DE102006042796A1 - Adhesive or sealant with modified inorganic particles - Google Patents

Abstract

Epoxy-based adhesive or sealant containing, based on the total adhesive, 5 to 30% by weight of inorganic particles whose surface has been coated by reaction with organic molecules carrying at least two terminal functional groups, each functional group being at least one Heteroatom containing at least one lone pair of electrons.

Description

The The present invention relates to an epoxy-based adhesive or sealant. which, based on the total adhesive, 5 to 30 wt .-% of inorganic Contains particles, their surface was evidenced by reaction with organic molecules that at least two terminal ones bear functional groups, each functional group being at least contains a heteroatom with at least one lone pair of electrons. Through this Addition, important performance properties are improved, in particular the peel strength at low temperatures. A special field of application is the Use as structural adhesive in vehicle construction.

reactive Epoxy-based hot melt adhesives are known. In machine, vehicle or device construction, in particular in aircraft construction, rail vehicle construction or motor vehicle construction The components are made of the different metallic components and / or composites increasingly with the aid of adhesives together. For structural Adhesives with high strength requirements are widely used Epoxy adhesives used, especially as a thermosetting, one-component adhesives, often also called reactive hot melt adhesives be formulated. Reactive hot melt adhesives are adhesives, which are solid at room temperature and at temperatures up to about 80 to 90 ° C soften and behave like a thermoplastic material. Only at higher Temperatures from about 100 ° C The latent hardeners present in these hot melt adhesives become thermally activated, leaving an irreversible cure to a thermoset he follows. To join the components, eg. B. in the automotive industry, the adhesive warm at first applied to at least one substrate surface to be joined Components are then joined. At the cooling down The glue then solidifies and creates through this physical Solidify sufficient handling strength, d. H. a preliminary connection. The so interconnected components are in the different Wash, phosphating and dip baths further treated. First subsequently The adhesive is cured in an oven at higher temperatures.

conventional Adhesives and hot melt adhesives based on epoxy resins are in the cured state hard and brittle. The adhesives obtained with you usually have one very high tensile shear strength. For peeling, beating or impact peeling stress, especially at lower temperatures, but these are bursting, so that it is easy for this type of stress the adhesive joint Binding loss comes. So there have already been many suggestions Epoxy resins through flexible additives to modify so that their brittleness significantly reduced becomes. A common one Method is based on the use of special rubber adducts epoxy resins, which act as a heterodisperse phase in the epoxy resin matrix are embedded so that the epoxies are impact resistant, this Epoxy resin compositions are also referred to as "toughened". A common, well-known modification of epoxy resins of the aforementioned type consists in the implementation of a Polybutadiene-co-acrylonitrile copolymer having carboxyl end groups with an epoxy resin. This rubber epoxide adduct is then in a or several different epoxy resins dispersed. there must the Reaction of the epoxy resin with the carboxyl-containing butadiene-acrylonitrile rubber so led be that it does not lead to premature curing of the adduct. Even though such modified epoxy resin compositions with respect to their impact resistance is already a significant improvement over the unmodified epoxy resins, their behavior towards peeling or impact peeled Demands still insufficient.

WO 01/94492 has the task to further improve reactive adhesives of the type mentioned in that they have sufficient flexibility, an increased peel strength not only at room temperature but in particular at low temperatures below 0 ° C. In particular, the peel strength at low temperatures and sudden load should have the highest possible value, so that structurally bonded components in the event of an accident (crash behavior) meet the modern safety requirements in vehicle. These improvements should be achieved without affecting the peel strength and tensile shear strength at high temperatures. In addition, the reactive adhesives must have sufficient wash-out resistance immediately after application and before final curing. For this purpose, the adhesive compositions must be formulated as a hot melt adhesive or as a highly viscous, warm adhesive to be processed. Another possibility is the formulation as an adhesive, which can be gelled by a thermal pre-reaction in the so-called "shell furnace" or by induction heating of the parts to be joined.

• A) mindestens ein Epoxidharz mit durchschnittlich mehr als einer Epoxidgruppe pro Molekül
• B) ein Copolymeres mit einer Glasübergangstemperatur von –30°C oder niedriger und gegenüber Epoxiden reaktiven Gruppen oder ein Umsetzungsprodukt dieses Copolymeren mit einem stöchiometrischen Überschuß eines Epoxidharzes gemäß A)
• C) einen latenten, bei erhöhter Temperatur aktivierbaren, Härter für Komponente A), und entweder
• D) ein Reaktionsprodukt herstellbar aus einem difunktionellen aminoterminierten Polymer und einem Tri- oder Tetracarbonsäureanhydrid, gekennzeichnet durch im Mittel mehr als eine Imidgruppe und Carboxylgruppe pro Molekül, oder
• E) ein Reaktionsprodukt herstellbar aus einem tri- oder mehrfunktionellen Polyol oder einem tri- oder mehrfunktionellen aminoterminierten Polymer und einem cyclischen Carbonsäureanhydrid, wobei das Reaktionsprodukt im Mittel mehr als eine Carboxylgruppe pro Molekül enthält, oder
• F) eine Mischung der Reaktionsprodukte gemäß D) und E).

This document WO 01/94492 solves this problem by providing compositions containing the following components:

• A) at least one epoxy resin having on average more than one epoxide group per molecule
• B) a copolymer having a glass transition temperature of -30 ° C or lower and to epoxides reactive groups or a reaction product of this copolymer with a stoichiometric excess of an epoxy resin according to A)
• C) a latent, activatable at elevated temperature, hardener for component A), and either
• D) a reaction product preparable from a difunctional amino-terminated polymer and a tri- or tetracarboxylic anhydride, characterized by an average of more than one imide group and carboxyl group per molecule, or
• E) a reaction product preparable from a tri- or polyfunctional polyol or a tri- or polyfunctional amino-terminated polymer and a cyclic carboxylic anhydride, wherein the reaction product contains on average more than one carboxyl group per molecule, or
• F) a mixture of the reaction products according to D) and E).

Farther teaches this document that said adhesives known per se fillers can contain such as the various ground or precipitated crayons, Carbon black, calcium magnesium carbonates, Barite and in particular silicatic fillers of the aluminum-magnesium-calcium silicate type, z. B. wollastonite, chlorite.

As in the said WO document, the requirements for modern structural adhesives in vehicle construction are increasing constantly continue, as more and more structural elements of load-bearing nature Adhesive method added become. Therefore, must the adhesives meet a practice-relevant aspects of manufacturing, this belong automatable processing in short cycle times, liability on oiled Sheet metal, adhesion to different types of sheet metal and compatibility with the process conditions the paint shop (Resistance against Washing and phosphating baths, curable while the stoving of the KTL primer, resistance to the subsequent painting and drying operations). Furthermore have to modern structural adhesives, even in the cured state, increasing strength and deformation properties. For this belong the high corrosion resistance or bending stiffness of the structural components as well as the deformability with mechanical stress of the bond. One possible high ductility of the components ensures a considerable Safety advantage with impact-like Load (crash behavior) in an accident. This behavior can be best by determining the impact work for cured bonds determine here are both at high temperatures up to + 90 ° C as well especially at low temperatures down to -40 ° C sufficiently high values for the impact work or Schlagschälarbeit desirable or required. It should additionally one possible high tensile shear strength can be achieved. Both strengths have to be on a variety of substrates, mainly oiled sheets, such. B. body steel sheet, after galvanized sheet steel, sheets made of various methods various aluminum alloys or magnesium alloys as well coated with organic coatings of the type "Bonazinc" or "Granocoat" in the coil coating process Steel sheets are achieved.

The The object of the present invention is epoxy-based adhesives or sealants to disposal at least in some of the above requirements lead to improvements.

