Technical field

The present invention pertains to the field of expandable one-component thermosetting epoxy resin adhesives and also to the use thereof particularly in vehicle construction.

Prior art

Thermosetting, expandable one-component epoxy resin adhesives have already been used for some considerable time as adhesives in body construction.

CN 105 694 790 A describes a two-component room temperature curing epoxy adhesive used for bonding metal to metal, containing epoxy resin, an epoxy diluent, a mixture containing a furan-maleimide addition product, a curing agent, amido modified carbon nanotubes and thermally expanding microspheres. The adhesive displays high bonding strength at room temperature and is easy to remove at medium temperature.

CN 111 139 010 A relates to a structural adhesive with excellent low-temperature impact peel strength and a preparation method thereof. The structural adhesive contains epoxy resin, a toughening agent, dicyandiamide, an accelerant, a filler and a physical foaming agent. The adhesive can achieve good low-temperature impact resistance and meets the performance requirements of automobiles in cold weather.

CN 101 679 828 A describes an epoxy adhesive compositions containing a rubber- modified epoxy resin containing a bisphenol. The bisphenol can be pre-reacted with the rubber-modified epoxy resin to improve the resin. The adhesives show resistance to thermal degradation occurring in so-called "overbake" conditions, in which the adhesive is heated to high temperatures for prolonged periods of time. In addition, expanded micro balloons are included in epoxy structural adhesives to promote a desired fracture mode.

One important field of use of expandable one-component thermosetting epoxy resin adhesives, accordingly, is in vehicle construction, where typically there are metal substrates such as steel sheets and aluminium present, particularly in the context of adhesive bonding. Following the application of the epoxy resin composition, the bodywork is heated in the CEC (cathodic electrocoating) oven, by means of which the thermosetting epoxy resin composition as well is cured.

Such expandable structural adhesives must fulfil a variety of requirements including good adhesion on metal substrates such as steel sheets, especially oiled steel sheets, and aluminium, sufficient expansion rates and preferably a closed surface of the cured foamed material. These requirements are particularly difficult to meet when low curing temperatures are needed, especially if these compositions have a viscosity of 500 to 5000 Pas at room temperature.

However, efforts are currently underway in the market to provide expandable structural adhesives in a pumpable form due to the ease of robustic application. Thus, there is a great need in the market for expandable one-component epoxy resin adhesives with a viscosity of 500 to 5000 Pas that have good adhesion on metal substrates such as steel sheets, sufficient expansion rates and preferably have a closed surface of the cured foamed material.

Summary of the invention

It is an object of the present invention, therefore, to provide room temperature pumpable expandable one-component thermosetting epoxy resin adhesives with a viscosity of 500 to 5000 Pas that have good adhesion on metal substrates, sufficient expansion rates and preferably have a closed surface of the cured foamed material.

Surprisingly it has been found that this object can be achieved with the one-component thermosetting epoxy resin adhesive as defined in Claim 1.

Further aspects of the invention are subjects of further independent claims. Particularly preferred embodiments of the invention are subjects of the dependent claims. Certain embodiments of the invention

The present invention therefore relates to a one-component thermosetting epoxy resin adhesive, comprising a) at least one epoxy resin A having on average more than one epoxide group per molecule, preferably a liquid epoxy resin, the fraction of the epoxy resin A being from 30 - 80 wt.-%, based on the total weight of the one-component thermosetting epoxy resin adhesive; and b) 1.25 - 2.5 wt.-% of heat-expandable microspheres HEM, based on the total weight of the one-component thermosetting epoxy resin adhesive, with an expansion-initiation temperature (T _s ) between 90 °C - 115 °C and a mean particle size D (0.5) between 30 - 75 pm; c) at least one latent hardener B for epoxy resins; and d) preferably at least one accelerator C for epoxy resins; and e) at least one toughness improver D, the fraction of toughness improver D being from 5 - 40 wt.-%, based on the total weight of the one-component thermosetting epoxy resin adhesive; and the epoxy resin adhesive has a viscosity of 500 to 5000 Pas, 500 to 2000 Pas, 500 to 1500 Pas, preferably 500 to 1300 Pas at 25°C, the viscosity being determined oscillographically by means of a rheometer with heatable plate (MCR 301 , AntonPaar) (slot 1000 pm, measuring plate diameter: 25 mm (plate/plate), deformation 0.01 at 5 Hz, temperature: 25°C).

The epoxy resin adhesive is one-component, meaning that the constituents of the epoxy resin adhesive, more particularly the epoxy resin and the hardener, are present in one component, without curing taking place at usual ambient temperature or room temperature. The one-component epoxy resin adhesive is therefore storage-stable. It can therefore be handled in this form, whereas with two-component systems the components cannot be mixed until immediately prior to use.

The curing of the one-component epoxy resin adhesive is accomplished by heating, typically at a temperature of more than 70°C, as in the range from 100 to 220°C, for example. The prefix “poly” in expressions such as polyol or polyisocyanate denotes that the compound has two or more of the stated groups. A polyisocyanate, for example, is a compound having two or more isocyanate groups.

