EP2094792A2

EP2094792A2 - Bonding agent containing a silane reaction product

Info

Publication number: EP2094792A2
Application number: EP06819630A
Authority: EP
Inventors: Wolf-Rüdiger Huck
Original assignee: Sika Technology AG
Current assignee: Sika Technology AG
Priority date: 2006-11-20
Filing date: 2006-11-20
Publication date: 2009-09-02
Also published as: WO2008061556A3; US20100323203A1; CN101605857B; US8263185B2; WO2008061556A2; CN101605857A

Abstract

The invention relates to compositions containing or consisting of a reaction product obtained from a reaction mixture of an aminosilane of formula (I), a mecaptosilane of formula (II) and an epoxysilane of formula (III). Said compositions are suitable as bonding agents, especially in the form of primers. The are highly adhesive and especially suitable for low-temperature applications and especially for sticking glass together.

Description

ADHESIVE INCLUDING A SILANE REACTION PRODUCT

Technical area

The present invention relates to the field of adhesion promoters, in particular the primer compositions.

State of the art

Bonding is a widely used connection technology. Due to the large number of possible substrates which are glued together, there are always substrates that can build up with some adhesives no or insufficient adhesion. In order to improve the adhesion of adhesives and sealants to these substrates, adhesion promoters have been used for some time, especially in primers.

As adhesion promoters are usually silanes, often used as mixtures. For example, WO-A-2005/059056 describes a primer which comprises, in addition to an organotitanate and an organic solvent, a mercaptosilane and a polyaminosilane and secondary aminosilane.

It is also known to use adducts of aminosilanes and epoxysilanes. Such adducts as a component of primers are described, for example, in US Pat. No. 5,336,748 and EP-A-1 172 424.

However, the adhesion promoters of the prior art, in particular with regard to moisture-curing one-component polyurethane adhesives, frequently have adhesion problems at a low application temperature.

Presentation of the invention

The object of the present invention is therefore to provide adhesion promoters which have good adhesions of one-component moisture-curing polyurethane adhesives, in particular on glass and glass ceramics, and in particular at low application temperatures.

Surprisingly, it has now been found that the compositions according to claim 1 can achieve this object. The compositions are particularly suitable as primers for one-component moisture-curing polyurethane adhesives and are advantageously used for the bonding of glass and glass ceramic. Particularly suitable they have shown in use as a primer for the glazing of means of transport, especially road vehicles. Particularly surprisingly, they show improved low-temperature adhesion and are therefore particularly suitable for repair glazing, which is often carried out outdoors in every season.

Further advantageous embodiments of the invention are objects of further independent and dependent claims.

Ways to carry out the invention

The invention relates, on the one hand, to compositions according to claim 1. Such compositions comprise at least one

Reaction product obtained from a reaction mixture comprising at least one aminosilane of the formula (I)

R ^J -Si (OR ² ) _(3.a) (R ³ ) _£ (I);

at least one mercaptosilane of the formula (II)

at least one epoxy silane of the formula

1 "

R -Si (OR ^{2 "} ) (3-c) (R ^3" ) _c

or they consist of at least one such reaction product.

R ¹ here stands for an n-valent organic radical having at least one primary and / or secondary amino group. R ¹ stands for a m valent organic radical having at least one mercapto group. R ¹ is a p-valent organic radical having at least one epoxy group. Furthermore, R ² , R ² and R ² independently of one another represent an alkyl group having 1 to 4 C atoms and R ³ , R ³ and R ³ independently of one another represent H or an alkyl group having 1 to 10 C atoms. Finally, a, b and c are independently of each other 0, 1 or 2 and n, m and p are independently 1, 2, 3 and 4.

The aminosilane, mercaptosilane and epoxysilane may thus have one or more silane groups.

In a preferred embodiment, a is 0 and R ² is methyl or ethyl. Furthermore, b is preferably 0 and R ^{2 is} methyl or ethyl. Furthermore, c is preferably 0 and R ^{2 is} methyl or ethyl.