The The present invention relates to an epoxy-based adhesive or sealant. which, based on the total adhesive, 5 to 30 wt .-% of inorganic Contains particles, their surface was evidenced by reaction with organic molecules that at least two terminal ones bear functional groups, each functional group being at least contains a heteroatom with at least one lone pair of electrons.

at a proportion of less than 5 wt .-% of inorganic particles leaves the reinforcing Effect increasingly after. The upper limit of the content of inorganic Particle is dependent from the self-adjusting viscosity of the adhesive or sealant at the processing temperature. The viscosity increases with increasing content on inorganic particles. But it must not be so high that the adhesive or sealant at the intended application temperature no longer flowable. An upper limit of 30% by weight of inorganic particles is indicative, optionally exceeded with particularly low viscosity adhesives or sealants can be. An upper limit of 20% by weight of inorganic particles leads technically usual Epoxy-based adhesives or sealants usually still to one suitable viscosity at the application temperature and is therefore preferred as the upper limit.

The use of inorganic particles as fillers and / or reinforcing agents in adhesives or sealants is known. These particles must have a particle size which is compatible with the intended use of the adhesive or sealant. The lower limit of the size of the inorganic particles is given on the one hand by their manufacturability and on the other hand by their influence on the viscosity of the adhesive or sealant. The smaller the particle size of the inorganic particles, the higher the viscosity of the adhesive or sealant becomes at the same weight fraction of the inorganic particles. A technical Zweckmä The lower limit of the mean particle size is 10 nm, preferably 50 nm and in particular 100 nm. The upper limit of the particle size is given by the intended thickness of the adhesive joint. Usually, however, one chooses the upper limit much smaller than the thickness of the adhesive joint. Upper limits of 20 microns, in particular of 10 microns are common and suitable for the present invention.

The mean particle size of the particles can according to usual Method be determined, for example by light scattering or electron microscopy. By "particles" are meant those particles which present dispersed in the organic matrix. These can be agglomerates represent smaller units.

in the For the purposes of the present invention, functional groups are considered to be "terminal" if they are Groups at the ends of a pure or interrupted by heteroatoms Hydrocarbon chain, which has at least 5 atoms in the chain having. These functional groups can in turn be further organic Carry radicals such as alkyl groups or alkanol groups, which, for example may be the case with amino groups as "terminal groups".

As usual will under a "free Electron pair " Electron pair in the valence shell denotes that no bond enters into another atom. In the context of the present invention are such heteroatoms in particular nitrogen, oxygen or sulfur atoms.

The functional groups are preferably selected from -OH groups (the part an alcohol or a carboxylic acid), -SH groups, epoxide groups and -NHR groups, where R is hydrogen or an organic radical with 1 to 12 carbon atoms.

• a) Verbindungen der Formel HX-CHR¹-CHR²-[O-CHR¹-CHR²]_n-O-CHR²-CHR¹-XH wobei X = O oder S bedeutet und R¹ und R² entweder beide H-Atome oder R¹ ein H-Atom und R² eine Methylgruppe, oder R¹ eine Methylgruppe und R² ein Wasserstoffatom darstellen und n eine Zahl im Bereich von 0 bis 10 ist. Ein konkretes Beispiel ist 3,6-Dioxaoctan-1,8-dithiol der Formel HS-C₂H₄-O-C₂H₄-O-C₂H₄-SH.
• b) Verbindungen der Formel HRN-CHR¹-CHR²-[O-CHR¹-CHR²]_n-O-CHR²-CHR¹-NRH, wobei R Wasserstoff oder einen organischen Rest mit 1 bis 12 C-Atomen bedeutet und R¹ und R² entweder beide H- Atome oder R¹ ein H-Atom und R² eine Methylgruppe, oder R¹ eine Methylgruppe und R² ein Wasserstoffatom darstellen und n eine Zahl im Bereich von 0 bis 10 ist.
• c) Verbindungen der Formel Y[-O-CHR¹-CHR²-[O-CHR¹-CHR²]_n-O-CHR²-CHR¹-XH]_z, wobei Y einen organischen Molekülteil darstellt, der zur Ausbildung von z Ether- und/oder Estergruppen geeignet ist, X = O oder S bedeutet und R¹ und R² entweder beide H-Atome oder R¹ ein H-Atom und R² eine Methylgruppe, oder R¹ eine Methylgruppe und R² ein Wasserstoffatom darstellen und n eine Zahl im Bereich von 0 bis 10 und z eine ganze Zahl im Bereich von 2 bis 6, insbesondere von 3 bis 4 ist. Die Zahl n kann in jeder der z Gruppen gleich oder verschieden sein.
• d) Verbindungen der Formel Y[-O-CHR¹-CHR²-[O-CHR¹-CHR²]_n-O-CHR²-CHR¹-NRH]_z, wobei Y einen organischen Molekülteil darstellt, der zur Ausbildung von z Ether- und/oder Estergruppen geeignet ist, R Wasserstoff oder einen organischen Rest mit 1 bis 12 C-Atomen bedeutet und R¹ und R² entweder beide H-Atome oder R¹ ein H-Atom und R² eine Methylgruppe, oder R¹ eine Methylgruppe und R² ein Wasserstoffatom darstellen und n eine Zahl im Bereich von 0 bis 10 und z eine ganze Zahl im Bereich von 2 bis 6, insbesondere von 3 bis 4 ist. Die Zahl n kann in jeder der z Gruppen gleich oder verschieden sein.

It is preferred that the organic molecules contain ether groups in addition to the mentioned terminal functional groups. For example, the organic molecules can be selected from those which contain one or more ethylene oxide or propylene oxide group (s) incorporated with the opening of the epoxide ring as an ether, and terminal -OH groups, -SH groups, or -NHR groups where R is hydrogen or an organic radical having 1 to 12 carbon atoms. Specific examples are:

• a) compounds of the formula HX-CHR ¹ -CHR ² - [O-CHR ¹ -CHR ² ] _n -O-CHR ² -CHR ¹ -XH where X = O or S and R ¹ and R ^{2 are} either both H atoms or R ^{1 is} an H atom and R ^{2 is} a methyl group, or R ^{1 is} a methyl group and R ^{2 is} a hydrogen atom and n is a number in the range of 0 to 10 is. A concrete example is 3,6-dioxaoctane-1,8-dithiol of the formula HS-C ₂ H ₄ -OC ₂ H ₄ -OC ₂ H ₄ -SH.
• b) compounds of the formula HRN-CHR ¹ -CHR ² - [O-CHR ¹ -CHR ² ] _n -O-CHR ² -CHR ¹ -NRH, where R is hydrogen or an organic radical having 1 to 12 C atoms and R ¹ and R ^{2 are} either both H atoms or R ^{1 is} an H atom and R ^{2 is} a methyl group, or R ^{1 is} a methyl group and R ^{2 is} a hydrogen atom and n is a number in the range of 0 to 10.
• c) compounds of the formula Y [-O-CHR ¹ -CHR ² - [O-CHR ¹ -CHR ² ] _n -O-CHR ² -CHR ¹ -XH] _z , wherein Y represents an organic moiety suitable for forming z ether and / or ester groups, X = O or S, and R ¹ and R ^{2 are} either both H or R ^{1 is} H and R ^{2 is} methyl or R ^{1 is} a methyl group and R ^{2 is} a hydrogen atom and n is a number in the range of 0 to 10 and z is an integer in the range of 2 to 6, in particular 3 to 4. The number n may be the same or different in each of the z groups.
• d) compounds of the formula Y [-O-CHR ¹ -CHR ² - [O-CHR ¹ -CHR ² ] _n -O-CHR ² -CHR ¹ -NRH] _z , wherein Y represents an organic moiety suitable for forming z ether and / or ester groups, R represents hydrogen or an organic radical of 1 to 12 carbon atoms, and R ¹ and R ^{2 are} either both H or R ¹ H atom and R ^{2 is} a methyl group, or R ^{1 is} a methyl group and R ^{2 is} a hydrogen atom and n is a number in the range of 0 to 10 and z is an integer in the range of 2 to 6, in particular from 3 to 4. The number n may be the same or different in each of the z groups.

Examples of organic moieties Y in the formulas c) and d) are the molecular residues of the OH groups reduced by the H atoms of: ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, the positional isomers of butylene glycol, glycerol, the positional isomers of trismethylolethane and trismethylolpropane, in particular 1,1,1-trismethylolpropane, erythritol, pentaerythritol, pentites and hexites, and sugars of the pentoses and hexoses type and also the corresponding carboxylic acids which are derived from the abovementioned di- or polyhydric alcohols, one or more -CH ₂ -OH groups is replaced by one carboxylate group each.

