AU6197299A - Impact-resistant epoxide resin compositions - Google Patents

Description

WO 00/20483 1 PCT/EP99/07143 Impact-resistant Epoxide Resin Compositions This invention relates to mixtures of special copolymers having at least one glass transition temperature of -30 0 C or lower and phenol terminated polyamides or polyimides, mixtures of these components with epoxy resins and/or adducts of epoxy resins with the copolymer having a 5 low glass transition temperature and/or the polyamide or the polyimide and heat-activatable latent hardeners for the resin components and optionally accelerators, fillers, thixotropicizing agents and other typical additives. The invention also relates to a process for the production of these compositions and to their use as a reactive adhesive. 10 Reactive epoxy-based hotmelt adhesives are known. In machine and vehicle construction and especially in the construction of aircraft, railway vehicles and motor vehicles, components of various metals and/or composite materials are increasingly being joined together with the aid of adhesives. Epoxy adhesives are widely used for high-strength structural 15 bonding, more particularly as heat-curing one-component adhesives which, in many cases, are also formulated as reactive hotmelts. Reactive hotmelts are adhesives which are solid at room temperature and which soften and behave like a thermoplastic material at temperatures of up to about 80 to 90 0 C. It is only at relatively high temperatures of about 1 00 0 C 20 and higher that the latent hardeners present in these hotmelt adhesives are thermally activated so that irreversible curing to a thermoset occurs. To join the components together, for example in the vehicle industry, the adhesive is first applied warm to at least one substrate surface, after which the parts to be joined are then fitted together. The adhesive then solidifies 25 on cooling and, through this physical solidification, establishes adequate handling resistance, i.e. a temporary bond. The parts thus joined together are further treated in various washing, phosphating and dip painting baths.

