EP3676344A1 - Procédé amélioré de préfixation et de collage de pièces - Google Patents

Procédé amélioré de préfixation et de collage de pièces

Info

Publication number
EP3676344A1
EP3676344A1 EP18756463.8A EP18756463A EP3676344A1 EP 3676344 A1 EP3676344 A1 EP 3676344A1 EP 18756463 A EP18756463 A EP 18756463A EP 3676344 A1 EP3676344 A1 EP 3676344A1
Authority
EP
European Patent Office
Prior art keywords
adhesive
accelerated
accelerator composition
accelerated adhesive
optionally
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
EP18756463.8A
Other languages
German (de)
English (en)
Inventor
Florian ALTENWEGNER
Dirk Urbach
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 EP3676344A1 publication Critical patent/EP3676344A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • 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
    • C09J2483/00—Presence of polysiloxane

Definitions

  • the invention relates to a method for prefixing and bonding of parts which are bonded with moisture-curing compositions.
  • bonding has long been used to join parts of the article of manufacture.
  • the bonding has the advantage that, in contrast to welding, it can be used universally and, since no boreholes and the like are necessary, does not result in any mechanical weakening or visual impairment of the article of manufacture.
  • the pre-fixing adhesive is usually a rigid, high-modulus adhesive because only those processes normally have a sufficiently high early strength.
  • the bond has an inhomogeneous rigidity. This results in an uneven loading of the adhesive surface under mechanical stress on the bonded production counterpart, whereby the higher modulus components are subjected to greater stress and mechanical damage or undesired effects such as vibrations or deformations can occur.
  • Another disadvantage of using two different adhesives is that it makes the production line more complex and expensive and requires different application devices for the different adhesives.
  • thermosetting or heat-accelerated adhesives for prefixing. It can thus be achieved that the prefixing adhesive, if it is heated upright before, during or after the application, has the required strength fast enough to ensure the prefixing.
  • a disadvantage of this method is that, in turn, an additional process step has to be carried out by the heat treatment, which prolongs and increases the cost of production.
  • this method can not be used in every case. In particular, in the connection of thermoplastic materials, this is often not possible, since thermally induced deformations can occur on the parts.
  • this object is achieved by a method according to claim 1.
  • the present invention relates to methods for prefixing and bonding two parts T1 and T2, comprising the steps:
  • steps b) and c) are performed in any order and the application amount of the accelerated adhesive KB1 to the first part T1 is less than the application amount of the optional accelerated adhesive KB2 to the first part T1;
  • the term also encompasses derivatives of such a collective of macromolecules from polyreactions, compounds which have been obtained by reactions, such as additions or substitutions, of functional groups on given macromolecules and which may be chemically uniform or chemically nonuniform.
  • the term also includes so-called prepolymers, that is reactive oligomeric pre-adducts whose functional groups are involved in the construction of macromolecules.
  • polyurethane polymer encompasses all polymers which are prepared by the so-called diisocyanate-polyaddition process, including those polymers which are almost or completely free of urethane groups.
  • silane-functional polymers describes silane-group-containing polymers, in particular silane-group-containing organic polymers, which are usually and in this document synonymously also termed “silane-functional polymers", “silane-modified polymers” (SMP) or “silane-terminated polymers Polymers "(STP).
  • SMP silane-modified polymers
  • STP silane-terminated polymers
  • Their crosslinking proceeds via the condensation of silanol groups to form siloxane bonds and is conventionally catalyzed by means of organotin compounds, in particular dialkyltin (IV) carboxylates.
  • silane-containing polyether also includes silane-containing organic polymers, which in addition to polyether units may also contain urethane groups, urea groups or thiourethane groups. Such silane-containing polyethers may also be referred to as "silane-containing polyurethanes”.
  • silane or "organosilane” designate compounds which have on the one hand at least one, usually two or three, alkoxy groups or acyloxy groups bonded via Si-O bonds directly to the silicon atom, and at least one, via an Si-C bond, directly to the silicon atom bonded organic radical.
  • silanes are also known to the person skilled in the art as organoalkoxysilanes or organoacyloxysilanes.
  • silane group refers to the silicon-bonded group attached to the organic group of the silane bound via the Si-C bond
  • silanes, or their silane groups have the property of hydrolyzing on contact with moisture nosilanols, that is, organosilicon compounds containing one or more silanol groups (Si-OH groups) and, by subsequent condensation reactions, organosiloxanes, that is, organosiloxanes containing one or more siloxane groups (Si-O-Si groups)
  • silane-functional denotes compounds which have silane groups.”
  • Silane-functional polymers "are therefore polymers which have at least one silane group.
  • hydroxysilane denotes organoalkoxysilanes which have one or more hydroxyl, isocyanato, amino or mercapto groups on the organic radical in addition to the silane group.
  • Amino-silanes which have a primary amino group, that is to say an NHb group which is bonded to an organic radical are referred to as "primary aminosilanes.”
  • Amino-silanes which have a secondary amino group, that is to say an NH group are referred to as “secondary aminosilanes”. which is bound to two organic radicals.