In the case of the general formulas mentioned under a) to d), it is customary for the degree of ethoxylation or propoxylation to fluctuate around an average value and for this mean value to be indicated as number n. Because in ethoxylation or propoxylation no uniform compounds, but mixtures of molecules which have a different number of ethylene oxide or propylene oxide groups. By choosing the reaction conditions and the use of special catalysts, the variation in the degree of alkoxylation can be varied. In the abovementioned formulas, n therefore indicates the average number of ethylene oxide or propylene oxide groups ring-opened under ether formation in the abovementioned molecules. Therefore, n can also represent a fractional number.

organic molecules with epoxy groups can for example, selected those which carry glycidyl ether groups. In particular, the Glycidyl ether groups directly or indirectly to the phenyl rings be bound by bisphenols. Specific examples are bisphenol A glycidyl ether, in which the glycidyl ether groups in the 2- or 4-position on the Phenyl rings, as well as the corresponding bisphenol F-glycidyl ethers.

It is particularly preferred if the surface of the inorganic particles has been coated to such an extent with the inorganic molecules that at least 4 carbon atoms of the organic molecules are present per nm ² surface. Preferably, at least 6 and in particular at least 8 carbon atoms of the organic molecules are present per nm ² surface area. How the coverage density can be measured will be described below.

The inorganic particles are preferably selected from oxides, hydroxides, Carbonates and silicas or silicates. Oxides of titanium, in particular, are oxides For example, rutile or anatase suitable. Aluminas or Hydroxides can also be used. Zinc oxides are also suitable. As carbonates Carbonates of calcium and / or magnesium are preferably used. Examples are chalk and dolomite. The inorganic particles can also mixed oxides / hydroxides such as basic aluminas or basic zinc oxides. Also mixed carbonates / hydroxides like For example, basic zinc carbonate can be used.

Further preferred inorganic particles are silicic acids or silicates. As "silicic acids" are (hydroxide-containing) Silicon oxides, for example, from silicon-halogen compounds by Pyrolysis or can be obtained by hydrolysis. Silicates can be salts of silicas in particular with alkaline earth metals. Also the naturally occurring ones Aluminosilicates, for example, fiber or layer structures can have are suitable. Examples of this are bentonites. Also calcium silicates such as wollastonite are suitable, as well as chlorites. Further examples will be given below in connection with a special manufacturing method with organic molecules called inorganic particles called.

In a preferred embodiment, the organic molecules are bonded to the surface of the inorganic particles via silicon atoms. This can be done by a reaction sequence that in WO2005 / 061631 and those cited herein EP 1526115 is described.

These Documents describe methods for surface modification of particles from oxidic compounds of metals and / or semimetals M, on their surface M-O-H groups are present, it being possible in a reaction step b) the particles with silicon-halogen compounds under such conditions in Contact brings the M-O-H groups with the silicon-halogen compounds under Formation of M-O-Si-X groups (X = halogen) react. Under "oxidic Connections "in silicic acids, Silicates and aluminosilicates. On carbonates is the one described here Reaction analog transferable, as long as conditions are met, not to complete decomposition lead the carbonates.

For the present Invention can contain the particles as a semi-metal M exclusively silicon, ie For example, from silicon dioxide or "silicas" or semi-metallic component M is only partially composed of silicon, as is the case, for example, with aluminosilicate minerals. Such compounds as, for example, phyllosilicates, such as mica, Bentonites etc. are described by the present invention as "inorganic Particles "includes. Further, not final Examples of the "inorganic particles" encompassed by the invention are oxidic compounds such as titanium dioxide, zirconium oxides, zinc oxide, iron oxides, Nickel oxides, manganese oxides, cerium oxides, aluminum oxides or mixed Oxides containing the metals titanium, zinc, zirconium, iron, cobalt, nickel, Cerium and / or aluminum included.

Even though no MOH groups are given in the chemical formula of the oxidic compounds or the carbonates, such groups are at the particle surface to the valence heel often available. That this is the case, it can be seen that the reaction with silicon-halogen compounds is detectable. If a higher density of MOH groups on the particle surface is desired for the reaction with silicon-halogen compounds than is usual with the oxidic or carbonaceous particles, then the number of MOH groups on the particle surface can thereby be determined increase the fact that the particle surface is brought into contact with a strong acid in a reaction step a) upstream of the reaction step b). This is preferably done in the aqueous phase and under conditions in which the oxidic particles or the carbonates are superficially attacked, but not dissolved. Variable parameters for this are in particular the strength of the acid, the reaction temperature and the reaction time. As strong acids here are acids of the strength of phosphoric acid and stronger acids such as sulfuric acid in particular suitable. After the superficial reaction with the acid, the particles are preferably washed before the reaction step b) and then dried.

The Silicon-halogen compounds which in the reaction step b) with the inorganic particles are brought into contact, are preferably selected of silicon chlorides and silicon bromides, for example of silicon tetrachloride and silicon tetrabromide. The reaction is possible from the gas phase, takes place but preferably in liquid Phase in as possible anhydrous environment. The liquid Phase should therefore contain as little water as technically possible. For example the water content should be below 1 ppm. This will guaranteed that the Si-halogen bonds are not or at least due to water only to a lesser extent be hydrolyzed while the majority of the silicon-halogen molecules by reaction with the superficial M-O-H groups are bound to the particle surface. there the reaction is preferably controlled so that per silicon atom 1 to 3 form M-O-Si bonds, while 3 to 1, preferably 1 to 2 Si-halogen bonds are retained. These are then available for further Functionalization reactions available. As a liquid phase For example, the silicon-halogen compounds that come with the oxide particles are to be implemented, even considered. These serve not only as a reagent, but at the same time as Reaction medium. However, the silicon-halogen compounds can also in dry non-erotic solvents with the particles the oxidic compounds are brought into contact. Examples suitable non-erotic solvent are cyclohexane and diethyl ether. As another non-erotic solvent come liquid aromatic or aliphatic hydrocarbons such as Benzene, toluene or petroleum ether into consideration.

Of the next Process step is that after the reaction step b) in a further reaction step c) the particles with at least an organic compound whose molecules have at least two terminal functional Bear groups, each functional group being at least one heteroatom containing at least one lone pair of electrons, under such conditions causes Si-X bonds to be split and become Instead, bonds of Si to the organic compound or to to train a rest of it. Examples of such organic molecules that in the context of the present invention have been further aforementioned. For This reaction step are in particular those organic molecules suitable, the terminal Carry -OH groups, -SH groups, or -NHR groups. This implementation leads under Cleavage of H-X to -Si-O, -Si-S or -Si-N bonds, whereby the organic molecules with the one functional end to the surface of the inorganic particles be bound. The other end, which is still a free -OH group, -SH group or -NHR group can in the usual way with the epoxy resin under opening of the oxirane ring and attachment of the organic molecules to the epoxy resin react. As a result, the occupied inorganic particles covalently incorporated into the organic matrix of the adhesive or sealant.

If it is desired to prove the inorganic particles by reaction with organic molecules which carry terminal epoxide groups, it is advisable first to convert the Si-X bonds into Si-OH groups by hydrolysis (a reaction step which is likewise in WO2005 / 061631 described) and then to carry out the reaction with the organic molecules carrying epoxide groups. By reaction with the Si-OH group, an oxirane ring of the organic molecules is opened and the molecule is bound to the inorganic particles to form a -Si-O-C bond. The other end of the organic molecule still has an epoxy group, which react with the hardener components during curing of the adhesive or sealant and so can be covalently incorporated into the organic matrix of the adhesive or sealant.

In order to prevent that in this reaction step c) the Si-X bonds are hydrolyzed to Si-OH bonds, one must work according to the reaction step b) under conditions as low as possible in water. The reaction conditions indicated above in reaction step b) apply correspondingly to this reaction step c). In the European patent application EP 1526115 are examples match called the reactions performed on silica particles having surface Si-Cl groups. The details given there can be transferred to the present invention in an analogous manner. The EP document also contains further details on how the particles obtained after reaction step c) can be characterized in more detail analytically.