The expression “independently of one another” as used below means that in the same molecule, two or more identically denoted substituents may have identical or different meanings in accordance with the definition.

The dashed lines in the formulae in this document represent in each case the bond between the substituent in question and the associated remainder of the molecule.

Room temperature refers here to a temperature of 23°C, unless otherwise indicated.

The thermosetting one-component epoxy resin adhesive comprises at least one epoxy resin A having on average more than one epoxide group per molecule.

Preferably, the at least one epoxy resin A having on average more than one epoxide group per molecule is a liquid epoxy resin.

In contrast to the liquid epoxy resins A, solid epoxy resins having on average more than one epoxide group per molecule are solid at room temperature. The glass transition temperature of solid resins is above room temperature, meaning that they can be comminuted to pourable powders at room temperature.

Preferred liquid epoxy resins A having on average more than one epoxide group per molecule have the formula (II)

In this formula the substituents R’” and R”” independently of one another are either H or CH3. Moreover, the index r is from 0 to 1 . Preferably r is less than 0.2. The resins in question are therefore preferably diglycidyl ethers of bisphenol-A (DGEBA), of bisphenol-F, and of bisphenol-A/F. Liquid resins of these kinds are available for example as Araldite® GY 250, Araldite® PY 304, Araldite® GY 282 (Huntsman) or D.E.R.™ 331 or D.E.R.™ 330 (Dow) or Epikote 828 (Hexion).

Additionally, suitable as liquid epoxy resins A are what are called novolaks. These resins have in particular the following formula: methyl and z = 0 to 7.

More particularly these are phenol or cresol novolaks (R2 = CH2).

Epoxy resins of these kinds are available commercially under the trade name EPN or ECN and also Tactix®556 from Huntsman, or among the D.E.N.™ product series from Dow Chemical.

The fraction of the epoxy resin A is from 30 - 80 wt.-%, based on the total weight of the one-component thermosetting epoxy resin adhesive, preferably from 40 - 70 wt.-%, most preferably 50 - 60 wt.-%.

The thermosetting one-component epoxy resin adhesive comprises 1 .25 - 2.5 wt.-% of heat-expandable microspheres HEM, based on the total weight of the one- component thermosetting epoxy resin adhesive.

Preferably, the amount of the heat-expandable microspheres HEM is 1 .5 - 2.5 wt.-%, most preferably 1.75 - 2.25 wt.-%, based on the total weight of the one-component thermosetting epoxy resin adhesive. When the heat-expandable microspheres having such properties are heated, the contained substance expands in volume and the resin material constituting the outer shell softens, so that capsules (expanded capsules) expanded by internal pressure can be obtained.

Preferably, the heat-expandable microspheres HEM contain a liquid compound inside an outer shell made of a resin material (resin composition).

The liquid compound which is the inclusion substance constituting the heatexpandable microsphere preferably has a boiling point (atmospheric pressure condition) equal to or lower than the softening temperature of the resin material constituting the outer shell of the heat-expandable microsphere.

Preferably, the liquid compound is selected from the list consisting of n-butane, isopentane, cyclobutane, n-pentane, isopentane, cyclopentane, n-hexane, 2- methylpentane, 2,2-dimethylbutane, cyclohexane, n-heptane, cycloheptane, n-octane, cyclooctane and hydrocarbons, preferably hydrocarbons, more preferably hydrocarbons having 1 to 5 carbon atoms, most preferably hydrocarbons having 4 to 5 carbon atoms.

The liquid compound may be only one kind or two or more kinds. The liquid compound is preferably a hydrocarbon, and particularly preferably contains a low boiling point hydrocarbon having 4 to 5 carbon atoms.

The resin material constituting the outer shell preferably has thermoplasticity. Preferably, the resin material contains a structural unit derived from the list consisting of acrylonitrile, methacrylonitrile, acrylic acid alkyl ester, methacrylic acid alkyl ester, vinyl chloride, vinylidene chloride, vinyl acetate and aromatic vinyl compound, preferably acrylonitrile. More preferably, the resin material is a acrylonitrile-based copolymer. Preferably, the shape of the heat-expandable microspheres HEM is spherical or elliptical.

The heat-expandable microspheres HEM have a mean particle size D (0.5) between 30 - 75 pm, preferably between 30 - 60 pm, most preferably between 35 - 50 pm.

The term “mean particle size” here preferably relates to the D (0.5) value of the cumulative volume distribution curve, in which 50% by volume of the particles have a particle size that is smaller than the value. The mean particle size or the D (0.5) value is preferably determined by laser diffractometry.

The expansion-initiation temperature (T _s ) of the heat-expandable microspheres HEM is between 90 °C - 115 °C, preferably between 95 °C - 115 °C, most preferably between 100 °C - 115 °C.

