WO2021037349A1

WO2021037349A1 - Multi-component crosslinkable materials based on organyloxysilane-terminated polymers and epoxy-functional compounds

Info

Publication number: WO2021037349A1
Application number: PCT/EP2019/072908
Authority: WO
Inventors: Volker Stanjek; Lars Zander
Original assignee: Wacker Chemie Ag
Priority date: 2019-08-28
Filing date: 2019-08-28
Publication date: 2021-03-04

Abstract

The invention relates to multi-component crosslinkable materials of silane-crosslinking prepolymers, characterized in that component (K1) contains 20 to 250 parts by weight of compounds (A) of formula (I) and 1 to 50 parts by weight of an accelerator (B) for the epoxide curing and component (K2) contains 100 parts by weight of an epoxy resin (C) having a number-average molar mass M_n of at least 700 g/mol, 0 to 10 parts by weight of water and 10 to 200 parts by weight of one or more compounds (D), which are selected from monomeric silanes (D1) of formula (II) and silicon resins (D2) with a number-average molar weight M_n of not more than 4000 g/mol containing units of formula (III), wherein die radicals and indices have the meaning given in claim 1. The invention also relates to processes for the production thereof and to their use as coatings, adhesives and sealants.

Description

Multi-component crosslinkable compounds based on organyloxysilane-terminated polymers and epoxy-functional compounds

The invention relates to multicomponent crosslinkable compositions of silane crosslinking prepolymers, processes for their production and their use as coatings, adhesives and sealants.

Polymer systems which have reactive alkoxysilyl groups have long been known. When they come into contact with water or air moisture, these alkoxysilane-terminated polymers are already able to condense with one another at room temperature with elimination of the alkoxy groups. One of the most important uses of such materials is the production of adhesives, especially elastic adhesive systems.

For example, adhesives based on alkoxysilane-crosslinking polymers show very interesting mechanical properties in the cured state; in particular, they can convince with very good elastic properties, but their hardness and tear resistance are generally rather moderate. In this way, adhesives and coatings with significantly higher strength can be produced on the basis of polyurethane or epoxy systems. For this reason, silane-crosslinking polymer systems can usually not be used in applications in which corresponding properties are required.

At the same time, however, the alternative polyurethane and epoxy systems also have significant disadvantages inherent in the system. One-component PU adhesive systems, for example, usually only have moderate curing speeds. It is true that the isocyanate crosslinking can in principle be greatly accelerated by catalysis. But since such a catalysis basically also catalyze undesired side reactions of the isocyanate groups (e.g. formation of allophanates, uretdiones, isocyanurates etc.) _/ the corresponding systems then no longer have adequate storage stability.

Another disadvantage of isocyanate-curing adhesives is their health classification, which ranges from sensitizing to toxic. The critical factor here is the amount of remaining monomeric isocyanates, which are difficult to remove. This is problematic for the end user, ie the craftsman or do-it-yourself user, since he not only comes into contact with the cured and thus isocyanate-free and completely harmless product, but also with the isocyanate-containing adhesive or monomeric isocyanates comes. For inexperienced do-it-yourselfers, there is a particular risk that the products may not be used expertly and / or properly. With professional users, on the other hand, there may be the problem that they have to deal with the isocyanate-containing material extremely regularly - possibly even several times a day.

In addition, isocyanate-crosslinking adhesives can usually not be applied to moist substrates, since the CCy development associated with isocyanate hardening can otherwise lead to the formation of bubbles, which is particularly unacceptable for mechanically highly stressed bonds or coatings.

Epoxy systems, on the other hand, have a very high level of hardness, but are usually extremely stiff and brittle and are therefore not suitable for applications where, in addition to high strength, a certain ductility is required. In addition, reactive epoxy systems often contain components that are classified as water-endangering, toxic, irritant and / or sensitizing and can lead to contact dermatitis during processing, for example. Accordingly, such epoxy systems are subject to labeling in Europe, among others.

Mixing systems which contain both product types represent an option that has long been known for obtaining products that have neither the low hardness of systems based on alkoxysilane-terminated polymers nor the high brittleness of epoxy systems. Mixing systems of this type are described in EP-A 0186191, EP-A 1179571 or EP-A 1695989, among others. Typically, these are so-called 2-component systems (2K systems) in which one component contains a reactive epoxy resin and the second component optionally contains an amine hardener or a catalyst, in the presence of which the epoxides condense with one another.

Typically, one component also contains the silane-mined polymer and the other component water, so that silane and epoxy curing can take place in parallel after the two components have been combined, directly before use.

However, this approach does not solve the problem that these mixed systems contain the same reactive epoxides that are classified as hazardous to water, toxic, irritant and / or sensitizing. For reasons of environmental protection, safety and industrial hygiene, label-free formulations would be desirable here that have no or only a significantly reduced sensitizing potential.

In this regard, it is known that reactive epoxy resins with a molar mass of at least 700 g / mol are not sensitizing and do not require labeling. Examples are high molecular weight solids based on diglycidyl ethers Bisphenol A (DGEBA) and liquid epoxy-terminated polyethers. However, these toxicologically uncritical epoxides have the disadvantage that, because of their comparatively low content of epoxy functions, they do not lead to products which show the desired strength after curing. Other high molecular weight epoxides with a high content of epoxy groups, the so-called novolaks, are solid or highly viscous at room temperature. Mixtures based on this material are difficult or impossible to process at room temperature.

The object of the invention was therefore to provide curable formulations which contain both alkoxysilane-terminated polymers and reactive epoxides which are advantageous from a toxicological and dermatological point of view and yet have no disadvantages in use, in particular no excessively high viscosities.

The invention relates to multicomponent crosslinkable masses (K) containing at least one component (Kl) and one component (K2), characterized in that component (Kl)

20 to 250 parts by weight of compounds (A) of the formula

Y - [(CR ¹ _{2) b} -SiR _a (OR ² ) 3- _a ] x (I), where

Y denotes an x-valent polymer residue bound via nitrogen, oxygen, sulfur or carbon,

R can be the same or different and represents a monovalent, optionally substituted hydrocarbon radical, R ^{1 can be} identical or different and represents a hydrogen atom or a monovalent, optionally substituted hydrocarbon radical, which via nitrogen, phosphorus, oxygen The substance, sulfur or carbonyl group can be attached to the carbon atom,

R ^{2 can be the} same or different and is a hydrogen atom or a monovalent, optionally substituted hydrocarbon radical, x is an integer from 1 to 10, preferably 1, 2 or 3, particularly preferably 1 or 2, a can be identical or different and 0, 1 or 2, preferred

0 or 1, and b can be identical or different and is an integer from 1 to 10, preferably 1, 3 or 4, particularly preferably 1 or 3, in particular 1, as well as

Contains 1 to 50 parts by weight of an accelerator (B) for epoxy curing and component (K2)

100 parts by weight of an epoxy resin (C) with a number average molar mass M _n of at least 700 g / mol,

0 to 10 parts by weight of water and

Contains 10 to 200 parts by weight of one or more compounds (D) selected from monomeric silanes (Dl) of the formula

R ⁴ _c -Si (OR ³ ) _4-C (II) where

R ^{3 can be} identical or different and represent monovalent hydrocarbon radicals with 1 to 10 carbon atoms, optionally substituted with halogen atoms, R ^{4 can be the} same or different and denotes a monovalent, optionally substituted hydrocarbon radical, where any substituents present are free of basic nitrogen, and c is 0, 1 or 2, and silicone resins (D2) with a number average molecular weight M _n of a maximum of 4000 g / mol containing units of the formula

R ⁶ _e (R ⁵ 0) SiO (4-de) / 2 (III) wherein

R ^{5 can be} identical or different and represent monovalent hydrocarbon radicals with 1 to 10 carbon atoms, optionally substituted with halogen atoms,

R ^{6 may be the} same or different and denote a monovalent, optionally substituted hydrocarbon radical, where any substituents present do not contain any nitrogen atom, d is 0, 1, 2 or 3, preferably 0, 1 or 2, and e is 0, 1, 2 or 3, preferably 1 or 2, where the sum of d + e is less than or equal to 3 and at least 50% of the units of the formula (III) e is 0 or 1.

