WO1999007774A1 - Adhesifs solubles a base de liant contenant des composes di- ou polysulfure - Google Patents

Adhesifs solubles a base de liant contenant des composes di- ou polysulfure Download PDF

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Publication number
WO1999007774A1
WO1999007774A1 PCT/EP1998/004667 EP9804667W WO9907774A1 WO 1999007774 A1 WO1999007774 A1 WO 1999007774A1 EP 9804667 W EP9804667 W EP 9804667W WO 9907774 A1 WO9907774 A1 WO 9907774A1
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WIPO (PCT)
Prior art keywords
adhesive
bonds
compounds
components
adhesives
Prior art date
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Ceased
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PCT/EP1998/004667
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German (de)
English (en)
Inventor
Andreas Ferencz
Herbert Fischer
Michael Hirthammer
Hubert Schenkel
Manfred Schumann
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to EP98942625A priority Critical patent/EP1002007A1/fr
Priority to AU90692/98A priority patent/AU9069298A/en
Priority to JP2000506265A priority patent/JP2001512762A/ja
Priority to CA002299353A priority patent/CA2299353A1/fr
Publication of WO1999007774A1 publication Critical patent/WO1999007774A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/36—Hydroxylated esters of higher fatty acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
    • C08G18/3863—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms
    • C08G18/3865—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms
    • C08G18/3868—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms the sulfur atom belonging to a sulfide group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6696—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8054—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/38
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4064—Curing agents not provided for by the groups C08G59/42 - C08G59/66 sulfur containing compounds
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/28—Non-macromolecular organic substances