Preferably, the maximum expansion temperature (Tmax) of the heat-expandable microspheres HEM is between 130 °C - 170 °C, preferably between 140 °C - 165 °C, most preferably between 150 °C - 165 °C.

Preferably, the expansion-initiation temperature (T _s ) and the maximum expansion temperature (Tmax) are determined with a dynamic mechanical analysis (DMA Q800, manufactured by TA Instruments), more preferably in the following way:

In an aluminum cup 4.8 mm deep and 6.0 mm in diameter (5.65 mm in inside diameter), 0.5 mg of heat-expandable microspheres are placed, and the cup is covered with an aluminum cap 0.1 mm thick and 5.6 mm in diameter to prepare a sample.

The sample is subjected to the pressure of 0.01 N with the compression unit of the device, and the height of the sample is measured. The sample is then heated at temperatures elevating at a rate of 10 °C/min in the temperature range from 20 to 300 °C, being subjected to the pressure of 0.01 N with the compression unit, and the vertical change of the position of the compression unit is measured. The temperature at which the compression unit starts to change its position to the positive direction is determined as the expansion-initiation temperature (Ts), and the temperature at which the compression unit indicats the greatest change is determined as the maximum expansion temperature (Tmax). Preferred thermally expandable microsphere HEM are commercially available as "FN- 78D": microspheres containing hydrogen carbide (acrylonitrile-based copolymer shell type), product name: Matsumoto Microsphere FN-78D (manufactured by Matsumoto Yushi-Seivaku Co., Ltd.), average particle diameter: 35 - 50 mm, expansion initiation temperature (T _s ): 100 - 115 °C, maximum expansion temperature (Tmax): 150 - 165 °C.

Preferably, the thermosetting one-component epoxy resin adhesive further comprises at least one epoxy-bearing reactive diluent G. Such reactive diluents are known to those skilled in the art. Preferred examples of epoxy-bearing reactive diluents are:

- glycidyl ethers of monofunctional saturated or unsaturated, branched or unbranched, cyclic or open-chain C4-C30 alcohols, e.g. butanol glycidyl ether, hexanol glycidyl ether, 2-ethylhexanol glycidyl ether, allyl glycidyl ether, tetrahydrofurfuryl and furfuryl glycidyl ether, trimethoxysilyl glycidyl ether etc.;

- glycidyl ethers of difunctional saturated or unsaturated, branched or unbranched, cyclic or open-chain C2-C30 alcohols, for example ethylene glycol glycidyl ether, butanediol glycidyl ether, hexanediol glycidyl ether, octanediol glycidyl ether, cyclohexanedimethanol diglycidyl ether, neopentyl glycol diglycidyl ether etc.;

- glycidyl ethers of tri- or polyfunctional, saturated or unsaturated, branched or unbranched, cyclic or open-chain alcohols, such as epoxidized castor oil, epoxidized trimethylolpropane, epoxidized pentaerythritol or polyglycidyl ethers of aliphatic polyols such as sorbitol, glycerol or trimethylolpropane etc.;

- glycidyl ethers of phenol compounds and aniline compounds, such as phenyl glycidyl ether, cresyl glycidyl ether, p-tert-butylphenyl glycidyl ether, nonylphenol glycidyl ether, 3-n-pentadecenyl glycidyl ether (from cashewnutshell oil), N, N-diglycidylaniline, etc.;

- epoxidized amines such as N,N-diglycidylcyclohexylamine etc.;

- epoxidized mono- or dicarboxylic acids, such as glycidyl neodecanoate, glycidyl methacrylate, glycidyl benzoate, diglycidyl phthalate, tetrahydrophthalate and hexahydrophthalate, diglycidyl esters of dimeric fatty acids etc.; - epoxidized di- or trifunctional, low to high molecular weight polyether polyols, such as polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether etc.

Particular preference is given to hexanediol diglycidyl ether, cresyl glycidyl ether, p- tert-butylphenyl glycidyl ether, polypropylene glycol diglycidyl ether and polyethylene glycol diglycidyl ether.

Preferably, the fraction of the epoxy-bearing reactive diluent G is from 1 - 10 wt.-%, 1 .5 - 7.5 wt.-%, 2 - 5 wt.-%, more preferably 2 - 3 wt.-%, based on the total weight of the one-component thermosetting epoxy resin adhesive.

The thermosetting one-component epoxy resin adhesive further comprises at least one latent hardener B for epoxy resins. Latent hardeners are substantially inert at room temperature and are activated by elevated temperature, typically at temperatures of 70°C or more, thereby initiating the curing reaction. The customary latent hardeners for epoxy resins can be used. Preference is given to a latent epoxy resin hardener B containing nitrogen.

The latent hardener B is preferably selected from dicyandiamide, guanamines, guanidines, aminoguanidines and derivatives thereof, substituted ureas, imidazoles and amine complexes, preferably dicyandiamide.