The number average molar mass M _n is determined within the scope of the present invention by means of size exclusion chromatography (SEC) against polystyrene standard, in THF, at 60 ° C, flow rate 1.2 ml / min and detection with RI (refractive index detector) on a column set Styragel HR3-HR4-HR5-HR5 from Waters Corp. USA determined with an injection volume of 100 mΐ. The compositions (K) according to the invention are preferably two-component compositions which consist of components (Kl) and (K2).

Components (K1) and (K2) are preferably kept separately during storage and mixed with one another shortly before or during application.

Examples of radicals R are alkyl radicals such as methyl, ethyl, n-propyl, iso-propyl, 1-n-butyl, 2-n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl, tert-pentyl radical; Hexyl radicals, such as the n-hexyl radical; Heptyl radicals, such as the n-heptyl radical; Octyl radicals, such as the n-octyl radical, iso-octyl radical and the 2,2,4-trimethylpentyl radical; Nonyl radicals, such as the n-nonyl radical; Decyl radicals, such as the n-decyl radical; Dodecyl radicals, such as the n-dodecyl radical; Octadecyl radicals, such as the n-octadecyl radical; Cycloalkyl radicals, such as the cyclopentyl, cyclohexyl, cycloheptyl radical and methylcyclohexyl radicals; Alkenyl radicals, such as the vinyl, 1-propenyl and 2-propenyl radical; Aryl radicals, such as the phenyl, naphthyl, anthryl and phenanthryl radical; Alkaryl radicals, such as o-, m-, p-tolyl radicals; Xylyl residues and ethylphenyl residues; and aralkyl radicals, such as the benzyl radical, the α- and the β-phenylethyl radical.

Examples of substituted radicals R are haloalkyl radicals, such as the 3,3,3-trifluoro-n-propyl radical, the 2,2,2,2 ', 2', 2'-hexafluoroisopropyl radical and the heptafluoroisopropyl radical, and haloaryl radicals, such as the o-, m- and p-chlorophenyl radical.

The radical R is preferably monovalent hydrocarbon radicals with 1 to 6 carbon atoms, optionally substituted with halogen atoms, particularly preferably unsubstituted alkyl radicals with 1 or 2 carbon atoms, in particular the methyl radical. Examples of radicals R ¹ are hydrogen, the radicals indicated for R and optionally substituted hydrocarbon radicals bound to the carbon atom via nitrogen, phosphorus, oxygen, sulfur, carbon or carbonyl groups.

The radical R ¹ is preferably a hydrogen atom or hydrocarbon radicals having 1 to 20 carbon atoms, in particular a special hydrogen atom.

Examples of radical R ² are hydrogen or the examples given for radical R.

The radical R ² is preferably a hydrogen atom or alkyl radicals with 1 to 10 carbon atoms which are optionally substituted by halogen atoms, particularly preferably alkyl radicals with 1 to 4 carbon atoms, in particular the methyl or ethyl radical.

Polymers on which the polymer radical Y is based are to be understood in the context of the present invention as all polymers in which at least 50%, preferably at least 70%, particularly preferably at least 90%, of all bonds in the main chain are carbon-carbon, carbon Nitrogen or carbon-oxygen bonds are.

Examples of polymer radicals Y are polyester, polyether, polyurethane, polyalkylene and polyacrylate radicals.

Polymer radical Y is preferably organic polymer radicals, the polymer chain being polyoxyalkylenes such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer and polyoxypropylene len-polyoxybutylene copolymer; Hydrocarbon polymers such as polyisobutylene and copolymers of polyisobutylene with isoprene; Polychloroprene; Polyisoprenes; Polyurethanes; Polyester; Polyamide; Polyacrylates; Polymetacrylates; Vinyl polymer and polycarbonates contain and which are preferably via -OC (= 0) -NH-, -NH- C (= 0) 0-, -NH-C (= 0) -NH-, -NR'-C (= 0) -NH-, NH-C (= 0) -NR'-, -NH- C (= 0) -, -C (= 0) -NH-, -C (= 0) -0-, -0 -C (= 0) -, -0-C (= 0) -0-, -S- C (= 0) -NH-, -NH-C (= 0) -S-, -C (= 0) -S-, -SC (= 0) -, -SC (= 0) -S-,

—C (= 0) -, -S-, -0-, -NR'- are bonded to the group or groups - [(CR ¹ 2) _b ^_ SiR _a (OR ² ) 3_ _a ], where R ' can be identical or different and has a meaning given for R or represents a group -CH (COOR ") - CH2-COOR", in which R "can be identical or different and has a meaning given for R.

The radical R 'is preferably a group -CH (COOR ") - CH2-COOR" or an optionally substituted hydrocarbon radical having 1 to 20 carbon atoms, particularly preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms or an aryl group with 6 to 20 carbon atoms which is optionally substituted by halogen atoms.

Examples of radicals R 'are cyclohexyl, cyclopentyl, n- and iso-propyl, n-, iso- and t-butyl, the various sterioisomers of the pentyl radical, hexyl radical or heptyl radical and the phenyl radical.

The radicals R ″ are preferably alkyl groups with 1 to 10 carbon atoms, particularly preferably methyl, ethyl or propyl radicals. Component (A) can have the groups attached in the manner described - [(CR ^) _b -SiR _a (OR ² ) 3_ _a ] at any points in the polymer, such as chain and / or terminal.

The radical Y is preferably polyurethane radicals or polyoxyalkylene radicals, particularly preferably chain-like polyurethane radicals or chain-like polyoxyalkylene radicals, each with 0 to 3 branching points with end-attached groups - [(CR ^) _b ^_ SiR _a (OR ² ) 3_ _a ], where branch points in the context of the invention are to be understood as all branches from the main chain with more than one carbon atom and the radicals and indices have the meanings given above.

In particular, radical Y in formula (I) is chain-like polyurethane radicals or chain-like polyoxyalkylene radicals without branching points with end-attached groups - [(CR ^) _b ^_ SiR _a (OR ² ) 3_ _a ], the radicals and indices being the have the above meanings.

The polyurethane radicals Y are preferably those whose chain ends are via -NH-C (= 0) 0-, -NH-C (= 0) -NH-, -NR'- C (= 0) -NH- or -NH-C (= 0) -NR'-, in particular via -OC (= 0) -NH- or -NH-C (= 0) -NR'-, to the group or groups - [(CR ¹ 2) _b ^_

SiR _a (OR ² ) 3_ _a ] are bound, all radicals and indices having one of the above meanings. The polyurethane radicals Y can preferably be produced from linear or branched polyoxyalkylenes, in particular from polypropylene glycols, and di- or polyisocyanates. The radicals Y preferably have mean molar masses M _n (number average) of 400 to 30,000 g / mol, preferably from 4,000 to 20,000 g / mol. Suitable processes for the preparation of a corresponding component (A) as well as examples of component (A) itself are, inter alia, in EP 1093 482 B1 (paragraphs [0014] - [0023], [0039] - And Example 1 and Comparative Example 1) or EP 1 641 854 B1 (paragraphs [0014] - [0035], Examples 4 and 6 and Comparative Examples 1 and 2), which are to be included in the disclosure of the present application .