  • molecular weight is meant in this document the molar mass (in grams per mole) of a molecule or part of a molecule, also referred to as “residue”.
  • average molecular weight is meant the number average Mn of an oligomeric or polymeric mixture of molecules or residues. th, which is usually determined by gel permeation chromatography (GPC) against polystyrene as a standard.
  • a “stable substance” or “composition” is defined as a substance or composition which may be stored at room temperature in a suitable dressing for a prolonged period of time, typically at least 3 months to 6 months or more, without being present in its own state Use or performance, in particular the viscosity and the rate of crosslinking, changed by the storage in a relevant for their use to the extent.
  • room temperature refers to a temperature of approx. 23 ° C.
  • weight percent refers to a percentage by weight which, unless otherwise stated, refers to the mass (weight) of the total composition, or to the context of the entire molecule.
  • open time describes the time during which two parts to be bonded can still be joined without problems after the adhesive has been applied and begins to harden.
  • the process according to the invention comprises the provision of a one-component, moisture-curing adhesive K. It contains at least one moisture-crosslinkable polymer.
  • “Monocomponent” means that the adhesive is admixed without admixing further components solely by moisture, for example from air, and optionally by feeding
  • the crosslinkable polymer is an isocyanate group-containing polyurethane polymer which is obtainable, in particular, by the reaction of at least one polyol with at least one polyisocyanate.
  • Particularly suitable as polyol are polyether polyols, polyester polyols, polycarbonate polyols, polyacrylate polyols and hydrocarbon polyols, preferably polyether polyols.
  • Preferred polyether polyols are polyoxypropylene polyols and polyoxypropylene polyoxyethylene polyols, in particular the diols and triols.
  • Suitable polyisocyanates are in particular diisocyanates.
  • Preferred diisocyanates are 1,6-hexamethylene diisocyanate (HDI), 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl cyclohexane (isophorone diisocyanate or IPDI), perhydro 2,4'- and -4,4'-diphenylmethane diisocyanate (HMDI or H12MDI), 2,4- and 2,6-toluene diisocyanate and any mixtures of these isomers (TDI) and 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanate and any mixtures of these isomers (MDI ).
  • HDI 1,6-hexamethylene diisocyanate
  • the polyurethane polymer is prepared in a known manner. It has a molecular weight of 500 to 50 ⁇ 00 g / mol, preferably between
  • the polyurethane polymer preferably has an average NCO functionality of 1.8 to 3.
  • the crosslinkable polymer is a silane-functional polymer, in particular a silane-terminated polyether, a silane-terminated poly (meth) acrylate or a silane-terminated polyurethane.
  • a silane-functional polymer in particular a silane-terminated polyether, a silane-terminated poly (meth) acrylate or a silane-terminated polyurethane.
  • Such polymers are in particular obtainable by reacting a polyol with an isocyanatosilane, by reacting an isocyanate group-containing prepolymer with an amino, hydroxy or mercaptosilane, by reacting a polyamine with a (meth) acrylsilane or by reacting a (meth) acryl-terminated polymer with an amino or mercaptosilane.
  • a preferred silane-functional polymer is the reaction product of an optionally chain-extended, isocyanate-group-terminated polymer with an aminosilane, in particular a secondary aminosilane.
  • Preferred secondary aminosilanes for this reaction are alkylaminosilanes, for example a 3- (n-butylamino) propylalkoxysilane or a
  • Michael adducts are the conversion cationic products of primary aminosilanes, in particular 3-aminopropylalkoxysilanes, with acrylates, for example n-butyl acrylate or isobornyl acrylate, and in particular maleic acid dialkyl esters.
  • Michael adducts of 3-aminopropyl-dialkoxyalkylsilanes or 3-aminopropyltrialkoxysilanes with maleic acid dialkyl esters, especially diethyl malonate are particularly preferred.
  • the silane groups are in particular dialkoxyalkylsilane groups and preferably trialkoxysilane groups.
  • Preferred alkoxy groups on the silane groups are ethoxy groups and especially methoxy groups.
  • silane-functional polymers are commercially available under the trade name Polymer ST, for example polymer ST50 from the company Hanse Chemie AG, Germany, and under the trade name Desmoseal ® from Bayer MaterialScience AG, Germany.
  • silane-functional polymers are commercially available under the trade names SPUR + ® 1010LM, 1015LM and 1050MM from the company Momentive Performance Materials Inc., USA, and under the trade names Geniosil® ® STP-E15, STP-10 and STP-E35 from Wacker Chemie AG, Germany.
  • silane-functional polymers commercially available under the trade names MS Polymer TM S203H, S303H, S227, S810, MA903 and S943, Silyl TM SAX22Q, SAX350, SAX400 and SAX725, Silyl TM SAT350 and SAT400, and XMAP TM SA100S and SA310S by the company Ka neka Corp., Japan, and sold under the trade name Excestar ® S24 0, S2420, S3430, S3630, W2450 and MSX931 of Asahi Glass Co, Ltd., Japan.