Of course, in the Reaction step c) not just a single corresponding organic compound, but a mixture of different compounds are used. this leads to then to inorganic particles that differ on their surface carry organic radicals.

In order to determine the occupation density per nm ² , the particle surface and, if necessary, the porosity are first measured by the BET method (for example using nitrogen). The total content of organic radicals or of the carbon atoms herein and / or of silicon on the particles can be determined by elemental analysis. For the latter, a thermogravimetric analysis and / or DSC measurement can be used. In a thermogravimetric analysis with access of air burn at elevated temperature, the organic radicals, resulting in a loss of mass. This combustion reaction manifests itself in an exothermic effect in a DSC measurement. For safety, the comparison can be made with a thermogravimetric analysis and / or DSC measurement of the non-occupied with the silicon-containing groups starting material. If the chemical nature of the organic radicals and their number per Si atom is known, the total number of organic radicals in moles and thus the occupation density can be determined from the weight loss. This analysis can be supported or supplemented by catching up the carbon dioxide and water produced during the combustion of the organic residues in the course of a combustion analysis and deducing the amount of collected carbon back to the number of organic residues. If the chemical nature of the organic radicals and / or their number per Si atom is unknown in the case of an unknown sample, then at least the number of carbon atoms per nm ² surface can be deduced from such analyzes. In addition, mass spectroscopic techniques can be used to elucidate the chemical nature of the organic radicals. If the total amount of coating groups or of C atoms thus obtained is based on the measured particle surface, the coverage density in groups per nm ² can be calculated. Further information can be cited EP patent application EP 1526115 be removed. Instead of the number of carbon atoms per nm ² surface, the coverage density may also be as in EP 1526115 and in WO2005 / 061631 be characterized by the number of bound organic molecules per nm ² surface. In the context of the present invention, this is preferably at least 2, in particular at least 3 and particularly preferably at least 4, corresponding to the two cited documents EP 1526115 and WO2005 / 061631 ,

As it is often the case with epoxy adhesives or sealants, so it is in the context of the present invention, that it is in two Components is present, wherein a component A of one or more Epoxy (s) consists of or contains and a second component B from one or more hardeners for epoxides exists or contains. Immediately before the application, these two components mixed together. In the context of the present invention Epoxies and hardener systems suitable, those in the art usually be used as adhesives or sealants. Preferably the components A and B are composed so that the same application Volumes can be mixed.

at 2-component systems is a preferred embodiment in that component B comprises said inorganic particles contains in such an amount the proportion of inorganic particles in the entire adhesive or sealant after mixing components A and B in the range of 5 to 30 wt .-%, preferably from 5 to 20 wt .-%, wherein the surface of the inorganic particles evidenced by reaction with organic molecules which was at least two terminal carry functional groups selected from -OH groups, -SH groups and -NHR groups, where R is hydrogen or an organic radical with 1 to 12 carbon atoms. These functional groups correspond typical functional groups in hardener systems and can with the epoxy component A under opening of the oxirane ring and addition of the organic molecule.

An alternative embodiment is that the component A contains the said inorganic particles in such an amount that the proportion of the inorganic particles in the entire adhesive or sealant after mixing the components A and B in the range of 5 to 30 wt. %, preferably in the range of 5 to 20% by weight, wherein the surface of the inorganic particles has been coated by reaction with organic molecules carrying at least two terminal functional groups selected from epoxide groups. As a result, the occupied inorganic particles "epoxy resin-like" and can with the hardener molecules of component B with opening of the oxirane ring and Ad dition of the organic molecule.

The according to the invention or sealants can but also exist as one-component systems, the epoxy resins and activatable or latent hardeners contain. additionally are the inorganic particles mentioned with proportions in the Range of 5 to 30 wt .-%, preferably from 5 to 20 wt .-%.

When Epoxy resins are suitable for a variety of polyepoxides, at least 2 1,2-epoxy groups per molecule to have. The epoxide equivalent of these polyepoxides can be between 150 and 4000 vary. The polyepoxides can in principle be saturated, unsaturated, cyclic or acyclic, aliphatic, alicyclic, aromatic or heterocyclic polyepoxide compounds. Examples of suitable Polyepoxides include the Polyglycidylether, which by reaction of epichlorohydrin or Epibromohydrin produced with a polyphenol in the presence of alkali become. Therefor suitable polyphenols are, for example, resorcinol, pyrocatechol, Hydroquinone, bisphenol A (bis (4-hydroxy-phenyl) -2,2-propane), bisphenol F (bis (4-hydroxyphenyl) methane), bis (4-hydroxyphenyl) -1,1-isobutane, 4,4'-dihydroxybenzophenone, Bis (4-hydroxyphenyl) -1,1-ethane, 1,5-hydroxynaphthalene.

Further in principle suitable polyepoxides are the polyglycidyl ethers of Polyalcohols or diamines. These polyglycidyl ethers are derived of polyalcohols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, Triethylene glycol, 1,5-pentanediol, 1,6-hexanediol or trimethylolpropane.

Further Polyepoxides are polyglycidyl esters of polycarboxylic acids, for example Reactions of glycidol or epichlorohydrin with aliphatic or aromatic polycarboxylic acids like oxalic acid, Succinic acid, glutaric, terephthalic acid or dimer fatty acid.

Further Epoxides are derived from the epoxidation products of olefinically unsaturated cycloaliphatic compounds or of native oils and Fats off.

All Particular preference is given to the epoxy resins which are formed by reaction derived from bisphenol A or bisphenol F and epichlorohydrin. there are usually mixtures of liquid and solid epoxy resins used, the liquid Epoxy resins are preferably based on bisphenol A and a have sufficiently low molecular weight. In particular, be at room temperature liquid epoxy resins used, which is usually an epoxy equivalent weight from 150 to about 220, most preferred is an epoxide equivalent weight range from 182 to 192.

When thermally activated or latent hardener for the epoxy resin in the case of One-component systems can Guanidines, substituted guanidines, substituted ureas, melamine resins, Guanamine derivatives, cyclic tertiary amines, aromatic amines and / or mixtures thereof are used. The can Harder both stoichiometric in the curing reaction be involved, they can but also be catalytically effective. Examples of substituted Guanidines are methylguanidine, dimethylguanidine, trimethylguanidine, Tetramethylguanidine, methylisobiguanidine, dimethylisobiguanidine, Tetramethylisobiguanidine, hexamethylisobiguanidine, hepamethylisobiguanidine and especially cyanoguanidine (dicyandiamide). As a representative for suitable Guanamine derivatives its alkylated benzoguanamine resins, benzoguanamine resins or methoxymethyl-ethoxymethylbenzoguanamine. For the one-component, thermosetting Hotmelt adhesives is of course the selection criterion the low solubility these substances at room temperature in the resin system, so here solid, finely ground hardeners have preference, in particular dicyandiamide is suitable. In order to is a good storage stability ensured the composition.

In addition to or instead of the aforementioned hardeners, catalytically active substituted ureas can be used. These are in particular the p-chlorophenyl-N, N-dimethylurea (monuron), 3-phenyl-1,1-dimethylurea (Fenuron) or 3,4-dichlorophenyl-N, N-dimethylurea (diuron). In principle, it is also possible to use catalytically active tertiary aryl or alkyl amines, such as, for example, benzyldimethylamine, tris (dimethylamino) phenol, piperidine or piperidine derivatives, but these have too high a solubility in the adhesive system, so that there is no useful storage stability of the one-component Systems is achieved. Furthermore, various, preferably solid, imidazole derivatives can be used as catalytically active accelerators. Representative examples include 2-ethyl-2-methylimidazole, N-butylimidazole, benzimidazole and NC ₁ to C ₁₂ alkylimidazoles or N-arylimidazoles.

The adhesives according to the invention can be formulated on the one hand as one-component adhesives, these can be formulated both as highly viscous adhesives that can be applied warmly, and as thermally curable enamel adhesives. Furthermore, these adhesives can be formulated as one-component, pre-gelling adhesives, in the latter case, the compositions contain either finely divided thermoplastic powders, such. As polymethacrylates, polyvinyl butyral or other thermoplastic (co) polymers or the curing system is tuned so that a two-stage curing process takes place, the gelling step causes only a partial curing of the adhesive and the final curing in vehicle z. B. in one of the paint ovens, preferably in the KTL furnace takes place.