The polyoxyalkylene radicals Y are preferably linear or branched polyoxyalkylene radicals, particularly preferably polyoxypropylene radicals, the chain ends of which are preferably connected to the group or groups via -OC (= 0) -NH- or -0- [(CR ¹ 2) _b ^_

SiR _a (OR ² ) 3_ _a ] are bonded, the radicals and indices having one of the meanings given above. Preferably at least 85%, particularly preferably at least 90%, in particular at least 95%, of all chain ends via -OC (= 0) -NH- to the group - [(CR ^) _b ^_ SiR _a (OR ² ) _{3- a} ] bound. The polyoxyalkylene radicals Y preferably have average molar masses M _{n of} from 4,000 to 30,000 g / mol, preferably from 8,000 to 20,000 g / mol. Suitable processes for producing a corresponding component (A) and also examples of component (A) itself are, inter alia, in EP 1535 940 B1 (paragraphs [0005] - [0025] and examples 1-3 and comparative examples 1-4) or EP 1896 523 B1 (paragraphs [0008] - [0047]), which are to be included in the disclosure content of the present application.

The end groups of the compounds (A) used according to the invention are preferably those of the general formulas

-NH-C (= 0) -NR '- (CR ² ₂ ) _b -SiR _a (OR ² ) _3-a (IV),

-OC (= 0) -NH- (CR ² ₂ ) _b -SiR _a (OR ² ) _3-a (V) or

-o- (CR ¹ ₂ ) _b ^_ SiR _a (OR ² ) _3-a (VI), where the radicals and indices have one of the meanings given above for it.

If the compounds (A) are polyurethanes, which is preferred, they preferably have one or more of the end groups -NH-C (= 0) -NR '- (CH ₂₎ s-Si (OCH _{3) 3} ,

-NH-C (= 0) -NR '- (CH ₂₎ s-Si (OC ₂ H _{5) 3} ,

-OC (= 0) -NH- (CH ₂₎ 3-Si (OCH _{3) 3} or

-OC (= 0) -NH- (CH _{2) 3} -Si (OC ₂ H _{5) 3} , where R 'has the meaning given above.

If the compounds (A) are polypropylene glycols, which is particularly preferred, they preferably have one or more of the end groups -0- (CH _{2) 3} -Si (CH _{3) (} OCH _{3) 2} ,

-0- (CH _{2) 3} -Si (OCH _{3) 3} ,

-OC (= 0) -NH- (CH _{2) 3} -Si (OC ₂ H _{5) 3} ,

-OC (= 0) -NH-CH ₂ -Si (CH _{3) (} OC ₂ H _{5) 2} ,

-OC (= 0) -NH-CH ₂ -Si (OCH _{3) 3} ,

-0-C (= 0) -NH-CH ₂ -Si (CH _{3) (} OCH _{3) 2} or -OC (= 0) -NH- (CH _{2) 3} -Si (OCH _{3) 3} , where the the latter two end groups are particularly preferred.

The average molecular weights M _{n of} the compounds (A) are preferably at least 400 g / mol, particularly preferably at least 4000 g / mol, in particular at least 10,000 g / mol, and preferably at most 30,000 g / mol, particularly preferably at most 20,000 g / mol mol, in particular at most 19,000 g / mol.

The viscosity of the compounds (A) is preferably at least 0.2 Pas, preferably at least 1 Pas, particularly preferably at least 5 Pas, and preferably at most 700 Pas, preferably at most 100 Pas, each measured at 20 ° C.

In the context of the present invention, the viscosity of non-pasty liquids is determined after heating to 23 ° C. with a DV 3 P rotary viscometer from A. Paar (Brookfield systems) using spindle 6 at 5 Hz in accordance with ISO 2555 .

The compounds (A) used in accordance with the invention are commercially available products or can be prepared by methods customary in chemistry.

The polymers (A) can be prepared by known processes, such as addition reactions such as hydrosilylation, Michael addition, Diels-Alder addition or reactions between isocyanate-functional compounds with compounds which have isocyanate-reactive groups.

The component (A) used according to the invention can contain only one type of compound of the formula (I) as well as mixtures of different types of compounds of the formula (I). Component (A) can exclusively contain compounds of the formula (I) in which more than 90%, preferably more than 95% and particularly preferably more than 98%, of all silyl groups bonded to the radical Y are identical. However, it is then also possible to use a component (A) which at least partially contains compounds of the formula (I) in which different silyl groups are bonded to a radical Y. Finally, as component (A) it is also possible to use mixtures of different compounds of the formula (I) in which a total of at least 2 different types of silyl groups bonded to radicals Y can be used are present, but all of the silyl groups bonded to one radical Y are identical.

Component (Kl) preferably contains compounds (A) in concentrations of at most 90% by weight, particularly preferably at most 70% by weight, and preferably at least 10% by weight, particularly preferably at least 30% by weight.

Component (Kl) preferably contains 40 to 200 parts by weight, particularly preferably 60 to 170 parts by weight, of compounds (A) of the formula (I), each based on 100 parts by weight of compound (C) in component (K2).

Suitable accelerators (B) used according to the invention are substances which accelerate the reaction of epoxy groups with amino and / or hydroxyl groups.

All compounds can be used as accelerators (B) who have also been used to date to accelerate the reaction of epoxy groups with amino and / or hydroxyl groups.

The accelerator (B) used according to the invention is preferably acids such as organic carboxylic acids such as acetic acid, benzoic acid, salicylic acid, 2-nitrobenzoic acid and lactic acid, organic sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid and 4-dodecylbenzenesulfonic acid, inorganic acids such as, in particular, phosphoric acid, or mixtures of the aforementioned acids; tertiary amines, such as triethylamine, tributylamine, N, N-bis (N, N-dimethyl-2-aminoethyl) methylamine, N, N-dimethylcyclohexylamine, N, N-dimethylphenylamine, 1,4-diazabicyclo [ 2. 2.2] octane, benzyldimethylamine, o-methylbenzyldimethylamine, triethanolamine, dimethyl-aminopropyl-dimethylamine, imida Zoles, such as N-methylimidazole, N-vinylimidazole, 1,2-dimethylimidazole, N, N-dimethyl-1,3-propanediamine, 2- (dimethylaminomethyl) phenol and 2,4,6-tris (dimethylaminomethyl) phenol; Mannich bases; Salts of tertiary amines; quaternary ammonium salts such as benzyltrimethylammonium chloride; Amidines, such as, in particular, 1,8-diazabicyclo- [5.4.0] undec-7-ene (DBU) and 1,8-diazabicyclo- [4.3.0] non-5-ene (DBN); Guanidines, such as mono-, di-, tri-, tetra- and penta-methylguanidines; Phenols, in particular bisphenols, phenol resins, or polymers made from phenol, aldehydes, such as formaldehyde; Phosphites such as di- or triphenyl phosphites; or compounds containing mercapto groups.

