EP2268694A1 - Polyurethane polymer based on an amphiphilic block copolymer and its use as impact modifier - Google Patents

Abstract

The present invention relates to novel impact modifiers which are obtained by reaction of amphiphilic block copolymers. These impact modifiers are particularly suitable for use in heat-curing epoxy resin adhesives.

Description

 BASED ON AMPHIPHILEM BLOCK COPOLYMER

POLYURETHANE POLYMER AND ITS USE AS IMPACTORITY MODIFIER

Technical area

The invention relates to the field of impact modifiers and the field of thermosetting epoxy resin compositions.

Background Art Impact modifiers have long been used to improve the strength of adhesives in the event of sudden impact. In particular, epoxy resin compositions generally have high mechanical strengths, but are very brittle, that is, in a sudden force, such as occurs in a collision of vehicles breaks the cured epoxy resin and leads to destruction of the composite.

Proposals have long been made to increase impact strength through the use of impact modifiers. Liquid rubbers have long been used for toughening. For example, liquid rubbers based on acrylonitrile / butadiene copolymers, such as those available under the name Hypro ™ (formerly Hycar®), have been used.

EP 0 338 985 A2 describes impact-resistant epoxy resin compositions which, in addition to liquid rubbers based on acrylonitrile / butadiene copolymers, additionally comprise liquid rubbers based on polyurethane prepolymers which are terminated with a phenol or a lactam.

WO 2005/007766 A1 discloses epoxy resin compositions which contain a reaction product of an isocyanate-terminated prepolymer and a blocking agent which is selected from the group bisphenol, phenol, benzyl alcohol, aminophenol or benzylamine. However, such epoxy resin compositions have weaknesses in low temperature impact strength (<0 ° C).

WO 03/093387 A1 discloses impact-resistant epoxy resin compositions which contain adducts of dicarboxylic acids with glycidyl ethers or of bis (aminophenyl) sulfone isomers or aromatic alcohols with glycidyl ethers. However, these compositions also have deficiencies in low temperature impact strength (<0 ° C).

Recently, e.g. in WO 2006/052725 A1, WO 2006/052726 A1, WO 2006/052727 A1, WO 2006/052728 A1, WO 2006/052729 A1, WO 2006/052730 A1, WO 2005/097893 A1, proposed amphiphilic block copolymers for To use epoxy resin compositions.

However, it has been shown that these impact modifiers act, but that this increase in impact strength, in particular that of low-temperature impact strength, is still insufficient.

Presentation of the invention

Object of the present invention is therefore to provide new impact modifiers available, which have an improvement in impact resistance, especially at low temperatures. Surprisingly, it has now been found that this task is accomplished by

Impact modifiers according to claim 1 can be solved.

It has been found that these impact modifiers are best suited for use in thermosetting epoxy resin adhesives.

In particular, it has been found that combinations of different impact modifiers according to the invention with one another and / or with other impact modifiers are particularly advantageous. It has been shown that by using impact modifiers the

Glass transition temperature (Tg) of the cured matrix are not affected or not significantly negatively. It can be with epoxy resins easily Tg of about 100 ⁰ C at times even above 125 ° C, to achieve.

Further aspects of the present invention are the subject of further independent claims. Particularly preferred embodiments are the subject of the dependent claims. Ways to carry out the invention

The present invention relates in a first aspect to an impact modifier which is an isocyanate group-containing polyurethane polymer PU1 or a reaction product PU2 of this polyurethane product PU1 with at least one NCO-reactive compound. The isocyanate group-containing polyurethane polymer PU1 is in this case prepared from at least one polyisocyanate and at least one amphiphilic block copolymer which has at least one hydroxyl group, and optionally at least one compound having at least two NCO-reactive groups.

Throughout the specification herein, the prefix "poly" in "polyisocyanate", "polyol", "polyphenol" and "polymercaptan" refers to molecules that formally contain two or more of the respective functional groups present

Document an addition to a plastic matrix, in particular an epoxy resin, understood that even at low surcharges, in particular from 0.1 to 35 wt .-%, preferably from 0.5 to 15 wt .-%, causes a significant increase in the toughness of the cured matrix and thus is able to absorb higher bending, tensile, impact or impact stress before the matrix breaks or breaks.

As amphiphilic block copolymer is understood in the present document, a copolymer containing at least one block segment which is miscible with epoxy resin, and at least one block segment which is immiscible with epoxy resin contains. In particular, amphiphilic block copolymers are those disclosed in WO 2006/052725 A1, WO 2006/052726 A1, WO 2006/052727 A1, WO 2006/052728 A1,

WO 2006/052729 A1, WO 2006/052730 A1, WO 2005/097893 A1, the content of which is hereby incorporated by reference. Examples of epoxy resin-miscible block segments are particularly

Polyethylene oxide, polypropylene oxide, poly (ethylene oxide-co-propylene oxide) and poly (ethylene oxide-ran-propylene oxide) blocks and mixtures thereof. Examples of block segments which are immiscible in epoxy resin are, on the one hand, in particular polyether blocks prepared from alkylene oxides which have at least 4 C atoms, preferably butylene oxide, hexylene oxide and / or dodecylene oxide. Especially preferred as such polyether blocks are polybutylene oxide, polyhexylene oxide and poly-dodecylene oxide blocks and mixtures thereof.

On the other hand, examples of block segments which are immiscible in epoxy resin are polyethylene, polyethylene-propylene, polybutadiene, polyisoprene, polydimethylsiloxane and polyalkyl methacrylate blocks and mixtures thereof.

In one embodiment, the at least one hydroxyl group-containing amphiphilic block copolymer is a block copolymer of ethylene oxide and / or propylene oxide and at least one further alkylene oxide having at least 4 C atoms, preferably from the group consisting of butylene oxide, hexylene oxide and dodecylene oxide.

In another preferred embodiment, the amphiphilic block copolymer having at least one hydroxyl group is selected from the group consisting of poly (isoprene-block-ethylene oxide) block copolymers (PI-b-PEO), poly (ethylene-propylene-b-ethylene oxide) block copolymers (PEP-b - PEO), poly (butadiene-b-ethylene oxide) block copolymers (PB-b-PEO), poly (isoprene-b-ethylene oxide-b-isoprene) block copolymers (PI-b-PEO-PI), poly ( isoprene-b-ethylene oxide-methyl methacrylate) block copolymers (PI-b-PEO-b-PMMA) and poly (ethylene oxide) -b-poly (ethylene-old-propylene) block copolymers (PEO-PEP).

The amphiphilic block copolymers may be present in particular as diblock, triblock or tetrablock. In multiblocks, ie in particular in Trioder tetrablocks, these may be linear or branched, in particular as a star block (star block) present. The preparation of the amphiphilic block copolymers is known to those skilled in the art, for example from Macromolecules 1996, 29, 6994-7002 and Macromolecules 2000, 33, 9522-9534 and J. Polym. Be. Part B: Polym. Phys. 2007, 45, 3338-3348, the disclosure of which is hereby incorporated by reference Reference is known. The amphiphilic block copolymer has at least one hydroxyl group. Depending on the preparation method, the amphiphilic block copolymer may have one or more hydroxyl groups.

If, for example, the polymerization of alkylene oxides is started with methanol and terminated with acid, an amphiphilic block copolymer having a hydroxyl group is formed.

If, however, with a diol, e.g. Ethylene glycol, started, produces an amphiphilic block copolymer with two hydroxyl groups.

If alcohols having three, four or even more hydroxyl groups are used as initiators, accordingly amphiphilic block copolymers having three, four or even more hydroxyl groups are formed.

The preparation can be carried out, for example, in a sequential synthesis process in which first the first monomer, e.g. Butylene oxide is polymerized with the aid of a starter, followed by the addition of the second monomer, e.g. Ethylene oxide, which is grafted onto the end of the resulting polymer of the first monomer. Thus, for example, using a monol as a starter, an amphiphilic diblock copolymer poly (ethylene oxide) -b-poly (butylene oxide) (PEO-PBO) can be prepared. By using a diol, for example, an amphiphilic tri-block copolymer poly (ethylene oxide) -b-poly (butylene oxide) -poly (ethylene oxide) (PEO-PBO-PEO) is formed.

However, it is also possible first to polymerize a first monomer, for example butylene oxide, with the aid of a starter, followed by the addition of a mixture of two or more monomers, for example a mixture of ethylene oxide and butylene oxide, which is attached to the end of the resulting polymer of the first Monomers are polymerized. Thus, for example, an amphiphilic block copolymer poly (ethylene oxide / butylene oxide) -poly (butylene oxide) -poly (ethylene oxide / butylene oxide) (PEO / BO-PBO-PEO / BO) can be prepared. In addition to the at least one amphiphilic block copolymer which has at least one hydroxyl group, it is also possible to use at least one compound having at least two NCO-reactive groups. In particular, polymers Q _PM with terminal amino, thiol or hydroxyl groups; and / or optionally substituted polyphenols QPP such compound having at least two NCO-reactive groups.

As polymers Q _PM with terminal amino, thiol or hydroxyl groups are particularly suitable polymers QPM having two or three terminal amino, thiol or hydroxyl groups.

The polymers QPM advantageously have an equivalent of 300 - 6OOO ₁ in particular of 600 - 4'00O, preferably 700 - 2200 g / equivalent of NCO-reactive groups.

