the total weight of the silicone sealant.
  • the silicone sealants preferably contain at least one linear
  • Polydiorganosiloxane with at least two hydrolyzable end groups Preferably, a hydroxy-terminated polydiorganosiloxane of the general formula (IV) is used
  • R 6 independently of one another is unsubstituted or substituted alkyl and / or alkenyl and / or aryl radicals, preferably methyl, and n assumes values of 20 to 3000, preferably values of 100 to 1600.
  • the polydiorganosiloxanes of the general formula (IV) used are known. Usually, they are prepared either by polymerization of cyclic siloxanes in the presence of strongly basic or acidic catalysts and small amounts of water or by polycondensation of short-chain linear oligomers having OH end groups. Since the starting compounds used for the synthesis in addition to the main desired difunctional units but can also contain trifunctional and tetrafunctional units, compounds are always included in the polymers containing one or more branches in the molecule. The greater the content of tri- or tetrafunctional units in the starting materials and the greater the molecular weight of the polymer, the greater the likelihood that the molecules will contain branching sites.
  • the polydiorganosiloxane is an ⁇ , ⁇ -dihydroxypolydialkylsiloxane or an ⁇ , ⁇ -dialkoxysilylpolydialkylsiloxane.
  • Preferred substituents R 6 are methyl, ethyl, phenyl, vinyl and trifluoropropyl radicals. Owing to their ready availability, particular preference is given to ⁇ , ⁇ -dihydroxypolydimethylsiloxanes in which n in the formula (IV) assumes values of from 100 to 1,600. Although the use of purely linear polymers is preferred, those polymers containing branching sites may also be used.
  • the silicone sealant of the present invention usually contains from 30 to 70% by weight of polydiorganosiloxanes of the general formula (IV).
  • the silicone sealant may optionally contain further constituents.
  • Such additional constituents are plasticizers, catalysts, inorganic and / or organic fillers, curing accelerators, pigments, adhesion promoters, processing aids, dyes, inhibitors, heat stabilizers, antistatic agents, flame retardants, biocides, waxes, leveling agents, thixotropic agents and other common raw materials and additives known to the person skilled in the art.
  • the silicone gum contains, in addition to at least one polydiorganosiloxane and at least one crosslinking agent, at least one plasticizer, at least one catalyst and optionally at least one filler.
  • plasticizers are alkyl-terminated polydialkylsiloxanes, in particular methyl-terminated polydimethylsiloxanes.
  • methyl-terminated polydimethylsiloxanes Preferably trimethylsilyl-terminated polydimethylsiloxanes with viscosities between 0.01 and 10 Pas. Viscosities between 0.1 and 1 Pas are particularly preferred.
  • methyl-terminated polydimethylsiloxanes in which some of the methyl groups have been replaced by other organic groups such as, for example, phenyl, vinyl or trifluoropropyl.
  • plasticizers Although preference is given to using linear trimethylsilyl-terminated polydimethylsiloxanes as plasticizers, it is also possible to use those compounds which contain some branching points, which arise from the fact that small amounts of tri- or tetrafunctional silanes are contained in the starting materials used for the preparation of the plasticizers. But it is also possible instead of siloxanes, up to 25% by weight, based on the total mixture, other organic compounds such. B. certain aromatic hydrocarbon mixtures to use as a plasticizer.
  • a catalyst In order to achieve a sufficiently high crosslinking rate, preferably 0.01 to 5% by weight, based on the total weight of the silicone sealant, of a catalyst is used.
  • organotin compounds preferably dialkyltin compounds, such as. As dibutyltin dilaurate or diacetate, or titanium compounds such as tetrabutyl or Tetraisopropyltitanat, or titanium chelates. It is also possible to use catalyst mixtures.
  • active or inactive fillers can be used.
  • Preferred high surface area fillers are fumed silica or precipitated calcium carbonate.
  • low surface area fillers can be used as extenders.
  • inactive fillers chemical or physical interactions with the polymer do not occur or occur only to a minor extent.
  • calcium carbonates, aluminum silicates, quartz flour, diatomaceous earth, iron oxides, etc. are used. Preference is given here ground calcium carbonate.
  • the silicone sealant of the inventive adhesive composite contains fumed silica as a filler.
  • adhesion promoters are preferably alkoxysilanes which are substituted by functional groups.
  • the functional group is, for example, an aminopropyl, glycidoxypropyl or mercaptopropyl group. Preference is given to amino-functional groups.
  • the alkoxy group of the silane is usually a methoxy or ethoxy group. Particularly preferred are aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2- Aminoethyl) -aminopropyltriethoxysilane and 3-mercaptopropyltriethoxysilane. It is also possible to use a mixture of alkoxysilanes substituted with functional groups.
  • Particularly suitable silicone sealants have the following properties:
  • the preparation of the silicone sealant can be carried out continuously or discontinuously according to the methods and apparatus known to the person skilled in the art.
  • the disc is adhered to the metallic support via a chemically curing (meth) acrylate adhesive encased in a silicone sealant comprising ⁇ , ⁇ -dialkoxypolydimethylsiloxane, an alkoxysilane, trimethylsilyl-terminated polydimethylsiloxane, and dibutyltin diacetate.
  • a chemically curing (meth) acrylate adhesive encased in a silicone sealant comprising ⁇ , ⁇ -dialkoxypolydimethylsiloxane, an alkoxysilane, trimethylsilyl-terminated polydimethylsiloxane, and dibutyltin diacetate.
  • the present invention relates to
  • the support structure may be, for example, a facade of a building or a metallic structure which is attached to a facade.
  • the support structure may also be any building in civil engineering, industrial goods or a part thereof, such as a table leg, or a part of a means of transport, such as the body of a vehicle, ship or aircraft.