WO 00/20483 2 PCT/EP99/07143 It is only after this that the adhesive is cured at relatively high temperatures in an oven. Conventional adhesives and hotmelt adhesives based on epoxy resins are hard and brittle in the cured state. Although the bonds obtained 5 with them are generally characterized by very high tensile shear strength, the adhesives flake off under peel, impact or impact/peel stress, particularly at relatively low temperatures, so that loss of bond strength readily occurs when the adhesive joint is subjected to that kind of stress. Accordingly, numerous proposals have already been put forward with a view to so 10 modifying epoxy resins by flexible additives that their brittleness is clearly reduced. One known process is based on the use of special rubber/epoxy resin adducts which are incorporated as heterodisperse phase in the epoxy resin matrix so that the epoxies become more impact-resistant. These epoxy resin compositions are also referred to as "toughened". Another 15 known modification of epoxy resins of the above-mentioned type consists in the reaction of a carboxyl-terminated polybutadiene-co-acrylonitrile copolymer with an epoxy resin. This rubber/epoxy adduct is then dispersed in one or more different epoxy resins. The reaction of the epoxy resin with the carboxyl-containing butadiene/acrylonitrile rubber has to be conducted 20 in such a way that the adduct is not prematurely cured. Although correspondingly modified epoxy resin compositions already represent a clear improvement over unmodified epoxy resins in relation to their impact strength, their behavior under peel or impact/peel stress is still not satisfactory. 25 EP-A-0 343 676 describes hotmelt adhesive compositions made up of a mixture of several epoxy resins, a phenolic resin and a polyurethane/epoxy adduct. The polyurethane/epoxy adduct present therein consists of a reaction product of several polyalkylene glycol homopolymers and copolymers containing primary and secondary OH 30 groups, a diisocyanate and at least one epoxy resin. According to the WO 00/20483 3 PCT/EP99/07143 document in question, these hotmelt adhesive compositions show improved shear resistance, peel strength and impact strength in relation to various commercial one-component hotmelt adhesive compositions. Unfortunately, there is no reference to the adhesive properties of the cured 5 adhesive joint at low temperatures. US-A-5 290 857 describes an epoxy resin adhesive composition containing an epoxy resin and a powder-form core/shell polymer and a heat-activatable hardener for the epoxy resin. The powder-form core/shell polymer is composed of a core containing an acrylate or methacrylate 10 copolymer with a glass transition temperature of -30 0 C or lower and a shell containing an acrylate or methacrylate copolymer which contains crosslinking monomer units and which has a glass transition temperature of 70 0 C or higher, the ratio by weight of the core to the shell being between 10:1 and 1:4. These compositions are said to have excellent adhesive 15 properties, such as peel strength, tensile shear strength and T-peel strength, and also good partial gellability. No mention is made of the properties of bonds with these adhesives at low temperatures. Similarly, US-A-5,686,509 describes an adhesion-strengthening composition for epoxy resins consisting of powder-form copolymer particles 20 ionically crosslinked with a mono- or divalent metal cation. The core of the core/shell polymer is composed of a diene monomer and optionally crosslinking monomer units and has a glass transition temperature of -30*C or lower. The shell copolymer has a glass transition temperature of at least 70*C and is made up of acrylate or methacrylate monomer units and 25 radically polymerizable unsaturated carboxylic acid units. The adhesive composition is said to contain 15 to 60 parts by weight of the adhesion strengthening copolymer powder and 3 to 30 parts by weight of a heat activatable hardening agent to 100 parts of epoxy resin. These compositions are recommended for use as structural adhesives for 30 automobile parts. No mention is made of the low temperature properties of WO 00/20483 4 PCT/EP99/07143 corresponding bonds. EP-A-0 308 664 describes epoxy resin compositions which contain an epoxide adduct of a carboxyl-containing copolymer based on butadiene/acrylonitrile or similar butadiene copolymers and a reaction 5 product of an elastomeric isocyanate-terminated prepolymer soluble or dispersible in epoxy resins with a polyphenol or aminophenol and subsequent reaction of this adduct with an epoxy resin. In addition, these compositions may contain one or more epoxy resins. Furthermore, aminofunctional hardeners, polyaminoamides, polyphenols, polycarboxylic 10 acids and their anhydrides or catalytic hardeners and optionally accelerators are proposed for hardening these compositions. The compositions in question are said to be suitable as adhesives which can have high strength, a high glass transition temperature, high peel strength, high impact strength or high tear propagation resistance according to their 15 particular composition. Similarly, EP-A-0 353 190 describes epoxy resin compositions containing an adduct of an epoxy resin and a carboxylated butadiene/acrylonitrile copolymer and a reaction product of a hydroxyl-, mercapto- or amino-terminated polyalkylene glycol with a phenol carboxylic 20 acid with subsequent reaction of the phenolic group with an epoxy resin. According to EP-A-0 353 190, these compositions are suitable for the production of adhesives, adhesive films, patches, sealing compounds, paints or matrix resins. According to the teaching of EP-A-0 354 498 or EP-A-0 591 307, 25 reactive hotmelt adhesive compositions can be produced from a resin component, at least one heat-activatable latent hardener for the resin component and optionally accelerators, fillers, thixotropicizing agents and other typical additives, the resin component being obtainable by the reaction of an epoxy resin solid at room temperature and an epoxy resin 30 liquid at room temperature with one or more linear or branched amino- WO 00/20483 5 PCT/EP99/07143 terminated polyoxypropylenes. The epoxy resins are said to be used in such a quantity, based on the amino-terminated polyoxypropylene, that an excess of epoxy groups, based on the amino groups, is guaranteed. These adhesive compositions have a high peel resistance in the T-peel test 5 which they retain even at low temperatures. The problem addressed by the present invention was further to improve reactive adhesives of the type mentioned at the beginning to the extent that they would have adequate flexibility and increased peel strength not only at room temperature but also - and in particular - at low 10 temperatures below 0*C. In particular, they would show high peel strength at low temperatures and under sudden stress so that, even in the event of a crash, structurally bonded parts would meet modern safety standards in vehicle construction. These improvements would be obtained without any deterioration in peel strength at high temperatures or in tensile shear 15 strength. In addition, the reactive adhesives would have to exhibit adequate wash-out resistance immediately after application and before final curing. To that end, the adhesive compositions would have to lend themselves as hotmelts to formulation as a highly viscous adhesive suitable for warm application. Another possibility would be to formulate the 20 compositions as an adhesive that could be gelled by a thermal preliminary reaction in a so-called "white body oven" or by induction heating of the joined parts. The solution provided by the invention to the problem as stated above is defined in the claims and consists essentially in the provision of 25 compositions which contain A) a copolymer having at least one glass transition temperature of -30'C or lower and epoxy-reactive groups, B) a reaction product of a di- or polyamine with a carboxylic anhydride and a polyphenol or aminophenol and 30 C) at least one epoxy resin.