Definitions

  • the present invention relates to adhesive compositions based on binders which contain di- or polysulfide bonds and are suitable for producing releasable adhesive bonds.
  • the present invention further relates to cleavage reagents for detaching adhesive bonds and a method for producing and detaching adhesive bonds.
  • EP-A-735121 describes an adhesive film section for a residue-free and damage-free and releasable bond consisting of a double-sided adhesive film with a handle protruding from the adhesive film, on which the bond can be released by pulling in the direction of the bond plane.
  • this method can only be used if the adhesive layer of the adhesive film is a pressure sensitive adhesive. With such adhesive connections, however, only slight tensile or peel strengths so that this method can only be used for fixing small objects such as hooks and the like in the household area.
  • DE-A-4230116 describes an adhesive composition containing a mixture of an aliphatic polyol with an aromatic dianhydride.
  • This adhesive composition enables the bond to be dissolved in aqueous alkaline systems, specifically called soda solutions or alkali solutions. It is proposed to use these aqueous alkaline-soluble adhesives for the rational production of magnetic parts and other small parts, the adhesive only being used for the production of auxiliary pushings in material processing.
  • Very similar adhesives are also known as labeling adhesives, which allow the labels to be peeled off in an aqueous or aqueous alkaline environment in beverage bottles and similar containers.
  • DE-A-4328108 describes an adhesive for floor coverings and a method for detaching these bonded floor coverings with the aid of microwave energy.
  • the adhesive should be electrically conductive and softenable by a microwave device.
  • Solvent-free contact adhesives based on (aqueous) polymer dispersions containing copper powder or aluminum powder are specifically proposed.
  • the glued pieces of floor covering are to be placed in a microwave device to release the adhesive connection, so that the adhesive layer can be softened, so that the pieces of floor covering can be removed manually after the adhesive layer has softened.
  • WO 94/12582 describes a pressure sensitive adhesive based on a mixture of an aqueous polymer dispersion and an adhesive dissolved in an organic solvent, as well as tackifiers and production agents.
  • This pressure sensitive adhesive has a constant adhesive force over a wide temperature range and enables mechanical separation of the adhesive bonds. It is stated that these adhesive connections are suitable for bonding insulation and / or decorative surface parts such as, for example, dam materials or plastic films.
  • EP-A-521825 describes a releasable adhesive connection in which the parts connected to one another are joined by means of an adhesive bead inserted between them. This bead of adhesive contains a flat thermoplastic separating element.
  • thermoplastic separating layer When the adhesive connection is heated by current or radiation supply, this thermoplastic separating layer is softened, so that the parts connected to one another can be mechanically separated from one another.
  • EP-A-521825 suggests using such releasable adhesive bonds in direct glazing in vehicle construction.
  • DE-A-19526351 describes a solvent gel for lacquers, paints and adhesives based on organic solvents with the addition of network thickeners and other conventional agents.
  • the use as a stripping agent in the stripping of 2-component paints is mentioned as a specific field of application. Although it is mentioned that such mixtures are also suitable for use with 2-component adhesives, there is no concrete information on how to loosen such adhesive connections.
  • Another object of the present invention is a method for producing and releasing adhesive bonds with the following essential process steps:
  • This adhesive composition can be a one-component system that the user can apply directly without mixing components.
  • the adhesive system can also consist of 2 or more components to be stored separately, which are only mixed with one another immediately before application.
  • Curing of the adhesive at room temperature i.e. by reaction of the individual components with one another in the case of multi-component systems or by reaction of the single-component system with atmospheric moisture and / or atmospheric oxygen.
  • Other options for curing are the supply of heat, UV light or electron beams. The curing process depends on the crosslinking mechanism of the components.
  • the adhesive connection is loosened by applying a cleavage reagent composition or by immersing the glued component in the cleavage reagent.
  • this release process can be further accelerated by heating the bonded component or the bond point. If necessary, the separation of the bonded components can be further accelerated by mechanical stress on the adhesive joint.
  • An essential constituent of the structural components of the binder according to the invention are therefore compounds which have at least one di- or polysulfide bond of the general formula
  • R 1 and R 2 are divalent alkyl and / or aryl residues, in the simplest case a C to C 8 alkylene group or a divalent aromatic residue such as 1,2-, 1,3- or 1,4-phenylene, Diphenylene. Naphtylene or similar aromatic residues.