Particularly preferably, a, b and c are each 0 and R ² , R ² and R ^{2 are} each methyl or ethyl, in particular methyl.

The indices m and p are preferably each given the value 1 and the index n is the value 1 or 2.

In the present document, the term "organoalkoxysilane" or "SNan" for short denotes compounds in which at least one, usually two or three, alkoxy groups are bonded directly to the silicon atom (via a Si-O bond), and on the other hand have at least one directly to the silicon atom (via a Si-C bond) bound organic radical and have no Si-O-Si bonds. Accordingly, the term "silane group" denotes the silicon-containing group bonded to the organic radical of the organoalkoxysilane The organoalkoxysilanes, or their silane groups, have the property of hydrolyzing on contact with moisture, forming organosilanols, ie organosilicon compounds containing one or more silanol groups (Si-OH groups) and, by subsequent condensation reactions, organosiloxanes, that is, organosiloxanes containing one or more siloxane groups (Si-O-Si groups). Terms such as "aiminosilane", "epoxy silane" and "mercaptosilane" refer to silanes which have the corresponding functional group (primary amino, secondary amino or tertiary amino group, -SH, COC).

The aminosilane of the formula (I) preferably has at least one primary and / or secondary amino group and is preferably an aminosilane of the formula (IV), (V), (VI) or (VII):

H ₂ NR ⁴ -Si (OR ² ) _(3.a) (R ³ ) _a (IV)

H ₂ N ^^ NR ⁴ -Si (OR ² ) _(3.a) (R ³ ) _{a (V} )

H ₂ NN NR ⁴ -Si (OR ² ) _(3.a) (R ³ ) _{a (V} |)

where R ^{4 is} a linear or branched alkylene group having 1 to 6 C atoms, in particular propylene. Examples of such aminosilanes of the formula (IV), (V), (VI) or (VII) are 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-amino-2-methylpropyltrimethoxysilane, 4-aminobutyltrimethoxysilane, 4-amino-butyl-dimethoxymethylsilane, 4-amino-3-methylbutyl-trimethoxysilane, 4-amino-3,3-dimethylbutyl-thmethoxysilane, 4-amino-3,3-dimethylbutyl-dimethoxymethyl-silane, 2-aminoethyl-thmethoxysilane, 2-aminoethyl-dimethoxymethylsilane, aminomethyl-thmethoxysilane, aminomethyl-dimethoxymethylsilane, amino-methylmethoxydimethylsilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3- [2- (2-aminoethylamino) -ethylamino] -propyl-thmethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, bis (trimethoxysilylpropyl) amine, and their analogues with ethoxy or isopropoxy groups instead of the methoxy groups on the silicon.

It has been shown that secondary aminosilanes have better properties than primary aminosilanes. Particularly suitable aminosilanes of the formula (IV), (V),

(VI) or (VII) in which R ^{4 is} propylene, a is 0 and R ^{2 is} methyl or ethyl. Most preferred are the aminosilanes which are selected from the group consisting of 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyl-thmethoxysilane and bis (thmethoxysilylpropyl) amine,

The mercaptosilane of the formula (II) is preferably a mercaptosilane of the formula (VIII):

HS-R ⁴ -Si (OR ^{2 '} ) _(3.b) (R ^3' ) _b (VIII) where R ^{4 is} a linear or branched alkylene group having 1 to 6 C atoms, in particular propylene.

Mercaptosilanes of the formula (VIII) in which R ^{4 is} propylene, b is 0 and R ^{2 is} methyl or ethyl are particularly suitable. Particularly preferred mercaptosilanes are 3-mercaptopropyl-thmethoxysilane and 3-mercaptopropyl-triethoxysilane.

The epoxysilane of the formula (III) is preferably an epoxysilane of the formula (IX) or (XI):

where R ^{4 is} a linear or branched alkylene group having 1 to 6 C atoms, in particular propylene. Particularly suitable epoxysilanes of the formula (IX) or

(X) in which R ^{4 is} propylene, c is 0 and R ^{2 is} methyl or ethyl.