WO 00/20483 6 PCT/EP99/07143 Components A), B) and C) may also be mixtures of compounds of the type mentioned. Components A) and B) are preferably reacted with a large stoichiometric excess of epoxy resins in separate reactions and then optionally mixed with other epoxy resins, heat-activatable hardeners and/or 5 other additives. Examples of the copolymers of component A) are 1,3-diene polymers containing carboxyl groups and other polar ethylenically unsaturated comonomers. The diene may be butadiene, isoprene or chloroprene and is preferably butadiene. Examples of polar ethylenically 10 unsaturated comonomers are acrylic acid, methacrylic acid, lower alkyl esters of acrylic or methacrylic acid, for example methyl or ethyl esters thereof, amides of acrylic or methacrylic acid, fumaric acid, itaconic acid, maleic acid or lower alkyl esters or semiesters thereof or maleic acid or itaconic anhydride, vinyl esters, such as for example vinyl acetate or - more 15 particularly - acrylonitrile or methacrylonitrile. Most particularly preferred copolymers A) are carboxyl-terminated butadiene/acrylonitrile copolymers (CTBN) which are commercially available in liquid form under the name of Hycar from B.F. Goodrich. These copolymers have molecular weights of 2,000 to 5,000 and acrylonitrile contents of 10% to 30%. Actual examples 20 are Hycar CTBN 1300 X 8,1300 X 13 or 1300 X 15. The core/shell polymers known from US-A-5,290,857 and from US A-5,686,509 may also be used as component A). The core monomers should have a glass transition temperature of or below -30 0 C and may be selected from the group of diene monomers as mentioned above or 25 suitable acrylate or methacrylate monomers. The core polymer may optionally contain crosslinking monomer units in small quantities. The shell is made up of copolymers which have a glass transition temperature of at least 60*C. The shell is preferably made up of lower alkyl acrylate or methacrylate monomer units (methyl or ethyl esters) and polar monomers, 30 such as (meth)acrylonitrile, (meth)acrylamide, styrene or radical- WO 00/20483 7 PCT/EP99/07143 polymerizable unsaturated carboxylic acids or carboxylic anhydrides. However, the adducts of epoxy resins and the liquid CTBN rubbers mentioned above are particularly preferred for component A). Component B) may be represented by the following formula I: 5 R' --- [N --- (C=0) --- X--- (C=0) --- Y---R 3---(ZMm~n()

R

2 10 in which m = 1 or 2, n = 2 or 3,

R

1 is an amino-terminated residue of a polyalkylene glycol after removal of the functional groups, 15 R 2 = H, C 1

.

6 alkyl, aryl or -(C=O)-; where R 2 = -(C=O)-, the two carbonyl groups, the nitrogen and X form a five-membered cyclic imide ring, X = C 2

-

6 alkyl or the residue of an aromatic carboxylic anhydride or dianhydride after removal of the cyclic anhydride group(s), Y = -0-, -S- or -NR 4 -, where R 4 = H or C 1 _ alkyl or phenyl, 20 R 3 is a carbocyclic-aromatic or araliphatic m+1-functional residue with groups Z directly attached to the aromatic ring and Z = 0, H or -NHR 4 . Component B) is a reaction product of a di- or polyamine and a carboxylic anhydride, the stoichiometric ratio being selected so that the carboxylic anhydride is preferably in a two-fold excess over the amino 25 groups, after which the remaining carboxylic anhydride groups or carboxylic acid groups are reacted with a polyphenol or aminophenol in a stoichiometric excess so that the condensation product bears terminal phenolic or amino groups. This condensation product is generally mixed directly into the compositions according to the invention although it may 30 also be reacted with a large stoichiometric excess of epoxy resins so that an epoxy-terminated condensation product is formed.