Component (B) is particularly preferably acids, tertiary amines, amidines, guanidines, particularly preferably tertiary amines, 2,4,6-tris (dimethylaminomethyl) phenol being a particularly preferred example of a tertiary amine.

Component (Kl) preferably contains accelerator (B) in concentrations of 2 to 25% by weight, particularly preferably 3 to 15% by weight.

Component (Kl) preferably contains 2 to 25 parts by weight, particularly preferably 3 to 15 parts by weight, accelerator (B), based in each case on 100 parts by weight of compound (C) in component (K2).

Component (C) preferably does not contain any silicon atoms.

Examples of epoxy resins (C) used according to the invention with a number average molar mass of at least 700 g / mol are compounds containing epoxy groups based on diglycidyl ethers of bisphenol A (DGEBA), with epoxy groups termi- Nated polyethers and epoxy group-containing reaction products made from epichlorohydrin with one or more novolak resins.

In the context of the invention, novolak resins are condensation products of phenol derivatives with formaldehyde, where a formaldehyde-phenol ratio of less than 1: 1 is used. They are preferably obtained under acidic conditions, such as phenol novolaks, cresol novolaks or bisphenol F novolaks.

Novolaks preferred according to the invention which are used for the reaction with epichlorohydrin are the polycondensation products of formaldehyde with phenol, cresol and / or bisphenol such as bisphenol-F, the polycondensation products of formaldehyde with phenol and / or cresol being particularly preferred.

The epoxy resins (C) used according to the invention are preferably reaction products containing epoxy groups of epichlorohydrin with novolak resins.

The epoxy resins (C) used according to the invention are preferably compounds with an epoxy equivalent weight of at least 150 g / mol, particularly preferably at least 175 g / mol. The epoxy resins (C) used according to the invention preferably have an epoxy equivalent weight of at most 300 g / mol, particularly preferably of at most 250 g / mol.

The epoxy equivalent weight results from the number average molecular weight M _n , determined by the above method, divided by the number or by the average number of epoxy functions per molecule. The epoxy group-containing reaction products of epichlorohydrin with novolak resins (C) with a number average molar mass of at least 700 g / mol which are preferably used according to the invention are preferably compounds which have an epoxy functionality of at least 3 epoxy groups per molecule on average, particularly preferably an average at least 3.5 epoxy groups per molecule.

The epoxy resins (C) used according to the invention with a number-average molar mass of at least 700 g / mol can be solid or liquid.

If component (C) is liquid, it has a viscosity at 23 ° C. of preferably at least 1 Pas, preferably at least 10 Pas, particularly preferably at least 20 Pas, in particular at least 40 Pas.

The epoxy resins (C) used according to the invention are commercially available products or can be prepared by processes common in chemistry.

Particularly preferred epoxy resins (C) according to the invention are available, inter alia, under the trade names DEN 439 from Dow Chemical, Araldite ECN from Huntsman or Epikote 154 from Hexion.

The crosslinkable composition (K), in particular component (K2), preferably contains less than 50 parts by weight, particularly preferably less than 25 parts by weight, epoxy resins with a molar mass of less than 700 g / mol, in each case based on 100 parts by weight of epoxy resins according to the invention (C ). In particular, the crosslinkable mass (K) does not hold epoxy resins with a molar mass of less than 700 g / mol.

In a preferred embodiment, component (K2) according to the invention contains 10 to 90% by weight of epoxy resins (C), particularly preferably 30 to 85% by weight of epoxy resins (C) and in particular 50-80% by weight of epoxy resins ( C), each based on the total weight of all components of component (K2).

The water optionally used according to the invention can be any type of water, such as natural water such as rainwater, groundwater, spring water, river water and seawater, chemical water such as demineralized water, distilled or (multiple) redistilled water , Waters for medical or pharmaceutical purposes, such as purified water (Aqua purificata; Pharm. Eur. 3), Aqua deionisata, Aqua destillata, Aqua bidestillata, Aqua ad injectionam or Aqua conservata, drinking water in accordance with the German Drinking Water Ordinance and mineral water. The water optionally used according to the invention is preferably completely deionized water, distilled or (repeatedly) re-distilled water.

Component (K2) preferably contains water, amounts of preferably 0.1 to 10 parts by weight, particularly preferably 0.2 to 5 parts by weight, particularly preferably 0.3 to 3 parts by weight, in each case based on 100 parts by weight of compound (C) in component (K2).

Component (D) used according to the invention can be exclusively silanes (Dl), exclusively silicone resins (D2) or mixtures of silanes (Dl) and silicone resins (D2), component (D) being preferred around Silanes (Dl) or mixtures of silanes (Dl) and Siliconhar zen (D2) is, particularly preferably silanes (Dl).

Examples of radical R ³ in formula (II) are hydrogen and the examples given for radical R.

The radical R ³ is preferably a hydrogen atom or alkyl radicals with 1 to 10 carbon atoms which are optionally substituted by halogen atoms, particularly preferably alkyl radicals with 1 to 4 carbon atoms, in particular the methyl or ethyl radical.

Examples of radical R ⁴ are the examples given for radical R and epoxy-functional radicals such as the glycidoxypropyl radical, urea-alkyl radicals and O-alkyl-carbamatoalkyl radicals.

The radical R ⁴ is preferably alkyl radicals with 1 to 16 carbon atoms, in particular methyl, ethyl, propyl, n-octyl, iso-octyl or hexadecyl radicals, aryl radicals, in particular phenyl radicals, alkenyl radicals, in particular Vinyl radicals, O-alkyl-carbamatoalkyl radicals, in particular O-methylcarbamatopropyl or O-ethyl-carbamatopropyl radicals, or glycidoxypropyl radicals, whereby radical R ^{4 is} particularly preferably alkyl radicals with 1 to 16 carbon atoms or aryl radicals, especially about phenyl residues.

Index c is preferably 1 or 2, particularly preferably 1.

Preferred examples of silanes (Dl) are phenyltrimethoxysilane, phenyltriethoxysilane, phenylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethethoxysilane, ethoxysilane, ethoxysilane, Ethylmethyldimethoxysilane, propyltrimethoxysilane, propyltrimethoxysilane, propylmethyldimethoxysilane, n- or iso-octyltrimethoxysilane, n- or iso-octyltriethoxysilane, hexadecyltrimethoxysilane, trimethoxysilane, hexadecyltriethox-methylsilane, hexadecyltriethox-methyl-ethoxysilane, hexadecyltriethox-methyl-ethoxysilane, hexadecyltriethox-methyl-ethoxysilane, hexadecyltriethox-methyl-ethox-methyl-silane, hexadecyltriethox-methyl-ethoxysilane, hexadecyl-methyl-ethox-methyl-silane, hexadecyltriethox-methyl-ethox-methyl-silane, hexadecyltriethox-ethox-methyl-silane, hexadecyltriethox-ethox-methyl-silane, hexadecyl-methyl-ethox-methyl-silane, hexadecyl-methyl-dimethox-methyl-silane, methyl-ethox-methyl-silane, O-Ethylcarbamato- methyl-triethoxysilane, glycidoxypropyl trimethoxysilane, glycidoxypropyl methyldimethoxysilane, silane Glycidoxypropyltriethoxy-, glycidoxypropyl metyhldiethoxysilan, 3-Methacryloxypro- propyl-trimethoxysilane, methacryloxymethyl trimethoxy silane, methacryloxymethyl-methyldimethoxysilane, methacryloxymethyl triethoxysilane, methacryloxymethyl methyldiethoxysilane, 3-acryloxypropyl-trimethoxysilane, acryloxymethyl-trimethoxysilane, acryloxymethyl-methyldimethoxysilane, acryloxymethyl-triethoxysilane or acryloxymethyl-methyldiethoxysilane.