Suitable polymers Q _PM are polyols, for example the following commercially available polyols or any mixtures thereof:

- Polyoxyalkylenpolyole, also called polyether polyols or oligoetherols, which are polymerization of ethylene oxide, 1, 2-propylene oxide, 1, 2- or 2,3-butylene oxide, oxetane, tetrahydrofuran or mixtures thereof, possibly polymerized with the aid of a starter molecule with two or a plurality of active hydrogen atoms such as water, ammonia or compounds having several OH or NH groups such as 1, 2-ethanediol, 1, 2- and 1, 3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, the isomeric dipropylene glycols and tripropylene glycols, the isomeric butanediols, pentanediols, hexanediols, heptanediols, octanediols, nonanediols, decanediols, undecanediols, 1,3- and 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, 1,1,1-trimethylolethane, 1,1,1 Trimethylolpropane, glycerol, aniline, and mixtures of the aforementioned compounds. Both polyoxyalkylene polyols having a low degree of unsaturation (measured according to ASTM D-2849-69 and expressed in milliequivalents of unsaturation per gram of polyol (mEq / g)) prepared, for example, by means of so-called double metal cyanide complex catalysts (DMC) can be used. Catalysts), as well as polyoxyalkylene polyols having a higher degree of unsaturation, prepared for example with the aid of anionic catalysts such as NaOH, KOH, CsOH or alkali metal alkoxides. Particularly suitable are polyoxyalkylenediols or polyoxyalkylenetriols, in particular polyoxypropylenediols or polyoxypropylenetriols. Especially suitable are polyoxyalkylenediols and -triols having a degree of unsaturation lower than 0.02 meq / g and having a molecular weight in the range from 10 000 to 30 000 g / mol, and also polyoxypropylenediols and -triols having a molecular weight of 400-800 g / mol. Also particularly suitable are so-called ethylene oxide-terminated ("EO" endcapped) polyoxypropylene polyols, the latter being specific polyoxypropylene polyoxyethylene polyols obtained, for example, by pure polyoxypropylene polyols, especially polyoxypropylene diols and triols, upon completion of the polypropoxylation reaction with ethylene oxide alkoxylated and thereby have primary hydroxyl groups.

Hydroxy-terminated polybutadiene polyols, such as those prepared by polymerization of 1,3-butadiene and allyl alcohol or by oxidation of polybutadiene, and their hydrogenation products; Styrene-acrylonitrile or acrylonitrile-methyl methacrylate-grafted polyether polyols, in particular as supplied, for example, by Elastogran under the name Lupranol®;

Polyesterpolyols, also called oligoesterols, prepared for example from dihydric to trihydric alcohols such as 1, 2-ethanediol, diethylene glycol, 1, 2-propanediol, dipropylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1 , 6-hexanediol, neopentyl glycol, glycerol, 1, 1, 1-trimethylolpropane or mixtures of the abovementioned alcohols with organic dicarboxylic acids or their anhydrides or esters such as succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid , Isophthalic acid, terephthalic acid and hexahydrophthalic acid or mixtures of the aforementioned acids, as well as polyester polyols from lactones such as ε-caprolactone.

Polycarbonate polyols as obtainable by reacting, for example, the abovementioned alcohols used to form the polyesterpolyols with dialkyl carbonates, diaryl carbonates or phosgene.

Polyacrylate and polymethacrylate polyols.

Polyhydroxy-functional fats and oils, for example natural fats and oils, in particular castor oil; or by chemical modification of natural lene fats and oils - so-called oleochemical polyols obtained, for example, the epoxy-polyester or epoxy polyether obtained by epoxidation of unsaturated oils and subsequent ring opening with carboxylic acids or alcohols, or polyols obtained by hydroformylation and hydrogenation of unsaturated oils; or from natural fats and oils by degradation processes such as alcoholysis or ozonolysis and subsequent chemical linkage, for example by transesterification or dimerization, of the resulting degradation products or derivatives thereof obtained polyols. Suitable degradation products of natural fats and oils are in particular fatty acids and fatty alcohols and fatty acid esters, in particular the methyl esters (FAME), which can be derivatized by hydroformylation and hydrogenation to hydroxy fatty acid esters, for example.

Polyhydrocarbyl polyols, also called oligohydrocarbonols, such as, for example, polyhydroxy-functional ethylene-propylene, ethylene-butylene or ethylene-propylene-diene copolymers, for example produced by Kraton Polymers, or polyhydroxy-functional copolymers of dienes, such as 1,3-butanediene or diene mixtures and vinyl monomers such as styrene, acrylonitrile or isobutylene, or polyhydroxy-functional polybutadiene polyols, such as those which are prepared by copolymerization of 1, 3-butadiene and ailyl alcohol and may also be hydrogenated.

Polyhydroxy-functional acrylonitrile / butadiene copolymers, such as, for example, epoxides or amino alcohols and carboxyl-terminated acrylo nitrile / butadiene copolymers (commercially available under the name Hypro ™ (formerly Hycar®) CTBN and CTBNX from Nanoresins AG, Germany, respectively Emerald Performance Materials LLC available).

In addition to these mentioned polyols, small amounts of low molecular weight di- or polyhydric alcohols such as 1, 2-ethanediol, 1, 2- and 1, 3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, the isomeric dipropylene glycols and tripropylene glycols, the isomeric Butanediols, pentanediols, hexanediols, heptanediols, octanediols, nonanediols, decanediols, undecanediols, 1, 3- and 1, 4-cyclohexanedimethanol, hydrogenated bisphenol A, dimeric fatty alcohols, 1,1,1-trimethylolethane, 1,1,1-methylolpropane, glycerol, pentaerythritol, sugar alcohols such as xylitol, sorbitol or mannitol, sugars such as sucrose, other higher alcohols, low molecular weight alkoxylation products of the aforementioned two - And polyhydric alcohols, as well as mixtures of the aforementioned alcohols in the production of the polymer Q _P M be used. Similarly, small amounts of polyols having an average OH functionality of more than 3 may be included, for example, sugar polyols.

Advantageously, the polymers Q _PM di- or higher functional polyols having OH equivalent weights of 300 to 6000 g / OH equivalent, in particular from 600 to 4000 g / OH equivalent, preferably 700 - 2200 g / OH equivalent. Also advantageous are the polyols selected from the group consisting of polyethylene glycols, polypropylene glycols, polyethylene glycol-polypropylene glycol block co-polymers, polybutylene glycols, hydroxyl-terminated polybutadienes, hydroxyl-terminated butadiene / acrylonitrile copolymers, hydroxyl-terminated synthetic rubbers, their hydrogenation products and mixtures of said polyols ,

For certain applications, suitable polymers Q _{PM are} in particular hydroxyl-containing polybutadienes or polyisoprenes or their partially or completely hydrogenated reaction products.

Furthermore, as polymers QPM, di- or higher-functional amino-terminated polyethylene ethers, polypropylene ethers, such as those sold under the name Jeffamine® by Huntsman, polybutylene ethers, polybutadienes, butadiene / acrylonitrile copolymers, such as those known under the name Hypro ™ (formerly Hycar®) ATBN from Nanoresins AG, Germany, or Emerald Performance Materials LLC), as well as other amino-terminated synthetic rubbers or mixtures of said components.

It is also possible to use as polymers Q _P M hydroxyl, mercapto or amino-terminated polysiloxanes.

It is also possible that the polymers QP _{M can} also be chain-extended, as is known in the art by the Reaction of polyamines, polyols and polyisocyanates, especially diamines, diols and diisocyanates, can be performed.

For the chain extension in particular diols and / or

Diamines and diisocyanates are preferred. Of course, it is clear to the person skilled in the art that it is also possible to use higher-functionality polyols, such as trimethylolpropane or pentaerythritol, or higher-functional polyisocyanates, such as isocyanurates of diisocyanates, for chain extension.

In the polyurethane polymers PU1 in general and in the chain-extended polyurethane polymers in particular, it is advantageous to ensure that the polymers do not have too high viscosities, especially when higher functional compounds are used for chain extension.

Preferred polymers Q _PM are polyols having molecular weights 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-terminated butadiene-acrylonitrile copolymers and mixtures thereof.

Polymers Q _P M, particularly preferred are α, ω-Dihydroxypoly- glycols with C ₂ -C ₆ -alkylene groups or having mixed C ₂ -C ₆ - alkylene groups which are terminated with amino, thiol or, preferably, hydroxyl groups , Particularly preferred are polypropylene glycols or polybutylene glycols. Also particularly preferred are hydroxyl-terminated polyoxybutylenes.

As polyphenol Q _PP are particularly suitable Bis, Tris and

Tetra phenols. These are understood to mean not only pure phenols, but optionally also substituted phenols. The type of substitution can be very diverse. In particular, this is understood to mean a substitution directly on the aromatic nucleus to which the phenolic OH group is bonded. Phenols are furthermore not only understood as mononuclear aromatics, but also as polynuclear or condensed aromatics or heteroaromatics which have the phenolic OH group directly on the aromatic or heteroaromatic compounds. Due to the nature and position of such a substituent, among other things, the reaction necessary for the formation of the polyurethane polymer PU1 with isocyanates is influenced.

The bis- and trisphenols are particularly suitable. Suitable bisphenols or trisphenols are, for example, 1,4-dihydroxybenzene, 1,3-dihydroxybenzene, 1,2-dihydroxybenzene, 1,3-dihydroxytoluene, 3,5-dihydroxybenzoates, 2,2-bis (4-hydroxyphenyl) propane (= Bisphenol A), bis (4-hydroxyphenyl) methane (= bisphenol F), bis (4-hydroxyphenyl) sulfone (= bisphenol-S), naphthororcinol, dihydroxynaphthalene, dihydroxyanthraquinone, dihydroxybiphenyl, 3,3-bis (p-hydroxyphenyl) phthalides, 5,5-bis (4-hydroxyphenyl) hexahydro-4,7-methanoindane, phenolphthalein, fluorescein, 4,4 '- [bis (hydroxyphenyl) -1, 3-phenylene-bis - (i-methyl-ethylidene)] (= bisphenol-M), 4,4 '- [bis- (hydroxyphenyl) -1, 4-phenylenebis (1-methyl-ethylidene)] (= bisphenol-P), 2 , 2'-diallyl-bisphenol-A, diphenols and dicresols prepared by reacting phenols or cresols with di-isopropylidenbenzol, phloroglucinol, bile acid esters, phenol or cresol novolaks with -OH functionality of 2.0 to 3.5 and all isomers of the aforementioned compounds.

