EP1799745A1 - Revetements et composites adhesifs resistants au vieillissement - Google Patents

Revetements et composites adhesifs resistants au vieillissement

Info

Publication number
EP1799745A1
EP1799745A1 EP05798088A EP05798088A EP1799745A1 EP 1799745 A1 EP1799745 A1 EP 1799745A1 EP 05798088 A EP05798088 A EP 05798088A EP 05798088 A EP05798088 A EP 05798088A EP 1799745 A1 EP1799745 A1 EP 1799745A1
Authority
EP
European Patent Office
Prior art keywords
curable
component
curable composition
composition according
group
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Withdrawn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
EP05798088A
Other languages
German (de)
English (en)
Inventor
Olaf Lammerschop
Steve DÖRING
Michael Kux
Andreas Ferencz
Stefan Kreiling
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1799745A1 publication Critical patent/EP1799745A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • 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
    • C08G59/62—Alcohols or phenols
    • C08G59/625—Hydroxyacids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether
    • Y10T428/31529—Next to metal

Definitions

  • the present invention relates to curable compositions that are resistant to aging in a cured state, especially in a humid environment.
  • the invention relates to coating compositions and adhesives containing aging resistance-imparting additives, as well as the use of these additives in coating compositions and adhesives.
  • the adhesion of a surface coating agent on a substrate surface is of great importance in view of a permanent function of the coating composition.
  • high demands are made in this regard.
  • the bond strength of such an adhesive depends on the compatibility between the adhesive and the substrate to which the adhesive is to be applied, d. h., Adhesion between adhesive and substrate.
  • Adhesion also relies on the cohesion of the adhesive itself. Even small changes in the composition of the adhesive can produce a drastic reduction in bond strength, either rendering the adhesive unusable in the first place or weakening, or even weakening, an adhesive bond obtained using such an adhesive completely destroy.
  • the adhesive may lose flexibility, cohesion or adhesion or one or more other important properties.
  • heat-curing epoxy resin adhesives are known from the state of the art which have sufficient adhesion to aluminum surfaces under customary conditions.
  • a disadvantage of these adhesives is often that the aging resistance for applications under extreme conditions is not sufficient.
  • GB 2 222 592 A describes the pretreatment of metallic surfaces with polyhydroxylated benzene derivatives. To avoid this further working step, the addition of additives to the adhesive composition is sometimes recommended.
  • GB 2 222 592 A describes the coating of metallic surfaces with heat-curable 1-component systems, ie systems which are self-curing without the addition of a further component, for example a chemical hardener under the action of heat, and their hardening at temperatures of at least 100 ° C, wherein the compositions may contain polyhydroxylated benzene derivatives.
  • EP 0 458 521 A2 delimits the metal oxides to be used according to claim 1 of EP 0 458 521 A2 from oxides which have other functions, such as, for example, thixotroping of the composition or serve as fillers.
  • EP 0 458 521 describes oxides of the transition metals of the Periodic Table, in particular those of the copper and zinc subgroups, as the metal oxides to be used. However, the use of such transition metal oxides is undesirable for various, especially economic reasons.
  • JP 08198945 discloses amine-curing epoxy resins containing aromatic hydroxy compounds and fillers.
  • WO 00/34405 A discloses adhesive compositions containing an aromatic carboxylic acid and a hydroxyl-containing polymer, the latter having to contain a small amount of carboxy-functional monomer units for the adhesive composition to possess corrosion resistance.
  • WO 03/014236 A2 describes binder components which contain compounds with chelating properties.
  • be Compounds having chelating properties are disclosed as containing amino or mercapto groups.
  • the object underlying the invention was, in particular, to increase the aging resistance of adhesive composites even under extreme conditions, such as high humidity, by providing adhesives which can be used without the use of primers on many substrates, but in particular on metals, and are excellent Adhesion to the substrate and have an excellent cohesion. Furthermore, it should be possible, for example, to dispense with the use of additive combinations with transition metal oxides, in particular those of the copper and zinc groups, and moreover also the use in 2-component adhesive systems (2K adhesives), i. be possible in usually without heat-curing systems.