The latent hardener B is preferably used in a stoichiometric amount based on the epoxy groups in the composition. The molar ratio of the epoxy groups to the active hydrogen of the latent hardener B is preferably 0.8 to 1.2, in particular 0.9 to 1.1 , preferably 0.95 to 1 .05.

The fraction of the latent hardener B is preferably 0.5 to 12 wt%, more preferably 1 to 8 wt%, more particularly 2-6 wt%, based on the total weight of the epoxy resin adhesive. The thermosetting one-component epoxy resin adhesive preferably further comprises at least one accelerator C for epoxy resins.

Such accelerating curing agents are preferably substituted ureas, for example 3-(3- chloro-4-methylphenyl)-1 ,1 -dimethylurea (chlortoluron) or phenyldimethylureas, especially p-chlorophenyl-N,N-dimethylurea (monuron), 3-phenyl-1 ,1 -dimethylurea (fenuron) or 3,4-dichlorophenyl-N,N-dimethylurea (diuron). In addition, it is possible to use compounds from the class of the imidazoles, such as 2-isopropylimidazole or 2- hydroxy-N-(2-(2-(2-hydroxyphenyl)-4,5-dihydroimidazol-1-yl)e thyl)benzamide, imidazolines, trihalide complexes, preferably BF3 complexes, blocked amines and encapsulated amines.

Preferably, the accelerator C for epoxy resins is selected from the list consisting of substituted ureas, imidazoles, imidazolines and blocked amines, preferably substituted ureas.

More preferably, the accelerator C for epoxy resins is selected from the list consisting of substituted ureas and blocked amines, especially when the latent hardener B is a guanidine, especially dicyandiamide.

Most preferably, the latent hardener B is a guanidine, especially dicyandiamide, and the one-component thermosetting epoxy resin composition additionally includes an accelerator C for epoxy resins, selected from the list consisting of substituted ureas and blocked amines, especially substituted ureas.

Preferably, the fraction of the accelerator C for epoxy resins is from 0.05 - 2 wt.-%, 0.1 - 1 wt.-%, 0.15 - 0.5 wt.-%, more preferably 0.2 - 0.3 wt.-%, based on the total weight of the one-component thermosetting epoxy resin adhesive.

The one-component thermosetting epoxy resin adhesive comprises at least one toughness improver D. The toughness improvers D may be solid or liquid. n

The fraction of toughness improver D is from 5 - 40 wt.-%, preferably from 7.5 - 35 wt.- %, 10 - 30 wt.-%, more preferably 15 - 25 wt.-%, based on the total weight of the epoxy resin adhesive. More particularly the toughness improver D is selected from the group consisting of terminally blocked polyurethane polymers D1 , liquid rubbers D2 and core-shell polymers D3. With preference the toughness improver D is selected from the group consisting of terminally blocked polyurethane polymers D1 and liquid rubbers D2, most preferably a terminally blocked polyurethane polymer D1.

Where the toughness improver D is a terminally blocked polyurethane polymer D1 , it is preferably a terminally blocked polyurethane prepolymer of the formula (I).

In this formula, R ¹ is a p-valent radical of a linear or branched polyurethane prepolymer terminated by isocyanate groups, following the removal of the terminal isocyanate groups, and p has a value of 2 to 8.

Moreover, R ² independently at each occurrence is a substituent which is selected from the group consisting of

In these formulae, R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently of one another are an alkyl or cycloalkyl or aralkyl or arylalkyl group, or R ⁵ together with R ⁶ , or R ⁷ together with R ⁸ , forms part of a 4- to 7-membered ring which is optionally substituted.

Moreover, R ⁹ ’ and R ¹⁰ each independently of one another are an alkyl or aralkyl or arylalkyl group or are an alkyloxy or aryloxy or aralkyloxy group, and R ¹¹ is an alkyl group.

R ¹² , R ¹³ and R ¹⁴ each independently of one another are an alkylene group having 2 to 5 carbon atoms, which optionally has double bonds or is substituted, or are a phenylene group or are a hydrogenated phenylene group.

R ¹⁵ , R ¹⁶ and R ¹⁷ each independently of one another are H or are an alkyl group or are an aryl group or an aralkyl group, and R ¹⁸ is an aralkyl group or is a mono- or polycyclic, substituted or unsubstituted aromatic group which optionally has aromatic hydroxyl groups.

Lastly, R ⁴ is a radical of an aliphatic, cycloaliphatic, aromatic or araliphatic epoxide containing a primary or secondary hydroxyl group, after the removal of the hydroxyl and epoxide groups, and m has a value of 1 , 2 or 3.

R ¹⁸ should be considered to comprise, in particular, on the one hand, phenols or polyphenols, more particularly bisphenols, after removal of a hydroxyl group. Preferred examples of such phenols and bisphenols are, in particular, phenol, cresol, resorcinol, pyrocatechol, cardanol (3-pentadecenylphenol (from cashew nut shell oil)), nonylphenol, phenols reacted with styrene or with dicyclopentadiene, bisphenol A, bisphenol F and 2 ,2’-diallylbisphenol A. R ¹⁸ should be considered on the other hand to comprise, in particular, hydroxybenzyl alcohol and benzyl alcohol after removal of a hydroxyl group.