Preferred diphenols and dicresols prepared by reacting phenols or cresols with di-isopropylidenbenzene have a chemical structural formula as shown below for cresol, for example:

Particularly preferred are low-volatility bisphenols. Most preferred are bisphenol-M, bisphenol-S and 2,2'-diallyl-bisphenol-A. Preferably, the Q _{PP has} 2 or 3 phenolic groups. At least one polyisocyanate is used for the preparation of the polyurethane polymer PU1. This polyisocyanate used for this purpose is in particular a diisocyanate or triisocyanate.

Suitable diisocyanates are aliphatic, cycloaliphatic, aromatic or araliphatic diisocyanates, especially commercial ones

Products such as methylene diphenyl 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, 1,5-naphthalene diisocyanate (NDI), dicyclohexylmethyl diisocyanate (Hi ₂ MDI ), p-phenylene diisocyanate (PPDI), m-tetramethylxylylene diisocyanate (TMXDI), etc. as well as their dimers. Preferred are

HDI, IPDI, MDI or TDI.

Suitable triisocyanates are trimers or biurets of aliphatic, cycloaliphatic, aromatic or araliphatic diisocyanates, especially the isocyanurates and biurets of the diisocyanates described in the previous paragraph.

Of course, suitable mixtures of di- or triisocyanates can be used.

The polyisocyanate is preferably HDI, IPDI, MDI or TDI.

In one embodiment, the polyurethane polymer PU1 is prepared from at least one diisocyanate or triisocyanate and, in addition to at least one amphiphilic block copolymer having at least one hydroxyl group, from a polymer Q _P M having terminal amino, thiol or hydroxyl groups. The preparation of polyurethane polymer PU1 is carried out in a manner known to those skilled in the polyurethane art, in particular by reacting the diisocyanate or triisocyanate in a stoichiometric excess with respect to the amino, thiol or hydroxyl groups of the polymer Q _P M and the hydroxyl-containing amphiphilic block copolymer is used. In a further embodiment, the polyurethane polymer PU1 is prepared from at least one diisocyanate or triisocyanate and, in addition to at least one amphiphilic block copolymer which has at least one hydroxyl group, from an optionally substituted polyphenol Q _PP . The preparation of the polyurethane polymer PU1 is carried out in a

Polyurethane specialist known manner, in particular by the

Diisocyanate or triisocyanate in a stoichiometric excess in

Reference to the phenolic groups of the polyphenol Q _PP and the

Hydroxyl-containing amphiphilic block copolymer is used.

In a further embodiment, the polyurethane polymer PU1 is prepared from at least one diisocyanate or triisocyanate and at least one amphiphilic block copolymer which has at least one hydroxyl group from a polymer Q _P M with terminal amino, thiol or hydroxyl groups and from an optionally substituted polyphenol QPF> manufactured.

For the preparation of the polyurethane polymer PU1 from at least one polyisocyanate and at least one amphiphilic block copolymer having at least one hydroxyl group, and optionally from at least one polymer Q _PM with terminal amino, thiol or hydroxyl groups and / or at least one, optionally substituted, polyphenol Q _PP Different options are available.

Depending on the way of the sequence and stoichiometry between

Polyisocyanate and NCO-reactive compounds, the exact sequence of the blocks in the polyurethane polymer PU1 formed can be made specifically. The polyurethane polymer PU1 has isocyanate groups and preferably has elastic character and shows a glass transition temperature (Tg) of less than 0 ° C.

The polyurethane polymer PU1 can be reacted with at least one NCO-reactive compound to form a reaction product PU2. It has been found that both polyurethane polymer PU1 and its reaction product PU2 can be used in an outstanding manner as impact modifiers, in particular in epoxy resins. It has been shown that these impact modifiers occur evenly distributed in the cured matrix, in particular the epoxy resin matrix and already satisfy small amounts in order to increase the impact resistance of the matrix very strong. These impact modifiers self-form on curing a morphology, which is due to phase separation of epoxy resin and impact modifier (s), and depending on the used amphiphilic copolymer ball, Wurmoder vesicle-like. The size of these separate phases is especially in the nanometer range.

As NCO-reactive compound for the reaction to the reaction product PU2 are in particular compounds having OH, SH, NH, NH ₂ as an NCO-reactive group is suitable.

In a particularly preferred embodiment, the reaction product PU2 has the formula (I).

Here, Y ^{1 is} a m + nϊ isocyanate-terminated linear or branched polyurethane polymer PU1 after removal of all terminal isocyanate groups.

Furthermore, Y ^{2 is} independently of one another a blocking group which splits off at a temperature above 100 ⁰ C.

Furthermore, Y ³ hereby independently of one another represents a group of the formula (I ').

(i ¹ ) R ⁴ stands for a residue of a primary or secondary hydroxyl group-containing aliphatic, cycloaliphatic, aromatic or araliphatic epoxide, after removal of the hydroxide and epoxide groups.

In this document, the use of the term "independently of one another" in connection with substituents, radicals or groups is to be construed as meaning that in the same molecule the identically named substituents, radicals or groups may simultaneously occur with different meanings.

Finally, p = 1, 2 or 3 and m and m 'each represent values between 0 and 8, with the proviso that m + m' stands for a value of 1 to 8.

The possible blocking groups Y ² are basically very diverse and the person skilled in the art knows a large number of such

Blocking groups, for example from the review articles by Douglas A.

Wick in Progress in Organic Coatings 36 (1999), 148-172 and Progress in

Organic Coatings 41 (2001), 1-83.

As radicals Y ² are in particular radicals which are selected from the group consisting of

for an alkyl or cycloalkyl or aryl or aralkyl or arylalkyl group.

Or R ⁵ forms together with R ⁶ , or R ⁷ together with R ⁸ , part of a

4- to 7-membered ring which is substituted at most. Furthermore, R ⁹ , R ⁹ and R ¹⁰ each independently represent a

Alkyl or aralkyl or aryl or arylalkyl group or for an alkyloxy or aryloxy or aralkyloxy group and R ¹¹ stands for an alkyl group.

In addition, R ¹² , R ¹³ and R ¹⁴ each independently represent an alkylene group having 2 to 5 C atoms, which optionally has double bonds or is substituted, or represents a phenylene group or a hydrogenated phenylene group.

R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently H or one

Alkyl group or an aryl group or an aralkyl group and R ¹⁸ is an aralkyl group or a mono- or polynuclear substituted or unsubstituted aromatic group, which may be aromatic

Has hydroxyl groups.

The dashed lines in the formulas of this document in each case represent the bond between the respective substituent and the associated molecular residue.

As R ¹⁸ , on the one hand, in particular, phenols or bisphenols are to be considered after removal of a hydroxyl group. As examples of such phenols and bisphenols are in particular phenol, cardanol (3-penta-decenylphenol (from cashew nut shell oil)), nonylphenol, diallyl-bisphenol A, with styrene or dicyclopentadiene reacted phenols, bis-phenol-A, bis - call phenol-F. On the other hand, as R ¹⁸ , in particular, hydroxybenzyl alcohol and benzyl alcohol are considered 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 is in particular a linear or branched C ₁ -C ₂₀ -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 grouping is in particular a methylene-bonded aromatic group, in particular a benzyl group. The radicals R ⁵ and / or R ⁶ are in particular methyl or ethyl.

If R ^5, R ^6, R ^7, R ^8, R ^9, R ^{9 'or} R ¹⁰ is an alkylaryl group, this is particularly a group bonded through phenylene Cr to C ₂ o alkyl group, such as tolyl or xylyl.

As Y ² is especially a remainder, which is selected from the

Group consisting of

Here, Y is a saturated or olefinically unsaturated

Hydrocarbon radical having 1 to 20 C atoms, in particular having 1 to 15 C atoms. There may be present in the impact modifier of the formula (I) different radicals Y ² and / or Y ³ . If different radicals Y ² are present, it is advantageous if the deblocking temperatures of the blocking groups Y ² differ significantly from each other. Insbesonde- re it is advantageous if the difference of the deblocking temperatures of the Y ² involved least 2O ⁰ C, preferably at least 30 ⁰ C, is. This makes it possible to design targeted multi-stage crosslinking processes, which opens up a variety of possibilities in adhesives.

In addition, it is advantageous if the impact modifier of the

Formula (I) different end groups are present, i. in particular, that m is different from 0, or that they come from different groups, as indicated above. For example, it is advantageous to use, on the one hand, hydroxyl-functional epoxides of the formula (T) and phenols or, on the other hand, phenols and oxazolinones as blocking agents. Of course, all other combinations of the blocking agents described, as well as ternary or quaternary mixtures of blocking agents, conceivable.

An impact modifier PU2 of the formula (I) is obtained from a

Isocyanate group having impact modifiers PU1 of the formula (III) the NCO-reactive compounds Y ² -H and / or Y ³ -H produced.

OCN-4 J mY ¹ + NCO LJ m (III)

For the formation of so-called "asymmetrically" blocked impact modifiers of the formula (I), ie when neither m nor m 'have a value of 0, or when different radicals Y ² or Y ^{3 are present} in the same molecule, such a reaction can be of

Isocyanate group-containing polyurethane polymer PU1 either with a

Mixture of different Y ² -H and / or Y ³ -H reach or it can be a sequential reaction over an intermediate of the formula (IVa) or

(IVb).