The adhesive compositions according to the invention can also be formulated as two-component epoxy adhesives, at the two reaction components just before the application are mixed together, the curing then at room temperature or moderately elevated temperature takes place. As a second reaction component can here for the two-component epoxy adhesives per se known reaction components are used, for example di- or polyamines, amino-terminated Polyalkylene glycols (eg Jeffamine, amino-poly-THF) or polyaminoamides. Other reactive partners can mercapto-functional prepolymers such as. As the liquid thiokol polymers. Basically, the Epoxy compositions also with carboxylic acid anhydrides as second reaction component cured in two-component adhesive formulations.

Farther can the adhesive compositions of the invention common other auxiliaries and additives such. As plasticizers, reactive diluents, rheology aids, Wetting agents, anti-aging agents, stabilizers and / or color pigments contain.

• A) ein Copolymeres mit mindestens einer Glasübergangstemperatur von –30°C oder niedriger und gegenüber Epoxiden reaktiven Gruppen oder ein Reaktionsprodukt dieses Copolymeren mit einem Polyepoxid sowie
• B) ein Reaktionsprodukt aus einem Polyurethan-Prepolymer und einem Polyphenol oder Aminophenol sowie
• C) mindestens ein Epoxidharz enthalten

As adhesive or sealant matrix which according to the invention contains the inorganic solids coated with said organic molecules, in particular:
According to WO00 / 37554 Compositions that

• A) a copolymer having at least a glass transition temperature of -30 ° C or lower and epoxide-reactive groups or a reaction product of this copolymer with a polyepoxide and
• B) a reaction product of a polyurethane prepolymer and a polyphenol or aminophenol and
• C) contain at least one epoxy resin

More detailed information can he called WO00 / 37554 be removed.

• A) mindestens ein Epoxidharz mit durchschnittlich mehr als einer Epoxidgruppe pro Molekül
• B) ein Copolymeres mit einer Glasübergangstemperatur von –30°C oder niedriger und gegenüber Epoxiden reaktiven Gruppen oder ein Umsetzungsprodukt dieses Copolymeren mit einem stöchiometrischen Überschuß eines Epoxidharzes gemäß A)
• C) einen latenten, bei erhöhter Temperatur aktivierbaren Härter für Komponente A), und entweder
• D) ein Reaktionsprodukt herstellbar aus einem difunktionellen aminoterminierten Polymer und einem Tri- oder Tetracarbonsäureanhydrid, gekennzeichnet durch im Mittel mehr als eine Imidgruppe und Carboxylgruppe pro Molekül, oder
• E) ein Reaktionsprodukt herstellbar aus einem tri- oder mehrfunktionellen Polyol oder einem tri- oder mehrfunktionellen aminoterminierten Polymer und einem cyclischen Carbonsäureanhydrid, wobei das Reaktionsprodukt im Mittel mehr als eine Carboxylgruppe pro Molekül enthält, oder
• F) eine Mischung der Reaktionsprodukte gemäß D) und E).

According to WO01 / 94492 Compositions containing

• A) at least one epoxy resin having on average more than one epoxide group per molecule
• B) a copolymer having a glass transition temperature of -30 ° C or lower and epoxide-reactive groups or a reaction product of this copolymer with a stoichiometric excess of an epoxy resin according to A)
• C) a latent, high temperature activatable hardener for component A), and either
• D) a reaction product preparable from a difunctional amino-terminated polymer and a tri- or tetracarboxylic anhydride, characterized by an average of more than one imide group and carboxyl group per molecule, or
• E) a reaction product preparable from a tri- or polyfunctional polyol or a tri- or polyfunctional amino-terminated polymer and a cyclic carboxylic anhydride, wherein the reaction product contains on average more than one carboxyl group per molecule, or
• F) a mixture of the reaction products according to D) and E).

More detailed information can he called WO01 / 94492 be removed.

• A) ein Copolymeres mit mindestens einer Glasübergangstemperatur von –30°C oder niedriger und gegenüber Epoxiden reaktiven Gruppen
• B) ein Reaktionsprodukt herstellbar durch Umsetzung eines Carbonsäureanhydrids oder -dianhydrids mit einem Di- oder Polyamin und ei-nem Polyphenol oder Aminophenol
• C) mindestens ein Epoxidharz.

According to WO00 / 20483 Compositions containing

• A) a copolymer having at least a glass transition temperature of -30 ° C or lower and epoxide-reactive groups
• B) a reaction product preparable by reacting a carboxylic anhydride or dianhydride with a di- or polyamine and egg nem polyphenol or aminophenol
• C) at least one epoxy resin.

More detailed information can he called WO00 / 20483 be removed.

• a) eine kontinuierliche Phase bestehend aus einem gegebenenfalls vernetztem Polymer P1 mit einer Glasübergangstemperatur oberhalb von 100°C, vorzugsweise oberhalb von 120°C,
• b) einer heterodisperse Phase bestehend aus einzelnen kontinuierlichen Bereichen eines thermoplastischen oder elastomeren Polymeren P2 mit einer Glasübergangstemperatur von weniger als –30°C und einer mittleren Teilchengröße zwischen 0,5 und 50 μm, welche ihrerseits separierte Phasen eines weiteren thermoplastischen oder elastomeren Polymeren P3 mit einer Glasübergangstemperatur von weniger als –30°C und einer Größe zwischen 1 nm und 100nm enthält, die teilweise zu größeren Agglomeraten aggregiert vorliegen können, sowie
• c) eine in der kontinuierlichen Phase eingebetteten weiteren heterodispersen Phase bestehend aus Bereichen eines thermoplastischen oder elastomeren Polymeren P3 mit einer Glasübergangstemperatur von weniger als –30°C, die zumindest teilweise eine mittlere Teilchengröße zwischen 1 nm und 50 nm haben wobei P3 nicht identisch ist mit P2,

aufweist.According to WO03 / 055957 a thermosetting structural adhesive with multiphase polymer morphology, where at the binder matrix of the cured reaction adhesive

• a) a continuous phase consisting of an optionally crosslinked polymer P1 having a glass transition temperature above 100 ° C., preferably above 120 ° C.,
• b) a heterodisperse phase consisting of individual continuous regions of a thermoplastic or elastomeric polymer P2 having a glass transition temperature of less than -30 ° C and an average particle size between 0.5 and 50 microns, which in turn separated phases of another thermoplastic or elastomeric polymer P3 with a glass transition temperature of less than -30 ° C and a size between 1 nm and 100nm, which may be partially aggregated to larger agglomerates, and
• c) a further heterodisperse phase embedded in the continuous phase and consisting of regions of a thermoplastic or elastomeric polymer P3 having a glass transition temperature of less than -30 ° C, which at least partially have an average particle size between 1 nm and 50 nm, where P3 is not identical to P2,

having.

Details of this can be mentioned WO03 / 055957 be removed.

• A) eine Epoxy-Komponente enthaltend a) mindestens ein Epoxidharz mit einer Epoxy-Funktionalität größer als 1, b) mindestens einen hitzeaktivierbaren Härter für das Epoxidharz,
• B) eine flüssige oder pastöse Härterkomponente enthaltend Amine, Polyaminoamide, Mannich-Basen oder mercaptogruppenhaltige Verbindungen.

According to DE 103 51 687 a two-part epoxy resin composition containing

• A) an epoxy component comprising a) at least one epoxy resin having an epoxy functionality greater than 1, b) at least one heat-activatable hardener for the epoxy resin,
• B) a liquid or pasty hardener component containing amines, polyaminoamides, Mannich bases or mercapto group-containing compounds.

Details of this can be mentioned DE 103 51 687 be removed.

Next the aforementioned Applications can the adhesive compositions of the invention also as potting compounds in the electrical or electronics industry, as a die-attach adhesive in electronics for bonding components be used on printed circuit boards. Further uses the compositions of the invention are matrix materials for Composite materials such. B. fiber reinforced composites.