If R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ⁹ ’, R ¹⁰ , R ¹¹ , R ¹⁵ , R ¹⁶ or R ¹⁷ is an alkyl group, this group more particularly is a linear or branched C1-C20 alkyl group.

If R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ⁹ ’, R ¹⁰ , R ¹⁵ , R ¹⁶ , R ¹⁷ or R ¹⁸ is an aralkyl group, this moiety is more particularly an aromatic group bonded via methylene, more particularly a benzyl group.

If R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ⁹ ’ or R ¹⁰ is an alkylaryl group, this group is more particularly Ci to C20 alkyl group bonded via phenylene, such as tolyl or xylyl, for example.

The radicals R ² are preferably the substituents of the formulae _or

A preferred substituent of the formula -caprolactam after removal of the NH proton.

_ _ D ¹⁸

Preferred substituents of the formula are monophenols or polyphenols, more particularly bisphenols, after removal of a phenolic hydrogen atom. Particularly preferred examples of such radicals R ² are radicals which are selected from the group consisting of

The radical Y in these formulae is a saturated, aromatic or olefinically unsaturated hydrocarbyl radical having 1 to 20 carbon atoms, more particularly having 1 to 15 carbon atoms. Preferred as Y are, in particular, allyl, methyl, nonyl, dodecyl, phenyl, alkyl ether, carboxylic ester or an unsaturated C15 alkyl radical having 1 to 3 double bonds.

Most preferably R ² is .

The terminally blocked polyurethane prepolymer of the formula (I) is prepared from the linear or branched polyurethane prepolymer, terminated by isocyanate groups, with one or more isocyanate-reactive compounds R ² H. If two or more such isocyanatereactive compounds are used, the reaction may take place sequentially or with a mixture of these compounds.

The reaction preferably takes place such that the one or more isocyanate-reactive compounds R ² H are used stoichiometrically or in a stoichiometric excess, in order to ensure that all of the NCO groups have undergone reaction. The polyurethane prepolymer having isocyanate end groups on which R ¹ is based may be prepared from at least one diisocyanate or triisocyanate and also from a polymer QPM having terminal amino, thiol or hydroxyl groups and/or from an optionally substituted polyphenol Qpp.

Suitable diisocyanates are aliphatic, cycloaliphatic, aromatic or araliphatic diisocyanates, especially commercial products such as methylenediphenyl diisocyanate (MDI), hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), tolidine diisocyanate (TODI), isophorone diisocyanate (IPDI), trimethylhexamethylene diisocyanate (TMDI), 2,5- or 2,6-bis(isocyanatomethyl)bicyclo[2.2.1]heptane, naphthalene 1 ,5-diisocyanate (NDI), dicyclohexylmethyl diisocyanate (H12MDI), p- phenylene diisocyanate (PPDI), m-tetramethylxylylene diisocyanate (TMXDI), etc., and also their dimers. Preferred are HDI, IPDI, MDI or TDI.

Suitable triisocyanates are trimers or biurets of aliphatic, cycloaliphatic, aromatic or araliphatic diisocyanates, more particularly the isocyanurates and biurets of the diisocyanates described in the preceding paragraph. It is of course also possible to use suitable mixtures of di- or triisocyanates.

Particularly suitable as polymers QPM having terminal amino, thiol or hydroxyl groups are polymers QPM having two or three terminal amino, thiol or hydroxyl groups.

The polymers QPM advantageously have an equivalent weight of 300-6000, more particularly of 600-4000, preferably of 700-2200 g/equivalent of NCO-reactive groups.

Preferred polymers QPM are polyols having average molecular weights of between 600 and 6000 daltons, selected from the group consisting of polyethylene glycols, polypropylene glycols, polyethylene glycol-polypropylene glycol block polymers, polybutylene glycols, hydroxyl-terminated polybutadienes, hydroxyl-term inated butadiene-acrylonitrile copolymers, and mixtures thereof.

Especially preferred as polymers QPM are a,®-dihydroxypolyalkylene glycols having C2-C6 alkylene groups or having mixed C2-C6 alkylene groups, which are terminated with amino, thiol or, preferably, hydroxyl groups. Particularly preferred are polypropylene glycols or polybutylene glycols. Further particularly preferred are hydroxyl-group-terminated polyoxybutylenes.

Especially suitable as polyphenol Qpp are bis-, tris- and tetraphenols. The term refers not only to pure phenols, but instead also, where appropriate, to substituted phenols. The nature of the substitution can be very diverse. Understood more particularly by this is substitution directly on the aromatic ring system to which the phenolic OH group is bonded. Phenols, moreover, are not only monocyclic aromatics, but also polycyclic or fused aromatic or heteroaromatics, having the phenolic OH group directly on the aromatic or heteroaromatic moiety.