In a second step, this NCO group-containing intermediate of the formula (IVa) with Y ³ H, or this NCO group-containing intermediate of the formula (IVb) with Y ² H, is then converted to the reaction product PU 2 of the formula (I) , This sequential reaction has the advantage that the reaction can be better controlled so that the formation of symmetrical adducts ("equal" blocked) is reduced, which is particularly advantageous when the NCO reactivities of the compounds Y ² -H and Y. ³ -H is very different.

For the formation of so-called "symmetrical" blocked impact modifiers of the formula (I), that is, when having m or m 'has a value of 0, and the residues involved Y ² and Y ³ are identical, the reaction of the isocyanate groups-containing polyurethane polymer PU1 with Y ² -H or Y ³ -H performed.

In a preferred embodiment, in which Y ^{3 is} the group of the formula (I '), the corresponding reaction of the polyurethane polymer PU1, which has the formula (III), with a monohydroxyl epoxy compound of the formula (V).

The monohydroxyl epoxy compound of the formula (V) has 1, 2 or 3 epoxide groups. The hydroxyl group of this monohydroxyl epoxy compound (V) may be a primary or a secondary hydroxyl group. Such monohydroxyl epoxy compounds can be produced, for example, by reacting polyols with epichlorohydrin. Depending on the reaction, the reaction also produces the corresponding monohydroxy-epoxy compounds in various concentrations in the reaction of polyfunctional alcohols with epichlorohydrin as by-products. These can be isolated by conventional separation operations. In general, however, it is sufficient to use the product mixture obtained in the glycidylation reaction of polyols from completely and partially reacted to the glycidyl ether polyol. Examples of such hydroxyl-containing epoxides are butanediol monoglycidyl ether (contained in butanediol diglycidyl ether), hexanediol monoglycidyl ether (contained in hexanediol diglycidyl ether), cyclohexanedimethanol glycidyl ether, trimethylolpropane diglycidyl ether (contained in trimethylolpropane triglycidyl ether mixture), glycerol diglycidyl ether (contained in glycerol triglycidyl ether mixture), pentaerythritol triglycidyl ether (as Mixture contained in pentaerythritol tetraglycidyl ether). Preferably, trimethylolpropane diglycidyl ether, which occurs in a relatively high proportion in commonly prepared Trimethylolpropantriglycidylether used.

However, it is also possible to use other similar hydroxyl-containing epoxides, in particular glycidol, 3-glycidyloxybenzyl alcohol or hydroxymethylcyclohexene oxide. Preference is furthermore given to the β-hydroxy ether of the formula (IX) which is present in commercially available liquid epoxy resins prepared from bisphenol A (R =CH ₃ ) and epichlorohydrin and contains about 15%, and the corresponding β-hydroxy ethers of the formula (IX ) formed in the reaction of bisphenol-F (R = H) or the mixture of bisphenol-A and bisphenol-F with epichlorohydrin.

Also preferred are distillation residues, which are obtained in the production of high purity, distilled epoxy liquid resins. Such distillation residues have an up to three times higher concentration of hydroxyl-containing epoxides than commercially available undistilled epoxy liquid resins. In addition, a wide variety of epoxides with a ß-hydroxy ether group, prepared by the reaction of (poly) epoxides with a deficit of monovalent nucleophiles such as carboxylic acids, phenols, thiols or seα-amines can be used.

The free primary or secondary OH functionality of the monohydroxyl

Epoxide compound of the formula (V) allows efficient reaction with terminal isocyanate groups of prepolymers without having to use disproportionate excesses of the epoxide component.

To implement the polyurethane prepolymers PU1 of the formula (III), it is possible to use a total of stoichiometric amounts of Y ³ H, in particular of the monohydric epoxy compound of the formula (V), and Y ² H. If a sequential reaction is carried out to form an intermediate of the formula (IVa) or (IVb), it may be advantageous to use a stoichiometric excess of the compound Y ³ H or Y ² H used in the second step to ensure in that all NCO groups are reacted off.

Both the impact modifier, which is an isocyanate group-containing polyurethane polymer PU1, or which or a reaction product PU2 of this polyurethane product PU1 with at least one NCO-reactive compound, advantageously has an elastic character and is also advantageously soluble or dispersible in epoxy liquid resins.

Another aspect of the present invention is a one-component thermosetting epoxy resin composition which

at least one epoxy resin A having on average more than one epoxide group per molecule; - At least one hardener B for epoxy resins, which is activated by elevated temperature; such as

- contains at least one previously described in detail impact modifier PU1 or PU2.

The epoxy resin A having an average of more than one epoxy group per molecule is preferably an epoxy liquid resin or a solid epoxy resin. The term "solid epoxy resin" is well known to the person skilled in the art and is used in contrast to "liquid epoxy resins". The glass transition temperature of solid resins is above room temperature, i. they can be ground at room temperature to give pourable powders.

Preferred solid epoxy resins have the formula (X)

Here, the substituents R 'and R "are independently of one another either H or CH _3. Furthermore, the subscript s stands for a value of> 1.5, in particular from 2 to 12.

Such solid epoxy resins are commercially available, for example, from Dow or Huntsman or Hexion.

Compounds of formula (X) with an index s between 1 and 1.5 are referred to by the skilled person as semisolid epoxy resins. For the present invention, they are also considered as solid resins.

However, preferred are epoxy resins in the narrower sense, i. where the index s one

Value of> 1.5. Preferred liquid epoxy resins have the formula (XI)

Here, the substituents R '"and R""independently of one another are either H or CH _3. Furthermore, the index r stands for a value from 0 to 1. Preferably, r stands for a value of less than 0.2 Diglycidyl ether of bisphenol

A (DGEBA), bisphenol-F and bisphenol A / F (The term 'A / F' refers to a mixture of acetone with formaldehyde, which is used as starting material in its preparation). Such liquid resins 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).

Also suitable as epoxy resin A are so-called novolacs. These have in particular the following formula:

H or methyl and z = 0 to 7.

In particular, these are phenol or cresol Novolake (R2 = CH ₂ ).

Such epoxy resins are commercially available under the tradename EPN or ECN and Tactix®556 from Huntsman or under the product series DEN ™ from Dow Chemical. Preferably, the epoxy resin A is an epoxy liquid resin of the formula (XI). In a more preferred embodiment, the thermosetting epoxy resin composition contains both at least one epoxy liquid resin of the formula (XI) and at least one solid epoxy resin of the formula (X).

The proportion of epoxy resin A is preferably 10 to 85% by weight, in particular 15 to 70% by weight, preferably 15 to 60% by weight, of the weight of the composition.

The proportion of the previously described impact modifier PU1 or PU2 is preferably 1-45% by weight, in particular 3-30% by weight, based on the weight of the composition.

The inventive composition further contains at least one hardener B for epoxy resins, which is activated by elevated temperature. It is preferably a curing agent which is selected from the group consisting of dicyandiamide, guanamines, guanidines, aminoguanidines and derivatives thereof. Also possible are accelerating effective curing agents, such as substituted ureas, such as 3- (3-chloro-4-methylphenyl) -1, 1-dimethylurea (chlorotoluron), or phenyl-dimethylureas, in particular p-chlorophenyl-N, N-dimethylurea ( Monuron), 3-phenyl-1, 1-dimethylurea (fenuron) or 3,4-dichlorophenyl-N, N-dimethylurea (diuron). Furthermore, compounds of the class of imidazoles and amine complexes can be used.

Hardener B is preferably a hardener which is selected from the group consisting of dicyandiamide, guanamine, guanidines, aminoguanidines and derivatives thereof; substituted ureas, in particular 3- (3-chloro-4-methylphenyl) -1, 1-dimethylurea (chlorotoluron), or phenyl-dimethylureas, in particular p-chlorophenyl-N, N-dimethylurea (monuron), 3-phenyl- 1, 1-dimethylurea (fenuron), 3,4-dichloro phenyl-N, N-dimethylurea (diuron), N, N-dimethylurea as well as imidazoles, imidazole salts and amine complexes.

Particularly preferred as curing agent B is dicyandiamide.

Advantageously, the total amount of the curing agent B is 1 to 10% by weight, preferably 2 to 8% by weight, based on the weight of the total composition.

The thermosetting epoxy resin composition may further include

Thixotropic agent C based on a urea derivative included. In particular, the urea derivative is a reaction product of an aromatic monomeric diisocyanate with an aliphatic amine compound. It is also quite possible to react several different monomeric diisocyanates with one or more aliphatic amine compounds or a monomeric diisocyanate with several aliphatic amine compounds. The reaction product of 4,4'-diphenylmethylene diisocyanate (MDI) with butylamine has proved to be particularly advantageous.

The urea derivative is preferably present in a carrier material. The carrier material may be a plasticizer, in particular a phthalate or an adipate, preferably a diisodecyl phthalate (DIDP) or dioctyl adipate (DOA). The carrier may also be a non-diffusing carrier. This is preferred to ensure as little as possible migration after curing of unregulated components. Preferred non-diffusing carriers are blocked polyurethane prepolymers.

The preparation of such preferred urea derivatives and support materials are described in detail in the patent application EP 1 152 019 A1. The support material is advantageously a blocked polyurethane polymer, in particular obtained by reacting a trifunctional polyether polyol with IPDI and subsequent blocking of the terminal isocyanate groups with ε-caprolactam.

Advantageously, the total amount of thixotropic agent C is 0-40% by weight, preferably 5-25% by weight, based on the weight the entire composition. The ratio of the weight of the urea derivative to the weight of the carrier possibly present is preferably from 2:98 to 50:50, in particular from 5:95 to 25:75.

It has also been shown that it is particularly advantageous if the heat-curing one-component epoxy resin composition additionally contains at least one further impact modifier D in addition to the previously described impact modifier PU1 or PU2.

The additional impact modifiers D may be solid or liquid.