  • 2K adhesives 2-component adhesive systems
  • Y is a carboxyl group, a carboxylate group or a straight-chain or branched, optionally substituted with hydroxyl groups, amino groups, carboxyl groups and / or carboxylate groups alkyl group; and R 1 , R 2 and R 3 are independently the same or different and represent hydrogen or a hydroxyl group, and R 1 and R 3 are not simultaneously a hydroxyl group; with the proviso that, if the curable component is a thermosetting component of an epoxy-based multi-component system, the curable composition is free of transition metal oxides of the copper and zinc group, and if so curable component is an epoxy-based thermosetting component, it is not a self-curing component, are extremely suitable to increase the aging resistance of adhesive bonds and coatings.
  • Particularly preferred as aging inhibitors are those in which one or two of the radicals R 1 , R 2 and R 3 represent a hydroxyl group.
  • Suitable aging inhibitors in which Y represents a carboxyl group or carboxylate group are, in particular, 3-hydroxybenzoic acid, 3-hydroxysalicylic acid, 3,5-dihydroxybenzoic acid and 3,4,5-
  • Trihydroxybenzoic acid and salts thereof.
  • Suitable salts are, in particular, the alkali metal salts, such as sodium salts and potassium salts or ammonium salts of the acids mentioned.
  • Suitable aging inhibitors in which Y represents a straight-chain or branched alkyl group are in particular those in which the alkyl group contains 1 to 12, more preferably 1 to 6, and most preferably 1 to 4 carbon atoms. Very particularly preferred are the methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl and tert-butyl radicals. These may preferably be further substituted and carry one or more of the following radicals selected from the group hydroxy, amino, carboxyl and carboxylate.
  • the curable compositions thus obtained are also subject of the invention.
  • the compound of general formula (I) interacts with iron (III), wherein it is particularly preferred if said compound of general formula (I) is in the form of an iron (III) complex.
  • aging inhibitors of the general formula (I) are used in the context of the present invention, it is particularly preferred if they interact with iron (III), it being particularly preferred if the said compound of general formula (I) is in the form of an iron (III) complex.
  • a curable composition comprising a curable component and at least one m-hydroxybenzene derivative of the general formula (I):
  • Y is a carboxyl group, a carboxylate group or a straight-chain or branched, optionally substituted with hydroxyl groups, amino groups, carboxyl groups and / or carboxylate groups alkyl group; and R 1 , R 2 and R 3 are independently the same or different and represent hydrogen or a hydroxyl group, and R 1 and R 3 are not simultaneously a hydroxyl group; with the proviso that, if the curable component is a thermosetting component of an epoxy-based multi-component system, the curable composition is free of transition metal oxides of the copper and zinc group, and if the curable component is an epoxy-based thermosetting component is, it is not a self-curing component, provided by the invention.
  • the curable component contained in the compositions of the present invention may be cured by radiation, heat, catalytic or a chemical hardener and includes, for example, epoxy compounds, (meth) acrylates (which term means both acrylates and methacrylates), (meth) acrylic acid or polyol-curing polyisocyanates ,
  • the curable component is usually one that is curable by means of a chemical hardener.
  • 2-component epoxy adhesives may be amine-cured epoxy systems wherein the curing component is an epoxy component and the curing agent is an amine.
  • Polyepoxides containing on average at least two epoxide groups per molecule are usually used as the epoxy component in such systems.
  • These epoxy compounds can be both saturated and unsaturated and aliphatic, cycloaliphatic, aromatic or heterocyclic and also have hydroxyl groups.
  • epoxy components are preferably polyglycidyl ethers based on polyhydric, preferably dihydric alcohols, phenols, hydrogenation products of these phenols and / or novolacs (reaction products of mono- or polyhydric phenols with aldehydes, in particular formaldehyde in the presence of acidic catalysts).
  • polyglycidyl ethers of polyhydric alcohols are also suitable.