In one preferred embodiment, the polyurethane prepolymer is prepared from at least one diisocyanate or triisocyanate and also from one polymer QPM having terminal amino, thiol or hydroxyl groups. The polyurethane prepolymer is prepared in a manner known to the person skilled in the polyurethane art, more particularly by using the diisocyanate or triisocyanate in a stoichiometric excess in relation to the amino, thiol or hydroxyl groups of the polymer QPM.

The polyurethane prepolymer having isocyanate end groups is preferably elastic in nature. It preferably exhibits a glass transition temperature Tg of less than 0°C.

The toughness improver D may be a liquid rubber D2. This may be, for example, a carboxyl-term inated or epoxide-terminated polymer.

In a first embodiment, this liquid rubber may be a carboxyl- or epoxide-terminated acrylonitrile/butadiene copolymer or a derivative thereof. Liquid rubbers of this kind are available commercially, for example, under the name Hypro/Hypox® CTBN and CTBNX and ETBN from Emerald Performance Materials. Suitable derivatives are, in particular, elastomer-modified prepolymers containing epoxide groups, of the kind marketed commercially under the product line Polydis®, especially from the product line Polydis® 36.., by the company Struktol® (Schill+Seilacher Group, Germany), or under the product line Albipox (Evonik, Germany). In a second embodiment, this liquid rubber may be a polyacrylate liquid rubber, which is fully miscible with liquid epoxy resins and which separates only when the epoxy resin matrix is cured, to form microdroplets. Liquid polyacrylate rubbers of this kind are available, for example, under the designation 20208-XPA from Dow.

It is of course also possible to use mixtures of liquid rubbers, more particularly mixtures of carboxyl- or epoxide-terminated acrylonitrile/butadiene copolymers or of derivatives thereof.

The toughness improver D in a third embodiment may be a core-shell polymer D3. Core-shell polymers consist of an elastic core polymer and a rigid shell polymer. Particularly suitable core-shell polymers are composed of a core of elastic acrylate polymer or butadiene polymer, surrounded by a rigid shell of a rigid thermoplastic polymer. This core-shell structure either forms spontaneously by separation of a block copolymer, or is dictated by the polymerization regime as latex or suspension polymerization with subsequent grafting. Preferred core-shell polymers are those known as MBS polymers, which are available commercially under the trade name Clearstrength™ from Arkema, Paraloid™ from Dow or F-351 ™ from Zeon.

With particular preference the one-component thermosetting epoxy resin adhesive comprises terminally blocked polyurethane polymers D1 , most preferably only terminally blocked polyurethane polymers D1.

In one preferred embodiment, the one-component thermosetting epoxy resin adhesive further comprises at least one filler F. Preference here is given to mica, talc, kaolin, wollastonite, feldspar, syenite, chlorite, bentonite, montmorillonite, calcium carbonate (precipitated or ground), dolomite, quartz, silicas (fumed or precipitated), cristobalite, calcium oxide, aluminium hydroxide, magnesium oxide, hollow ceramic beads, hollow glass beads, hollow organic beads, glass beads, colour pigments. Particularly preferred are fillers selected from the group consisting of calcium carbonate, calcium oxide and fumed silicas. The total fraction of the overall filler F is advantageously 5 - 40 weight-%, preferably 10 - 30 weight-%, 10 - 25 weight-%, most preferably 10 - 20 weight-%, based on the total weight of the epoxy resin adhesive.

The one-component thermosetting epoxy resin adhesive may comprise further constituents, especially stabilizers, particularly heat and/or light stabilizers, plasticizers, solvents, dyes and pigments, corrosion inhibitors, surfactants, defoamers and adhesion promoters.

The one-component thermosetting epoxy resin adhesive has a viscosity of 500 to 5000 Pas at 25°C. Preferably, the viscosity is from 500 to 2000 Pas, 500 to 1500 Pas, preferably 500 to 1300 Pas at 25°C. The viscosity is determined oscillographically by means of a rheometer with heatable plate (MCR 301 , AntonPaar) (slot 1000 pm, measuring plate diameter: 25 mm (plate/plate), deformation 0.01 at 5 Hz, temperature: 25°C).

A particularly preferred thermosetting one-component epoxy resin adhesive comprises:

-40 - 70 wt.-%, preferably 50 - 60 wt.-%, based on the total weight of the one- component thermosetting epoxy resin adhesive, of at least one epoxy resin A having on average more than one epoxide group per molecule, preferably a liquid epoxy resin;

-1 .5 - 2.5 wt.-%, preferably 1 .75 - 2.25 wt.-%, of heat-expandable microspheres HEM, based on the total weight of the one-component thermosetting epoxy resin adhesive, with an expansion-initiation temperature (T _s ) between 95 °C - 115 °C, preferably between 100 °C - 115 °C, and a mean particle size D (0.5) between 30 - 60 pm, preferably between 35 - 50 pm;