Further preferred applications for the adhesive compositions of the invention both in one-component thermosetting Form as well as in two-component form are their use as Structural foam, for example for the formation of internal stiffeners of cavities in vehicle construction, wherein the expanding structural foams the Cavity construction of the vehicle stiffen or their energy absorption mark up. Furthermore you can the compositions for the production of so-called "stiffening pads" or for stiffening Coatings thin-walled Sheets or plastic components, preferably used in vehicle construction become.

One very particularly preferred field of application of the adhesives according to the invention However, structural bonding in vehicle construction.

at the use according to the invention As a structural adhesive, the adhesive is after the connection of Metal parts at a temperature in the range of 100 to 150 ° C for a period of time thermally cured in the range of 30 to 120 minutes. In particular, the hardening for one Duration in the range of 50 to 70 minutes at a temperature in the range of 110 to 130 ° C carried out become. In the following examples, curing took place for one hour at 120 ° C. The optimal curing time and curing temperature depends on the concrete epoxy hardener system used and can be optimized through routine experimentation.

The can be glued to metal parts consist of those metals that are currently used in the automotive industry. Examples of this are steel, galvanized or alloy-galvanized steel and aluminum. Also a bonding of magnesium parts is possible. The to be glued Metal parts can subjected to a corrosion-protective treatment before bonding or coated with an organic primer, such as it is currently technically common is. Not pretreated, possibly even oiled parts can also be glued.

embodiments

The different fillers mentioned below were reacted with the following functional end-group ("nucleophile") molecules as described in U.S.P. WO2005 / 061631 documented method. The filled fillers (and blank fillers for comparison) were incorporated in varying amounts (expressed in weight percent based on the final filler-containing product) in a 2-part epoxy adhesive: Formulation: 2-K-EPO Component A Equiv. Wt. Dimensions [%] equivalents Constituents [%] Epon 828 182 100 0.549 50 Component B Equiv. Wt. Dimensions [%] equivalents Constituents [%] Polypox P 502 Hycar ATBN 1300X16 92,900 66.67 33.33 0.725 0.037 33.33 16.67

• Härtung: 1h bei 120°C

Messparameter: Zugscher-Festigkeit: Material des Prüfkörpers: Blech Länge der Verklebung: 10 mm Breite des Prüfkörpers: 25 mm Prüfgeschwindigkeit: 15 mm/min Winkelschäl-Festigkeit: Material des Prüfkörpers: Blech Breite des Prüfkörpers: 25 mm Messweg: 200 mm Prüfgeschwindigkeit: 100 mm/min Abkürzungen: oberfl. oberflächennaher Bruch cf cohesive failure schräg gez. ungleichmäßiges Verbiegen der Fügeteile bei Prüfung der Winkelschäl-Festigkeit Rutil (Kronos 3025)

Tab. 1: Zuscher-Festikeit unmodifizierter Füllstoff modifizierter Füllstoff W (Füllstoff) [%] F_max [N·mm^–2] Bem. ⌀ F_max [N·mm^–2] F_max [N·mm^–2] Bem. ⌀ F_max [N·mm^–2] 0 % 21,50 25,68 24,86 10 % cf 0 % cf 0 % cf 24,1 – – – 5 % 26,58 26,52 25,68 27,40 25,11 0 % cf 0 % cf 0 % cf 0 % cf 0 % cf 26,3 27,53 29,29 27,89 0 % cf 0 % cf 0 % cf 28,2 10 % 19,20 20,43 17,03 16,41 20,52 100 % cf, oberfl. 100 % cf, oberfl. 100 % cf, oberfl. 100 % cf 100 % cf 18,7 25,76 27,77 29,39 50 % cf, oberfl. 95 % cf 95 % cf 27,6 20 % 20,05 23,49 23,02 100 % cf, oberfl. 100 % cf, oberfl. 100 % cf, oberfl. 22,2 18,40 20,55 19,24 95 % cf, oberfl. 100 % cf, oberfl. 100 % cf, oberfl. 19,4 Tab. 2: Winkelschäl-Festigkeit unmodifizierter Füllstoff modifizierter Füllstoff W (Füllstoff) [%] F_mittel [N·mm^–1] Bem. ⌀ F_mittel [N·mm^–1] F_mittel [N·mm^–1] Bem. ⌀ F_mittel [N·mm^–1] 0 % 6,14 6,96 80 % cf 60 % cf 6,6 – – – 5 % 6,58 6,73 5 % cf 90 % cf, oberfl. 6,7 5,14 6,12 0 % cf 0 % cf, schräg gez. 5,6 10 % 5,24 5,44 90 % cf, ungl. 50 % 5,3 7,63 8,02 100 % cf, oberfl., schräg g. 85 % cf 7,8 20 % 3,93 5,65 100 % cf 100 % cf, oberfl. 4,8 6,38 5,79 100 % cf, 100 % cf, schräg gez. 6,1 Rutil (Kronos 3025)

Tab. 3: Zugscher-Festigkeit unmodifizierter Füllstoff modifizierter Füllstoff W(Füllstoff) [%] F_max [N·mm^–2] Bem. ⌀ F_max [N·mm^–2] F_max [N·mm^–2] Bem. ⌀ F_max [N·mm^–2] 0 % 21,50 25,68 24,86 10 % cf 0 % cf 0 % cf 24,1 – – – 5 % 26,58 26,52 25,68 27,40 25,11 0 % cf 0 % cf 0 % cf 0 % cf 0 % cf 26,3 28,63 29,66 29,31 0 % cf 0 % cf 0 % cf 29,2 10 % 19,20 20,43 17,03 16,41 20,52 100 % cf, oberfl. 100 % cf, oberfl. 100 % cf, oberfl. 100 % cf 100 % cf 18,7 27,65 27,75 28,71 5 % cf 0 % cf 0 % cf 28,0 20 % 20,05 23,49 23,02 100 % cf, oberfl. 100 % cf, oberfl. 100 % cf, oberfl. 22,2 21,75 24,41 22,00 100 % cf 100 % cf 100 % cf 22,7 Tab. 4: Winkelschäl-Festigkeit unmodifizierter Füllstoff modifizierter Füllstoff W (Füllstoff) [%] F_mittel [N·mm^–1] Bem. ⌀ F_mittel [N·mm^–1] F_mittel [N·mm^–1] Bem. ⌀ F_mittel [N·mm^–1] 0 % 6,14 6,96 80 % cf 60 % cf 6,6 – – – 5 % 6,58 6,73 5 % cf 90 % cf, oberfl. 6,7 5,83 6,14 0 % cf 0 % cf 6,0 10 % 5,24 5,44 90 % cf, ungl. 50 % cf 5,3 6,59 6,95 30 % cf 90 % cf, oberfl. 6,8 20 % 3,93 5,65 100 % cf 100 % cf, oberfl. 4,8 4,15 4,79 100 % cf 100 % cf 4,5 Rutil (Kronos 3025)

Tab. 5: Zugscher-Festigkeit unmodifizierter Füllstoff modifizierter Füllstoff W (Füllstoff) [%] F_max [N·mm^–2] Bem. ⌀ F_max [N·mm^–2] F_max [N·mm^–2] Bem. ⌀ F_max [N·mm^–2] 0 % 21,50 25,68 24,86 10 % cf 0 % cf 0 % cf 24,1 – – – 5 % 26,58 26,52 25,68 27,40 25,11 0 % cf 0 % cf 0 % cf 0 % cf 0 % cf 26,3 28,30 28,22 28,65 0 % cf 5 % cf 5 % cf 28,4 10 % 19,20 20,43 17,03 16,41 20,52 100 % cf, oberfl. 100 % cf, oberfl. 100 % cf, oberfl. 100 % cf 100 % cf 18,7 26,50 25,11 26,42 85 % cf, oberfl. 90 % cf, oberfl. 95 % cf, oberfl. 26,0 20 % 20,05 23,49 23,02 100 % cf, oberfl. 100 % cf, oberfl. 100 % cf, oberfl. 22,2 25,78 27,81 26,09 75 % cf, oberfl. 60 % cf, oberfl. 80 % cf, oberfl. 26,6 Tab. 6: Winkelschäl-Festigkeit unmodifizierter Füllstoff modifizierter Füllstoff W (Füllstoff) [%] F_mittel [N·mm^–1] Bem. ⌀ F_mittel [N·mm^–1] F_mittel [N·mm^–1] Bem. ⌀ F_mittel [N·mm^–1] 0 % 6,14 6,96 80% cf 60 % cf 6,6 – – – 5 % 6,58 6,73 5 % cf 90 % cf, oberfl 6,7 7,08 6,61 0 % cf 10 % cf 6,8 10 % 5,24 5,44 90 % cf, ungl. 50 % cf 5,3 5,67 5,64 95 % cf 80 % cf 5,7 20 % 3,93 5,65 100 % cf 100 % cf, oberfl. 4,8 4,78 4,79 85 % cf, oberfl. 100 % cf, oberfl. 4,8 Kreide (Socal U1)