  • Polyglycidyl ethers of polycarboxylic acids can also be used, which are obtained by the reaction of epichlorohydrin or similar epoxy compounds with an aliphatic, cycloaliphatic or aromatic polycarboxylic acid such as oxalic, succinic, adipic, glutaric, phthalic, terephthalic, hexahydrophthalic, 2,6-naphthalenedicarboxylic and dimerized Linolenic acid, receives.
  • an aliphatic, cycloaliphatic or aromatic polycarboxylic acid such as oxalic, succinic, adipic, glutaric, phthalic, terephthalic, hexahydrophthalic, 2,6-naphthalenedicarboxylic and dimerized Linolenic acid, receives.
  • an aliphatic, cycloaliphatic or aromatic polycarboxylic acid such as oxalic, succinic, adipic, glutaric,
  • Particularly suitable epoxy compounds are those based on reaction products between epichlorohydrin and bisphenol A or bisphenol F.
  • amine hardeners in 2K epoxy systems are primary and / or secondary amines for use.
  • the amines used are preferably polyamines having at least two nitrogen atoms and at least two active amino hydrogen atoms per molecule.
  • Aliphatic, aromatic, aliphatic-aromatic, cycloaliphatic and heterocyclic di- and polyamines can be used.
  • Suitable amine hardeners are straight-chain or branched polyalkyleneamines, such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,3-pentanediamine, 1 , 6-hexanediamine, 3,3,5-trimethyl-1,6-hexanediamine, 3,5,5-trimethyl-1,6-hexanediamine, 2-methyl-1,5-pentanediamine, bis (3-aminopropyl) amine , N, N'-bis (3-aminopropyl) -1, 2-ethanediamine, N- (3-aminopropyl) -1,2-ethanediamine, cycloaliphatic polyamines, such as 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1 , 4-di
  • Poly (alkylene oxide) diamines and triamines such as. Jeffamine D-230, Jeffamine D-400, Jeffamine D-2000, Jeffamine D-4000, Jeffamine T-403, Jeffamine EDR-148, Jeffamine EDR-192, Jeffamine C-346, Jeffamine ED-600, Jeffamine ED.
  • aromatic polyamines such as, meta-xylylenediamine, phenylenediamine, 4,4'-diaminodiphenylmethane, toluenediamine, isophoronediamine, S.S'-dimethylM '' - diaminodicyclohexylmethane, 4,4'-diaminodicyclohexylmethane, 2,4 ' Diaminodicyclohexylmethane, the mixture of poly (cyclohexyl aromatic) amines linked via a methylene bridge (also known as MBPCAA) and polyaminoamides.
  • methylene bridge also known as MBPCAA
  • the curing component is a (meth) acrylate or (meth) acrylic acid
  • the curing is usually carried out by free-radical polymerization, initiated by radical-forming substances, such as peroxides, hydroperoxides or azo compounds or photochemically, indge with help of photoinitiators in combination with ultraviolet light.
  • ionic polymerization especially the anionic polymerization by means of suitable bases.
  • a polymerization can already be done by the admission of humidity.
  • the aging inhibitors according to the invention can also be used in polyurethane adhesive systems. Curing takes place here in particular by polycondensation of polyisocyanates, preferably diisocyanates with polyols, in particular diols.
  • polyisocyanates compounds having at least two isocyanate groups.
  • the polyisocyanates used are preferably the aromatic isocyanates, for example diphenylmethane diisocyanate, either in the form of the pure isomers, as isomer mixture of the 2,4 '- / 4,4'-isomers or else the diphenylmethane diisocyanate (MDI) liquefied with carbodiimide, for example under the trade name Isonate 143 L is known.
  • MDI diphenylmethane diisocyanate
  • the so-called "crude MDI" ie, the isomers / oligomer mixture of MDI can be used, as they are commercially available, for example, under the trade name PAPI or Desmodur VK.
  • quasi-prepolymers ie reaction products of MDI or toluene diisocyanate (TDI) with low molecular weight diols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol or triethylene glycol can be used.
  • isocyanates are the most preferred isocyanates, it is also possible to use aliphatic or cycloaliphatic di- or polyisocyanates, for example the hydrogenated MDI (H 12MDI) 1 tetramethylxylylene diisocyanate (TMXDI), 1-isocyanatomethyl-3-isocyanato-1,5,5 trimethylcyclohexane (IPDI), hexane-1,6-diisocyanate (HDI), biuretization product of HDI, isocyanuration product of HDI or dimer fatty acid diisocyanate.
  • H 12MDI hydrogenated MDI 1 tetramethylxylylene diisocyanate
  • IPDI 1-isocyanatomethyl-3-isocyanato-1,5,5 trimethylcyclohexane
  • HDI hexane-1,6-diisocyanate
  • biuretization product of HDI isocyanuration product of HDI or dimer fatty acid di
  • Suitable polyols are compounds having at least two hydroxyl groups. Suitable polyols are preferably the liquid polyhydroxy compounds having two or three hydroxyl groups per molecule, such as di- and / or trifunctional polypropylene glycols in the molecular weight range from 200 to 6000, preferably in the range of 400 to 3000. It may also be random and / or block copolymers of Ethylene oxide and propylene oxide are used.