The silanes (Dl) used according to the invention are particularly preferably phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, n- or iso-octo-silane, octyltrimethoxysilane, octo-octyltrimethoxysil, octyltrimethoxysil, or iso-octo-silane, octyltrimethoxysil, n- or iso-octyltrimethoxysilane, n- or iso-octyltrimethoxysilane, n- or iso-octyltrimethoxysilane, n- or iso-octyltrimethoxysilane, n- or iso-octo-silane, octyltrimethoxysilane, n- or iso-octyltrimethoxysilane, Glycidoxypropyltrimethoxysilane or glycidoxypropyltriethoxysilane, where phenyltrimethoxysilane or phenyltriethoxysilane are particularly preferred.

Examples of radical R ⁵ in formula (III) are hydrogen or the examples given for radical R.

The radical R ⁵ is preferably a hydrogen atom or alkyl radicals optionally substituted by halogen atoms and having 1 to 10 carbon atoms, particularly preferably alkyl radicals having 1 to 4 carbon atoms, especially around the methyl or ethyl radical.

Examples of radical R ⁶ are the examples given for radical R and epoxy-functional radicals such as the glycidoxypropyl radical.

^{The R 6} radical is preferably an alkyl radical having 1 to 10 carbon atoms, a phenyl radical or a glycidoxypropyl radical, methyl or phenyl radicals being particularly preferred.

The silicone resins (D2) optionally used in the compositions according to the invention are preferably silicone resins containing units of the formula (III) with at least one radical R ⁶ equal to a phenyl radical. As components (D2), preference is given to using silicone resins in which at least 90% of all R ⁶ radicals are phenyl radicals.

Component (D2) consists preferably of at least 90% by weight of units of the formula (III). Component (D2) particularly preferably consists exclusively of units of the formula (III).

The silicone resins (D2) optionally used according to the invention are particularly preferably those which are 80%, preferably 90%, in particular exclusively, composed of T units of the formulas PhSiO3 _/ 2, PhSi (OR ⁵ ) O2 _/ 2, PhSi (OR ⁵ ) 2O1 _/ 2, MeSi03 _/ 2, MeSi (OR ⁵ ) O2 / 2 and / or MeSi (OR ⁵ ) 2O1 / 2 exist, whereby the proportion of PhSi03 _/ 2, PhSi (OR ⁵ ) O2 / 2 and / or PhSi (oR ⁵⁾ 2O1 / is 2 virtue ^¬ example at least 40%, especially at least 50%, wherein Ph is phenyl, Me is methyl radical and R ^5, for hydrogen atom or optionally substituted with halogen atoms substitu ierte alkyl radicals having 1 to 10 carbon atoms preferred for unsubstituted alkyl radicals with 1 to 4 carbon atoms, based in each case on the total number of units.

The silicone resins (D2) optionally used according to the invention preferably have an average molar mass (number average) M _n of at least 400 g / mol and particularly preferably of at least 600 g / mol. The mean molar mass M _n is preferably at most 2000 g / mol, particularly preferably at most 1500 g / mol.

The silicone resins (D2) used according to the invention are preferably liquid at 23 ° C. and 1000 hPa. The silicone resins (D2) preferably have a viscosity of 0.01 to 4 Pas, preferably 0.05 to 4 Pas, in particular 0.1 to 2 Pas, each Weil at 23 ° C.

Examples of useful compounds (D2) phenyl silicone resins are commercially available products, such as various SILRES ^® - grades from Wacker Chemie AG, as SILRES ^® IC 368, IC 678 or SILRES ^® SILRES ^® IC 231, SILRES ^® SY231..

In addition to their presence in component (K2), silanes (Dl) and / or silicone resins (D2) can also be contained in component (Kl). If component (Kl) contains compounds (Dl), the amounts involved are preferably 0.1 to 30 parts by weight, particularly preferably 0.5 to 5 parts by weight, based on 100 parts by weight of compound (C) in component ( K2). If component (Kl) contains compounds (D2), the amounts involved are preferably from 1 to 100 parts by weight, particularly preferably from 5 to 50 parts by weight, in each case based on 100 parts by weight of compound (C) in component (K2). Component (K2) preferably contains 10 to 100 parts by weight, particularly preferably 15 to 50 parts by weight, of compounds (D1) and / or (D2), each based on 100 parts by weight of compound (C) in component (K2).

Component (K2) preferably contains 10 to 100 parts by weight, particularly preferably 10 to 50 parts by weight, especially preferably 15 to 30 parts by weight of compounds (Dl), each based on 100 parts by weight of compound (C) in component (K2).

In addition to constituents (A), (B), (C), (D) and, if appropriate, water, the compositions (K) according to the invention can contain all other substances that have also previously been used in silane-crosslinkable compositions and that differ from compounds (A), (B), (C), (Dl), (D2) and water, such as basic nitrogen-containing organosilicon compound (E), fillers (F), catalysts (G), non-reactive plasticizers (H) , organic solvents (I), additives (J) and aggregates (L).

The compounds (E) optionally used in the compositions (K) according to the invention are preferably organosilicon compounds containing units of the formula

D _h Si (OR ⁷ ) _g R ⁸ _f O (4-fgh) / 2 (VII), wherein

R ^{7 can be the} same or different and denotes hydrogen atom or optionally substituted hydrocarbon radicals,

D can be the same or different and denotes a monovalent, SiC-bonded radical with basic nitrogen, R ^{8 can be} identical or different and denotes a monovalent, optionally substituted, SiC-bonded organic radical free of basic nitrogen, f is 0, 1, 2 or 3, preferably 1 or 0, g is 0, 1, 2 or 3, preferably 1, 2 or 3, particularly preferred

2 or 3, and h is 0, 1, 2, 3 or 4, preferably 1, with the proviso that the sum of f + g + h is less than or equal to 4 and at least one radical D is present per molecule.

The organosilicon compounds (E) optionally used according to the invention can be both silanes, ie compounds of the formula (VII) with f + g + h = 4, and also siloxanes, ie compounds containing units of the formula (VII) with f + g + h <3, which are preferably silanes.

Examples of optionally substituted hydrocarbon radicals R ⁷ are the examples given for radical R.

The radicals R ⁷ are preferably hydrogen or optionally halogen-substituted hydrocarbon radicals with 1 to 18 carbon atoms, particularly preferably hydrogen or hydrocarbon radicals with 1 to 10 carbon atoms, in particular methyl or ethyl radicals.

Examples of radical R ⁸ are the examples given for R.