WO 00/20483 8 PCT/EP99/07143 In principle, a large number of diamines or polyamines may be used for the condensation although amino-terminated polyalkylene glycols, more particularly di- or trifunctional amino-terminated polypropylene glycols, polyethylene glycols or copolymers of propylene glycol and ethylene glycol, 5 are preferably used. These glycols are also known under the name of "Jeffamine" (Huntsman). The amino-terminated polyoxytetramethylene glycols, also known as Poly-THF, are also particularly suitable. Other suitable synthesis components are amino-terminated polybutadienes. The amino-terminated polyalkylene glycols have molecular weights of 400 to 10 5,000. Examples of suitable carboxylic anhydrides are maleic, succinic, glutaric, adipic, pimelic, suberic, azelaic or sebacic anhydride or, more particularly, anhydrides or dianhydrides of aromatic carboxylic acids or hydrogenation products thereof, such as phthalic anhydride, 15 benzenetricarboxylic anhydride, tetrahydrophthalic dianhydride, mellophanic dianhydride, pyromellitic dianhydride, 1,8:4,5- and 2,3:6,7 naphthalenetetracarboxylic dianhydride, perylene dianhydride, biphenyl tetracarboxylic acid dianhydride, diphenylether tetracarboxylic dianhydride, diphenylmethane tetracarboxylic dianhydride, 2,2-diphenylpropane 20 tetracarboxylic dianhydride or benzophenone tetracarboxylic dianhydride and mixtures thereof. Besides the carboxylic anhydrides mentioned above, maleinized oils and fats may also be used as anhydride components for the preparation of condensation product B). Maleinized oils and fats and low molecular 25 weight polyenes are known to be prepared by ene reaction or by free radical reaction of maleic anhydride with unsaturated compounds. The polyphenols or aminophenols to be used for condensation product B) are either aromatic di- or trihydroxy compounds derived from a mono- or polynuclear carbocyclic-aromatic radical or the corresponding 30 aminohydroxy compounds. The aromatic rings may either be condensed WO 00/20483 9 PCT/EP99/07143 or attached to one another by binding links or by a covalent bond. Examples of the compounds mentioned first are hydroquinone, resorcinol, pyrocatechol, isomers of dihydroxynaphthalene (pure isomers or mixture of several isomers), isomers of dihydroxyanthracene and the 5 corresponding aminohydroxy compounds. The polyphenols or aminophenols, which are derived from carbocyclic-aromatic compounds of which the aromatic nuclei are attached by binding links, may be represented by the following general formula 11: 10 Z---AR---B---AR---Z (II) in which Z is as defined above, AR is a mononuclear aromatic radical which may optionally be further substituted by alkyl or alkenyl radicals, 15 B stands for the binding link which may be selected from the group consisting of a covalent bond, -CR 5

R

6 -, -0-, -S-, -SO 2 -, -CO-, -Coo-,

-CONR

7 - and SiR 8

R

9 - where R 5 , R 6 and R 7 independently of one another represent hydrogen, -CF 3 or C1.