  • polyether polyols are the polytetramethylene glycols, for example by the acidic Polymerization of tetrahydrofuran, wherein the molecular weight range of the polytetramethylene glycols is preferably between 200 and 6000, more preferably in the range of 400 to 4000.
  • polyols are the liquid polyesters obtained by condensation of di- or tricarboxylic acids, such as adipic acid, sebacic acid, glutaric acid with low molecular weight diols or triols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1, 4-butanediol, 1, 6-hexanediol, glycerol or trimethylolpropane can be prepared.
  • di- or tricarboxylic acids such as adipic acid, sebacic acid, glutaric acid
  • triols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1, 4-butanediol, 1, 6-hexanediol, glycerol or trimethylolpropane can be prepared.
  • lactones-based polyesters such as caprolactone or valerolactone.
  • polyester polyols can be prepared, for example, by complete ring opening of epoxidized triglycerides of a fat mixture containing at least partially olefinically unsaturated fatty acid with one or more alcohols having 1 to 12 carbon atoms and subsequent partial transesterification of the triglyceride derivatives to alkyl ester polyols having 1 to 12 carbon atoms in the alkyl radical.
  • suitable polyols are polycarbonate polyols and dimer diols, and in particular castor oil and its derivatives.
  • the hydroxy-functional polybutadienes such as those obtainable, for example, under the trade name "poly-BD", can also be used as polyols for the compositions according to the invention.
  • the aging inhibitors can be used independently of the adhesive system according to the invention.
  • both epoxy-based systems and polyurethane or (meth) acrylate adhesive systems are particularly suitable.
  • a particular advantage of the aging inhibitors according to the invention is therein, even in 2K systems, for example at temperatures below 100 0 C, preferably at a temperature between 15 0 C and 95 0 C, more preferably 50 0 C to 90 0 C to develop their effect.
  • the invention usable, aging inhibitor-containing, epoxy-polyamine-based 2K systems show excellent aging resistance.
  • Even small amounts of the additive of less than 10 wt .-% based on the curable composition are usually sufficient to increase the aging resistance according to the invention. In individual cases, however, even much smaller amounts, of about 0.1% by weight, are sufficient to develop the properties according to the invention.
  • the aging inhibitor may be premixed with either the curable component or, if a chemical hardener component is required for curing, may be supplied by blending it with the curable composition of the present invention.
  • the aging inhibitor may also be present in both components or, if the processing time permits, may be added to the 2K system only after mixing the two components.
  • the aging inhibitors can also be used in systems containing more than two components. Thus, these are also applicable in systems with multiple curable components and / or multiple curing agents.
  • the curable composition is a coating agent or an adhesive.
  • the composition is characterized in that there is no need for transition metal oxides as a co-component to the aging inhibitor necessary to act according to the invention.
  • the invention further provides a process which comprises coating a substrate with a curable composition, the curable composition comprising a curable component and at least one m-hydroxybenzene derivative of the general formula (I):
  • Y is a carboxyl group, a carboxylate group or a straight-chain or branched, optionally substituted with hydroxyl groups, amino groups, carboxyl groups and / or carboxylate groups alkyl group; and R 1 , R 2 and R 3 are independently the same or different and represent hydrogen or a hydroxyl group, and R 1 and R 3 are not simultaneously a hydroxyl group; with the proviso that, if the curable component is a thermosetting component of an epoxy-based multi-component system, the curable composition is free of transition metal oxides of the copper and zinc group, and if the curable component is an epoxy-based thermosetting component is, it is not a self-curing component.
  • the curable composition used in the process according to the invention is preferably one which is curable by a chemical hardener or by heat or radiation and cured after application.
  • the curable composition preferably contains a chemical hardener and / or is thermosetting.