The radical R ⁸ is preferably a hydrocarbon radical optionally substituted with halogen atoms and having 1 to 18 carbon atoms, particularly preferably a hydrocarbon radical having 1 to 5 carbon atoms, in particular the methyl radical. Examples of radicals D are radicals of the formulas H2N (CH2) 3-, H ₂ N (CH2) 2NH (CH ₂ ) 3-, H ₂ N (CH2) 2NH (CH2) 2NH (CH ₂ ) 3-, H ₃ CNH (CH ₂₎ ₃ -, C ₂ H ₅ NH (CH 2) 3, C ₃ H ₇ NH _(CH2) 3-, C ₄ H ₉ NH (CH ₂₎ 3, C ₅ H ₁₁ NH (CH ₂ ) ₃ -, C ₆ H ₁₃ NH (CH2) 3-, C ₇ H ₁₅ NH (CH ₂ ) 3-, H ₂ N (CH ₂ ) ₄ -, H ₂ N-CH ₂ -CH (CH ₃ ) - CH ₂ -, H ₂ N (CH ₂ ) ₅ -, cyclo-C ₅ H ₉ NH (CH ₂ ) 3-, cyclo-C ₆ HuNH (CH ₂ ) ₃ -, phenyl-NH (CH ₂ ) 3-, H ₂ N (CH ₂ ) -, H ₂ N (CH2) 2NH (CH ₂ ) H ₂ N (CH2) 2NH (CH2) 2NH (CH ₂ ) H ₃ CNH (CH ₂ ) -, C ₂ H ₅ NH ( CH ₂ ) C ₃ H ₇ NH (CH ₂ ) C ₄ H ₉ NH (CH ₂ )

C ₅ H ₄₁ NH (CH2) C ₆ H ₁₃ NH (CH ₂ ) C ₇ H ₁₅ NH (CH ₂ ) cyclo-C ₅ H ₉ NH (CH ₂ ) cyclo-C ₆ HiiNH (CH ₂ ) -, phenyl- NH (CH ₂ ) -, (CH ₃ 0) ₃ Si (CH ₂ ) ₃ NH (CH ₂ ) 3-,

(C ₂ H ₅ 0) ₃ Si (CH ₂ ) ₃ NH (CH ₂ ) 3- _/ (CH ₃ 0) ₂ (CH ₃ ) Si (CH ₂ ) 3NH (CH ₂ ) 3- and

(C2H5O) 2 (CH ₃₎ Si (CH ₂₎ 3 NH (CH ₂₎ ₃ - containing groups, and reaction products of said top ^¬ primary amino groups with compounds containing primary amino groups over reactive double bonds or Epoxidgrup.

The radical D is preferably a monovalent, SiC-bonded radical with primary or secondary amino groups, particularly preferably H ₂ N (CH ₂ ) 3 _{-, H 2} N (CH ₂ ) 2 NH (CH ₂ ) ₃ - or cyclo- C ₆ H ₄₁ NH (CH ₂ ) 3 radical.

Examples of the silanes of the formula (VII) optionally used according to the invention are H ₂ N (CH ₂ ) ₃ -Si (OCH ₃ ) ₃ ,

H ₂ N (CH ₂ ) ₃ -Si (OC ₂ H ₅ ) 3, H ₂ N (CH ₂ ) ₃ -Si (OCH ₃ ) ₂ CH ₃ ,

H ₂ N (CH ₂ ) ₃ -Si (OC ₂ H ₅ ) ₂ CH ₃ , H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ -Si (OCH ₃ ) 3,

H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ -Si (OC ₂ H ₅ ) 3, H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ -Si (OCH ₃ ) ₂ CH ₃ ,

H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ -Si (OC ₂ H ₅ ) ₂ CH ₃ , H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ -Si (OH) ₃ ,

H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ -Si (OH) ₂ CH ₃ , H ₂ N (CH _{2) 2} NH (CH _{2) 2} NH (CH _{2) 3} -Si (OCH ₃₎ 3 , H ₂ N (CH _{2) 2} NH (CH _{2) 2} NH (CH _{2) 3} -Si (OC ₂ H ₅₎ 3, cyclo-CeHiiNH (CH _{2) 3} -Si (OCH ₃₎ 3, cyclo-CeHiiNH (CH _{2) 3} -Si (OC ₂ H ₅₎ 3, cyclo-CeHuNH (CH _{2) 3} -Si (OCH _{3) 2} CH ₃ , cyclo-CeHiiNH (CH _{2) 3} -Si (OC ₂ H _{5) 2} CH ₃ , cyclo-CeHuNH (CH _{2) 3} -Si (OH) 3, cyclo-CeHuNH (CH _{2) 3} -Si (OH) ₂ CH ₃ , phenyl-NH (CH _{2) 3} -Si (OCH ₃₎ 3 , Phenyl-NH (CH _{2) 3} -Si (OC ₂ H ₅₎ 3, Phenyl-NH (CH _{2) 3} -Si (OCH _{3) 2} CH ₃ , Phenyl-NH (CH ₂ ) ₃ -Si (OC ₂ H ₅ ) ₂ CH ₃ , phenyl-NH (CH ₂ ) ₃ -Si (OH) ₃ , phenyl-NH (CH ₂ ) ₃ -Si (OH) ₂ CH ₃ , HN ((CH ₂ ) ₃ -Si (OCH ₃ ) ₃ ) ₂ ,

HN ((CH ₂ ) ₃ -Si (OC ₂ H ₅ ) ₃ ) ₂ HN ((CH ₂ ) ₃ -Si (OCH ₃ ) ₂ CH ₃ ) ₂ ,

HN ((CH ₂ ) ₃ -Si (OC ₂ H ₅ ) ₂ CH ₃ ) 2, cyclo-C ₆ H ₁₁ NH (CH ₂ ) -Si (OCH ₃ ) ₃ , cyclo- CgHuNH (CH ₂ ) -Si ( OC ₂ H ₅ ) ₃ , cyclo-C ₆ HuNH (CH ₂ ) -Si (OCH ₃ ) ₂ CH ₃ , cyclo- C ₆ HnNH (CH ₂ ) -Si (OC ₂ H ₅ ) ₂ CH ₃ , cyclo-C ₆ HuNH (CH ₂₎ -Si (OH) ₃ , cyclo- CeHuNH (CH ₂ ) -Si (OH) ₂ CH ₃ , Phenyl-NH (CH ₂ ) -Si (OCH ₃ ) ₃ ,

Phenyl-NH (CH ₂ ) -Si (OC ₂ H ₅ ) ₃ , Phenyl-NH (CH ₂ ) -Si (OCH ₃ ) ₂ CH ₃ , Phenyl- NH (CH ₂ ) -Si (OC2H5) 2CH3, Phenyl- NH (CH ₂ ) -Si (OH) 3 and phenyl-NH (CH ₂ ) -Si (OH) ₂ CH ₃ and their partial hydrolysates, where H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ -Si (OCH ₃ ) ₃ , H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ -Si (OC ₂ H ₅ ) ₃ ,

H ₂ N (CH _{2) 2} NH (CH _{2) 3} -Si (OCH _{3) 2} CH ₃ , cyclo-CgHuNH (CH _{2) 3} -Si (OCH _{3) 3} , cyclo-CeHnNH (CH _{2) 3} -Si (OC ₂ H _{5) 3} or cyclo-C ₆ HuNH (CH _{2) 3} -Si (OCH _{3) 2} CH ₃ and their partial hydrolysates are preferred and H ₂ N (CH _{2) 2} NH (CH _{2) 3} -Si ( OCH _{3) 3} , H ₂ N (CH _{2) 2} NH (CH _{2) 3} -Si (OCH _{3) 2} CH ₃ , cyclo- C ₆ Hn NH (CH _{2) 3} -Si (OCH _{3) 3} or cyclo-C ₆ HuNH (CH _{2) 3} -Si (OCH _{3) 2} CH ₃ and in each case their partial hydrolysates are particularly preferred.