  • Plasticizers for example esters of organic carboxylic acids or their anhydrides, phthalates, such as, for example, dioctyl phthalate or diisodecyl phthalate, Adipates such as dioctyl adipate, sebacates, organic phosphoric and sulfonic acid esters, polybutenes and other isocyanate-unreacted compounds; Reactive thinner and crosslinker, for example polyhydric alcohols, polyamines, polyaldimines, polyketimines or aliphatic isocyanates such as 1, 6-hexamethylene diisocyanate, 2,2,4- and 2,4,4-trimethyl-1, 6-hexamethylene diisocyanate, 1, 12-dodecamethylene diisocyanate , Cyclohexane-1, 3- and 1, 4-diisocyanate and any mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane
  • IPDI isophorone diisocyanate
  • IPDI isophorone diisocyanate
  • perhydro-2,4'- and -4,4'-diphenyl methane diisocyanate 1, 3- and 1, 4-tetramethylxylylene diisocyanate
  • inorganic and organic fillers such as, for example, ground or precipitated calcium carbonates, which are optionally coated with stearates, in particular finely divided coated calcium carbonate, Russian, kaolins, aluminum oxides, silicas and PVC powders or hollow spheres
  • Fibers such as polyethylene; pigments;
  • Catalysts such as organotin compounds such as dibutyltin dilaurate, dibutyltin dichloride, dibutyltin diacetylacetonate, bismuth organic
  • Particularly suitable adhesives K are one-component, moisture-curing compositions based on isocyanate-functional polyurethane polymers or silane-functional polymers. Such compositions are commercially available from Sika AG Switzerland, for example, under the trade name of Sikaflex ® or SikaBond ®.
  • the inventive method further comprises the provision of an accelerator composition B, which contains between 10 and 80 wt .-% water, based on the accelerator composition B.
  • the accelerator composition B contains between 10 and 60 wt .-% water, in particular between 15 and 40 wt % Of water, based on the total accelerator composition B.
  • the accelerator composition B initially contains at least water. In order to obtain a good incorporation of the water into the accelerator composition B, it is advantageous if the accelerator composition B contains a carrier which, on the one hand, reduces the viscosity of the
  • Accelerator composition B increases and on the other hand advantageously influenced the mixing ratio. Due to the small amount of water needed for the accelerated cure, and such a small interference can at best lead to problems of homogeneous interference, the use of a carrier material, the volume ratio of adhesive K to accelerator composition B is reduced, so that reduces the mixing problems become. Furthermore, it is known that the mixing of two in the Viscosity drastically different components is associated with difficulties. This difficulty is reduced by the use of a carrier material.
  • the carrier material is advantageously an organic polymer having ionic groups. Such ionic groups are in particular carboxylic acid group and / or sulfonic acid groups. On the one hand advantageous as such organic polymers are poly (meth) acrylic acids and copolymers of (meth) acrylic acids.
  • the support material is a polyurethane having at least one carboxylic acid group and / or sulfonic acid group.
  • Particularly suitable as support materials are polyurethanes, for the synthesis of which carboxylic acid-containing diols, in particular dimethyloipropanecarboxylic acid, and polyisocyanates are used. Using such carrier materials, the water is reversibly bound by the carrier material with ionic groups and forms a gel-like paste.
  • the amount of water relative to the moisture-reactive groups may be from substoichiometric to superstoichiometric, particularly suitable is a ratio of the reactive groups [H 2 O] / [NCO] or [H 2 O] / [silicon-bonded alkoxy] from 1 to 3.0, especially 1 to 2.6. Stoichiometric is preferred, in particular with a ratio of 1 to 2.
  • water with fine fillers such as fumed silica, such as Aerosil ® , available from Degussa, or chalk or molecular sieves.
  • the filler is reversibly bound by the water at the surfaces or in the pores.
  • preferred carriers are organic polymers with ionic groups.
  • Water pastes with organic polymers which contain ionic groups and can be used for the use according to the present invention as accelerator composition B are basically already known and are, for example, Sikaflex®-254 or SikaTack®-Plus, which are one-part warmmelt polyurethane adhesives, im Sikaflex®-254 Booster System or SikaTack®-Plus Booster System added. It may be advantageous if the accelerator composition B contains, in addition to water, additionally polyols and / or polyamines. This can, for example, lead to the hardening being done even faster and the final strength being reached faster.
  • the water may be present in the accelerator composition B either as free water or it may be bound to a carrier material.
  • the bond must be reversible, that is, the water must be accessible after mixing the adhesive K and the accelerator composition B for reaction with the moisture-reactive groups in the adhesive K, in particular isocyanate groups, alkoxy groups and / or aldimine.
  • Suitable support materials for the accelerator composition B may be hydrates or aquo complexes, in particular inorganic compounds which have bound water in a coordinative manner or as water of crystallization.
  • examples of such hydrates are Na 2 SO 4 .10H 2 O, CaSO 4 .2H 2 O,
  • suitable carrier materials are porous materials which trap water in cavities.
  • these are special silicates and zeolites.