The most preferred epoxysilanes are 2- (3,4-epoxycyclohexyl) ethyl-th-methoxysilane, 2- (3,4-epoxycyclohexyl) -ethyl-thethoxysilane, 3-glycidyloxypropyl-thethoxysilane and 3-glycidyloxypropyl-thmethoxysilane.

The epoxy silane preferably carries a glycidyloxy group. Preferred epoxysilanes are 3-glycidyloxypropyl-triethoxysilane and 3-glycidyloxypropyl-thmethoxysilane. The most preferred epoxysilane is 3-glycidyloxypropyl-thmethoxysilane.

From the reaction mixture aminosilane of the formula (I), mercaptosilane of the formula (II) and epoxysilane of the formula (III), a reaction product is formed. This can be seen on the one hand by a heat of reaction and on the other hand by a change in the IR spectra. Since the reactions that take place are sometimes very complex, it is extremely difficult to specify the structures that are precisely formed in the reaction mixture. Typically, structures of the formula (XI) and / or (XII) are formed here.

(R ³ ) _b (R ^{2 '} O) ₍₃ - _b) Si-RS ⁴ OR ⁴ -Si (OR ^2' ) _(3.c) (R ^{3 '} ) _{c (χ |} _I ₎

OH R ^{5 in} this case represents H, a C ₁ -C 20 -alkyl, cycloalkyl or aryl radical or a radical of the formula -R ⁴ -Si (OR ² ) ₍₃ - _a ) (R ³ ) a and R ⁴ and R ^{4 "are} independently of each other a linear or branched alkylene group having 1 to 6 C-atoms, in particular propylene.

Mercaptosilane and epoxysilane typically react faster than epoxysilane and aminosilane. The first reaction results in a structural element of the formula (XIII) and in the second reaction a structural element of the formula (XIV) When the aminosilane is a primary aminosilane, sometimes the structural element of the formula (XV) is also formed.

These structural elements of the formulas (XIII), (XIV) and (XV) may also be present simultaneously.

The reaction product is obtained from a reaction mixture comprising aminosilane, epoxysilane and mercaptosilane.

The epoxysilane of the formula (III) is preferably used substoichiometrically with respect to the mercaptosilane of the formula (II). In one embodiment, the aminosilane of formula (I), which is

Mercaptosilane of the formula (II) and the epoxy silane of the formula (III) are used in such a ratio that the number of epoxy groups is equal to or greater than the sum of the number of mercapto groups and the number of primary amino groups. Preference is given to mercaptosilane of the formula (II) and aminosilane

Formula (I) in the total non-stochiomethsch to Epoxysilan of formula (III). In particular, this ratio is more than 2 or less than 0.5.

The aminosilane of the formula (I) and the mercaptosilane of the formula (II) are preferably initially charged and then the epoxysilane of the formula (III) is added. However, it may also be advantageous to initially introduce the epoxysilane of the formula (III) and then add the aminosilane of the formula (I) and the mercaptosilane of the formula (II) separately or together. The addition is in each case of advantage with intensive stirring.

The composition may optionally have other ingredients. However, such further ingredients should not affect the storage stability of the composition. As additional constituents are, for example, solvents, inorganic fillers, catalysts and stabilizers, surfactants, acids, dyes, pigments and other adhesion promoter substances.

It has proven particularly advantageous if the composition contains a solvent. On the one hand, in particular organic solvents, especially those having a boiling point below 100 ° C are suitable. Particularly suitable as such organic solvents are hydrocarbons, ketones, carboxylic esters or alcohols. Examples of these are hexane, heptane, methyl ethyl ketone, acetone, butyl acetate, ethyl acetate, methanol, ethanol, propanol, isopropanol or butanol.

On the other hand, water is suitable as a solvent.

Suitable adhesion promoter substances are, in particular, tetraalkoxysilanes, organoalkoxysilanes, organotitanium compounds and organozirconium compounds, and mixtures thereof. As organoalkoxysilanes are in addition to the already mentioned aminosilanes, epoxy silanes and mercaptosilanes in particular (meth) acrylatosilane and vinyl silane, in particular 3- (meth) acryloxypropyl triethoxysilane, 3- (meth) acryloxypropylthmethoxysilane, vinylthmethoxysilane and vinyltriethoxysilane to call.