  • the coating located on the substrate is then brought into contact with another substrate prior to curing so that the curable coating lies between the two substrates and, in a further step, the coating is cured.
  • the substrates used in the process according to the invention may in principle be any desired substrates, for example metallic substrates, plastics, glass and ceramic substrates or wood.
  • the substrates used are preferably metallic substrates such as, for example, light metals, aluminum, copper or steel such as, for example, ZE steel, ZEP steel or phosphated steel, the metallic substrates also being able to be used in the form of their alloys or in galvanized or oiled form Shape.
  • the hardenable binder component was an epoxy resin of bisphenol A and epichlorohydrin having a number average molecular weight of about 700 g / mol (DE R 331 P, available from The Dow Chemical Company) and, as a hardener, a terminal diaminofunctional polypropylene glycol having one molecular weight of 400 g / mol (Jeffamine® D400, available from Huntsman Chemical Company).
  • the composition according to the invention additionally contains 3,4,5-trihydroxybenzoic acid (see Example 2a) as an aging inhibitor.
  • test specimens were wrapped in a paper towel soaked in distilled water. This arrangement was then enclosed with aluminum foils and stored in an airtight plastic container at 70 0 C for one week, two weeks or four weeks. After the corresponding storage time the samples were taken in - frozen at -20 0 C, thawed and then tested immediately at room temperature on their tensile shear strength.
  • Example 2b and 2c produced in another identical test specimens were subjected to a Kataplasmatest at 70 0 C and examined immediately after removal in the wet state to their tensile shear strength. The results can also be found in Table 4 again.
  • Example 1 is not according to the invention
  • compositions were prepared according to Table 1, but with different inventive and non-inventive additives, these applied to a degreased aluminum test specimen AI6016 (100 x 25 x 0.8 mm), at 120 0 C for 1 hour hardened and stored partly under cataplasm conditions.
  • Table 5 shows the use of additives according to the invention, while Table 6 shows the use of additives not according to the invention.
  • the hydroxyl-containing organic compounds Macroplast UK 8202 (density: 1.45 +/- 0.05 g / cm 3 ; viscosity (Brookfield RVT, 20 ° C.): 27000 +/- 4000 were used as the curable binder component mPas; manufacturer: Henkel KGaA) and, as hardener, the isocyanate Macroplast UK 5400 (density: 1.22 +/- 0.05 g / cm 3 ; viscosity (Brookfield RVT, 20 ° C.): 250 +/- 100 mPas; manufacturer : Henkel KGaA).
  • the composition according to the invention additionally contains 3,4,5-trihydroxybenzoic acid as an aging inhibitor.
  • an adhesive prepared in this way aluminum sheets of dimensions 100 ⁇ 25 mm pretreated without chromium (bonding area 25 ⁇ 10 mm) bonded.
  • the test specimens obtained were stored at 20 ° C. for 14 days.
  • the bonded sheets were then examined for the tensile shear strength of the bond (determined according to DIN 53283 "Determination of the bond strength of single-lapped adhesive bonds" at a speed of 100 mm / min).
  • Identically prepared further specimens were subjected to a Cataplasmatest at 70 0 C and examined immediately after removal in the wet state to their tensile shear strength.
  • Example 15 is not according to the invention.
  • Macroplast UK 8202, Macroplast UK 5400 and 3,4,5-trihydroxy benzoic acid were mixed at 20 0 C.
  • the additional amount of curing agent used over Example 3 was calculated so that the benzene derivative used was compensated on the basis of its hydroxyl number by an equivalent amount of hardener based on its NCO number.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne une composition durcissable, comprenant un constituant durcissable et un dérivé de m-hydroxybenzène de formule générale (I), dans laquelle Y désigne un groupe carboxyle, un groupe carboxylate ou un groupe alkyle linéaire ou ramifié, éventuellement substitué par des groupes hydroxy, des groupes amino, des groupes carboxyle et/ou des groupes carboxylate ; R<sup
EP05798088A 2004-10-11 2005-10-10 Revetements et composites adhesifs resistants au vieillissement Withdrawn EP1799745A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200410049717 DE102004049717A1 (de) 2004-10-11 2004-10-11 Alterungsbeständige Beschichtungen und Klebeverbunde
PCT/EP2005/010884 WO2006040108A1 (fr) 2004-10-11 2005-10-10 Revetements et composites adhesifs resistants au vieillissement