6 alkyl or R 5 and R 6 together with the common C atom form a cycloaliphatic radical with 5 to7 ring C atoms, R 8 20 and R 9 represent C1.6 alkyl. The two groups B and Z in formula 11 independently of one another may be located in the ortho, meta or para position. Particularly preferred compounds corresponding to formula il are 4,4'-dihydroxydiphenyl or the bisphenols A and/or F. Suitable epoxy resins for component C) or for forming the epoxy 25 adduct or for mixing components A) and B) are any of a number of polyepoxides which contain at least two 1,2-epoxy groups per molecule. The epoxy equivalent of these polyepoxides may be between 150 and 4,000. Basically, the polyepoxides may be saturated, unsaturated, cyclic or acyclic, aliphatic, alicyclic, aromatic or heterocyclic polyepoxide 30 compounds. Examples of suitable polyepoxides include the polyglycidyl WO 00/20483 10 PCT/EP99/07143 ethers which are obtained by reaction of epichlorohydrin or epibromohydrin with a polyphenol in the presence of alkali. Polyphenols suitable for this purpose are, for example, resorcinol, pyrocatechol, hydroquinone, bisphenol A (bis-(4-hydroxyphenyl)-2,2-propane)), bisphenol F (bis(4 5 hydroxyphenyl)methane), bis-(4-hydroxyphenyl)1,1-isobutane, 4,4' dihydroxybenzophenone, bis-(4-hydroxyphenyl)-1, 1 -ethane, 1,5-hydroxy naphthalene. Other polyepoxides suitable in principle are the polyglycidyl ethers of polyalcohols or diamines. These polyglycidyl ethers are derived from 10 polyalcohols, such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, triethylene glycol, pentane-1,5 diol, hexane-1,6-diol or trimethylol propane. Other polyepoxides are polyglycidyl esters of polycarboxylic acids, for example reaction products of glycidol or epichlorohydrin with aliphatic or 15 aromatic polycarboxylic acids, such as oxalic acid, succinic acid, glutaric acid, terephthalic acid or dimer fatty acid. Other epoxides are derived from the epoxidation products of olefinically unsaturated cycloaliphatic compounds or from native oils and fats. 20 The epoxy resins obtained by reaction of bisphenol A or bisphenol F are most particularly preferred. Mixtures of liquid and solid epoxy resins are generally used, the liquid epoxy resins preferably being based on bisphenol A and having a sufficiently low molecular weight. Epoxy resins liquid at room temperature which generally have an epoxy equivalent 25 weight of 150 to about 220 and more particularly in the range from 182 to 192 are particularly preferred for the adduct formation of components A) and B). The hardness of the reactive adhesive in the cooled state, i.e. in particular after application to the substrate to be joined, but before curing, 30 depends on the degree of condensation and hence molecular weight of WO 00/20483 11 PCT/EP99/07143 component B) in particular and on the ratio of solid epoxy resin to liquid epoxy resin. The higher the degree of condensation (and hence the molecular weight) of condensation product B) and the greater the proportion of solid epoxy resin in the composition, the harder the cooled 5 semicrystalline adhesive will be. Suitable heat-activatable or latent hardeners for the epoxy resin binder system of components A), B) and C) are guanidines, substituted guanidines, substituted ureas, melamine resins, guanamine derivatives, cyclic tertiary amines, aromatic amines and/or mixtures thereof. The 10 hardeners may be stoichiometrically included in the curing reaction although they may also be catalytically active. Examples of substituted guanidines are methyl guanidine, dimethyl guanidine, trimethyl guanidine, tetramethyl guanidine, methyl isobiguanidine, dimethyl isobiguanidine, tetramethyl isobiguanidine, hexamethyl isobiguanidine, heptamethyl 15 isobiguanidine and, most particularly, cyanoguanidine (dicyanodiamide). Alkylated benzoguanamine resins, benzoguanamine resins or methoxymethyl ethoxymethyl benzoguanamine are mentioned as representatives of suitable guanamine derivatives. The selection criterion for the one-component heat-curing hotmelt adhesives is of course their low 20 solubility at room temperature in the resin system so that solid finely ground hardeners are preferred, dicyanodiamide being particularly suitable. The composition is thus guaranteed a long shelf life. Catalytically active substituted ureas may be used in addition to or instead of the hardeners mentioned above. These substituted ureas are, in 25 particular, p-chlorophenyl-N,N-dimethyl urea (Monuron), 3-phenyl-1,1 dimethyl urea (Fenuron) or 3,4-dichlorophenyl-N,N-dimethyl urea (Diuron). In principle, catalytically active tertiary aryl or alkyl amines, for example benzyl dimethyl amine, tris(dimethylamino)phenol, piperidine or piperidine derivatives, may also be used, but often have too high a solubility in the 30 adhesive system so that the one-component system is not guaranteed WO 00/20483 12 PCT/EP99/07143 useful shelf life in their case. In addition, various, preferably solid imidazole derivatives may be used as catalytically active accelerators. 2-Ethyl-2 methyl imidazole, N-butyl imidazole, benzimidazole and N-Cl.