In principle, all organotitanium compounds which are known to the person skilled in the art and which are used as adhesion promoters are suitable as organotitanium compounds. The organotitanium compound preferably carries at least one group which hydrolyzes under the influence of water and leads to the formation of a Ti-OH group. Preferably, such an organotitanium compound carries at least one functional group selected from the group consisting of alkoxy group, sulfonate group, carboxylate group Acetylacetonate, or mixtures thereof, and which is bonded via an oxygen-titanium bond directly to a titanium atom.

As alkoxy groups, in particular so-called neoalkoxy substituents have proven particularly suitable. Particularly suitable sulfonic acids are aromatic sulfonic acids whose aromatics are substituted by an alkyl group, in particular p-dodecylbenzenesulfonic acid. In particular, carboxylates of fatty acids have proved particularly suitable as carboxylate groups. Preferred carboxylates are decanoate.

As the organozirconium compound, basically all organozirconium compounds known to those skilled in the art which are used as adhesion promoters are suitable. The organozirconium compound preferably carries at least one group which hydrolyzes under the influence of water and leads to the formation of a Zr-OH group. Such an organozirconium compound preferably carries at least one functional group which is selected from the group comprising alkoxy group, sulfonate group, carboxylate group, phosphate or mixtures thereof, and which is bonded directly to a zirconium atom via an oxygen-zirconium bond.

Particularly suitable alkoxy groups are isopropoxy and so-called neoalkoxy substituents. Particularly suitable sulfonic acids are aromatic sulfonic acids whose aromatics are substituted by an alkyl group, in particular p-dodecylbenzenesulfonic acid. In particular, carboxylates of fatty acids have proved particularly suitable as carboxylate groups. Preferred carboxylates are stearate.

Organozirconium compounds and organotitanium compounds are widely available commercially, for example from Kenrich Petrochemicals or DuPont, such as NZ 38J, NZ TPPJ, KZ OPPR, KZ TPP, NZ 01, NZ 09, NZ 12, NZ38, NZ 44, NZ 97 from Kenrich Petrochemicals, Ken- React® KR TTS, KR 7, KR 9S, KR 12, KR 26S, KR 33DS, KR 38S, KR 39DS, KR44, KR 134S, KR 138S, KR 158FS, KR212, KR 238S, KR 262ES , KR 138D, KR 158D, KR238T, KR 238M, KR238A, KR238J, KR262A, LICA 38J, KR 55, LICA1, LICA 09, LICA 12, LICA 38, LICA 44, LICA 97, LICA 99, KR OPPR, KROPP2 from Kenrich Petrochemicals or Tyzor® ET, TPT, NPT, BTM AA, AA-75, AA-95, AA-105, TE, ETAM or OGT from DuPont.

In one embodiment of the invention, the composition is an aqueous composition which, in addition to the reaction product, contains water, a surfactant, and preferably an acid. Particularly suitable acids are an organic acid having a pKa of less than 5. In particular, organic carboxylic acids and sulfonic acids are suitable. As the carboxylic acid are in particular those to be mentioned which are selected from the group consisting of formic, acetic, propionic, trifluoroacetic, oxalic, malonic, succinic, maleic, fumaric and citric acid and amino acids, in particular aspartic acid and glutamic acid. Preference is given to acids which have a pK _a between 4.0 and 5. Such acids, because of their pK _a, have an excellent buffering effect in the optimum pH range of 3.5 to 4.5 of the aqueous composition for the present invention. By "pK _a " the chemist is known to mean the negative decadic logarithm of the acid dissociation constant K ₃ : pK _a = -log- ₁ K _a . Acetic acid is preferred as the carboxylic acid.