  • the inventive adhesive composite allows a very good
  • Adhesion in any weather For example, adhesive bonds can become extreme when gluing glass panels to parts of building facades Be exposed to weather conditions.
  • the complete encapsulation of the (meth) acrylate adhesive with silicone sealant maintains the good adhesion of the (meth) acrylate adhesive on the pane and on the metallic support, and rain or high humidity barely impairs the adhesion.
  • the invention relates to a method for attaching a metallic support to a disc comprising the steps
  • the contacting of the (meth) acrylate adhesive with the pane and / or the metallic holder takes place within the open time of the adhesive.
  • the (meth) acrylate adhesive is applied to the disc and joined within the open time with the metallic holder.
  • the pane and the metallic holder can also be brought into the desired distance from each other in advance, for example with a spacer, and then the (meth) acrylate adhesive can be applied between the pane and the metallic holder.
  • the spacer can additionally be used to apply the (meth) acrylate adhesive in the desired form, for example substantially circularly in the case of a point holder, and in the desired size. The height of the spacer determines the distance between the disc and the metallic holder.
  • the spacer is, for example, a ring with an opening through which the (meth) acrylate adhesive is applied after applying the metallic support to the spacer located between the washer and the metallic support.
  • the spacer is first to the desired Position on the disc brought filled with (meth) acrylate adhesive, and then the metallic holder is pressed onto the (meth) acrylate adhesive. In this case, the excess (meth) acrylate adhesive can be squeezed out through the opening of the spacer.
  • the spacer may for example be made of hot vulcanizing silicone rubber.
  • the curing of the adhesive preferably takes place in a further step.
  • the application of the silicone sealant around the (meth) acrylate adhesive can be done either immediately after the application of the (meth) acrylate adhesive or, preferably, after the curing of the (meth) acrylate adhesive.
  • the crosslinking of the adhesive begins immediately after exposure to atmospheric moisture or exposure to UV light.
  • the term of curing is not to be understood as the beginning of curing, that is to say the beginning of the crosslinking, but to the effect that the crosslinking has already progressed sufficiently far that the adhesive has already built up such a strength that it can transmit forces. and has reached the so-called early strength.
  • the curing is complete when the adhesive has reached its final strength.
  • the silicone sealant may be applied around the (meth) acrylate adhesive throughout the time of cure as well as after completion of cure.
  • Suitable methods for applying (meth) acrylate adhesive or the silicone sealant are, for example, the application of commercially available cartridges, which are preferably operated manually.
  • the pane and / or the metallic holder can be pretreated prior to the application of the adhesive and sealant.
  • Such pretreatments include in particular physical and / or chemical cleaning methods, for example grinding, sandblasting, brushing or the like or treating with cleaners or solvents; or the application of an adhesion promoter, a primer solution or a primer; or a flame treatment or a plasma treatment, in particular an air plasma pretreatment at atmospheric pressure.
  • an article which comprises an adhesive bond according to the invention.
  • Such an article may be a building, in particular a building construction or civil engineering, or it may be an industrial good or a consumer good such as a window, a household machine or a means of transport, such as a vehicle on land or water, especially an automobile , a bus, a truck, a train or a ship, or an attachment of it.
  • the article is a building or an industrial item or an attachment thereof.
  • the metallic mount 3 is glued to the window 4 via a (meth) acrylate adhesive 1.
  • the (meth) acrylate adhesive 1 is completely encased by the silicone sealant 2.
  • the metallic holder 3 is preferably a point holder.
  • the silicone sealant 2 is in direct contact with the (meth) acrylate adhesive 1.
  • the metallic mount 3 is fastened to a support structure 5 on the side opposite the bond.
  • the attachment can be done by a method known to those skilled in the art.
  • the support structure is, for example, a facade or an iron frame, which is attached to a facade.
  • Fig. 1B the silicone sealant 2 is not in direct contact with the (meth) acrylate adhesive 1, but there is a gap between the silicone sealant 2 and the (meth) acrylate adhesive 1.
  • Fig. 1C shows another version in which Silicone sealant 2 is not in direct contact with (meth) acrylate adhesive 1. There is also a distance between the silicone sealant 2 and the (meth) acrylate adhesive 1.
  • the silicone sealant 2 is located not only between the disc 4 and the metallic holder 3, but is attached to the outside of the metallic holder 3.
  • FIGS. 1 D and 1 E show further embodiments in which the (meth) acrylate adhesive 1 is completely encased by the silicone sealant 2 and the (meth) acrylate adhesive 1 is thus completely sealed off from the ambient air.
  • the cross section has a substantially circular shape, and the (meth) acrylate adhesive 1 forms a concentric one
  • the silicone sealant 2 is not in direct contact with the (meth) acrylate adhesive 1, but there is a gap between the silicone sealant 2 and the (meth) acrylate adhesive 1.
  • the silicone sealant 2 is in direct contact with the (meth) acrylate adhesive 1.
  • the cross section has a substantially oval shape.
  • the tensile shear strength was determined on the basis of ISO 4587 / DIN EN 1465 on a tractor Zwick / Roell Z005 (adhesive surface: 12mmx25mm, layer thickness: 1.5mm, measuring speed: 10mm / min, substrates: float glass plates, measuring temperature: 23 ° C).
  • the glass slides were arranged in the manner described in the standard, so that an adhesive-filled overlap of dimensions 12 mm wide, 25 mm long and 1.5 mm thick.