Publications (1)

Publication Number Publication Date
EP1799745A1 true EP1799745A1 (fr) 2007-06-27

Family

ID=35385839

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05798088A Withdrawn EP1799745A1 (fr) 2004-10-11 2005-10-10 Revetements et composites adhesifs resistants au vieillissement

Country Status (6)

Country Link
US (1) US7462658B2 (fr)
EP (1) EP1799745A1 (fr)
JP (1) JP2008516064A (fr)
CA (1) CA2583916A1 (fr)
DE (1) DE102004049717A1 (fr)
WO (1) WO2006040108A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009045488A1 (de) * 2009-10-08 2011-04-14 Henkel Ag & Co. Kgaa 2-Komponenten Klebstoff mit haftungsverbessernden Zusätzen
EP2325221A1 (fr) * 2009-11-24 2011-05-25 Cytec Surface Specialties Austria GmbH Dispersions aqueuses de resines epoxydiques
CA2961972C (fr) * 2014-09-26 2022-11-22 Dsm Ip Assets B.V. Composition d'osteointegration pour des implants medicaux

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3339633A (en) * 1965-07-27 1967-09-05 Shell Oil Co Polyepoxide consolidation of earthern materials
DE2113631C3 (de) * 1971-03-20 1979-07-26 Isar-Rakoll Chemie Gmbh, 8000 Muenchen Klebstoffe auf Basis von Polyesterurethanen für die Verklebung von Kautschuk-Materialien* mit anderen Werkstoffen
SU618390A1 (ru) * 1977-01-21 1978-08-05 Ленинградский Ордена Трудового Красного Знамени Технологический Институт Имени Ленсовета Полемерна композици
US4668718A (en) * 1984-10-05 1987-05-26 Ciba-Geigy Corporation Self-extinguishing, track-resistant epoxy resin moulding composition and use thereof
US4593056A (en) * 1985-06-21 1986-06-03 Union Carbide Corporation Epoxy/aromatic amine resin systems containing aromatic trihydroxy compounds as cure accelerators
JPS6363770A (ja) * 1986-09-03 1988-03-22 Rishiyou Kogyo Kk 銅張積層板用接着剤
JP2600258B2 (ja) 1988-03-25 1997-04-16 東レ株式会社 半導体封止用樹脂組成物
GB2222592B (en) * 1988-06-22 1992-03-18 Ici Plc Metal coating and bonding
EP0348919A3 (fr) * 1988-06-28 1990-08-22 SKW Trostberg Aktiengesellschaft Additif pour une masse de résine époxyde thermodurcissable
AU7711891A (en) * 1990-05-17 1991-11-21 Ici Australia Operations Proprietary Limited Heat curable adhesive
JPH0616889A (ja) * 1992-07-01 1994-01-25 Sekisui Chem Co Ltd 塩化ビニル系樹脂組成物及びそれを用いたガラス・塩化ビニル系樹脂一体成形体
JPH08198945A (ja) 1995-01-25 1996-08-06 Asahi Denka Kogyo Kk 湿潤面ないし水中施工用エポキシ樹脂組成物
JPH08283382A (ja) * 1995-04-13 1996-10-29 Hitachi Chem Co Ltd 印刷配線板用エポキシ樹脂組成物
JP3575645B2 (ja) * 1995-10-26 2004-10-13 富士写真フイルム株式会社 画像形成方法
US6653371B1 (en) * 1998-01-16 2003-11-25 Barry E. Burns One-part curable composition of polyepoxide, polythiol, latent hardener and solid organic acid
EP1047744B1 (fr) * 1998-01-16 2002-10-02 Loctite (R &amp; D) Limited Compositions durcissables a base d'epoxy
JP2000169825A (ja) 1998-12-10 2000-06-20 Minnesota Mining & Mfg Co <3M> 接着剤組成物および接着シート
JP3868179B2 (ja) * 1999-08-02 2007-01-17 住友ベークライト株式会社 液状封止樹脂組成物、半導体装置の製造方法及び半導体装置
US6887950B2 (en) * 2001-02-15 2005-05-03 Pabu Services, Inc. Phosphine oxide hydroxyaryl mixtures with novolac resins for co-curing epoxy resins
DE10138127A1 (de) * 2001-08-03 2003-02-27 Henkel Kgaa Bindemittelkomponente für Oberflächenbeschichtungsmittel mit verbesserten Hafteigenschaften
JP5364963B2 (ja) 2001-09-28 2013-12-11 住友ベークライト株式会社 エポキシ樹脂組成物及び半導体装置
JP2003268206A (ja) 2002-03-19 2003-09-25 Toray Ind Inc 精密部品用エポキシ樹脂組成物および精密部品
JP2011021205A (ja) * 2010-10-22 2011-02-03 Hitachi Chem Co Ltd プリント配線板用絶縁樹脂組成物及びその用途