In one embodiment, this impact modifier D is a liquid rubber D1, which is a carboxyl- or epoxide-terminated acrylonitrile / butadiene copolymer or a derivative thereof. Such liquid rubbers are commercially available, for example, under the name Hypro ™ (formerly Hycar®) CTBN and CTBNX and ETBN from Nanoresins AG, Germany, and Emerald Performance Materials LLC). The derivatives are in particular epoxy-containing elastomer-modified prepolymers, as under the product line Polydis®, preferably from the product line Polydis® 36 .., by the company Struktol® (Schill + Seilacher Group, Germany) or under the product line Albipox (Nanoresins, Germany) are commercially available suitable.

In another embodiment, the impact modifier is

D a polyacrylate liquid rubber D2, which is completely miscible with liquid epoxy resins and only separates into micro droplets when the epoxy resin matrix hardens. Such polyacrylate liquid rubbers are available, for example, under the designation 20208-XPA from Rohm and Haas. It is clear to the expert that, of course, mixtures of

Liquid rubbers can be used, in particular mixtures of carboxyl or epoxy-terminated acrylonitrile / butadiene copolymers or derivatives thereof with epoxy-terminated polyurethane prepolymers. In another embodiment, the impact modifier D is a solid impact modifier which is an organic ion-exchanged layered mineral DE1.

The ion-exchanged layered mineral DE1 can either be

Cation-exchanged layered mineral DE1c or an anion-exchanged layered mineral DE1a.

The cation-exchanged layered mineral DE1c is obtained here from a layered mineral DE1 'in which at least some of the cations have been replaced by organic cations. Examples of such cation-exchanged layered minerals DE1c are in particular those mentioned in US 5,707,439 or in US 6,197,849. Likewise, the process for producing these cation-exchanged layered minerals DE1c is described there. Preferred as layered mineral DE1 'is a layered silicate. The layered mineral DE1 'is particularly preferably a phyllosilicate, as described in US Pat. No. 6,197,849, column 2, line 38 to column 3, line 5, in particular a bentonite. Layer minerals DE1 'such as kaolinite or a montmorillonite or a hectorite or an illite have proven particularly suitable. At least part of the cations of the layered mineral DE1 'is replaced by organic cations. Examples of such cations are n-octyl ammonium, trimethyldodecyl ammonium, dimethyl dodecyl ammonium or bis (hydroxyethyl) octadecyl ammonium or similar derivatives of amines which can be obtained from natural fats and oils; or guanidinium cations or amidinium cations; or cations of the N-substituted derivatives of pyrrolidine, piperidine, piperazine, morpholine, thiomorpholine; or cations of 1,4-diazobicyclo [2.2.2] octane (DABCO) and 1-azobicyclo [2.2.2] octane; or cations of N-substituted derivatives of pyridine, pyrrole, imidazole, oxazole, pyrimidine, quinoline, isoquinoline, pyrazine, indole, benzimidazole, benzoxazole, thiazole phenazine and 2,2'-bipyridine. Also suitable are cyclic amidinium cations, in particular those disclosed in US Pat. No. 6,197,849 at column 3, line 6 to column 4, line 67. Cyclic ammonium compounds are distinguished from linear ammonium compounds by an increased thermal stability, since the thermal Hoffmann - degradation can not occur with them.

Preferred cation-exchanged layer minerals DE1c are the

Professional known under the term Organoclay or Nanoclay and are commercially available, for example, under the group names Tixogel® or Nanofil®

(Southern Chemistry), Cloisite® (Southern Clay Products) or Nanomer® (Nanocor

Inc.) or Garmite® (Rockwood).

The anion-exchanged layered mineral DE1a is in this case obtained from a layered mineral DE1 "in which at least some of the anions have been exchanged by organic anions An example of such an anion-exchanged layered mineral DE1a is a hydrotalcite DE1" in which at least one part the carbonate anions of the intermediate layers have been replaced by organic anions. It is quite possible that the composition simultaneously contains a cation-exchanged layered mineral DE1c and an anion-exchanged layered mineral DE1a.

In another embodiment, the impact modifier D is a solid impact modifier which is a block copolymer DE2.

The block copolymer DE2 is obtained from an anionic or controlled radical polymerization of methacrylic acid ester with at least one further olefinic double bond

Monomers. Preferred monomers having an olefinic double bond are those in which the double bond is conjugated directly with a heteroatom or with at least one further double bond. In particular, monomers are suitable which are selected from the group comprising styrene, butadiene, acrylonitrile and vinyl acetate.

Preferred are acrylate-styrene-acrylic acid (ASA) copolymers, available e.g. under the name GELOY 1020 from GE Plastics.

Particularly preferred block copolymers DE2 are block copolymers of methyl methacrylate, styrene and butadiene. Such block copoly- mers are available, for example, as triblock copolymers under the group name SBM from Arkema.

In another embodiment, the impact modifier D is a core-shell polymer DE3. Core-shell polymers consist of an elastic core polymer and a rigid shell polymer. Particularly suitable core-shell polymers consist of a core (core) of elastic acrylate or butadiene polymer which wraps around a rigid shell of a rigid thermoplastic polymer. This core-shell structure is formed either spontaneously by demixing a block copolymer or is given by the polymerization as latex or suspension polymerization with subsequent grafting. Preferred core-shell polymers are so-called MBS polymers, which are commercially available under the trade names Clearstrength ™ from Atofina, Paraloid ™ from Rohm and Haas or F-351 ™ from Zeon.

Particularly preferred are core-shell polymer particles which are already present as a dried polymer latex. Examples include GENIOPERL M23A from Wacker with polysiloxane core and acrylate shell, radiation-crosslinked

Rubber particles of the NEP series, manufactured by Eliokem or Nanoprene by Lanxess or Paraloid EXL by Rohm and Haas.

Further comparable examples of core-shell polymers are offered under the name Albidur ^™ by Nanoresins AG, Germany.

Also suitable are nano-sized silicates in Epoxid Matiix, as offered under the trade name Nonopox Nanoresins AG, Germany.

In another embodiment, the impact modifier D is a reaction product DE4 of a carboxylated solid nitrile rubber with excess epoxy resin.

Particularly suitable as impact modifier D which may be present in the composition are impact modifiers which correspond to the impact modifier of the formula (I) already described but which do not have an amphiphilic block copolymer having a hydroxyl group (n) but are terminated on a polymer Q _PM with endstability. or amino-substituted, thiol or hydroxyl groups and from an optionally substituted, polyphenol Q _PP , as they have already been disclosed for the preparation of the polyurethane polymer (PU1) based.

Particularly suitable as impact modifier D optionally present in the composition are those disclosed in the following articles or patent specifications, the contents of which are hereby incorporated by reference: EP 0 308 664 A1, in particular formula (I), especially page 5, Line 14 to page 13, line 24; EP 0 338 985 A1, EP 0 353 190 A1, WO 00/20483 A1, in particular formula (I), especially page 8, line 18 to page 12, line 2; WO 01/94492 A1, in particular the reaction products denoted D) and E), especially page 10, line 15 to page 14, line 22; WO 03/078163 A1, in particular the acrylate-terminated polyurethane resin designated B), especially page 14, line 6 to page 14, line 35; WO 2005/007766 A1, in particular formula (I) or (II), especially page 4, line 5 to page 11 to line 20; EP 1 728 825 A1, in particular formula (I), especially page 3, line 21 to page 4 to line 47; WO 2006/052726 A1, in particular the amphiphilic block copolymer designated as b), especially page 6, line 17 to page 9, line 10; WO 2006/052729 A1, in particular the amphiphilic block copolymer designated as b), especially page 6, line 25 to page 10, line 2; TJ. Hermel-Davidock et al., J. Polym. Be. Part B: Polym. Phys. 2007, 45, 3338-3348, in particular the ambiphilic block copolymers, especially page 3339, 2nd column to 3341 2nd column; WO 2004/055092 A1, in particular formula (I), especially page 7, line 28 to page 13 to line 15 ;. WO 2005/007720 A1, in particular formula (I), especially page 8, line 1 to page 17 to line 10; WO 2007/020266 A1, in particular formula (I), especially page 3, line 1 to page 11 to line 6, and DE-A-2 123 033, US 2008/0076886 A1, WO 2008/016889 and WO 2007/025007.

It has been found that in the composition advantageously several impact modifier are present, in particular several impact modifiers D. The proportion of impact modifiers D is advantageously used in an amount of 1 to 35% by weight, in particular 1 to 25% by weight, based on the weight of the composition.

In a further preferred embodiment, the composition additionally contains at least one filler F. This is preferably mica, talc, kaolin, wollastonite, feldspar, syenite, chlorite, bentonite, montmorillonite, calcium carbonate (precipitated or ground), dolomite, quartz, silicic acids (pyrogenic or precipitated), cristobalite, calcium oxide, aluminum hydroxide, magnesium oxide, ceramic hollow spheres, glass hollow spheres, organic hollow spheres, glass spheres, color pigments. Filler F is meant to mean both the organic coated and the uncoated commercially available and known to those skilled forms. Another example is functionalized alumoxanes such. In US

6,322,890.

Advantageously, the total content of the total filler F is 3 to 50% by weight, preferably 5 to 35% by weight, in particular 5 to 25% by weight, based on the weight of the total composition.

In a further preferred embodiment, the composition contains a physical or chemical blowing agent, as available, for example, under the trade name Expancel ™ from Akzo Nobel or Celogen ™ from Chemtura. The proportion of blowing agent is advantageously 0.1-3% by weight on the weight of the composition.

In a further preferred embodiment, the composition additionally contains at least one epoxy group-carrying reactive diluent G. These reactive diluents G are in particular:

Glycidyl ethers of monofunctional saturated or unsaturated, branched or unbranched, cyclic or open-chain C ₄ -C ₃₀

Alcohols, in particular selected from the group consisting of

Butanol glycidyl ether, hexanol glycidyl ether, 2-ethylhexanol glycidyl ether ethers, allyl glycidyl ethers, tetrahydrofurfuryl and furfuryl glycidyl ethers, trimethoxysilyl glycidyl ethers.