  • X and Y can independently of one another denote any functional group capable of reaction, preference being given to primary or secondary amino groups, hydroxyl groups, carboxyl groups.
  • X and / or Y can be mercapto groups, epoxy groups, isocyanate groups, alkoxysilyl groups or also olefinic double bonds, in the latter case R and / or R can be replaced by a covalent bond, x is an integer in the range between 2 and 8, particularly preferred is 2.
  • Examples of structural components according to formula I which contain olefinic double bonds can be prepared in the following way: In a first step, dithiodial alcohols or dithiodiamines are reacted with diisocyanates in such a way that isocyanate-terminated disulfide compounds result, ie the diisocyanate component is in a stoichiometric excess over the dithiodial alcohol - or dithiodiamine component used. In a second step, these NCO-terminated disulfide compounds are reacted with hydroxyalkyl acrylates or hydroxyalkymethacrylates, so that (meth) acrylate-terminated disulfide compounds are formed.
  • Examples of the hydroxyalkyl (meth) arcylates to be used are the corresponding ethyl, propyl or butyl compounds.
  • the (meth) acrylate-terminated disulfide compounds obtained in this way can be combined as usual with corresponding copolymerizable compounds and cured by free radical or ionic means.
  • Examples of such copolymerizable compounds known per se are in DE-C 19545123 column 5 line 24 called to 47.
  • the comonomers mentioned there are expressly part of this invention.
  • epoxy-functionalized di- or polysulfides can be produced from the NCO-terminated disulfide or polysulfide compounds by reaction with hydroxy group-containing epoxy compounds.
  • hydroxy-functional epoxides are glycidol and the various glycidyl ethers of bisphenol A, which as a rule carry free hydroxyl groups.
  • the corresponding alkoxysilane-terminated products can be prepared from the NCO-terminated di- or polysulfide compounds by reaction with amino-functional alkoxysilanes.
  • Very particularly preferred structural components according to formula I are cystamine, dithiodiethanol and dithiodipropionic acid.
  • One or more compounds of the general formula can be used as a further structural component of the adhesive composition according to the invention
  • the components of the formula II are usually so-called prepolymer compounds with a molecular weight range between 300 and 20,000, preferably between 700 and 10,000.
  • Particularly preferred components according to formula II are epoxy resins, isocyanate group-containing polyurethane prepolymers, novolak resins, phenolic resins or unsaturated polyesters.
  • the above-mentioned copolymerizable olefinically unsaturated compounds can also take the place of the components according to formula II.
  • polyglycidyl ethers of polyols such as ethylene glycol, dithylene glycol, triethylene glycol, 1,2-propylene glycol, 1,5-pentanediol, 1,2,6-hexanetriol, glycerol, 2,2-bis (4-hydroxycyclohexyl) are suitable as epoxy resins.
  • propane and polyalkylene glycols such as polypropylene glycol.
  • the polyglycidyl esters of aliphatic or aromatic polycarboxylic acids such as oxalic acid, succinic acid, glutaric acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid and dimer fatty acid, are also suitable.
  • epoxy compounds are the polyglycidyl ethers of polyphenols such as bisphenol A, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) isobutane, 1,5-dihydroxynaphthalene and novolak resins.
  • Preferred epoxy compounds include higher molecular weight resins such as the chain extended diglycidyl ether of bisphenol A, diglycidyl ether of dimer fatty acid extended bisphenol A and bisphenol A glycidyl ether terminated polyether polyurethanes.
  • the adducts of epoxy resins with carboxy-, amino- and / or hydroxy-functional nitrile rubbers (Hycar types) can also be used as the epoxy component.
  • the polyurethane prepolymers containing isocyanate groups are composed of aromatic, cycloaliphatic or aliphatic polyisocyanates and di- and / or polyols.
  • aromatic polyisocyanates examples include:
  • TDI tolylene diisocyanate
  • MDI diphenylmethane-4,4'-diisocyanate
  • MDI diphenylmethane-2,4'-diisocyanate
  • 4,4'-diphenylmethane diisocyanate with the 2,4'-isomer or their mixtures with higher-functional oligomers
  • suitable cycloaliphatic polyisocyanates are the hydrogenation products of the aromatic diisocyanates mentioned above.
  • nate such as 4,4'-dicyclohexylmethane diisocyanate (H ⁇ 2 MDI), l-isocyanatomethyl-3-isocyanato-l, 5,5-trimethyl-cyclohexane (isophorone diisocyanate, IPDI), cyclohexane-1,4-diisocyanate, hydrogenated Xylylene diisocyanate (H XDI), m- or p-tetramethylxylene diisocyanate (m-TMXDI, p-TMXDI) and dimer fatty acid diisocyanate.
  • H XDI 4,4'-dicyclohexylmethane diisocyanate
  • l-isocyanatomethyl-3-isocyanato-l 5,5-trimethyl-cyclohexane (isophorone diisocyanate, IPDI)
  • cyclohexane-1,4-diisocyanate hydrogen
  • aliphatic polyisocyanates examples include hexane-1,6-diisocyanate (HDI), 1,6-diisocyanato-2,2,4-trimethylhexane, 1,6-diisocyanato-2,4,4-trimethylhexane, butane 1, 4- Diisocyanate and 1,12-dodecane diisocyanate (C DI).
  • HDI hexane-1,6-diisocyanate
  • C DI 1,6-diisocyanato-2,2,4-trimethylhexane
  • C DI 1,12-dodecane diisocyanate