Organic sulfonic acids are compounds which have an organic radical having carbon atoms and at least one -SO ₃ H functional group. In particular, these are aromatic sulfonic acids which are mononuclear or polynuclear and may have one or more sulfonic acid groups. For example, these may be 1- or 2-naphthalenesulfonic acid, 1,5-naphthalenedisulfonic acid, benzenesulfonic acid or alkylbenzenesulfonic acids. Preferred aromatic sulfonic acids are p-alklylbenzenesulfonic acids, in particular p-toluenesulfonic acid and p-dodecylbenzylsulfonic acid.

The composition is excellent as a primer and can be widely used. In particular, it can be used as a primer or as a primer component. Under a primer is a primer understood, which is applied to a surface and after a certain waiting time after application, the so-called flash off time of an adhesive or sealant or a coating is covered and serves the adhesion of the adhesive or sealant or the coating on the substrate surface in question is improved ,

Typically, such a primer contains a binder which is preferably a reactive binder, especially epoxy or isocyanate based.

However, the composition may also be used as a primer in an adhesive or sealant or coating. Particularly suitable is the use in an adhesive or sealant.

In a first method of bonding or sealing, it comprises the following steps i) application of the described composition to a substrate to be bonded or sealed S1 ii) application of an adhesive or sealant to the aerated composition which is on the substrate S1 iii) contacting the adhesive or sealant with a second one

Substrate S2;

In a second method of bonding or sealing, it comprises the following steps i ') application of the described composition to a substrate to be bonded or sealed S1 ii') application of an adhesive or sealant to the surface of a second substrate S2 iii ') contacting the adhesive or Sealant having the aerated composition which is on the substrate S1;

In a third method of bonding or sealing, it comprises the following steps i ") application of the described composition to a substrate S1 ii" to be bonded or sealed.) aeration of the composition iii ") application of an adhesive or sealant between the surfaces of the substrate S1 and S2.

In all these three ways, the second substrate S2 is made of the same or different material as the substrate S1.

After step iii), iii ') or iii ") typically follows

Step of curing the adhesive or sealant. The person skilled in the art understands that, depending on the system used and reactivity of the adhesive, crosslinking reactions, and thus already curing, can already begin during the application. However, the main part of the crosslinking and thus in the narrower sense of the term curing takes place after the application, otherwise there are also problems with the buildup of adhesion to the substrate surface.

In particular, at least one of the substrates S1 or S2 is glass or glass ceramic. In particular, one substrate is glass or glass ceramic and the other substrate is a lacquer or a lacquered metal or a lacquered metal alloy. Thus, the substrate is S1, respectively S2, glass or glass ceramic and that the substrate S2, respectively S1, a paint or a painted metal or a painted metal alloy.

As adhesives or sealants, various adhesive or sealing systems can be used. In particular, these are moisture-curing adhesives or sealants based on prepolymers which are terminated with isocyanate groups and / or alkoxysilane. Suitable adhesives or sealants based on alkoxysilane-terminated prepolymers are one-component moisture-curing adhesives or sealants, the so-called MS polymers or alkoxysilane. terminated polyurethane prepolymers, in particular those prepared from polyols and isocyanates with subsequent reaction of an isocyanate-reactive organosilane or an isocyanate-functional organosilane.

Suitable adhesives or sealants based on isocyanate-terminated prepolymers are, on the one hand, two-component polyurethane adhesives or sealants whose first component comprises an amine or a polyol and whose second component comprises an NCO-containing prepolymer or a polyisocyanate. Examples of such two-component room temperature-curing polyurethane adhesives are those from SikaForce® product line, as are commercially available from Sika Schweiz AG.

Further suitable adhesives or sealants based on isocyanate-terminated prepolymers are reactive polyurethane hotmelt adhesives or sealants which comprise a thermoplastic polymer and an isocyanate-terminated prepolymer or a thermoplastic isocyanate-terminated prepolymer. Such reactive polyurethane hotmelts are melted and solidify on the one hand during cooling and on the other hand crosslink via a reaction with atmospheric moisture.

Suitable adhesives or sealants based on isocyanate-terminated prepolymers furthermore include one-component moisture-curing polyurethane adhesives. Such adhesives or sealants crosslink under the influence of moisture, in particular of

Humidity. Examples of such one-component moisture-curing

Polyurethane adhesives are those of the SikaFlex® and SikaTack® product line, as are commercially available from Sika Schweiz AG.