The organosilicon compounds (E) optionally used according to the invention can also assume the function of a curing catalyst or cocatalyst both for the silane and for the epoxide curing in the compositions according to the invention.

Furthermore, the organosilicon compounds (E) optionally used according to the invention can act as adhesion promoters and / or as water scavengers.

The organosilicon compounds (E) which may be used according to the invention are commercially available products or can be produced by processes common in chemistry. If organosilicon compounds (E) containing basic nitrogen are used, these are exclusively constituents of component (Kl).

If component (Kl) contains compounds (E), the amounts involved are preferably 0.1 to 25 parts by weight, particularly preferably 0.5 to 10 parts by weight, in each case based on 100 parts by weight of all of the components used in the mixture (K) ( A), (B), (C) and (D). The component (Kl) according to the invention preferably contains compounds (E).

The fillers (F) optionally used in the compositions (K) according to the invention can be any previously known fillers.

Examples of fillers (F) are non-reinforcing fillers, ie fillers with a BET surface area of preferably up to 50 m ² / g, such as quartz, diatomaceous earth, calcium silicate, zirconium silicate, talc, kaolin, zeolites, metal oxide powder, such as ground also calcined aluminum, titanium, iron or zinc oxides or their mixed oxides. In general, the morphology, whether sharp-edged to potato-shaped or spherical, is unlimited, as both broken and ground types can be used. The size of these fillers is preferably in a range from 0.01 µm to 100 µmi, in particular from 0.1 µm to 50 µmi.

Salts such as barium sulfate, calcium carbonate, gypsum, silicon nitride, silicon carbide, boron nitride, glass and plastic powders such as polyacrylonitrile powder are also suitable; reinforcing fillers, ie fillers with a BET surface area of more than 50 m ² / g, such as pyrogenic silica, precipitated silica, precipitated chalk, carbon black, such as furnace and acetylene black Silicon-aluminum mixed oxides with a large BET surface area; Aluminum trihydroxide, aluminosilicates, clay minerals, magnesium-aluminum silicates, such as those available under the trade name Micro- ^sorb® from BASF, hollow spherical fillers, such as ceramic microspheres, such as those obtainable under the trade name Zeeospheres ™ at the company 3M Germany GmbH in D-Neuss, elastic plastic spheres, such as those available under the trade name Expancel ^® at AKZO NOBEL, Expancel in Sundsvall, Sweden, or glass beads..; fibrous fillers such as asbestos and plastic fibers. The fillers mentioned can be made hydrophobic, for example by treatment with organosilanes or organosiloxanes or with stearic acid or by etherification of hydroxyl groups to alkoxy groups.

The optionally used fillers (F) are preferably calcium carbonate, talc, silica or aluminum trihydroxide.

Preferred types of calcium carbonate are ground or precipitated and optionally surface-treated with fatty acids such as stearic acid or their salts. The preferred silica is preferably pyrogenic silica.

Any fillers (F) used have a moisture content of preferably less than 1% by weight, particularly preferably less than 0.5% by weight.

Fillers (F) can be part of both component (Kl) and component (K2). They can also be contained in both components (Kl) and (K2). If the compositions (K) according to the invention contain fillers (F), the amounts involved are preferably 10 to 1000 parts by weight, particularly preferably 50 to 300 parts by weight, in particular 80 to 100 parts by weight, in each case based on 100 parts by weight of all in the mixture ( K) used connections (A), (B), (C) and (D). The compositions according to the invention

(K) preferably contain fillers (F).

In a preferred embodiment of the invention, the compositions (K) according to the invention contain, as fillers (F), a combination of a) calcium carbonate, aluminum trihydroxide and / or talc with b) silica, in particular pyrogenic silica.

If the compositions (K) according to the invention contain this particular combination of different fillers (F), they preferably contain 1 to 80 parts by weight, particularly preferably 5 to 40 parts by weight, of silica, in particular fumed silica, and preferably 10 to 500 parts by weight, particularly preferably 50 up to 300 parts by weight, calcium carbonate, aluminum trihydroxide, talc or mixtures of these materials, each based on 100 parts by weight of all compounds (A), (B), (C) and (D) used in the mixture (K).

If fillers (F) are used, they can be contained both in component (Kl) and in component (K2) and also in the components.

The catalysts (G) optionally used in the compositions according to the invention can be any desired catalysts for compositions which cure by silane condensation and are known to date. Preferred examples of metal-containing curing catalysts (G) are organic titanium and tin compounds, for example titanic acid esters, such as tetrabutyl titanate, tetrapropyl titanate, tetraisopropyl titanate and titanium tetraacetylacetonate; Tin compounds, such as dibutyl tin dilaurate, dibutyl tin maleate, dibutyl tin diacetate, dibutyl tin dioctanoate, dibutyl tin acetylacetonate, dibutyl tin oxide, and corresponding dioctyl tin compounds.

The compounds used according to the invention as accelerators (B) can also catalyze the silane condensation. The compositions (K) according to the invention preferably contain no further catalysts (G).

If the compositions (K) according to the invention contain catalysts (G), these are preferably constituents of component (Kl).

If the compositions (K) according to the invention contain catalysts (G), the amounts involved are preferably 0.01 to 20 parts by weight, particularly preferably 0.05 to 5 parts by weight, in each case based on 100 parts by weight of all in the mixture (K) compounds (A), (B), (C) and (D) used.

The optionally used non-reactive plasticizers (H) are phthalic esters, adipic esters, benzoic esters, glycol esters, esters of saturated alkanediols, phosphoric esters, sulfonic esters, polyesters, polyethers, polystyrenes, polybutadienes, polyisobutylenes, paraffinic hydrocarbons or high molecular weight, branched hydrocarbons Hydrocarbons.

Preference is given to non-reactive plasticizers (H) with molecular weights, or in the case of polymeric plasticizers, average molecular weights M _n , of 200 to 20,000 g / mol, particularly preferably from 500 to 10,000 g / mol, in particular from 900 to 8000 g / mol, are used.

Non-reactive plasticizers (H) can be part of both component (Kl) and component (K2). They can also be contained in both components (Kl) and (K2).

If the compositions (K) according to the invention contain non-reactive plasticizers (H), the amounts involved are preferably 1 to 200 parts by weight, particularly preferably 5 to 100 parts by weight, based in each case on 100 parts by weight of all used in the mixture (K) Compounds (A), (B), (C) and

(D). The compositions (K) according to the invention preferably contain no non-reactive plasticizers (H).

Examples of optionally used solvents (I) are low molecular weight ethers, esters, ketones, aromatic and aliphatic and optionally halogen-containing hydrocarbons and alcohols, the latter being preferred.

Solvent (I) can be part of both component (K1) and component (K2). They can also be contained in both components (Kl) and (K2).

To prepare the compositions (K) according to the invention, preferably no organic solvents (I) are added.

The additives (J) optionally used in the compositions according to the invention can be any desired additives typical of silane-crosslinking systems. The additives (J) optionally used according to the invention are preferably antioxidants, UV stabilizers, such as, for example, so-called HALS compounds, fungicides and pigments. Component (K2) can also contain emulsifiers, which improve the compatibility or emulsifiability of water and the other constituents of this component, as additives. This can be both ionic and nonionic emulsifiers.

The additives (J) which may be used according to the invention are preferably antioxidants or UV stabilizers, such as, for example, so-called HALS compounds.

Additives (J) can be part of both component (Kl) and component (K2). They can also be contained in both components, (Kl) and (K2).