  • the liquid polyhydroxy compounds with two or three hydroxyl groups per molecule such as e.g. di- and / or trifunctional polypropylene glycols in the molecular weight range from 200 to 6000, preferably in the range from 400 to 3000.
  • Statistical and / or block copolymers of ethylene oxide and propylene oxide can also be used.
  • Another group of polyethers to be used preferably are the polytetramethylene glycols, which e.g. be produced by the acidic polymerization of tetrahydrofuran, the molecular weight range of the polytetramethylene glycols being between 200 and 6000, preferably in the range from 400 to 4000.
  • liquid polyesters which are obtained by condensation of di- or tricarboxylic acids, e.g. Adipic acid, sebacic acid, glutaric acid, azelaic acid, hexahydrophthalic acid or phthalic acid with low molecular weight diols or triols such as e.g. Ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,4-butanediol, 1, 6-hexanediol, 1, 10-decanediol, glycerol or trimethylolpropane can be produced.
  • di- or tricarboxylic acids e.g. Adipic acid, sebacic acid, glutaric acid, azelaic acid, hexahydrophthalic acid or phthalic acid
  • diols or triols such as e.g. Ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol,
  • polyesters based on ⁇ -caprolactone also called “polycaprolactones”.
  • polyester polyols of oleochemical origin can also be used.
  • Such polyester polyols can be prepared, for example, by completely opening epoxidized triglycerides of a fat mixture containing at least partially olefinically unsaturated fatty acids with one or more alcohols having 1 to 12 carbon atoms and then partially transesterifying the triglyceride derivatives to alkyl ester polyols having 1 to 12 carbon atoms in the alkyl radical (see for example DE-A-3626223).
  • Other suitable polyols are polycarbonate polyols and dimer diols (from Henkel) and Castor oil and its derivatives.
  • the hydroxy-functional polybutadienes as are available, for example, under the trade name "Poly-bd", can also be used as polyols for the compositions according to the invention.
  • low molecular weight hydroxy-functional (meth) acrylate polymers disclosed in EP-A-205846 can be used as polyols.
  • the well-known condensation products of phenol and / or resorzine with formaldehyde can be used as novolak resins or phenolic resins.
  • the co-condensates with terpenes, i.e. the terpene phenolic resins are used.
  • the adhesive compositions according to the invention basically contain at least one structural component of the general formula I containing di- or polysulfide bonds and one structural component of the general formula II.
  • the two components must of course be matched to one another. Examples of useful combinations are:
  • a suitable combination of the structural components according to formula I and formula II can, however, also be in binders based on liquid rubbers which are polymerized with vulcanization systems containing sulfur and / or sulfur compounds. Specific examples of the liquid rubbers used for this are given on page 5 in WO 96/36660. Suitable sulfur-containing vulcanizing agents for this purpose are disclosed on page 6 last paragraph to page 7 first paragraph of WO 96/36660.
  • the adhesive compositions according to the invention can additionally contain plasticizers.
  • all common plasticizers can be used, for example the C 6 -C 4 -dialkyl esters of phthalic acid, alkyl benzyl esters of phthalic acid, benzoates of di- or trifunctional polyols such as, for example, dipropylene glycol dibenzoate.
  • the adhesive compositions can furthermore contain fillers in amounts of between 5 and 60% by weight.
  • suitable fillers are limestone flour, natural, ground chalk (calcium carbonate or calcium magnesium carbonate). precipitated chalks, heavy savings, talc, mica, clays, soot and color pigments such as Titanium dioxide or iron oxides.
  • the adhesives according to the invention can contain further auxiliaries and additives, such as e.g. Anti-aging agents and stabilizers, rheology aids such as fumed silicas, bentones, castor oil derivatives, as well as catalysts and accelerators and, if necessary, tackifying resins.
  • auxiliaries and additives such as e.g. Anti-aging agents and stabilizers, rheology aids such as fumed silicas, bentones, castor oil derivatives, as well as catalysts and accelerators and, if necessary, tackifying resins.
  • Splitting agents are used to detach the adhesive connection according to the present invention. These cleavage agents have the task of cleaving the di- or polysulfide bonds built into the polymer system again. These cleavage agents are either mercapto compounds, possibly with the addition of inorganic or organic basic compounds or other accelerators, or they are reducing agents for reductive cleavage of the SS bonds of the adhesive. If necessary, the cleavage agents can also contain further auxiliaries, in particular swelling agents, the latter facilitating and accelerating the attack of the cleavage agents by swelling of the crosslinked polymer matrix of the adhesive system.
  • mercapto compounds to be used according to the invention are mercaptocarboxylic acids, their esters or salts, elemental sulfur, mercaptobenz oxazole, mercaptobenzothiazole, mercaptoamines such as 2-mercaptoethylamine, mercapto alcohols such as 2-mercaptoethanol, dithiothreitol or sodium thiosulfate.
  • the basic compounds are alkali metal hydroxides such as sodium hydroxide, potassium hydroxide or organic amines.