- Glycidyl ethers of difunctional saturated or unsaturated, branched or unbranched, cyclic or open-chain C ₂ - C ₃₀ - alcohols, in particular selected from the group consisting of

Ethylene glycol, butanediol, hexanediol, octanediol glycidyl ethers, cyclohexanedimethane diglycidyl ethers and neopentyl glycol diglycidyl ethers.

Glycidyl ethers of trifunctional or polyfunctional, saturated or unsaturated, branched or unbranched, cyclic or open-chain alcohols, such as epoxidized castor oil, epoxidized trimethylolpropane, epoxidized pentaerythrol or polyglycidyl ethers of aliphatic polyols, such as sorbitol, glycerol or trimethylolpropane.

Glycidyl ethers of phenolic and aniline compounds, in particular selected from the group consisting of phenyl glycidyl ether, cresyl glycidyl ether, p-tert-butylphenyl glycidyl ether, nonylphenol glycidyl ether, 3-n-pentadecenyl glycidyl ether (from cashew nut shell oil), N, N-diglycidyl aniline and triglycidyl of p-aminophenol.

- Epoxidized amines such as N, N-diglycidylcyclohexylamine.

Epoxidized mono- or dicarboxylic acids, in particular selected from the group consisting of glycidyl neodecanoate, glycidyl methacrylate, glycidyl benzoate, diglycidyl phthalate, tetra- and hexahydrophthalate, and diglycidyl esters of dimeric fatty acids and cetyl terephthalic and trimelitic esters.

Epoxidized di- or trifunctional, low to high molecular weight polyether polyols, in particular polyethylene glycol diglycidyl ethers or polypropyleneglycol diglycidyl ethers.

Especially preferred are hexanediol diglycidyl ether, cresyl glycidyl ether, p-fe / f-butylphenyl glycidyl ether, polypropylene glycol diglycidyl ether and polyethylene glycol diglycidyl ether.

Advantageously, the total proportion of the epoxide group-carrying reactive diluent G is 0.1-20% by weight, preferably 1-8% by weight, based on the weight of the total composition. The composition may contain other ingredients, in particular

Catalysts, stabilizers, in particular heat and / or light stabilizers,

Thixotropic agents, plasticizers, solvents, mineral or organic fillers, blowing agents, dyes and pigments, corrosion inhibitors, surfactants, defoamers and adhesion promoters include.

Particularly suitable plasticizers are phenol alkyl sulfonic acid esters or benzenesulfonic acid N-butyl amide, such as are commercially available as Mesamoll® or Dellatol BBS from Bayer.

Particularly suitable stabilizers are optionally substituted phenols, such as BHT or Wingstay® T (elixirs), sterically hindered amines or N-oxyl compounds, such as TEMPO (Evonik). It has been shown that the described thermosetting

Epoxy resin compositions are particularly suitable as one-component adhesives. Such a one-component adhesive has a wide range of uses. In particular, hereby thermosetting one-component adhesives are feasible, which are characterized by a high impact strength, both at higher temperatures and especially at low temperatures, in particular between ^{0 0} C to -40 ° C. Such adhesives are needed for bonding heat stable materials. Heat-resistant materials are materials which at a curing temperature from 100 to 220 ⁰ C, preferably 120-200 ⁰ C are dimensionally stable at least during the curing time. In particular, these are metals and plastics such as ABS, polyamide, polyphenylene ethers, composite materials such as SMC, unsaturated polyester GRP, epoxy or acrylate composites. Preferred is the application in which at least one material is a metal. Particularly preferred use is the bonding of the same or different metals, especially in the shell in the automotive industry. The preferred metals are, above all, steel, in particular electrolytically galvanized, hot-dip galvanized, oiled steel, Bonazink-coated steel, and subsequently phosphated steel, as well as aluminum in particular in the variants typically occurring in the car industry.

With an adhesive based on a heat-curing composition according to the invention, it is possible to achieve the desired combination of high crash resistance both high and low operating temperature.

Such an adhesive is in particular first contacted with the materials to be bonded at a temperature of between 10 ° C and 80 ⁰ C, in particular between 10 ⁰ C and 60 ° C, and later cured at a temperature of typically 100 - 220 ° C, preferably 120-200 ° C.

A further aspect of the present invention relates to a method for bonding heat-stable substrates, comprising the steps of: i) applying a one-component thermosetting epoxy resin composition, as described in detail above, to the surface of a heat-stable substrate S1, in particular a metal; ii) contacting the applied thermosetting epoxy resin composition with the surface of another heat-stable substrate S2, in particular a metal; iii) heating the epoxy resin composition to a temperature of 100 to 130 ° C, preferably from 115 to 125 ⁰ C; iv) contacting the substrates S1 and S2 and in contact therewith thermosetting epoxy resin with a washing liquid at a temperature between 20 and 100 ⁰ C, in particular between 40 and 70 ° C; preferably between 50 and 70 ° C v) heating the composition to a temperature of 140-220 ⁰ C, in particular 140-200 ° C, preferably 160-190 ⁰ C.

The substrate S2 here consists of the same or a different material as the substrate S1. From such a method for bonding heat-stable materials results in a bonded article. Such an article is preferably a vehicle or an attachment of a vehicle.

Of course, with a composition according to the invention, in addition to heat-curing adhesives, sealing compounds or coatings can also be realized. Furthermore, the novel compositions are not only suitable for the automotive industry but also for other applications. Particularly noteworthy are related applications in transport engineering such as ships, trucks, buses or rail vehicles or in the construction of consumer goods such as washing machines.

The bonded by means of a composition according to the invention materials are used at temperatures between typically 12O ⁰ C and -4O ⁰ C, preferably between 100 ⁰ C and -40 ⁰ C, in particular between 80 ° C and -4O ⁰ C used. It is possible to formulate compositions which typically have fracture energies, measured according to ISO 11343, of more than 5.0 J at 23 ⁰ C and more than 2.0 J at -3O ⁰ C. Typically, compositions can be formulated which have fracture energies of more than 8.0 J at 23 ⁰ C and of more than 4.0 J at -30 ⁰ C. Particularly advantageous compositions have even fracture energies of more than 10.0 J at 23 ° C and more than 9.0 J at -3O ⁰ C.

A particularly preferred use of the inventive thermosetting epoxy resin composition is its use as a thermosetting structural adhesive in vehicle construction. A further aspect of the present invention relates to the use of an amphiphilic block copolymer having at least one hydroxyl group, for the production of impact modifiers comprising urethane groups. The at least one hydroxyl group-containing amphiphilic block copolymers and their use for producing urethane-containing impact modifiers have already been described in detail previously. Examples

In the following, some examples will be shown, which further illustrate the invention, but are not intended to limit the scope of the invention in any way. The raw materials used in the examples are listed in Table 1.

Table! Used raw materials. Exemplary preparation of a monohydroxyl-containing epoxide MHE1 trimethylolpropane glycidyl ether was prepared according to the process in US Pat. No. 5,668,227, Example 1 from trimethylolpropane and epichlorohydrin with tetramethylammonium chloride and sodium hydroxide solution. A yellowish product having an epoxide number of 7.5 eq / kg and a hydroxyl group content of 1.8 eq / kg is obtained. It can be concluded from the HPLC-MS spectrum that essentially a mixture of trimethylolpropane diglycidyl ether and trimethylolpropane triglycidyl ether is present.

Thixotropic agent TM1

As an example of a thixotropic agent based on a urea derivative in a non-diffusing carrier material, a thixotropic agent according to patent application EP 1 152 019 A1 was prepared in a blocked polyurethane prepolymer with the above-mentioned raw materials:

Vehicle: Blocked polyurethane prepolymer PUP.

600.0 g of a polyether polyol (Desmophen 3060BS; 3000 Dalton; OH number 57 mg / g KOH) were placed environmentally under vacuum and stirring at 90 ⁰ C with 140.0 g of IPDI, and 0.10g of dibutyltin dilaurate to form the isocyanate-terminated prepolymer. The reaction was performed until a constant NCO content of 3.41% after 2.5h (theoretical NCO content: 3.60%). The free isocyanate groups were blocked at 9O ⁰ C under vacuum with 69.2 g of caprolactam (2% surplus) , wherein an NCO content of <0.1% was reached after 3 h.

Urea derivative in blocked polyurethane prepolymer:

Under nitrogen and gentle warming, 68.7 g of MDI flakes were melted in 181.3 g of the above-described blocked prepolymer PL / P. Thereafter, 40.1 g of N-butylamine dissolved in 219.9 g of the above-described blocked prepolymer were added dropwise over two hours under nitrogen and with rapid stirring. After completion of the addition of the amine solution, the white paste was further stirred for a further 30 minutes. Thus, after cooling, a white, soft paste of a thixotropic agent TM1 was obtained, which had a free isocyanate content of <0.1% (proportion of urea derivative about 20%). Production of impact modifier PU2-1

100 g of Fortegra ™ 100 (OH number about 16 mg / g KOH) were dried under vacuum at 105 ^° C. for 30 minutes. After the temperature was reduced to 9O ⁰ C, 7.2 g of IPDI and 0.04 g of dibutyltin dilaurate were added. The reaction was performed under vacuum at 9O ⁰ C until a constant NCO content at 17.1%, after 2.5 h (calculated NCO content: 29.1%). Subsequently, 4.4 g of hydroquinone monomethyl ether were added as a blocking agent. It was further stirred at 115 ⁰ C under vacuum until the NCO content had dropped below 0.1% after 3.5 h.