The above-mentioned isocyanate-terminated prepolymers are prepared from polyols, in particular polyoxyalkylene polyols, and polyisocyanates, especially diisocyanates.

Preference is given to adhesives based on isocyanate-terminated prepolymers.

Most preferably they are one-component moisture-curing polyurethane adhesives based on isocyanate-terminated prepolymers. It has been shown that especially in moisture-curing

Polyurethane adhesives or sealants greatly improve the adhesion at low temperatures, ie in particular one

Temperature of below 5 ° C, in particular at a temperature between 5 ° and -20 ° C, can be achieved using the described composition. It goes without saying that aqueous compositions are rather unsuitable for application temperatures below 0 ° C. because of ice formation.

These adhesive and sealing methods are used in particular in the production of articles for industrial production, in particular of transport. Such articles are in particular automobiles, buses, trucks, rail vehicles, ships or aircraft.

The most preferred application is the vitrification of means of transport, in particular of road and rail vehicles to call.

Due to the excellent improvement of the adhesion of adhesives and sealants at low temperatures, this method is particularly suitable for repair glazing. Namely, vehicles can be glazed on the road on site, especially in winter, without the vehicle must first be placed in a temperature controlled garage. This is especially important for repairs of vehicle windows, in sprawling areas, especially where the roads often have loose stones or gravel. Such areas are frequently found, for example, in Scandinavia, Russia, China, Argentina, Chile, Canada or the USA. Examples

compositions

The compositions according to Tables 2 and 3 were prepared by, if used, the aminosilane and the mercaptosilane was initially charged, and then with stirring, if present, the epoxysilane was slowly added. Subsequently, it was stirred for 4 days and

Ethyl acetate added. In Comparative Example Ref.7 triethylamine was as

Catalyst added. The compositions were after the

Manufactured in closed glass bottles and stored until shortly before application at room temperature.

Table 1: Abbreviations used

Table 2: Composition.

Table 3: Further compositions. The compositions were the following grounds using soaked lint-free Kleenex® cloth at the application temperature ( "Tapp") of 23 ° C and -1 ⁰ ° C is applied and during the flash-off time ( "IP") flashed off "disk 1": Windshield an Audi A4 (Sigla) (application on

Glass ceramic rim) "Disc 2": windscreen of a Toyota Starlet (Safevue)

(Application on glass ceramic rim)

"Scheibe 3": windscreen of a Mazda 6 (Guardian) (application on glass ceramic rim)

Float Glass, tin side: Rocholl GmbH, Germany

Both the compositions and the substrates were conditioned at the application temperature for at least 12 hours. Ref.1 is Sika® activator, commercially available from Sika Schweiz AG.

At the application temperature of SikaTack®-Move Goes Cool, respectively SikaTack @ -Drive (both commercially available from Sika Schweiz AG) were applied as a triangular bead (12 mm base, 8 mm height) and baked to a layer thickness of 4 mm compressed.

The adhesive was cured as follows:

1 day storage at the application temperature

6 days at 23 ° C / 50% rel. Humidity The adhesion of the adhesive was then assessed by means of a crawler test ("KR" air-conditioning).

Subsequently, the further storage was carried out and each liability also assessed by means of track test:

7 days under water (23 ° C, "W" - water storage) 7 days 70 ° C / 100% relative humidity ("CP" -Cataplasma) Adhesion test ("track test")

The adhesion of the adhesive was tested by means of a 'bead test'. This is cut at the end just above the adhesive surface. The cut end of the caterpillar is held with a pair of pliers and pulled from the ground. This is done by carefully rolling up the bead on the nipper tip, and placing a cut to the bare ground perpendicular to the caterpillar pulling direction. The caterpillar pull-off speed should be selected so that a cut must be made approx. Every 3 seconds. The test track must be at least 8 cm. The adhesive that remains after the removal of the caterpillar from the substrate (cohesive failure) is assessed. The assessment of the adhesive properties is carried out by estimating the cohesive part of the adhesive surface:

1 => 95% cohesive failure

2 = 75 - 95% cohesive failure 3 = 25 - 75% cohesive failure

4 = <25% cohesive failure

5 = 0% cohesive failure (purely adhesive fracture)

Test results with cohesive failure values of less than 75% are considered insufficient. The results are summarized in Tables 3, 4, 5 and 6.