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2006040108A1 *

Also Published As

Publication number Publication date
WO2006040108A1 (fr) 2006-04-20
US20070231582A1 (en) 2007-10-04
US7462658B2 (en) 2008-12-09
DE102004049717A1 (de) 2006-04-13
CA2583916A1 (fr) 2006-04-20
JP2008516064A (ja) 2008-05-15

Similar Documents

Publication Publication Date Title
EP2917260B1 (fr) Composition d&#39;amine pour colle époxy bi-composant résistante aux crash-tests
DE602004004501T2 (de) Epoxidharz Klebstoffzusammensetzung
EP2917255B1 (fr) Nouveaux modificateurs de résilience pour des adhésifs à base d&#39;époxy
EP2085426B1 (fr) Colles en résine époxy durcissant à la chaleur et résistantes au lavage
EP2917254B1 (fr) Caoutchoucs liquides réactifs en prépolymères isocyanate-terminés bloqués avec collecteur de glycol
EP1741734A1 (fr) Composition réticulable à la chaleur et résistant au choc à basse température comprenant des résines époxydes solides
EP3402835B1 (fr) Adhesif epoxy thermodurcissable monocomposant a adherence amelioree
EP2532722A1 (fr) Composition d&#39;agent adhésif aqueuse à base de résine époxy
EP1876194A1 (fr) Composition thermodurcissable adaptée au collage de substrats revêtus
EP1412437B1 (fr) Composante de liant pour agent d&#39;enduction de surface a proprietes d&#39;adhesion ameliorees
EP1799745A1 (fr) Revetements et composites adhesifs resistants au vieillissement
EP1978048A1 (fr) Durcisseur pour résine époxy, procédé de durcissement d&#39;une résine époxy tout comme utilisation du durcisseur
EP3560980B1 (fr) Polyester à chaîne allongée, dérivés prépolymérisés dudit polyester et leur utilisation ainsi que masses de résine époxyde
EP3677611B1 (fr) Composition de résine époxy thermodurcissable à basse température de durcissement et à bonne stabilité au stockage
EP3844199A1 (fr) Matière durcissable à deux composants
EP2125925A2 (fr) Améliorants de viscosité terminés par des groupes époxydes, pré-allongés par des hydroxyesters et procédé de fabrication de ceux-ci
WO1991015550A1 (fr) Colles a fusion thermodurcissables
EP3428045A1 (fr) Adhésif époxy à un composant thermodurcissable présentant une résistance élevée au délavage par eau
EP0643103A1 (fr) Liants durcissables
EP4067405A1 (fr) Composition de résine époxy durcissant à la chaleur adaptée aux procédés de préchauffage sans techniques supplémentaires d&#39;assemblage des métaux
DE10138126A1 (de) Bindemittelkomponente für Oberflächenbeschichtungsmittel mit verbesserten Hafteigenschaften

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20070223

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

RIN1 Information on inventor provided before grant (corrected)

Inventor name: KREILING, STEFAN

Inventor name: DOERING, STEVE

Inventor name: FERENCZ, ANDREAS

Inventor name: LAMMERSCHOP, OLAF

Inventor name: KUX, MICHAEL

17Q First examination report despatched

Effective date: 20070810

RIN1 Information on inventor provided before grant (corrected)

Inventor name: LAMMERSCHOP, OLAF

Inventor name: KUX, MICHAEL

Inventor name: FERENCZ, ANDREAS

Inventor name: DOERING, STEVE

Inventor name: KREILING, STEFAN

DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: HENKEL AG & CO. KGAA

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20111228