Tab. 11: Zugscher-Festigkeit unmodifizierter Füllstoff modifizierter Füllstoff W (Füllstoff) [%] F_max [N·mm^–2] Bem. ⌀ F_max [N·mm^–2] F_max [N·mm^–2 Bem. ⌀ F_max [N·mm^–2] 0 % 21,50 25,68 24,86 10 % cf 0 % cf 0 % cf 24,1 – – – 5 % 21,85 26,34 25,78 100 % cf 100 % cf 99 % cf 24,7 24,56 22,90 20,93 100 % cf 100 % cf 100 % cf 22,8 20 % 25,97 28,47 26,69 100 % cf, oberfl., unr. 100 % cf, oberfl., unr. 100 % cf, oberfl., unr. 27,0 Topfzeit: 60 s – – Tab. 12: Winkelschäl-Festigkeit unmodifizierter Füllstoff modifizierter Füllstoff W(Füllstoff) [%] F_mittel [N·mm^–1] Bem. ⌀ F_mittel [N·mm^–1] F_mittel [N·mm^–1] Bem. ⌀ F_mittel [N·mm^–1] 0 % 6,14 6,96 80 % cf 60 % cf 6,6 – – – 5 % 5,39 5,88 100 % cf, sehr unr. 100 % cf, unr. 5,6 8,03 80 % cf 40 % cf 8,04 10 % 5,05 4,56 4,71 100 % cf, unr. 100 % cf, unr. 100 % cf, unr. 4,8 7,91 8,34 8,81 60 % cf, oberfl. 10 % cf, oberfl. 70 % cf, schräg gez 8,4 20 % 3,74 4,37 90 % cf, sehr unr. 95 % cf, unr. 4,1 Topfzeit: 60 s – – Kreide (Socal U1)

Tab. 11: Zugscher-Festigkeit unmodifizierter Füllstoff modifizierter Füllstoff W(Füllstoff) [%] F_max [N·mm^–2] Bem. ⌀ F_max [N·mm^–2] F_max [N·mm^–2] Bem. ⌀ F_max [N·mm^–2] 0 % 21,50 25,68 24,86 10 % cf 0 % cf 0 % cf 24,1 – – – 5 % 21,85 26,34 25,78 100 % cf 100 % cf 99 % cf 24,7 28,59 27,50 28,24 0 % cf 0 % cf 0 % cf 28,1 10 % 25,19 23,47 26,66 100 % cf, oberfl. 100 % cf, oberfl. 95 % cf, oberfl. 25,1 25,48 27,24 27,24 95 % cf 95 % cf 95 % cf 26,7 20 % 25,97 28,47 26,69 100 % cf, oberfl., unr. 100 % cf, oberfl., unr. 100 % cf, oberfl., unr. 27,0 31,72 28,00 0 % cf 0 % cf 29,9 Tab. 12: Winkelschäl-Festigkeit nmodifizierter Füllstoff modifizierter Füllstoff W(Füllstoff) [%] F_mittel [N·mm^–1] Bem. ⌀ F_mittel [N·mm^–1] F_mittel [N·mm^–1] Bem. ⌀ F_mittel [N·mm^–1] 0 % 6,14 6,96 80 % cf 60 % cf 6,6 – – – 5 % 5,39 5,88 100 % cf, sehr unr. 100 % cf, unr. 5,6 6,93 6,33 5 % cf 95 % cf 6,6 10 % 5,05 4,56 4,71 100 % cf, unr. 100 % cf, unr. 100 % cf, unr. 4,8 7,68 30 % cf 50 % cf 8,2 20 % 3,74 4,37 90 % cf, sehr unr. 95 % cf, unr. 4,1 8,78 7,07 30 % cf 85 % cf, schräg gez. 7,9

The individual components are: Epon 828: Epoxy resin based on bisphenol A and epichlorohydrin Polypox P 502: modified polyaminoamide oxide resin Hycar ATBN 1300X16: Amine-terminated butadiene-acrylonitrile copolymer

• Hardening: 1h at 120 ° C

Measurement parameters: Tensile shear strength: Material of the test specimen: sheet Length of the bond: 10 mm Width of the test specimen: 25 mm Test speed: 15 mm / min Peel strength: Material of the test specimen: sheet Width of the test specimen: 25 mm measuring range: 200 mm Test speed: 100 mm / min Abbreviations: surface-. near-surface fracture cf cohesive failure slanted Uneven bending of the joining parts when testing the angle peel strength Rutile (Kronos 3025)

Tab. 1: Tightness unmodified filler modified filler W (filler) [%] F _max [N × mm ^-2 ] Bem. ⌀ F _max [N × mm ^-2 ] F _max [N × mm ^-2 ] Bem. ⌀ F _max [N × mm ^-2 ] 0% 21,50 25,68 24,86 10% cf 0% cf 0% cf 24.1 - - - 5% 26,58 26,52 25,68 27,40 25,11 0% cf 0% cf 0% cf 0% cf 0% cf 26.3 27.53 29.29 27.89 0% cf 0% cf 0% cf 28.2 10% 19,20 20,43 17,03 16,41 20,52 100% cf, surface 100% cf, surface 100% cf, surface 100% cf 100% cf 18.7 25,76 27,77 29,39 50% cf, surface 95% cf 95% cf 27.6 20% 20.05 23,49 23,02 100% cf, surface 100% cf, surface 100% cf, surface 22.2 18,40 20,55 19,24 95% cf, surface. 100% cf, surface 100% cf, surface 19.4 Tab. 2: Angle peel strength unmodified filler modified filler W (filler) [%] F _average [N · mm ^-1 ] Bem. ⌀ F _medium [N · mm ^-1 ] F _average [N · mm ^-1 ] Bem. ⌀ F _medium [N · mm ^-1 ] 0% 6.14 6.96 80% cf 60% cf 6.6 - - - 5% 6,58 6,73 5% cf 90% cf, surface 6.7 5:14 6,12 0% cf 0% cf, skewed 5.6 10% 5.24 5.44 90% cf, unhealthy 50% 5.3 7.63 8.02 100% cf, surface, diagonal g. 85% cf 7.8 20% 3.93 5.65 100% cf 100% cf, surface 4.8 6.38 5.79 100% cf, 100% cf, skewed 6.1 Rutile (Kronos 3025)

Tab. 3: Tensile shear strength unmodified filler modified filler W (filler) [%] F _max [N × mm ^-2 ] Bem. ⌀ F _max [N × mm ^-2 ] F _max [N × mm ^-2 ] Bem. ⌀ F _max [N × mm ^-2 ] 0% 21,50 25,68 24,86 10% cf 0% cf 0% cf 24.1 - - - 5% 26,58 26,52 25,68 27,40 25,11 0% cf 0% cf 0% cf 0% cf 0% cf 26.3 28.63 29.66 29.31 0% cf 0% cf 0% cf 29.2 10% 19,20 20,43 17,03 16,41 20,52 100% cf, surface 100% cf, surface 100% cf, surface 100% cf 100% cf 18.7 27,65 27,75 28,71 5% cf 0% cf 0% cf 28.0 20% 20.05 23,49 23,02 100% cf, surface 100% cf, surface 100% cf, surface 22.2 21,75 24,41 22,00 100% cf 100% cf 100% cf 22.7 Tab. 4: Angle peel strength unmodified filler modified filler W (filler) [%] F _average [N · mm ^-1 ] Bem. ⌀ F _medium [N · mm ^-1 ] F _average [N · mm ^-1 ] Bem. ⌀ F _medium [N · mm ^-1 ] 0% 6.14 6.96 80% cf 60% cf 6.6 - - - 5% 6,58 6,73 5% cf 90% cf, surface 6.7 5.83 6,14 0% cf 0% cf 6.0 10% 5.24 5.44 90% cf, unhealthy 50% cf 5.3 6,59 6,95 30% cf 90% cf, surface 6.8 20% 3.93 5.65 100% cf 100% cf, surface 4.8 4,15 4,79 100% cf 100% cf 4.5 Rutile (Kronos 3025)