- preferably 2 - 5 wt.-%, more preferably 2 - 3 wt.-%, based on the total weight of the one-component thermosetting epoxy resin adhesive, of at least one epoxybearing reactive diluent G;

-1-8 wt%, preferably 2-6 wt%, based on the total weight of the one-component thermosetting epoxy resin adhesive, of at least one latent hardener B for epoxy resins, more particularly dicyandiamide; - preferably 0.05 - 2 wt.-%, more preferably 0.2 - 0.3 wt-%, based on the total weight of the one-component thermosetting epoxy resin adhesive, of at least one accelerator C for epoxy resins;

-7.5 - 35 wt.-%, preferably 15 - 25 wt.-%, based on the total weight of the one- component thermosetting epoxy resin adhesive, of at least one toughness improver D, preferably a terminally blocked polyurethane polymers D1 ;

-preferably 5 - 40 weight-%, more preferably 10 - 20 weight-%, based on the total weight of the one-component thermosetting epoxy resin adhesive, of a filler F selected from the group consisting of calcium carbonate, calcium oxide and fumed silicas.

Preferably, the thermosetting one-component epoxy resin adhesive has a viscosity of 500 to 2000 Pas, 500 to 1500 Pas, preferably 500 to 1300 Pas at 25°C.

It may further be advantageous if the preferred one-component thermosetting epoxy resin adhesive consists to an extent of more than 80 weight%, preferably more than 90 weight%, more particularly more than 95 weight%, especially preferably more than 98 weight%, most preferably more than 99 weight%, based on the total weight of the epoxy resin adhesive, of the aforementioned constituents.

It is advantageous when the cured one-component thermosetting epoxy resin adhesive of the invention has the following properties:

-Lap shear strength determined according to SAE J 1523, preferably as described in the experimental section: > 5.5 MPa, preferably > 6.0 MPa, most preferably > 6.25 MPa, after curing for 30 min at 180 °C; and

-T-peel strength determined according to ASTM D1876, preferably as described in the experimental section: > 1.4 MPa, preferably > 1.5 MPa, most preferably > 1.6 MPa, after curing for 30 min at 180 °C; and

-expansion, preferably determined as described in the experimental section: 100 - 400 %, preferably 150 - 350 %, most preferably 200 - 300 %, after curing for 30 min at 180 °C; and Adhesives of this kind are needed for the bonding of heat-stable materials. By heatstable materials are meant materials which are dimensionally stable, at least during the cure time, at a curing temperature of 100-220°C, preferably 120-200°C. They are, more particularly, metals and plastics such as ABS, polyamide, polyphenylene ethers, compounded materials such as SMC, unsaturated polyesters GRP and composite epoxide or acrylate materials. Particularly heat-stable plastics, furthermore, are polysulfones or polyethersulfones.

A preferred application is when at least one material is a metal.

Considered a particularly preferred use is the adhesive bonding of identical or different metals, particularly in body construction within the automotive industry. The preferred metals are, in particular, steel, especially electrolytically galvanized, hot dip galvanized, oiled steel, Bonazinc-coated steel, and subsequently phosphated steel, and also aluminium, particularly in the versions typically encountered in car making.

Such an adhesive is especially contacted first with the materials to be bonded at a temperature of between 10°C and 80°C, especially between 10°C and 60°C, and later cured at a temperature of typically 130-220°C, preferably 140-180°C, more preferably 150-170°C.

A further aspect of the present invention relates to a method of bonding heat-stable substrates, comprising the steps of: i) applying a heat-curing epoxy resin composition as described in detail above to the surface of a heat-stable substrate S1 , especially of a metal; ii) contacting the heat-curing epoxy resin composition applied with the surface of a further heat-stable substrate S2, especially of a metal; iii) heating the composition to a temperature of 100-220°C, especially of 120- 210°C, preferably between 130 and 190°C, 140 and 180°C more preferably between 150 and 170°C.

The substrate S2 here consists of the same material as or a different material than the substrate S1 . The substrates S1 and/or S2 are especially the aforementioned metals and plastics.

Preferably, in step iii) heating the composition to a temperature of 100-220°C, especially of 120-210°C, preferably between 130 and 190°C, 140 and 180°C more preferably between 150 and 170°C, the composition is left at the aforementioned temperature for 10 min - 6 h, 10 min - 2 h, 10 min - 60 min, 10 min - 30 min, 10 min - 20 min, more preferably 10 min - 15 min.

Such a method of bonding heat-stable materials results in an adhesive-bonded article. Such an article is preferably a motor vehicle or part of a motor vehicle.

A further aspect of the present invention is therefore an adhesive-bonded article obtained from the aforementioned method. In addition, the compositions of the invention are suitable not just for automobile construction but also for other fields of use. Particular mention should be made of related applications in the transportation sector such as ships, trucks, buses or rail vehicles, or in the construction of consumer goods, for example washing machines.