Table 3. Adhesion results of SikaTack®-Move Goes Cool on disc 1.

Table 4. Adhesion results of SikaTack®-Move Goes Cool on disc 2.

Table 5: Adhesion results on slice 3 (T _app = 23 ^< O).

Table 6: Oat results on float glass (tin side) (T _app = 23 ^< O).

The results show that the compositions according to the invention are very suitable as adhesion promoters. Furthermore, the beneficial effect of the secondary aminosilanes over the primary aminosilanes is shown.

In particular, they show the advantageous suitability for the use of titanium acetate rati cation.

Claims

claims

A composition consisting of or containing at least one reaction product which is obtained from a reaction mixture comprising at least one aminosilane of the formula (I)

R ^; -Si (OR ² ) _(3.a) (R ³ ) _£ (I);

at least one mercaptosilane of the formula

at least one epoxy silane of the formula

where R ^{1 is} an n-valent organic radical having at least one primary and / or secondary amino group,

R ^{1 is} an m-valent organic radical having at least one

Mercapto group stands,

R ^{1 is} a p-valent organic radical having at least one

Epoxy group stands,

R ² , R ² and R ² independently of one another represent an alkyl group having 1 to 4

C atoms stands;

R ³ , R ³ and R ³ independently of one another represent H or an alkyl group having 1 to 10 C atoms; a, b and c independently of one another represent a value of 0, 1 or 2; and n, m and p independently of each other for the values 1,

2, 3 and 4 stands.

A composition according to claim 1, characterized in that a is 0 and R ^{2 is} methyl or ethyl.

3. A composition according to claim 1 or 2, characterized in that b is 0 and R ^{2 is} methyl or ethyl.

4. Composition according to one of the preceding claims, characterized in that c is 0 and R ^{2 is} methyl or ethyl.

5. Composition according to one of the preceding claims, characterized in that m and p are each 1 and n is 1 or 2.

6. Composition according to one of the preceding claims, characterized in that the aminosilane has the formula (IV) or (V) (VI) or (VII)

H ₂ NR ⁴ -Si (OR% _.a) (R ³ ) _a (IV)

H ₂ N NR ⁴ -Si (OR ² ) _(3.a) (R ³ ) _{a (V} )

where R ^{4 is} a linear or branched alkylene group having 1 to 6 C atoms, in particular propylene.

7. Composition according to one of the preceding claims, characterized in that the mercaptosilane has the formula (VIII)

8. Composition according to one of the preceding claims, characterized in that the epoxy silane has the formula (IX) or (X)

9. Composition according to one of the preceding claims, characterized in that the composition additionally comprises at least one solvent.

10. The composition according to claim 9, characterized in that the solvent is an organic solvent, in particular an organic solvent having a boiling point below 100 ° C, in particular a hydrocarbon, a ketone, carboxylic acid ester or an alcohol.

1 1. A composition according to claim 9, characterized in that the solvent is water.

12. The composition according to claim 9, 10 or 1 1, characterized in that the composition further contains a surfactant.

13. A composition according to any one of claims 9 to 12, characterized in that the composition further comprises an acid, in particular an organic acid having a pKa of less than 5 contains.

14. A composition according to any one of the preceding claims, characterized in that the epoxysilane of the formula (III) is substoichiomethsch with respect to the mercaptosilane of the formula (II).

15. A composition according to any one of the preceding claims, characterized in that the aminosilane of the formula (I), the mercaptosilane of the formula (II) and the epoxy silane of the formula (III) are used in such a ratio that the number of epoxy groups is equal to or greater is the sum of the number of mercapto groups and the number of primary amino groups.