  • Particularly suitable are kieselguhr and molecular sieves.
  • the size of the cavities should be chosen so that they are optimal for the absorption of water. This is why molecular sieves with a pore size of 4 A are particularly suitable.
  • support materials are those which absorb water in non-stoichiometric amounts and have a pasty consistency or form gels.
  • These support materials may be inorganic or organic in nature. Examples thereof are silica gels, clays such as montmorillonite, bentonite, hectorite, or polysaccharides such as cellulose and starch, or polyacrylic acids and polyacrylonitriles, which are also known by the term "superabsorber" and are used, for example, in hygiene articles
  • Polyurethane polymers with carboxyl groups or sulmen are particularly preferred as carrier materials.
  • Fonklare phenomenon as side chains or their salts, in particular their ammonium salts.
  • the particularly preferred polyurethane polymers with carboxyl groups or sulfonic acid groups as side chains, or their salts can be obtained, for example, from polyisocyanates and polyols which contain carboxylic acid or sulfonic acid groups.
  • the acid groups can then be neutralized, for example in the fully reacted state, with bases, in particular tertiary amines.
  • the properties of the support material are highly dependent on the functional polyols and polyisocyanates used. In particular, attention must be paid to the hydrophilicity or hydrophobicity of the selected isocyanates and polyols. It has been shown that especially short-chain polyols give very suitable support materials.
  • the accelerator composition B when used in conjunction with a polyurethane adhesive, also contains at least one poly-dimine.
  • the polyaldimine can be prepared from at least one polyamine having aliphatic primary amino groups and at least one aldehyde by a condensation reaction with elimination of water. Such condensation reactions are well known and described, for example in Houben-Weyl, "Methods of Organic Chemistry", Vol. XI / 2, page 73 ff.
  • Suitable polyamines having aliphatic primary amino groups for the preparation of the polyaldimine are the polyamines known in polyurethane chemistry, such as are used, inter alia, for two-component polyurethanes.
  • Preferred polyamines are 1, 6-hexamethylenediamine, MPMD, DAMP, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, 4-aminomethyl-1, 8-octanediamine, IPDA, 1, 3 and 1, 4-xylylenediamine , 1, 3 and 1,4-bis (aminomethyl) cyclohexane, bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) -methane, 3 (4), 8 (9) Bis (aminomethyl) tricyclo [5.2.1.0 2 ' 6 ] decane, 1, 2, 1, 3 and 1, 4-diaminocyclohexane, 1, 4-diamino-2,2,6
  • the accelerator composition B preferably contains at least as much water as equivalent aldimine groups, or in other words: the accelerator composition B preferably has at least one molecule of water per aldimine group.
  • the accelerator composition B further contains at least one external emulsifier, in particular a nonionic emulsifier, for example a fatty alcohol ethoxylate.
  • the accelerator composition B preferably has an emulsifier content of ⁇ 10% by weight, in particular ⁇ 5% by weight.
  • the accelerator composition B optionally contains in particular a rheology aid or a filler, in particular pyrogenic silicic acids and ureas.
  • the accelerator composition B preferably additionally contains, in particular, additionally at least one polymer and / or at least one acid and / or at least one catalyst for the curing of moisture-curing adhesives.
  • the said polymer comprises in particular a water binding polymer, as described above, a polyol for reaction with isocyanate-containing prepolymers, if contained in the adhesive, or a polyaldi- min as described above.
  • the adhesive K with the accelerator composition B is mixed by means of a static or dynamic mixer into an accelerated adhesive KB1, the accelerated adhesive KB1 containing between 5 and 20% by volume of the accelerator composition B, based on the total accelerated Adhesive KB1.
  • step c) of the method according to the invention the adhesive K with the accelerator composition B is optionally mixed by means of a static or dynamic mixer to form an optionally accelerated adhesive KB2, wherein the optionally accelerated adhesive KB2 is less than 5
  • Volume% of accelerator composition B contains, based on the total accelerated adhesive KB2.
  • the optionally accelerated adhesive KB2 is purely optional accelerated; it can also consist purely of the adhesive K. Whether additionally at most 5% by weight of accelerator composition B is mixed in depends essentially on the desired bonding process and the associated cycle times. However, admixture of accelerator composition B is preferred if the method permits, since such a shortening of the curing time can be achieved.
  • the mixing of the adhesive K with the accelerator composition B is advantageously carried out continuously throughout the process during the application.
  • the mixing of the adhesive K with the accelerator composition B takes place by means of a metering attachment containing two intermeshing metering rotors.
  • a metering attachment containing two intermeshing metering rotors.
  • Such preferred metering attachments are described in detail in the patent EP 0 749 530.
  • the dosing attachment is preferably designed for smaller applications
  • a static mixer can additionally be attached to the outlet opening of this dosing attachment.
  • twin cartridges or so-called coaxial cartridges, each with a static mixer attached to the outlet opening.
  • the adhesive K and the accelerator composition B are in separate cartridges attached to one another, which open into a common outlet opening.