  • reducing agents are trialkyl or triaryl phosphines.
  • Organic solvents which can also serve as solvents and / or diluents for the above-mentioned cleavage agents and / or accelerators, are generally used as swelling agents.
  • examples include alcohols such as methanol, ethanol, isopropanol or higher alcohols, alkyl acetates, in particular ethyl acetate or butyl acetate.
  • the polar solvents such as ethers, in particular the cyclic ethers such as 1,4-dioxane or tetrahydrofuran or also glycol ethers or glycol ether esters, ketones, dimethyl sulfoxide or N-methylpyrrolidone (NMP) are also suitable.
  • Chlorinated hydrocarbons preferably dichloromethane, are also suitable in principle, but chlorinated hydrocarbons are no longer readily usable because of their toxicity and for reasons of environmental protection.
  • the dissolvability of adhesive bonds can be further improved by constructive design elements. This includes, for example, inserting gauze or other absorbent materials into the adhesive joint.
  • the cleavage reagent can be admixed in a form of the adhesive formulation which is inert at room temperature. The cleavage can take place after activation of the reagent at elevated temperature.
  • releasable adhesive connections according to the invention is that normal adhesives according to the prior art are used for the joining and that a cleavable primer is used.
  • a cleavable primer is used.
  • many adhesive bonds still require primers to be applied to at least one of the substrates to be joined.
  • the Primer contain a structural component according to the general formula I.
  • the primer layer can be cleaved with the cleavage agents according to the invention using the same principle of action as described above, so that the joined parts are loosened in the sense of this invention without the adhesive as such being subjected to the cleavage reaction.
  • the test for the dissolving behavior according to the invention was carried out in two ways, on the one hand the adhesive was applied in layers. Sealants on steel sheets that were initially hardened. The hardened mass was then treated with a wide variety of cleavage agents according to the invention and their effectiveness tested.
  • steel sheets were bonded with the adhesives to be detached according to the invention, which were then hardened and tested for their tensile shear strength.
  • the test for detachability ie releasability of the adhesive connection
  • the test specimens are placed in a 100 ml standing cylinder filled with the appropriate solution. The time until the bond loosens itself is observed. Unless stated otherwise, the stated amounts are parts by weight.
  • Tensile shear strengths are given in N / mm 2 with the type of fracture, AB means adhesive fracture. Examples
  • Terostat ISE was placed on a steel sheet with a spatula and cured at 2 hours / 150 ° C in a forced-air drying cabinet, and left at room temperature for 4 days.
  • Epikote 828 was cured with Terostat 998R or 998B in the ratios 1: 1 and 10: 1 with 5% catalyst (DMP: 2,4,6-tris (dimethylaminomethyl) phenol) for 24 hours at room temperature.
  • DMP 2,4,6-tris (dimethylaminomethyl) phenol
  • Epoxy / dithiodipropionic acid detackification (epoxy formulations III)
  • Shore A hardness (pressing time 60 seconds) 95. After treatment with a splitting reagent, the adhesive becomes brittle or viscous, the measuring needle penetrates the dissolved adhesive.
  • prepolymer I dithiodipropionic acid is reacted in a molar ratio of 1: 2 with epoxy Chem Res E 20 (2h, 120 ° C, 0.25% triphenylphosphine as catalyst) Tensile shear strength / detacking test (after curing and 7 days storage at room temperature)
  • Hardener component epoxy prepolymer with dithiopropionic acid (build-up component I)
  • Removable epoxy adhesive hardened with cystamine (epoxy formulation IV) 1.80 g Chem Res E 20 and 0.38 g cystamine are combined and hardened at 100 ° C for 1 h. Tensile shear strength after 1 day 11.4. Tensile shear strength after mixing and curing at room temperature for 7 days 6.1. Dissolve the cured adhesive after adding thioglycolic acid methyl ester within 10 min.
  • cystamine a mixture of cystamine dihydrochloride and NaOH can also be used.
  • Voranol CP455 / castor oil was mixed with a dithiodiethanol / MDI reaction product (Lupranat MIS with dithiodiethanol in a molar ratio of 2: 1 at 60 ° C, 3 hours): mixed and cured at RT for 24 hours.
  • a dithiodiethanol / MDI reaction product Liquiranat MIS with dithiodiethanol in a molar ratio of 2: 1 at 60 ° C, 3 hours
  • Voranol CP 455 glycerol-PO adduct
  • 0.07 g (0.007 mol) castor oil 2.43 g (1.05 mol) 2,2 '-dithiodiethanol 7.90 g ( 2.1 mol) 2,474,4'-MDI isomer mixture
  • Shore A hardness pressing time 60 seconds 50. Immediate penetration of the viscous mass after treatment with cleavage reagent.
  • Epoxy formulation III a Detachment after 8 hours with mechanical stress Urethane formulation II. Detachment after 8 hours with mechanical stress
  • Epikote 828 corresponds to ChemResE20 - epichlorohydrin / bisphenol A adduct, standard epoxy resin, epoxy equivalent weight 180-194, viscosity 8000-14000 mPas / 25 ° C
  • Thiokol LP 3 - polysulfide polymer average molecular weight 1000, 2% trifunctional monomer, average mercaptan content 2.06 mol / kg (information according to Int.J. Adhesion and Adhesives Vol. 12 No. 3 July 1992 p 171)