1 2 -alkyl imidazoles or N-arylimidazoles are mentioned as representatives of such 5 accelerators. In addition, the adhesives according to the invention contain fillers known per se such as, for example, the various ground or precipitated chalks, carbon black, calcium-magnesium carbonates, heavy spar and, in particular, silicate fillers of the aluminium-magnesium-calcium silicate type, 10 for example wollastonite, chlorite. The adhesive compositions according to the invention may also contain other typical auxiliaries and additives such as, for example, plasticizers, reactive diluents, rheology aids, wetting agents, antiagers, stabilizers and/or pigments. 15 The adhesives according to the invention may be formulated on the one hand as one-component adhesives which in turn may be formulated both as highly viscous adhesives designed form warm application and as heat-activatable hotmelt adhesives. These adhesives may also be formulated as one-component pregellable adhesives, in which case the 20 compositions contain either fine-particle thermoplastic powders such as, for example, polymethacrylates, polyvinyl butyral or other thermoplastic (co)polymers or the curing system is so adapted that a two-stage curing process occurs, the gelling step effecting only partial curing of the adhesive and final curing in vehicle construction taking place, for example, in one of 25 the paint ovens, preferably the cathodic electrodeposition oven. The adhesive compositions according to the invention may also be formulated as two-component epoxy adhesives where the two reaction components are only mixed just before application, curing then taking place at room temperature or moderately elevated temperature. The second 30 reaction component may be selected from the reaction components known WO 00/20483 13 PCT/EP99/07143 per se for two-component epoxy adhesives, for example di- or polyamines, amino-terminated polyalkylene glycols (for example Jeffamine, Amino-Poly THF) or polyaminoamides. Other reactants may be mercaptofunctional prepolymers such as, for example, the liquid Thiokol polymers. Basically, 5 the epoxy compositions according to the invention may also be cured with carboxylic anhydrides as the second reaction component in two-component adhesive formulations. Besides the applications mentioned at the beginning, the adhesive compositions according to the invention may also be used as potting 10 compounds in the electrical or electronics industries and as die-attach adhesives in electronics for bonding components to circuit boards. Other possible applications for the compositions according to the invention are as matrix materials for composite materials such as, for example, fiber reinforced composites. 15 However, a most particularly preferred application for the adhesives according to the invention is structural bonding in vehicle construction. The quantity ratios between the individual components may vary within relatively wide limits, depending on the requirements the adhesive is expected to satisfy in regard to its application properties, flexibility, impact 20 peel strength or tensile strength. Typical ranges for the key components are: " component A) 5-25% by weight, preferably 1-20% by weight * component B): 5-30% by weight, preferably 5-20% by weight * component C): 10-45% by weight, preferably 15-30% by weight; this 25 component may be composed of one or more liquid and/or solid epoxy resins in which case it may optionally contain low molecular weight epoxides as reactive diluents " fillers: 10-40% by weight * hardener component (for heat-curable one-component systems):1-10% 30 by weight, preferably 3-8% by weight WO 00/20483 14 PCT/EP99/07143 " accelerator: 0.01-3% by weight, preferably 0.1 to 0.8% by weight " rheology aid (thixotropicizing agent): 0.5-5% by weight. As mentioned at the beginning, the requirements modern structural adhesives are expected to meet in vehicle construction continue to 5 increase because more and more structural elements - including those with load-bearing functions - are being joined by bonding processes. As already stated in the article by G. LJtting and S. Singh entitled: "Anforderungen an Klebstoffe fur Strukturverbindungen im Karosseriebau" Adhesion 1988, No. 9, pages 19 to 26, the adhesives 10 are expected on the one hand to fulfil production aspects of practical relevance, including automatable application in short cycle times, adhesion to oil-covered metal panels, adhesion to various types of metal panels and compatibility with the process conditions on the paint line (resistance to washing and phosphating baths, curability during stoving of the CED 15 primer, resistance to the following painting and drying operations). In addition, modern structural adhesives have to exhibit improving strength and deformation properties, even in the cured state. These include the high corrosion resistance and flexural strength of the structural components and the deformability of the bond under mechanical stress. High 20 deformability of the structural components guarantees a considerable safety advantage in the event of a crash. This crash behavior can best be determined by determining the impact energy for cured bonds; sufficiently high values for impact energy or impact/peel energy are desirable both at high temperatures of up to +90*C and in particular at low temperatures 25 down to -40*C. High tensile shear strength should also be achieved. Both strengths should be achieved on a large number of substrates, mainly oil covered metal panels, for example steel bodywork panels, steel plate galvanized by various methods, panels of various aluminium alloys or even magnesium alloys and steel plates coated by coil coating with organic 30 coatings of the "Bonazinc" or "Granocoat" type. As shown in the following WO 00/20483 15 PCT/EP99/07143 Examples, the adhesive compositions according to the invention surprisingly satisfy these requirements to a very high degree. The following Examples are intended to illustrate the invention. All quantities in connection with the compositions are parts by weight, unless 5 otherwise indicated. General procedure for producing component A) A carboxy-terminated poly(butadiene-co-acrylonitrile) (Hycar CTBN 1300 X 13) was reacted for 3 hours with stirring under nitrogen at 140*C 10 with an approximately 10-molar excess of a liquid DGEBA epoxy resin until the reaction was constant. General procedure for preparing condensation product B) In a stirrable and heatable tank reactor, 1 mole of the carboxylic 15 anhydride or dicarboxylic anhydride were reacted under nitrogen for 3 to 4 hours at 120 0 C to 160'C with 0.4 to 0.7 mole of an amino-terminated polyalkylene glycol, the polyamine being introduced into the reactor first and heated initially to 130 0 C. The adduct thus formed was reacted with about 1.1 to 1.5 moles of a polyphenol until the reaction was constant. The 20 progress of the reaction was followed by gel permeation chromatography (GPC). This phenol-terminated polymer was then mixed with an epoxy resin, preferably a diglycidyl ether of bisphenol A (DGBEA). General production of the adhesive 25 In a kneader, components A), B) and a liquid epoxy resin and a solid epoxy resin were mixed to homogeneity at room temperature or optionally at 80 0 C in the presence of the fillers, hardeners, accelerators and rheology aids and the resulting mixture was poured into the storage containers optionally while still warm. 30 WO 00/20483 16 PCT/EP99/07143 Examples I to 6 The condensation products B) listed in Table 1 were prepared from Jeffamine-D-2000 (polyoxypropylenediamine, molecular weight 2000), pyromellitic dianhydride and resorcinol by the general method for preparing the condensation product B). Table 1. Example 1 2 3 4 5 6 D-2000 219.0 229.5 222.0 235.5 237.6 200.0 PMSA 48.0 42.0 48.0 41.4 36.9 31.3 Resorcinol 33.0 28.5 30.0 31.2 25.5 18.7 D-2000 = Jeffamine D-2000 PMSA = pyromellitic dianhydride Component A) was prepared from Hycar CTBN 1300 X13 and a liquid DGBEA resin by the method described above. The resulting composition contained 40% butyl rubber and had an epoxy equivalent weight of 900 and a viscosity at 800C of 200 Pa.s. Examples 7 to 12 Adhesive compositions according to the invention were prepared from components B) of to Examples 1 to 6, component A) and a liquid DGEBA resin (epoxy equivalent weight 189), fillers, dicyanodiamide as hardener and accelerators and hydrophobic silica as thixotropicizing agent. The compositions are set out in Table 2.