  • the application takes place by means of a suitable squeezing device, which squeezes both cartridges in parallel.
  • coaxial cartridges one of the two components is located in the core of the cartridge. The other component encloses them, the components being separated by a coaxial wall.
  • the two components are also pressed out at the same time by a suitable Auspressvorraumcardi in the application and open into a common
  • these are dual cartridges, as are known from two-component adhesives, wherein the arrangement of the chambers can be configured differently.
  • these may be cylindrical chambers, which may be arranged side by side or co-centric.
  • the walls of the chambers can be rigid or flexible.
  • An exemplary arrangement of the chambers and their configuration can be found in WO 01/44074 or in US 6,433,091 B1.
  • the adhesive K and the accelerator composition B are advantageously mixed with a dosing attachment, which is essentially characterized by the dosing attachment described above distinguishes that it has a hose connection for the accelerator composition B.
  • the accelerator composition B may be present in a package from which the accelerator composition B is metered and admixed with a stream of adhesive K.
  • a packaging or metering can be found, for example, in WO 95/24556.
  • Such packaging / dosing devices are advantageously screwed onto a cartridge outlet or onto an outlet opening of an adhesive pump.
  • the admixture of the accelerator composition B to the adhesive K and mixing by means of a dynamic mixer by means of a dynamic mixer.
  • the accelerator composition B is injected to the adhesive K, in particular via a plurality of distributed nozzles and then mixed.
  • the admixture of the accelerator composition B in the adhesive K can be homogeneous or in layers. Layers are obtained in particular when a small number, typically between 3 and 10, of mixing elements are arranged in a static mixer.
  • a homogeneous mixing preferably either a dynamic mixer or a plurality of mixing elements, typically more than 12, in particular more than 15 mixing elements, are used in a static mixer. Preference is given to a substantially homogeneous mixing. If the accelerator composition B and the adhesive K are mixed essentially in layers, for example by working with a static mixer with a small number of mixing elements, then after complete curing, a homogenously through-hardened product is usually still produced, in which the original layers are no longer visible.
  • the moisture-curing adhesive reacts over the contained one crosslinkable polymers with the water and / or with a hydrolyzed reagent, for example a hydrolyzed form of the polyaldimine possibly contained. Over all the reactions, the adhesive K hardens after application. In addition, there may be a subsequent reaction with water which is taken up from the air (atmospheric moisture), which leads at most to a further, complete aftercuring of the adhesive K.
  • the accelerated adhesive KB1 and / or the optionally accelerated adhesive KB2 are applied by means of a hand-guided applicator device, in particular a gun.
  • the mixing of the accelerator composition B and the adhesive K can be carried out directly in the applicator device, as described above.
  • the accelerated adhesive KB1 and / or the optionally accelerated adhesive KB2 are applied by means of an automatic applicator device which has a movable application nozzle.
  • the mixing of the accelerator composition B and the adhesive K can take place directly in the applicator device, as described above.
  • the applicator device in the aforementioned two preferred methods preferably comprises two separate chambers, wherein the adhesive K and the accelerator composition B are each located in one of the two chambers.
  • the applicator device preferably additionally comprises a mixing chamber into which both chambers open and which comprises a static or dynamic mixer.
  • the application of the accelerated adhesive KB1 and the optional accelerated adhesive KB2 can be carried out in the same or different ways. With regard to the application amount, however, it is advantageous if the accelerated adhesive KB1 is applied in the smallest possible amount, so that straight sufficient adhesive is present that the pre-fixing of the two parts to be bonded T1 and T2 is ensured without further fixation measures. This is preferably done with respect to statics critical points that are exposed during the movement of the bonded parts T1 and T2 particularly large forces.
  • the minimum amount of accelerated adhesive KB1 required in a specific bonding process essentially depends on the weight and the geometry of the parts to be bonded as well as on the mechanical properties of the adhesive K and can easily be determined by a person skilled in the art by routine tests.
  • B contains, based on the total accelerated adhesive KB1; 5) applying the accelerated adhesive KB1 to the part T1, wherein the application amount of the accelerated adhesive KB1 is less than the application amount of the optional accelerated adhesive KB2;
  • the optionally accelerated adhesive KB2 is first applied to the first part T1 and then, during the open time of the optionally accelerated adhesive KB2, the accelerated adhesive KB1 is not continuously applied to the first part T1.
  • This is preferably a punctiform application of the accelerated adhesive KB1, wherein the accelerated adhesive KB1 is applied next to or between the optionally accelerated adhesive KB2 on the first part.
  • Such a application produces a composite joint T12, which has an optionally accelerated adhesive KB2 applied over a large area and accelerated adhesive KB1 applied punctiform or in between or next to it.
  • the accelerated adhesive KB1 is applied in thin beads applied adjacent to or between the optional accelerated adhesive KB2, with less than half of the gap between the parts T1 and T2 being filled by accelerated adhesive KB1.
  • the adhesive in the T12 composite joint must consist of less than half of the accelerated adhesive KB1 and more than half of the optionally accelerated KB2 adhesive.