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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)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne des compositions adhésives solubles qui peuvent être formulées sur la base de liants dans lesquels au moins un constituant structural contenant des composés di- ou polysulfure. Ces adhésifs peuvent durcir selon des méthodes traditionnelles, soit comme adhésifs à deux composants, soit comme adhésifs thermodurcissables. Les composés adhésifs de ce type peuvent être dissous avec des agents de dissociation à base de composés mercapto ou à base d'agents de réduction, éventuellement par adjonction d'agents gonflants. Cette propriété permet de détacher par voie chimique des éléments collés dans le joint de collage.
PCT/EP1998/004667 1997-08-04 1998-07-25 Adhesifs solubles a base de liant contenant des composes di- ou polysulfure Ceased WO1999007774A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP98942625A EP1002007A1 (fr) 1997-08-04 1998-07-25 Adhesifs solubles a base de liant contenant des composes di- ou polysulfure
AU90692/98A AU9069298A (en) 1997-08-04 1998-07-25 Soluble adhesives with a base consisting of a bonding agent containing di- or polysulfide bonds
JP2000506265A JP2001512762A (ja) 1997-08-04 1998-07-25 ジまたはポリスルフィド結合を含む結合剤を基本成分として含有する解離可能な接着剤
CA002299353A CA2299353A1 (fr) 1997-08-04 1998-07-25 Adhesifs solubles a base de liant contenant des composes di- ou polysulfure