WO 00/20483 17 PCT/EP99/07143 Table 2. Adhesives according to the invention Example 7 8 9 10 11 12 Component B) of Example 1 13.5 Component B) of Example 2 -13.5 Component B) of Example 3 13.5 Component B) of Example 4 13.5 Component B) of Example 5 13.5 Component B) of Example 6 13.5 Component A) 17.0 17.0 17.0 17.0 17.0 17.0 DGEBA resin, liquid 28.0 28.0 28.0 28.0 28.0 280 Wollastonite 33.7 33.7 33.7 33.7 33.7 33.7 Dicyanodiamide 4.5 4.5 4.5 4.5 4.5 4.5 Fenuron 0.3 0.3 0.3 0.3 0.3 0.3 Silica, hydrophobic 3.0 3.0 3.0 3.0 3.0 3.0 Wollastonite filler Silica: Carbosil TS 720 The adhesive properties of the Examples according to the invention and the adhesive properties of known adhesives are compared in Table 3. The adhesive of Comparison Example 1 was Terokal 5051 of Henkel Teroson which had been made in accordance with the teaching of EP-A-0 354 498. The adhesive of Comparison Example 2 was Betamate 1044/3 made by Gurit Essex. It is assumed that this adhesive had been produced in accordance with the teaching of EP-A-0 308 664 WO 00/20483 18 PCT/EP99/07143 Table 3. Adhesive properties Example 7 8 9 10 11 12 Comp. I Comp. 2 Impact -40 0 C [J] 8.7 11.7 9.4 13.1 6.7 0.7 0.5 3.3 Impact -20 0 C [J] 12.7 14.7 13.4 16.2 10.5 1.9 0.4 2.6 Impact 00C [J] 13.2 13.6 15.0 16.8 12.1 3.9 0.9 4.4 Impact RT (J] 15.5 14.7 16.1 16.0 12.9 5.0 2.1 5.2 TSS -40*C [Mpa] 34.1 scf 31.1 scf 25.2 scf 30.9 cf 28.4 cf 37.8; 80% cf 19.8 cf 20.2 cf TSS RT [Mpa] 25.7 cf 22.7 cf 21.6 cf 22.5 cf 18.7 cf 16.4; 80% cf 21.8 f 21.6 cf TSS +90*C [Mpa] 14.8 c 11.9 cf 11.4 cf 12.0 cf 11.0 of 12.4 cf 10.9 cf 11.1 cf 500 h SST 20.3 c 17.0 cf 17.0 of 18.9 cf 17.0 of n.a. 19.3 of 18.8 cf 1000 h SST 19.1 c 17.9 cf 14.5 of 18.2 cf 16.6 cf n.a. 17.5 cf 16.7 cf Impact: impact peel test to ISO 11343 at 2 m/sec RT: room temperature TSS: tensile shear strength to DIN 53283 TSS: salt spray test to DIN 50021 cf: cohesive fracture pattern 100% unless otherwise indicated scf: cohesive fracture pattern with partial film residue on a substrate As these test results show, the impact peel energy to ISO 11343 of the adhesives according to the invention is several times higher than that of the known adhesives. At very low temperatures in particular, the impact peel energy of the adhesives according to the invention is clearly better than that of the known adhesives without any deterioration in tensile shear strength or ageing behavior in the salt spray test.