  • the total adhesive in the T12 composite joint is at most 25%, based on the area of the applied adhesives KB1 and KB2, of accelerated adhesive KB1 and at least 75% of optionally accelerated adhesive KB2. More preferably, the total adhesive in the composite joint T12 is at most 10%, based on the area of the applied adhesives KB1 and KB2 of accelerated adhesive KB1 and at least 90% of optionally accelerated adhesive KB2.
  • the accelerated adhesive KB1 and / or the adhesive KB2 may further be advantageous for the accelerated adhesive KB1 and / or the adhesive KB2 to be heated before, during or after application. This speeds up the buildup of the strength of the adhesive and shortens the open time.
  • the accelerator composition B is preferably used in such a ratio to the adhesive K that with the water present in the accelerator composition B at least 50%, preferably 100%, of all reactive groups of the crosslinkable polymer throughout is optional accelerated adhesive KB2 can be implemented.
  • the optionally accelerated adhesive KB2 it is also possible to apply the optionally accelerated adhesive KB2 entirely without admixing the accelerator composition B. In these cases, it hardens only by water from the environment, such as humidity.
  • the optionally accelerated adhesive KB2 contains between 0.5 and 5% by volume of the accelerator composition B.
  • the accelerator composition B is preferably used in a ratio to the adhesive K that corresponds to that in FIG 100% of all of the crosslinkable polymer reactive groups can be reacted throughout the accelerated KB1 adhesive. It is possible to use a molar excess of water with respect to the moisture-reactive groups of the adhesive. The excess of water causes an additional acceleration of the curing of the accelerated adhesive KB1.
  • the accelerated adhesive KB1 contains between 7.5 and 12.5% by volume of the accelerator composition B.
  • a composite joint T12 is created which connects the two parts T1 and T2 via the accelerated adhesive KB1 and the optionally accelerated adhesive KB2.
  • the accelerated adhesive KB1 Due to the different content of water in the accelerated adhesive KB1 and KB2 in the optionally accelerated adhesive a different open time of the two blends KB1 and KB2 is achieved, the accelerated adhesive KB1 has a shorter open time and faster early strength builds. Surprisingly, this has no significant influence on the mechanical values, in particular stiffness and modulus, of the adhesive K after complete curing. Both the accelerated adhesive KB1 and the optional accelerated adhesive KB2 have, after complete curing, very similar mechanical properties, in particular with regard to modulus, tensile strength and elongation at break, as well as the same adhesive properties. The contact of the accelerated adhesive KB1 and the optional accelerated adhesive KB2 with water in the form of humidity is not absolutely necessary for the curing, if in both cases water in the form of
  • Accelerator composition B was added, but it can also favor.
  • the postcuring of the composition can be carried out by means of atmospheric moisture.
  • the curing of the accelerated adhesive KB1 and the optionally accelerated adhesive KB2 takes place especially at room temperature.
  • the curing of the accelerated adhesive KB1 is such that, on the one hand, a sufficient open time is ensured and, on the other hand, curing has progressed within a period of a few minutes, or if rapid strength is built up so rapidly that the prefixing can be processed further or a bond carried out with the accelerated adhesive KB1 is self-supporting and can be transported.
  • the method according to the invention is suitable for the prefixing and bonding of various substrates, for example for bonding components in the production of automobiles, rail vehicles, ships or other industrial goods, but also for sealing joints in construction.
  • the method according to the invention is preferably used for adhesive and sealing applications in the construction and manufacturing industry and in vehicle construction, in particular for joint sealing, parquet bonding, bonded part bonding, seam sealing, cavity sealing, assembly,
  • the invention relates to a product comprising at least two parts bonded together, obtained by a method as described above.
  • this product (article) is a building, an industrial good or a means of transport, or a part thereof.
  • An exemplary list of such articles are houses, glass facades, windows, bathrooms, kitchens, roofs, bridges, tunnels, roads, automobiles, trucks, rail vehicles, buses, ships, mirrors, windows, tubs, white goods, household appliances, dishwashers, washing machines, Ovens, floodlights, fog lights or solar panels such as photovoltaic or solar thermal modules.
  • the substrates to be bonded comprising the first part T1 and the second part T2 may be made of a variety of materials.
  • plastics organic materials such as leather, fabrics, paper, wood, resin bonded wood materials, resin Texti I-Co m positive material e, glass, porcelain, ceramics and metals, especially painted metals are suitable.
  • plastics are polyvinyl chloride (PVC), acrylonitrile-butadiene-styrene copolymers (ABS), SMC (sheet molding composites), polycarbonate (PC), polyamide (PA), polyester (PE), polyoxymethylene (POM), Polyolefins, in particular polyethylene (PE) or polypropylene (PP), preferably PP or PE surface-treated with plasma, corona or flame.
  • PVC polyvinyl chloride
  • ABS acrylonitrile-butadiene-styrene copolymers
  • SMC sheet molding composites
  • PC polycarbonate
  • PA polyamide
  • PET polyester
  • POM polyoxymethylene
  • Polyolefins in particular polyethylene (PE) or polypropylene (PP), preferably PP or PE surface-treated with plasma, corona or flame.