16. A composition according to any one of the preceding claims, characterized in that the reaction product contains at least one compound of formula (Xl)

wherein R ^{5 is} H, a CrC ₂ O-alkyl, cycloalkyl or aryl radical or a

Radical of the formula -R ⁴ -Si (OR ² ) ₍₃ - _a ) (R ³ ) a, and R ⁴ and R ^{4 "} independently of one another represent a linear or branched alkylene group having 1 to 6 C atoms, in particular Propylene, stands.

17. A composition according to any one of the preceding claims, characterized in that the reaction product contains at least one compound of formula (XII)

(R ^{3 '} ) _b (R ^2' θ) ₍₃ - _b) Si-R ⁴ -S- ^ γ ^ OR ⁴ -Si (OR ² \ _3.c) (R ^{3 ''} ) _{c (χ | | )}

OH and R ⁴ and R ⁴ independently of one another are linear or branched

Alkylene group having 1 to 6 carbon atoms, in particular propylene, is.

18. A composition according to any one of the preceding claims, characterized in that the reaction product contains at least one compound which contains at least one structural element of the formula (XIII) and at least one structural element of the formula (XIV)

^{■ ~ ~ ~ S} '(XIII)

OH

R ⁵

wherein R ^{5 is} H, a CrC ₂ O-alkyl, cycloalkyl or aryl radical or a

Rest of the formula -R ⁴ -Si (OR ² ) ₍₃ - _a ) (R ³ ) a stands.

19. A composition according to any one of the preceding claims, characterized in that the reaction product contains at least one compound which contains at least one structural element of the formula (XIII) and at least one structural element of the formula (XV)

20. A process for preparing a composition according to any one of claims 1 to 19, characterized in that the aminosilane of the formula (I) and the mercaptosilane of the formula (II) are introduced and then the epoxysilane of the formula (III) is added.

21. Use of a composition according to any one of claims 1 to 19 as a primer.

22. Use of a composition according to any one of claims 1 to 19 as a primer.

23. Use of a composition according to any one of claims 1 to 19 as a primer in an adhesive or sealant.

24. A method for improving the adhesion of a one-component moisture-curing polyurethane adhesive or sealant at a temperature of less than 5 ° C, in particular at a temperature between 5 ° and -20 ° C, using a composition according to any one of claims 1 to 19.

25. Method for Bonding or Sealing comprising the Steps i) Application of a Composition according to one of Claims 1 to 19 to a substrate S1 to be bonded or sealed. Ii) Application of an adhesive or sealant to the vented article

Composition, which is located on the substrate S1 iii) contacting the adhesive or sealant with a second

Substrate S2; or i ') Application of a composition according to one of claims 1 to 19 to a substrate S1 to be bonded or sealed. Said application of an adhesive or sealant to the surface of a second substrate S2 iii') contacting the adhesive or sealant with the ventilated one

Composition which is on the substrate S1; or i ") application of a composition according to one of claims 1 to 19 to a substrate S1 ii" to be bonded or sealed off) air-drying of the composition iii ") application of an adhesive or sealant between the surfaces of the substrate S1 and S2, wherein the second substrate S2 is made of the same or different material as the substrate S1.

26. The method according to claim 25, characterized in that subsequent to step iii), iii ') or iii ") a step iv) of

Curing of the adhesive or sealant connects.

27. The method according to claim 25 or 26, characterized in that the step i), i ') or i ") at a temperature of 5 ° C to -20 ° C, in particular from 0 ° C to -15 ° C is performed ,

28. Method according to claim 25, characterized in that at least one of the substrates S1 or S2 is glass or glass ceramic.

29. The method according to any one of claims 25 to 27, characterized in that the substrate S1, respectively S2, glass or glass ceramic and that the substrate S2, respectively S1, a paint or a painted metal or a painted metal alloy.

30. Article for the production of a method according to one of claims 24 to 28 is performed.

31. An article according to claim 30, characterized in that the article is a means of transport, in particular an automobile, bus, truck,

Rail vehicle, a ship or an aircraft is.