Production of impact modifier PU2-2

100 g of Fortegra ™ 100 (OH number about 16 mg / g KOH) were dried under vacuum at 105 ^° C. for 30 minutes. After the temperature was reduced to 9O ⁰ C, 7.2 g of IPDI and 0.04 g of dibutyltin dilaurate were added. The reaction was carried out under reduced pressure at 90 ° C. until the NCO content remained constant at 1.17% after 2.5 h (calculated NCO content: 1.29%). Subsequently, 20.7 g of MHE1 (mixture of trimethylolpropane tri and trimethylolpropane diglycidyl ether) were added as blocking agents. It was further stirred at 100 ⁰ C under vacuum until the NCO content had fallen below 0.1% after 2.5 h.

Production of impact modifier PU2-3

57 g / g KOH), 40 g Fortegra ™ 100 (OH number about 16 mg / g KOH) and 40 g Liguiflex H (OH number 46 mg / g KOH ) wur- to 30 minutes under vacuum dried at 105 ⁰ C. After the temperature was reduced to 9O ⁰ C, 19.2 g of IPDI and 0.06 g of dibutyltin dilaurate were added. The reaction was carried out under vacuum at 90 ^° C. until the NCO content remained constant at 2.4% after 2.5 h (calculated NCO content: 2.6%). Subsequently, 3.2 g of benzoxazolinone and 3.0 g of hydroquinone monomethyl ether were added. After stirring for 3 h at 120 ° C. under reduced pressure, 26.5 g of MHE1 (mixture of trimethylolpropane tri- and trimethylolpropane diglycidyl ether) were added. It was further stirred at 100 ° C under vacuum until the NCO content had fallen below 0.1% after 2.5 h. Preparation of Attenuation Modifier PU-Ref1

150 g Acclaim 8200N (OH number of about 14.5 mg / g KOH) were dried for 30 minutes under vacuum at 105 ⁰ C. After the temperature had been reduced to 90 ⁰ C, 9.9 g IPDI and 0.05g of dibutyltin dilaurate were added. The reaction was carried out under reduced pressure at 90 ^° C. until the NCO content remained constant at 1.18% after 2.5 hours (calculated NCO content: 1.20%). Subsequently, 6.7 g of hydroquinone monomethyl ether were added as a blocking agent. It was further stirred at 115 ⁰ C under vacuum until the NCO content had dropped below 0.1% after 3.5 h.

Production of Impact Modifier PU-Ref2

150 g Acclaim 8200N (OH number of about 14.5 mg / g KOH) were dried for 30 minutes under vacuum at 105 ⁰ C. After the temperature was reduced to 90 ° C, 9.9 g of IPDI and 0.05 g of dibutyltin dilaurate were added. The reaction was performed under vacuum at 9O ⁰ C until a constant NCO content at 18.1%, after 2.5 h (calculated NCO content: 1.20%). Subsequently, 31.2 g of MHE1 (mixture of trimethylolpropane tri- and trimethylolpropane diglycidyl ether) were added as blocking agent. It was further stirred at 100 ⁰ C under vacuum until the NCO content had fallen below 0.1% after 2.5 h.

Production of impact modifier PU-Ref3

150 g of polyTHF 2000 (OH number 57 mg / g KOH) and 150 Liquiflex H

(OH number 46 mg / g KOH) were dried under vacuum at 105 ° C for 30 minutes. After the temperature had been reduced to 9O ⁰ C were

64.0 g of IPDI and 0.13 g of dibutyltin dilaurate were added. The reaction was reduced under vacuum at 90 ^° C. until the NCO content remained constant at 3.30%

2.5 h (calculated NCO content: 3.38%). Subsequently, 103.0 g of Cardolite NC-700 were added as a blocking agent. Stirring was continued at 105 ⁰ C under vacuum until the NCO content had fallen below 0.1% after 3.5 h.

Production of Impact Modifier PU-Ref4

60 g poly-THF 2000 (OH number about 57 mg / g KOH) and 60 g Liquiflex H (OH number 46 mg / g KOH) for 30 minutes under vacuum at 105 ⁰ C dried. After the temperature was reduced to 9O ⁰ C, 24.6 g of IPDI and 0.06 g of dibutyltin dilaurate were added. The reaction was performed under vacuum at 9O ⁰ C until a constant NCO content at 3:05% after 2.5 h (calculated NCO content: 3.22%). Subsequently, 4.3 g of benzoxazolinone and 3.9 g of hydroquinone monomethyl ether were added. After 3 h stirring at 12O ⁰ C under vacuum, 35.0 g of MHE1 (mixture of trimethylolpropane tri- and Trimethylolpropandiglycidylether) was added. It was further stirred at 100 ° C under vacuum until the NCO content had fallen below 0.1% after 2.5 h.

Preparation Impact modifier PU-Ref5

108 g of poly-THF 2000 (OH number of about 57.0 mg / g KOH) and 72 g of Dynacoll 7250 (OH number 22 mg / g KOH) were dried for 30 minutes under vacuum at 105 ⁰ C. After the temperature was reduced to 9O ⁰ C, 32.2 g of IPDI and 0.06 g of dibutyltin dilaurate were added. The reaction was carried out under reduced pressure at 9O ⁰ C until the NCO content remained constant at 2.87% after 2.5 h (calculated NCO content: 2.92%). Subsequently, 21.6 g of hydroquinone monomethyl ether were added. It was further stirred at 11O ⁰ C under vacuum until the NCO content had dropped below 0.1% after 3.5 h.

Production of impact modifier SM1

29 g Hypro ™ CTBN 1300X13 (acid number about 29 mg / g KOH), 60 g Hypro ™ CTBN 1300X8 (acid number about 32 mg / g KOH) and 23.2 g Araldite® GT7071 (EEW about 510 g / eg) were stirred together with 0.75 g of triphenylphosphine and 0.38 g of BHT for 2 hours under reduced pressure at 140.degree. Subsequently, 201.8 g DER 354 were added and it was further stirred for 2 h at 14O ⁰ C under vacuum. A viscous resin having an epoxide content of about 2.8 eq / kg was obtained.

Production of impact modifier SM2

318.0 g of Jeffamine T-3000 and 30.4 g of maleic anhydride was stirred for 2 hours under nitrogen at 120 ⁰ C. Subsequently, 802 g DER 331 and 2.9 g of triphenylphosphine were added and it was further stirred at 110 ° C under vacuum until a constant epoxide content was reached. After about 2 hours, a viscous resin having an epoxide content of about 3.5 eq / kg was obtained.

Preparation of impact modifier SM3 200.0 g (about 0.4 eq EP) D.E.R. 671 and 75.0 g (about 0.4 eq EP) D.E.R.

331 were stirred for 15 minutes at 12O ⁰ C under vacuum until a homogeneous solution had formed. Subsequently, 230.0 g (about 0.23 eq NH) of Jeffamine D-4000 and 0.5 g (about 0.007 eq of NH) of Jeffamine T-403 were added. After 3 h of stirring under vacuum at 120 ⁰ C and 1 h at 13O ⁰ C, a clear, viscous resin with a calculated epoxide content of from about 1.13 eq / kg (EEW = ca. 890) was obtained.

Production of impact modifier SM4

160 g of polyTHF 1800 (OH number 62.3 mg / g KOH), 110 g of Liquiflex H (OH number 46 mg / g KOH) and 130 g of Caradol ED 56-10 (OH number 56 mg / g KOH) Dried under vacuum at 105 ° C for 30 minutes. After the temperature was reduced to 9O ⁰ C, 92.5 g of IPDI and 0.08 g of dibutyltin dilaurate were added. The reaction was performed under vacuum at 9O ⁰ C until a constant NCO content at 3.60% after 2.5 h (calculated NCO content: 3.62%). Subsequently, 257.8 g of MHE1 (mixture of trimethylolpropane tri- and trimethylolpropane diglycidyl ether) were added and the reaction was continued at 9O ⁰ C under vacuum until the NCO content had fallen below 0.1% after 3 h.

Production of impact modifier SM5

At 11 ⁰ ° C. 123.9 g of a dimeric fatty acid and 71.3 g were removed under vacuum and stirring, 2,2-bis (4-hydroxyphenyl) sulfone (Clariant) with 658 g of a liquid DGEBA epoxy resin with an epoxide content of 5.45 eq / kg 5 hours long reacted until a constant epoxide concentration of 2.82 eq / kg was reached. After the end of the reaction, an additional 118.2 g of liquid DGEBA epoxy resin were added to the reaction mixture.

Preparation of adduct hexamethylene diisocyanate with dimethylamine AD1 50 ml of tetrahydrofuran and 20.0 g of an approximately 33% dimethylamine solution in ethanol (about 146 mmol of amine) were introduced into a 100 ml two-necked solvent. weighed with reflux condenser. Subsequently, 10.0 g of hexamethylene diisocyanate (about 119 mmol NCO) were slowly added dropwise over 30 minutes, with a slight exotherm was observed and immediately a white solid precipitated. After stirring for 2 hours at ambient temperature, the suspension was filtered. It was washed 3 times with 20 ml of THF each time. The resulting crude product was dried at 80 ⁰ C under vacuum for 3h. There were obtained 12.3 g of a white powder.

Preparation of Adduct AD2 22.97 g (0.22 mol) of diethylenetriamine is added dropwise with stirring to 102.6 g (0.68 mol) of methyl salicylate. This mixture is stirred at about 14O ⁰ C for 6 h, forming a white precipitate. After cooling to 30 ⁰ C acetone is added and the white precipitate is filtered off. The residue is washed twice with acetone and then dried in a vacuum oven at 6O ⁰ C. In this case, an intermediate product having a melting point of about 150 ⁰ C is obtained. This is then heated in a drying oven under vacuum for 90 minutes at 16O ⁰ C. The crude product is finely ground and treated again at 160 ° C under vacuum for one hour. Thus, about 47 g of a white powder having a melting point of about 290 ° C were obtained.