The materials adhesive-bonded by means of a composition of the invention are used at temperatures between typically 120°C and -40°C, preferably between 100°C and - 40°C, especially between 80°C and -40°C.

One particularly preferred use of the thermosetting epoxy resin adhesive of the invention is the use thereof as a thermosetting body construction adhesive in vehicle construction.

A further particularly preferred use of the thermosetting epoxy resin adhesive of the invention is the use thereof for adhesively bonding metal structures.

A further aspect of the present invention therefore relates to a cured epoxy resin adhesive which is obtained by the heating of a thermosetting epoxy resin adhesive, described in detail above, to a temperature of 100-220°C, preferably 120-210°C. After passing through a CEC bath, the bodywork enters a CEC oven, where the CEC coating material is baked at a temperature of typically 160 to 190°C. The thermosetting composition reacts here chemically with crosslinking, leading to the curing of the adhesive.

The invention further encompasses the use of heat-expandable microspheres HEM, as described before, for increasing the lap shear strength determined according to SAE J 1523 and the peel strength determined according to ASTM D1876, preferably as described in the experimental section, of a one-component thermosetting epoxy resin adhesive, more particularly of a thermosetting epoxy resin adhesive in vehicle construction and sandwich panel construction. This is preferably a thermosetting epoxy resin adhesive as described above. The increase in the lap shear strength and the T- peel strength relates to a comparison with one-component thermosetting epoxy resin adhesives containing heat-expandable microspheres HEM but not of the kind of the aforementioned heat-expandable microspheres HEM. The nature and amount of the heat-expandable microspheres HEM used is preferably as described above, and in particular the natures and amounts identified above as being preferred are also used with preference.

The invention is elucidated further in the text below by means of examples which, however, are not intended to restrict the invention in any way.

Examples

Raw materials used for preparing the impact modifier D1 and the reference compositions R1-13 and the inventive compositions E1-2 were as follows:

Table 1

Preparation of the toughness improver (D1)

300.0 g of PolyTHF®2000 (BASF) and 56.7 g of hexamethylene diisocyanate (HDI) were mixed together with 0.04 g of dibutyltin dilaurate (DBTL) in a vessel. After mixing had taken place under reduced pressure at 60°C for 2 hours, an NCO content of 4.1 % was measured. The NCO-terminated polyurethane polymer thus formed was admixed with 39.3 g of phenol (Aldrich), stirred further under reduced pressure at 100°C for 3 hours and stored at 70°C for 12 hours. Thereafter the NCO content measured was 0%.

Preparation of the base composition

Table 2

The composition as indicated in Table 2 was used as base formulation and the amount of microspheres as indicated in table 3 was added. The amount indicated in table 3 is the amount of microspheres in the final compositions E1-2, respectively R1-13. For example, in E2, 2 wt-% of microspheres were added to 98 wt.-% of the base compositions shown above to obtain the composition E2.

Viscosity

The viscosity of the compositions Ref, and Ex.1-Ex.3 were measured and found to be between 500 to 1300 Pas at 25°C, the viscosity being determined oscillographically by means of a rheometer with heatable plate (MCR 301 , AntonPaar) (slot 1000 pm, measuring plate diameter: 25 mm (plate/plate), deformation 0.01 at 5 Hz, temperature: Adhesion Strength (Lap shear strength)

The Lap shear strength was determined according to SAE J 1523 with 0.8 mm-thick hot dip galvanized steel (HDG) coupons, 0.25 mm adhesive bondline thickness, 13 mm length overlap, 13 mm/min pull rate. The samples were cured for 30 min at 180 °C.

T-Peel test

The T-peel strength was determined according to ASTM D1876 with 90 degree bend with 0.8 mm-thick 25mm x 100mm high strength hot dip galvanized steel (HDG) coupons, 0.25 mm adhesive bondline thickness, 76.2 mm length overlap, 127 mm/min pull rate. The samples were cured for 30 min at 180 °C.

Expansion

The Expansion is quantified for each sample by measuring the density of a bead of test material with approximately 5 mm radius and a length of 50 mm before and after expansion. The densities were determined according to DIN EN ISO 1183 using the water immersion method (Archimedes principle) in deionized water and a precision balance to measure the mass. The test materials were expanded at 180°C for 15 minutes.

Crack formation

The degree of crack formation in the expanded materials described above was quantified for each sample by assessing the surface structure of the cured expanded material using the following rating system: no open pores on surface structure, no cracks in the surface visible some open pores on surface structure, no cracks in the surface visible cracks in the surface visible

Testing examples

The base formulation used for epoxy resin adhesives was a formulation as described below. The viscosity of the compositions R1-13 and E1-2 were measured and found to be between 500 to 1300 Pas at 25°C, the viscosity being determined oscillographically by means of a rheometer with heatable plate (MCR 301 , AntonPaar) (slot 1000 pm, measuring plate diameter: 25 mm (plate/plate), deformation 0.01 at 5 Hz, temperature:

Table 3, n.d. = not determined