Claims (14)

1. A composition obtainable by reacting a carboxylic anhydride or carboxylic dianhydride with a diamine or polyamine and a polyphenol or aminophenol. 5

2. A composition containing A) a copolymer having at least one glass transition temperature of -30*C or lower and epoxy-reactive groups, B) a reaction product obtainable by reacting a carboxylic anhydride or dianhydride with a diamine or polyamine and a polyphenol or 10 aminophenol and C) at least one epoxy resin.

3. Compositions as claimed in claim 2, characterized in that component A) is a butadiene-based copolymer.

4. Compositions as claimed in claim 2 or 3, characterized in that 15 component A) is a carboxyl-containing copolymer based on buta diene/acrylonitrile, butadiene/(meth)acrylates, a butadiene/acrylo nitrile/styrene copolymer or a butadiene/(meth)acrylate/styrene copolymer.

5. A composition as claimed in claim 2, characterized in that component A) is a core/shell polymer of which the core polymer is a diene 20 polymer or a (meth)acrylate polymer with a glass transition temperature of -30*C or lower and which may optionally be crosslinked with 0.01 to 5% by weight of a diolefinic comonomer and of which the shell polymer has a glass transition temperature of 60*C or higher and is obtained from monomers from the group consisting of alkyl (meth)acrylate, 25 (meth)acrylonitrile, (methyl) styrene and olefinically unsaturated carboxylic acids or carboxylic anhydrides or mixtures thereof.

6. A composition as claimed in at least one of the preceding claims, characterized in that an adduct of an epoxy resin and a copolymer according to claims 2 to 5 is used as component A). 30

7. A composition as claimed in at least one of the preceding claims, WO 00/20483 20 PCT/EP99/07143 characterized in that component b) is prepared by condensation from a) a carboxylic anhydride selected from maleic, succinic, glutaric, adipic, pimelic, suberic, azelaic or sebacic anhydride or phthalic anhydride, benzenetricarboxylic anhydride, mellophanic dianhydride, pyromellitic 5 dianhydride, 1,8:4,5- and 2,3:6,7-naphthalenetetracarboxylic dianhydride, perylene dianhydride, biphenyl tetracarboxylic dianhydride, diphenylether tetracarboxylic dianhydride, diphenyl methane tetracarboxylic dianhydride, 2,2-diphenylpropane tetracarboxylic dianhydride or benzophenone tetracarboxylic 10 dianhydride and mixtures thereof and b) a polyamine selected from polyethylene glycol, polypropylene glycol, polyoxytetramethylene or polybutadiene diamine or triamine and c) a polyphenol or aminophenol.

8. A composition as claimed in claims 2 to 7, characterized in that 15 component B) according to claim 7 is dissolved in a liquid polyepoxide.

9. A composition as claimed in claims 1 to 5, characterized in that component B) according to claim 7 is reacted with a stoichiometric excess of a polyepoxide.

10. A composition as claimed in at least one of the preceding claims, 20 characterized in that, in addition to components A), B) and C), it contains A) a latent hardener from the group consisting of dicyanodiamide, guanamines, guanidines, aminoguanidines, solid aromatic diamines and/or a hardening accelerator and B) optionally plasticizers, reactive diluents, rheology aids, fillers, wetting 25 agents and/or antiagers and/or stabilizers.

11. A process for hardening components A), B), C), D) and optionally E) according to claim 10 by heating the composition to temperatures of 80*C to 210*C and preferably to temperatures of 120*C to 180*C.

12. The use of the compositions claimed in claim 10 as a high-strength 30 high-impact structural adhesive in vehicle construction, aircraft construction WO 00/20483 21 PCT/EP99/07143 or rail vehicle construction.

13. The use of the compositions claimed in claim 10 for the production of composite materials, as potting compounds in the electrical and electronics industries and as a die-attach adhesive in the production of 5 circuit boards in the electronics industry.

14. A process for bonding metallic and/or composite materials comprising the following key process steps: " applying the adhesive composition claimed in claim 10 to at least one of the substrate surfaces to be joined, optionally after cleaning and/or 10 surface treatment * fitting together the parts to be joined * optionally pregelling the adhesive composition and " curing the bond by heating the parts to temperatures of 80 0 C to 210 0 C and preferably to temperatures of 120 0 C to 180*C. 15