Preparation of the compositions

According to Tables 2 to 5, the reference compositions Ref.7 - Ref. 13 and the novel compositions 1 to 10 were prepared. The components are given in parts by weight. In particular, care has been taken that the compositions each have the same amounts of epoxide groups as the corresponding reference example. In the case of the comparative examples which contain unreacted amphiphilic block copolymer (Fortegra ™ 100) or polyol (Acclaim 8200N), the amount of the respective impact modifier according to the invention was chosen such that it contains the same amount of amphiphilic block copolymer as starting material for the corresponding examples according to the invention contain. Test Methods:

ZuQScherfestiakeit (ZSF) (DIN EN 1465)

The test specimens were produced from the described example compositions and with electrolytically galvanized DCO 4 steel (eloZn) with the dimensions 100 × 25 × 1.5 mm or 100 × 25 × 0.8 mm, the bond area being 25 × 10 mm at a layer thickness of 0.3 mm. Hardened for 30 min. At 18O ⁰ C. The train speed was 10mm / min.

Tensile Strength (TS) (DIN EN ISO 527) An adhesive sample was placed between two Teflon paper to a layer thickness of 2 mm verpresst.Anschliessend the adhesive for 30 minutes at 18O ⁰ C was cured. The Teflon papers were removed and the test specimens to DIN standard were punched out in the hot state. The specimens were measured after 1 day storage under standard conditions at a pulling speed of 2 mm / min. The tensile strength was determined according to DIN EN ISO 527. Percussion peeling (ISO 11343)

The test specimens were produced from the described example compositions and with electrolytically galvanized DC04 steel (eloZn) with the dimensions 90 × 20 × 0.8 mm, while the adhesive surface was 20 × 30 mm with a layer thickness of 0.3 mm. Hardened for 30 min. At 180 ° C. The measurement of the Schlagschälarbeit was carried out in each case at room temperature and at -30 ° C. The impact velocity was 2 m / s. The fracture energy (BE) in joules is the area under the measurement curve (from 25% to 90%, according to ISO 11343).

Glass transition temperature (T _α ) The glass transition temperature was determined by DSC. A device Mettler DSC822 ^{6 was} used for this purpose. 10-20 mg of the compositions were each weighed into an aluminum pan. After the sample had been cured in the DSC for 30 min. At 175 ⁰ C, the sample was cooled to -20O ⁰ C and then heated at a heating rate of 10 ° C / min to 15O ⁰ C. The glass transition temperature was determined from the measured DSC curve using the DSC software.

The results of these tests are summarized in Tables 2 to 5.

Table 3. Compositions and Results. BE = energy of breakage.

Table 3 (cont). Compositions and results. BE = energy of breakage.

Table 4. Compositions and Results. BE = energy of breakage.

Table 5. Compositions and Results. ¹ BE = fracture energy

Table 5 (cont). Compositions and results. BE = energy of breakage

Claims

claims

An impact modifier which comprises an isocyanate group-containing polyurethane polymer (PU1) which is prepared from at least one polyisocyanate and at least one amphiphilic block copolymer which has at least one hydroxyl group and optionally at least one compound having at least two NCO-reactive groups; or a reaction product (PU2) of this polyurethane product (PU1) with at least one NCO-reactive compound.

2. impact modifier according to claim 1, characterized in that the at least one hydroxyl group-containing amphiphilic block copolymer is a block copolymer of ethylene oxide and / or propylene oxide and at least one further alkylene oxide having at least 4 carbon atoms, preferably from the group consisting of butylene oxide, hexylene oxide and dodecylene oxide.

3. impact modifier according to claim 1, marked thereby, that the at least one hydroxyl group having amphiphilic

A block copolymer selected from the group consisting of poly (isoprene-block-ethylene oxide) block copolymers, poly (ethylene-propylene-b-ethylene oxide) block copolymers, poly (butadiene-b-ethylene oxide) block copolymers, poly (isoprene-b) ethylene oxide-b-isoprene) block copolymers, poly (isoprene-b-ethylene oxide-methyl methacrylate) block copolymers, and

Poly (ethylene oxide) -b-poly (ethylene-old propylene) block copolymers.

4. impact modifier according to any one of the preceding claims, characterized in that in addition to at least one amphiphilic block copolymer having at least one hydroxyl group, at least one polymer Q _PM with terminal amino, thiol or hydroxyl groups for the preparation of the polyurethane prepolymer PU1; and / or at least one, optionally substituted, polyphenol Qpp is used.

5. impact modifier according to claim 4, characterized in that the polymer Q _P M is an α, ω- Dihydroxypolyalkylenglykol with C ₂ - C ₆ alkylene groups or with mixed C ₂ -C ₆ alkylene groups, which with amino, thiol or , preferably, hydroxyl groups is terminated.

6. impact modifier according to claim 4 or 5, characterized in that the polymer QPM has an equivalent weight of 300-6O00 g / equivalent of NCO-reactive groups, in particular of 700 - 2200 g / NCO-reactive groups having.

7. impact modifier according to any one of claims 4 to 6, characterized in that the polyisocyanate used for the preparation of the polyurethane prepolymer PU1, in particular a diisocyanate or triisocyanate, preferably HDI, IPDI, MDI or TDI, is.

8. impact modifier according to any one of the preceding claims, characterized in that it has the formula (I)

wherein Y ^{1 stands} for a m + m 'isocyanate-terminated linear or branched polyurethane polymer PU1 after removal of all terminal isocyanate groups;

Y ² independently of each other for a blocking group which cleaves off at a temperature above 100 ⁰ C is; Y ^{3 is} independently of one another a group of the formula (I ') wherein R ^{4 is} a radical of a primary or secondary hydroxyl group-containing aliphatic, cycloaliphatic, aromatic or araliphatic epoxide after removal of the hydroxide and epoxide groups; p = 1, 2 or 3 and m and m 'are each values between 0 and 8, with the proviso that m + m' is a value from 1 to 8. Impact modifier according to claim 8, characterized in that Y ^{2 is} a radical which is selected from the group consisting of

in which

R ⁵ , R ⁶ , R ⁷ and R ^{8 are} each independently an alkyl or

Cycloalkyl or aryl or aralkyl or arylalkyl group or R ⁵ together with R ⁶ , or R ⁷ together with R ⁸ , part of a

Form 4- to 7-membered ring which is at most substituted;

R ⁹ , R ⁹ and R ¹⁰ each independently represent an alkyl or aralkyl or aryl or arylalkyl group or an alkyloxy or aryloxy or aralkyloxy group;

R ^{11 is} an alkyl group,

R ¹² , R ¹³ and R ¹⁴ each independently represent an alkylene group

2 to 5 C atoms, which optionally has double bonds or is substituted, or stand for a phenylene group or for a hydrogenated phenylene group; R ¹⁵ , R ¹⁶ and R ¹⁷ each independently represent H or an alkyl group or an aryl group or an aralkyl group; and R ^{18 is} an aralkyl group or a mono- or polynuclear substituted or unsubstituted aromatic group optionally having aromatic hydroxyl groups.

10. impact modifier according to claim 7 or 8, characterized in that Y ^{2 is} selected from the group consisting of

where Y is a saturated or olefinically unsaturated hydrocarbon radical having 1 to 20 C atoms, in particular having 1 to 15 C atoms.

11. impact modifier according to any one of claims 7 to 10, characterized in that the R ^{4 is} a trivalent radical of the formula

where R is methyl or H.

12. One-component thermosetting epoxy resin composition containing

at least one epoxy resin A having on average more than one epoxide group per molecule;

- At least one hardener B for epoxy resins, which is activated by elevated temperature;

- At least one impact modifier according to any one of claims 1-11.

13. One-component thermosetting epoxy resin composition according to claim 12, characterized in that the curing agent B is a curing agent which is selected from the group consisting of dicyandiamide, guanamines, guanidines, aminoguanidines and their derivatives; Substituted ureas, in particular 3- (3-chloro-4-methylphenyl) -1, 1-dimethylurea (chlorotoluron), or phenyldimethylureas, in particular p-chlorophenyl-N, N-dimethylurea (monuron), 3-phenyl-

1, 1-dimethylurea (fenuron), 3,4-dichlorophenyl-N, N-dimethylurea (diuron), N, N-dimethylurea and imidazoles, imidazole salts and amine complexes.

14. One-component heat-curing epoxy resin composition according to claim 12 or 13, characterized in that it additionally contains at least one further impact modifier D.

15. A method for bonding heat-stable substrates comprising the steps i) applying a one-component thermosetting epoxy resin composition according to any one of claims 12 to 14 on the surface of a heat-stable substrate S1, in particular a metal; ii) contacting the applied thermosetting epoxy resin composition with the surface of another heat-stable substrate S2, in particular a metal; iii) heating the epoxy resin composition to a temperature of 100 to 130 ⁰ C, preferably from 115 to 125 ⁰ C; iv) contacting the substrates S1 and S2 and in contact therewith thermosetting epoxy resin with a washing liquid at a temperature between 20 and 100 ⁰ C, in particular between 40 and 70 ° C; preferably between 50 and

70 ° C v) heating the composition to a temperature of 140 -

220 ° C, in particular from 140 to 200 ° C, preferably between 160 and 19O ⁰ C; .0 wherein the substrate S2 consists of the same or a different material as the substrate S1.

16. Use of a one-component thermosetting Epoxidharzzusammenam- composition according to one of the claims according to one of the claims

12 to 14 as a thermosetting one-component structural adhesive in vehicle construction.

17. Use of an amphiphilic block copolymer having at least one hydroxyl group, for the production of urethane-containing impact modifiers.

18. Use according to claim 17, characterized in that the impact modifier is an impact modifier according to any one of claims 1-11.