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  • Engineering & Computer Science (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Architecture (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Sealing Material Composition (AREA)

Abstract

L'invention concerne un composite adhésif (6) permettant de fixer une fixation (3) métallique sur un disque (4), ladite fixation (3) et le disque (4) étant collés ensemble par une colle (1) contenant du (méth)acrylate, cette dernière étant entièrement enrobée par un matériau d'étanchéité en silicone (2).
EP07786959A 2006-06-30 2007-06-29 Joint adhésif scellé au silicone Withdrawn EP2057341A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP07786959A EP2057341A1 (fr) 2006-06-30 2007-06-29 Joint adhésif scellé au silicone

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP06116466A EP1873344A1 (fr) 2006-06-30 2006-06-30 Agglutination étanchée par silicone
EP07786959A EP2057341A1 (fr) 2006-06-30 2007-06-29 Joint adhésif scellé au silicone
PCT/EP2007/056602 WO2008000833A1 (fr) 2006-06-30 2007-06-29 Joint adhésif rendu étanche par du silicone

Publications (1)

Publication Number Publication Date
EP2057341A1 true EP2057341A1 (fr) 2009-05-13

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ID=37560843

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Application Number Title Priority Date Filing Date
EP06116466A Withdrawn EP1873344A1 (fr) 2006-06-30 2006-06-30 Agglutination étanchée par silicone
EP07786959A Withdrawn EP2057341A1 (fr) 2006-06-30 2007-06-29 Joint adhésif scellé au silicone

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP06116466A Withdrawn EP1873344A1 (fr) 2006-06-30 2006-06-30 Agglutination étanchée par silicone

Country Status (5)

Country Link
US (1) US20090191375A1 (fr)
EP (2) EP1873344A1 (fr)
JP (1) JP2009541564A (fr)
CN (1) CN101506458A (fr)
WO (1) WO2008000833A1 (fr)

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WO2008000833A1 (fr) 2008-01-03
JP2009541564A (ja) 2009-11-26
US20090191375A1 (en) 2009-07-30
EP1873344A1 (fr) 2008-01-02
CN101506458A (zh) 2009-08-12

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