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19733643A DE19733643A1 (de) 1997-08-04 1997-08-04 Lösbare Klebstoffe
DE19733643.4 1997-08-04

Publications (1)

Publication Number Publication Date
WO1999007774A1 true WO1999007774A1 (fr) 1999-02-18

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PCT/EP1998/004667 Ceased WO1999007774A1 (fr) 1997-08-04 1998-07-25 Adhesifs solubles a base de liant contenant des composes di- ou polysulfure

Country Status (8)

Country Link
EP (1) EP1002007A1 (fr)
JP (1) JP2001512762A (fr)
AR (1) AR010937A1 (fr)
AU (1) AU9069298A (fr)
CA (1) CA2299353A1 (fr)
DE (1) DE19733643A1 (fr)
WO (1) WO1999007774A1 (fr)
ZA (1) ZA986945B (fr)

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EP1111020A2 (fr) 1999-12-22 2001-06-27 Henkel Kommanditgesellschaft auf Aktien Association par collage détachable
US6855760B1 (en) 1999-05-26 2005-02-15 Henkel Kommanditgesellschaft Auf Aktien Detachable adhesive compounds
US7147742B2 (en) 2000-08-03 2006-12-12 Henkel Kommanditgesellschaft Auf Aktien ( Henkel Kgaa) Method for accelerating the curing of adhesives
US7273580B2 (en) 2000-08-03 2007-09-25 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Ferromagnetic resonance excitation and its use for heating substrates that are filled with particles
US7407704B2 (en) 1999-10-27 2008-08-05 Henkel Kgaa Process for adhesive separation of bonded joints
US7479288B2 (en) 2001-12-21 2009-01-20 Henkel Kommanditgesellschaft Auf Aktien Nanoparticulate preparation
EP3885404A1 (fr) 2020-03-23 2021-09-29 Covestro Deutschland AG Utilisation des mélanges d'huiles essentielles pour séparer des collages
CN115084518A (zh) * 2022-05-20 2022-09-20 清华大学深圳国际研究生院 负极粘结剂及其应用
CN117701221A (zh) * 2023-12-25 2024-03-15 深圳市道丰宁科技有限公司 一种热熔胶黏剂及其制备方法
CN119081067A (zh) * 2024-08-30 2024-12-06 黑龙江省科学院石油化学研究院 一种含动态共价键的环氧树脂及其合成方法、自修复环氧结构胶粘剂的制备方法

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WO2024185554A1 (fr) 2023-03-03 2024-09-12 東洋紡株式会社 Résine de polyester réticulée ayant une liaison disulfure

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6855760B1 (en) 1999-05-26 2005-02-15 Henkel Kommanditgesellschaft Auf Aktien Detachable adhesive compounds
EP1785462A1 (fr) 1999-05-26 2007-05-16 Henkel Kommanditgesellschaft Auf Aktien Assemblages collés amovibles
US7407704B2 (en) 1999-10-27 2008-08-05 Henkel Kgaa Process for adhesive separation of bonded joints
EP1111020A2 (fr) 1999-12-22 2001-06-27 Henkel Kommanditgesellschaft auf Aktien Association par collage détachable
US7147742B2 (en) 2000-08-03 2006-12-12 Henkel Kommanditgesellschaft Auf Aktien ( Henkel Kgaa) Method for accelerating the curing of adhesives
US7273580B2 (en) 2000-08-03 2007-09-25 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Ferromagnetic resonance excitation and its use for heating substrates that are filled with particles
US7479288B2 (en) 2001-12-21 2009-01-20 Henkel Kommanditgesellschaft Auf Aktien Nanoparticulate preparation
US7651580B2 (en) 2001-12-21 2010-01-26 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Nanoparticulate preparation
EP3885404A1 (fr) 2020-03-23 2021-09-29 Covestro Deutschland AG Utilisation des mélanges d'huiles essentielles pour séparer des collages
WO2021191060A1 (fr) 2020-03-23 2021-09-30 Covestro Deutschland Ag Utilisation d'huiles essentielles pour la séparation de liaisons adhésives
CN115084518A (zh) * 2022-05-20 2022-09-20 清华大学深圳国际研究生院 负极粘结剂及其应用
CN117701221A (zh) * 2023-12-25 2024-03-15 深圳市道丰宁科技有限公司 一种热熔胶黏剂及其制备方法
CN119081067A (zh) * 2024-08-30 2024-12-06 黑龙江省科学院石油化学研究院 一种含动态共价键的环氧树脂及其合成方法、自修复环氧结构胶粘剂的制备方法

Also Published As

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AU9069298A (en) 1999-03-01
AR010937A1 (es) 2000-07-12
CA2299353A1 (fr) 1999-02-18
ZA986945B (en) 1999-02-03
EP1002007A1 (fr) 2000-05-24
DE19733643A1 (de) 1999-02-11
JP2001512762A (ja) 2001-08-28

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