  • Preferred materials for the substrates are metals and polyolefins, in particular painted metals and polypropylene or polyethylene surface-treated with plasma, corona or flame.
  • the accelerated adhesive KB1 and the optional accelerated adhesive KB2 are particularly suitable as assembly adhesives.
  • a "mounting adhesive” is referred to in this document, an adhesive, which is a fast Strength structure has, so that it is suitable to glue parts that must be moved after a short time after the adhesive application already.
  • the accelerated adhesive KB1 must therefore be able to transfer forces between the joining partners after a short time.
  • assembly adhesives are used in industrial manufacturing, especially in a conveyor belt process. Particularly preferred is the use of the adhesive in construction of means of transport, in particular of vehicles, more preferably of automobiles.
  • prefabricated modules can be prefixed and glued to a body of a vehicle using the method according to the invention.
  • the tensile strength, the elongation at break, and the modulus of elasticity ("modulus of elasticity") in the range 0.5-5% elongation were determined according to DIN EN ISO 527 (tensile speed: 200 mm / min, test specimen 5A) to dumbbells with a length of 75 mm, with a web length of 30 mm and a web width of 4 mm, which were produced by punching out of films of about 2 mm thickness of the adhesives KB1 and KB2 cured in the standard climate.
  • the open time was determined as follows: For each measurement of a measurement series, a triangular bead of the respective adhesive with a width of 10 mm and height of 10 mm under standard conditions (23 ° C., 50% rh) was applied to a cleaned and degreased glass plate (40 ⁇ 100 ⁇ 6 mm) are applied centrally and along the long side and, after a defined waiting time of 1, 3, 5 and 10 minutes (depending on the measurement), introduced into the sample holder of a Zwick Roell Zwicki 1020 testing machine. In the testing machine was a second glass plate, which was mounted horizontally parallel above the first plate with the adhesive, with a sufficiently large gap that the triangular caterpillar was not touched.
  • the time to reach the minimum necessary early strength, ie the curing time, which is required until a bond can be charged without further fixation, was determined by the following method: On a vertically hanging, KTL-coated steel sheet of 0.8 mm thickness, 500 mm length (horizontal) and width of 200 mm (vertical) (material: steel DC04 coated with BASF CathoGuard ® 800, available from Rocholl GmbH, Schonbrunn, Germany) has a rectangular PTFE disk with thickness of 1 cm over the entire length of the steel sheet was attached , At right angles between the steel plate and the PTFE disc, an adhesive bead was applied over the entire length of the right angle.
  • adhesive beads were applied to the corresponding substrates, exposed to different storage conditions and then at room temperature (23 ° C.) and 50% relative
  • Humidity is checked by means of a "caterpillar test", where the caterpillar is cut just above the adhesive surface at the end of the caterpillar, and the incised end of the caterpillar is held in place with circular tongs and pulled from the substrate. This is done by carefully rolling up the bead on the point of the pliers, and by placing a cut to the bare ground perpendicular to the caterpillar pulling direction.
  • the caterpillar removal speed should be selected so that a cut must be made approx. Every 3 seconds.
  • the test track must be at least 8 cm. It is assessed after the removal of the caterpillar on the substrate remaining adhesive
  • substrate 1 As the first substrate ( “substrate 1”) were CDL Iack Of steel plate of 0.8 mm thickness, 25 mm width and 100 mm length (steel DC04 coated with BASF CathoGuard ® 800, available from Rocholl GmbH, Schonbrunn, Germany), the front was cleaned with isopropanol and flashed for 10 min.
  • Substrate 2 As a second substrate (“Substrate 2”), the same cleaned platelets were used, which in this case, however, were treated with SikaPrimer-207 and flashed for 10 minutes before application of the adhesive.
  • relative humidity 7d RT
  • 7d water in addition to 7 days in a water bath at 20 ° C
  • d 80 ° C 50% relative humidity
  • 7d cataplasm 7 Days Cataplasmal storage at 70 ° C and 100% relative humidity
  • 7d cataplasm 7 days at 100 ° C (“7d 100 ° C”).
  • Adhesive K As a one-component, moisture-curing adhesive K is a polyurethane adhesive Sikaflex ® -270 was used (available from Sika Switzerland AG).
  • Accelerator Composition B Accelerator Composition B was Sika® Booster AC-30, a water-based paste available from Sika für AG containing 15-30% by weight of water.
  • the accelerated adhesive KB1 was obtained by mixing the adhesive K and the accelerator composition B in a volume ratio of 10: 1 (K: B) on a laboratory machine with a gear meter (Static mixer Sulzer MS 13-18G). This resulted in an accelerated adhesive KB1 containing about 10% by volume of accelerator composition B.
  • the adhesive K was heated to a temperature of 60 ° C. during the application.
  • the extrusion speed when applying the adhesive KB1 was 5 cm 3 / s.
  • the open time of KB1 was 1 min.