Tab. 5: Tensile shear strength unmodified filler modified filler W (filler) [%] F _max [N × mm ^-2 ] Bem. ⌀ F _max [N × mm ^-2 ] F _max [N × mm ^-2 ] Bem. ⌀ F _max [N × mm ^-2 ] 0% 21,50 25,68 24,86 10% cf 0% cf 0% cf 24.1 - - - 5% 26,58 26,52 25,68 27,40 25,11 0% cf 0% cf 0% cf 0% cf 0% cf 26.3 28,30 28,22 28,65 0% cf 5% cf 5% cf 28.4 10% 19,20 20,43 17,03 16,41 20,52 100% cf, surface 100% cf, surface 100% cf, surface 100% cf 100% cf 18.7 26,50 25,11 26,42 85% cf, surface. 90% cf, surface 95% cf, surface. 26.0 20% 20.05 23,49 23,02 100% cf, surface 100% cf, surface 100% cf, surface 22.2 25,78 27,81 26,09 75% cf, surface. 60% cf, surface. 80% cf, surface 26.6 Tab. 6: Angle peel strength unmodified filler modified filler W (filler) [%] F _average [N · mm ^-1 ] Bem. ⌀ F _medium [N · mm ^-1 ] F _average [N · mm ^-1 ] Bem. ⌀ F _medium [N · mm ^-1 ] 0% 6.14 6.96 80% cf 60% cf 6.6 - - - 5% 6,58 6,73 5% cf 90% cf, surface 6.7 7.08 6.61 0% cf 10% cf 6.8 10% 5.24 5.44 90% cf, unhealthy 50% cf 5.3 5.67 5.64 95% cf 80% cf 5.7 20% 3.93 5.65 100% cf 100% cf, surface 4.8 4.78 4.79 85% cf, surface. 100% cf, surface 4.8 Chalk (Socal U1)

Tab. 11: Tensile shear strength unmodified filler modified filler W (filler) [%] F _max [N × mm ^-2 ] Bem. ⌀ F _max [N × mm ^-2 ] F _max [N × mm ^-2 Bem. ⌀ F _max [N × mm ^-2 ] 0% 21,50 25,68 24,86 10% cf 0% cf 0% cf 24.1 - - - 5% 21,85 26,34 25,78 100% cf 100% cf 99% cf 24.7 24.56 22,90 20,93 100% cf 100% cf 100% cf 22.8 20% 25.97 28.47 26.69 100% cf, surface, unr. 100% cf, surface, unr. 100% cf, surface, unr. 27.0 Pot life: 60 s - - Tab. 12: Angle peel strength unmodified filler modified filler W (filler) [%] F _average [N · mm ^-1 ] Bem. ⌀ F _medium [N · mm ^-1 ] F _average [N · mm ^-1 ] Bem. ⌀ F _medium [N · mm ^-1 ] 0% 6.14 6.96 80% cf 60% cf 6.6 - - - 5% 5.39 5.88 100% cf, very unr. 100% cf, unr. 5.6 8.03 80% cf 40% cf 8.04 10% 5.05 4.56 4.71 100% cf, unr. 100% cf, unr. 100% cf, unr. 4.8 7.91 8.34 8.81 60% cf, surface. 10% cf, surface 70% cf, slanted 8.4 20% 3.74 4.37 90% cf, very bad 95% cf, unr. 4.1 Pot life: 60 s - - Chalk (Socal U1)

Tab. 11: Tensile shear strength unmodified filler modified filler W (filler) [%] F _max [N × mm ^-2 ] Bem. ⌀ F _max [N × mm ^-2 ] F _max [N × mm ^-2 ] Bem. ⌀ F _max [N × mm ^-2 ] 0% 21,50 25,68 24,86 10% cf 0% cf 0% cf 24.1 - - - 5% 21,85 26,34 25,78 100% cf 100% cf 99% cf 24.7 28.59 27.50 28.24 0% cf 0% cf 0% cf 28.1 10% 25.19 23.47 26.66 100% cf, surface 100% cf, surface 95% cf, surface. 25.1 25,48 27,24 27,24 95% cf 95% cf 95% cf 26.7 20% 25.97 28.47 26.69 100% cf, surface, unr. 100% cf, surface, unr. 100% cf, surface, unr. 27.0 31,72 28,00 0% cf 0% cf 29.9 Tab. 12: Angle peel strength modified filler modified filler W (filler) [%] F _average [N · mm ^-1 ] Bem. ⌀ F _medium [N · mm ^-1 ] F _average [N · mm ^-1 ] Bem. ⌀ F _medium [N · mm ^-1 ] 0% 6.14 6.96 80% cf 60% cf 6.6 - - - 5% 5.39 5.88 100% cf, very unr. 100% cf, unr. 5.6 6,93 6,33 5% cf 95% cf 6.6 10% 5.05 4.56 4.71 100% cf, unr. 100% cf, unr. 100% cf, unr. 4.8 7.68 30% cf 50% cf 8.2 20% 3.74 4.37 90% cf, very bad 95% cf, unr. 4.1 8.78 7.07 30% cf 85% cf, slanted 7.9

Claims (11)

Adhesive or sealant based on epoxy, the, related on the entire adhesive, 5 to 30 wt .-% of inorganic particles contains their surface was evidenced by reaction with organic molecules that at least two terminal ones bear functional groups, each functional group being at least contains a heteroatom with at least one lone pair of electrons. Adhesive or sealant according to claim 1, characterized in that the functional groups are selected from -OH groups, -SH groups, Epoxide groups and -NHR groups, where R is hydrogen or an organic Rest means having 1 to 12 carbon atoms Adhesive or sealant according to one or both of Claims 1 and 2, characterized in that the organic molecules except the said terminal functional groups containing ether groups. Adhesive or sealant according to one or more of Claims 1 to 3, characterized in that the surface of the inorganic particles has been coated to such an extent with the organic molecules that at least 4 carbon atoms of the organic molecules are present per nm ² surface. Adhesive or sealant according to one or more of claims 1 to 4, characterized in that the inorganic particles selected are oxides, hydroxides, carbonates and silicas or Silicates. Adhesive or sealant according to one or more of claims 1 to 5, characterized in that the organic molecules via silicon atoms with the surface the inorganic particles are connected. Adhesive or sealant according to one or more of claims 1 to 6, characterized in that it is present in two components, wherein a component A consists of one or more epoxide (s) or contains this and a second component B of one or more epoxy curing agents exists or contains. Adhesive or sealant according to claim 7, characterized in that that the component B, the said inorganic particles in a contains such amount, that the proportion of inorganic particles in the entire adhesive or sealant after mixing components A and B in the range from 5 to 30% by weight, preferably in the range from 5 to 20% by weight lies, with the surface the inorganic particle is evidenced by reaction with organic molecules which was at least two terminal carry functional groups selected from -OH groups, -SH groups and -NHR groups, where R is hydrogen or an organic radical with 1 to 12 carbon atoms. Adhesive or sealant according to claim 7, characterized in that that the component A, the said inorganic particles in a contains such amount, that the proportion of inorganic particles in the entire adhesive or sealant after mixing components A and B in the range from 5 to 30 wt .-%, preferably in the range of 5 to 20 wt%, wherein the surface the inorganic particle is evidenced by reaction with organic molecules which was at least two terminal carry functional groups selected from epoxide groups. Use of an adhesive according to one or more the claims 1 to 9 as a structural adhesive for the connection of metal parts in Automotive engineering. Use according to claim 10, characterized that the adhesive after the connection of the metal parts in a Temperature in the range of 100 to 150 ° C for a period of time in the range is thermally cured from 30 to 120 minutes.