  • the optional accelerated adhesive KB2 was obtained by mixing the adhesive K and the accelerator composition B in a volume ratio of 50: 1 (K: B) on a laboratory unit with a gear metering device (static mixer Sulzer MS 3-8G). This resulted in an optionally accelerated adhesive KB2 containing just under 2% by volume of accelerator composition B.
  • the adhesive K was heated to a temperature of 40 ° C. during the application.
  • the extrusion speed when applying the adhesive KB2 was 5 cm 3 / s.
  • the open time of KB2 was 5 min.
  • Table 1 shows that the prefixing adhesive KB1 already after 5 min sufficient early strength is achieved in order to burden a bond without additional pre-fixing.
  • the adhesive KB2 requires 30 min to reach the same early strength.
  • the lower final tensile shear strength of the adhesive KB1 does not play a major role in the bonding since the final attachment is achieved by the KB2 adhesive, which makes up the greater part of the bond in the process according to the invention.
  • the pre-fixing adhesive KB1 surprisingly has a modulus slightly lower than the final adhesive KB2. This avoids the effect that the total mechanical stress after the final bonding is on the much less applied prefixing adhesive, as is conventional in the art.
  • the stiffer, higher modulus adhesive portion of the bond is in fact inevitably mechanically more heavily loaded.
  • the difference in the module between KB1 and KB2 is also surprisingly small for a pre-fixed gluing. It also shows that the prefixing adhesive KB1 enables a strong, elastic pre-fixing bond. Adhesion is not adversely affected by the process according to the invention since both adhesives KB1 and KB2 show excellent adhesion behavior at all times.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

La présente invention concerne un procédé de préfixation et de collage de deux pièces (T1) et (T2), comprenant les étapes consistant à : a) fournir un adhésif (K) monocomposant durcissant à l'humidité et une composition accélératrice (B) contenant entre 10 et 80 % en poids d'eau ; b) fabriquer un adhésif accéléré (KB1) en mélangeant l'adhésif (K) et une composition accélératrice (B) aqueuse afin d'obtenir l'adhésif accéléré (KB1), l'adhésif accéléré (KB1) contenant entre 5 et 20 % en volume de composition accélératrice (B), puis déposer l'adhésif accéléré (KB1) facultatif sur la première pièce (T1) ; c) fabriquer un adhésif accéléré (KB2) facultatif en mélangeant facultativement l'adhésif (K) et la composition accélératrice (B)aqueuse pour obtenir l'adhésif accéléré (KB2) facultatif, l'adhésif accéléré (KB2) facultatif contenant moins de 5 % en volume de composition accélératrice (B), puis déposer l'adhésif accéléré facultatif (KB2) sur la première pièce (T1) ; les étapes b) et c) étant réalisées dans un quelconque ordre et la quantité d'adhésif accéléré (KB1) à déposer sur la première pièce (T1) étant inférieure à la quantité d'adhésif accéléré (KB2) facultatif à déposer sur la première pièce (T1) ; d) ajouter la seconde pièce (T2) sur l'endroit à coller de manière à créer une liaison (T12) reliant les deux pièces (T1) et (T2) au moyen de l'adhésif accéléré (KB1) et de l'adhésif accéléré (KB2) facultatif. Le procédé selon l'invention permet de préfixer et de coller des pièces devant être collées, en utilisant un adhésif unique, sans avoir besoin d'une préfixation supplémentaire et sans dégrader le collage obtenu avec un adhésif ayant durci mécaniquement de manière non homogène. Cela permet un collage meilleur et plus rapide qui peut être en outre réalisé à peu de frais.
EP18756463.8A 2017-09-01 2018-08-28 Procédé amélioré de préfixation et de collage de pièces Pending EP3676344A1 (fr)

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EP17189013 2017-09-01
PCT/EP2018/073086 WO2019042967A1 (fr) 2017-09-01 2018-08-28 Procédé amélioré de préfixation et de collage de pièces

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US5558116A (en) 1994-03-07 1996-09-24 Createchnic Ag Metering cap
DE19517452A1 (de) * 1995-05-12 1996-11-14 Henkel Teroson Gmbh Zweikomponenten-Kleb-/Dichtstoff mit hoher Anfangshaftfestigkeit
GB9821991D0 (en) * 1998-10-08 1998-12-02 Thorstone Business Man Ltd Coatings
WO2001044074A1 (fr) 1999-12-17 2001-06-21 Sika Ag, Vorm. Kaspar Winkler & Co. Adaptateur, dispositif et procede permettant de prelever des materiaux a partir de sachets tubulaires a plusieurs chambres, utilisation de l'adaptateur et sachet d'emballage tubulaire
US6433091B1 (en) 2001-05-10 2002-08-13 Henkel Loctite Corporation Adhesive composition
GB201104675D0 (en) * 2011-03-18 2011-05-04 Aston Martin Lagonda Ltd Methods of forming bonded structures and bonded structures formed thereby
EP2562192A1 (fr) * 2011-08-26 2013-02-27 Sika Technology AG Durcisseur pour compositions durcissant à l'humidité

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