If the compositions (K) according to the invention contain additives (J), the amounts involved are preferably 0.01 to 30 parts by weight, particularly preferably 0.1 to 10 parts by weight, in each case based on 100 parts by weight of all in the mixture (K) used compounds (A), (B), (C) and (D). The compositions (K) according to the invention preferably contain additives (J).

The additives (L) optionally used according to the invention are preferably rheological additives or flame retardants.

The rheology additives (L) are preferably polyamide waxes, hydrogenated castor oils or stearates. All typical flame retardants can be used as flame retardants (L), as they are typical for adhesive and sealant systems are, in particular halogenated compounds and derivatives, in particular esters of phosphoric acid.

Aggregates (L) can be part of both component (Kl) and component (K2). They can also be contained in both components, (Kl) and (K2).

If the compositions (K) according to the invention contain one or more components (L), the amounts involved are preferably 0.5 to 200 parts by weight, particularly preferably 1 to 100 parts by weight, in particular 2 to 70 parts by weight, each based on 100 parts by weight of all compounds (A), (B), (C) and (D) used in the mixture (K).

The compositions (K) according to the invention are preferably those consisting of a component (Kl) containing 20 to 250 parts by weight of compounds (A) of the formula (I),

1 to 50 parts by weight of accelerator (B), optionally silanes (Dl), optionally silicone resins (D2), optionally organosilicon compounds (E) containing basic nitrogen, optionally fillers (F), optionally catalysts (G), optionally non-reactive plasticizers ( H), optionally organic solvents (I), optionally additives (J) and optionally additives (L) and a component (K2) containing 100 parts by weight of epoxy resin (C),

0 to 10 parts of water, 10 to 100 parts by weight of compounds (D) selected from silanes (Dl) and silicone resins (D2), optionally fillers (F), optionally non-reactive plasticizers (H), optionally organic solvents (I), optionally additives (J ) and, if applicable, aggregates (L).

The compositions (K) according to the invention are particularly preferably those consisting of a component (Kl) contained tend

30 to 200 parts by weight of compounds (A) of the formula (I),

2 to 25 parts by weight of accelerator (B), optionally silanes (Dl), optionally silicone resins (D2),

Organosilicon compounds (E) containing 0.1 to 25 parts by weight of basic nitrogen, optionally fillers (F), optionally catalysts (G), optionally non-reactive plasticizers (H), optionally organic solvents (I), optionally additives (J) and optionally additives (L) and a component (K2) containing 100 parts by weight of epoxy resin (C),

0 to 10 parts by weight of water,

10 to 100 parts by weight of silanes (Dl), optionally silicone resins (D2), optionally fillers (F), optionally non-reactive plasticizers (H), optionally organic solvents (I), optionally additives (J) and if necessary, aggregates (L).

The compositions (K) according to the invention are particularly preferably those consisting of a component (Kl) containing

30 to 200 parts by weight of compounds (A) of the formula (I),

3 to 15 parts by weight of accelerator (B), optionally silanes (Dl), optionally silicone resins (D2),

Organosilicon compounds (E) containing 0.5 to 10 parts by weight of basic nitrogen, optionally fillers (F), optionally catalysts (G), optionally non-reactive plasticizers (H), optionally organic solvents (I), optionally additives (J) and optionally additives (L) and a component (K2) containing 100 parts by weight of epoxy resin (C),

0.2 to 5 parts by weight of water,

10 to 50 parts by weight of silanes (Dl), optionally silicone resins (D2), optionally fillers (F), optionally non-reactive plasticizers (H), optionally organic solvents (I), optionally additives (J) and optionally aggregates (L).

The component (Kl) used according to the invention contains, in addition to the compounds (A) and (B) and optionally (D), (E),

(F), (G), (H), (I), (J) and (L) preferably no further constituents. The component (K2) used according to the invention contains, in addition to the compounds (C) and (D) and optionally water, (F),

(G), (H), (I), (J) and (L) preferably no other constituent parts.

In addition to the compounds (A), (B), (C) and (D) and optionally (E), (F), (G),

(H), (I), (J), (L), (M) and water, preferably no others

Components.

The constituents used according to the invention can in each case be one type of such a constituent as well as a mixture of at least two types of a respective constituent.

The component (Kl) used according to the invention has viscosities of preferably 0.1 to 40 Pas, particularly preferably 0.5 to 20 Pas, in particular 0.5 to 10 Pas, in each case at 23 ° C.

The component (K2) used according to the invention has viscosities of preferably 0.1 to 40 Pas, particularly preferably 0.5 to 20 Pas, in particular 0.5 to 10 Pas, in each case at 23.degree.

The quantitative ratio of components (Kl) and (K2) can in principle be chosen as desired, as long as the quantitative ratios required above between compounds (A) and (B) in component (Kl) and compounds (C), (D) and possibly what water in component (K2) can be achieved. The proportions of (Kl) to (K2) are preferably between 5: 1 and 1: 5, particularly preferably between 2: 1 and 1: 2, based in each case on weight. Components (K1) and (K2) according to the invention can be produced in any manner known per se, such as by methods and mixing processes such as are customary for the production of moisture-curing compositions. The order in which the various components are mixed with one another can be varied as desired.

Another object of the present invention is a process for the production of the compositions (K) according to the invention by mixing together components (Kl) and (K2) and, if necessary, further components, the individual components by separately mixing together all the constituents of the respective components in any desired way Sequence have been established.

This mixing can take place at room temperature and the pressure of the surrounding atmosphere, ie about 900 to 1100 hPa.

If desired, this mixing can also take place at higher temperatures, e.g. at temperatures in the range from 30 to 130 ° C. It is also possible to mix temporarily or continuously under reduced pressure, e.g. at 30 to 500 hPa absolute pressure, in order to remove volatile compounds and / or air.

Component (Kl) is preferably mixed according to the invention with the exclusion of moisture.

The process according to the invention can be carried out continuously or batchwise. The individual components of the composition according to the invention are storage-stable premixes which can then be mixed shortly before or during processing, in particular on the spot.

The compositions (K) according to the invention are crosslinked during or after the components (C1) and (K2) are brought into contact, preferably at room temperature, mechanical mixing being preferred. If desired, it can also take place at temperatures higher or lower than room temperature, e.g. at -5 ° to 15 ° C or at 30 ° to 50 ° C.

The crosslinking is preferably carried out at a pressure of 100 to 1100 hPa, in particular at the pressure of the surrounding atmosphere.

The invention also relates to moldings produced by crosslinking the compositions (K) according to the invention.

The moldings according to the invention can be any moldings, such as seals, pressed articles, extruded profiles, coatings, insulating layers, impregnations, potting, lenses, prisms, polygonal structures, laminate or adhesive layers.

The compositions (K) according to the invention are preferably used as adhesives or sealants. They can be used to glue any materials such as wood, concrete, porous stones, paper, fabrics, leather, etc. In contrast to one-component compounds that only harden through contact with atmospheric moisture, they are also suitable for bonding water-impermeable materials such as metals, glass, water-impermeable ceramics, non-porous stones, plastics, painted surfaces. areas etc., suitable. This also applies if very deep bonded seams or very thick layers of adhesive make curing through the air humidity impossible or at least would slow it down massively. Both the same and different materials can be glued together.

The compositions (K) according to the invention can likewise be used for sealing any joints between the above-mentioned materials.

The invention also relates to methods for bonding or sealing substrates in which the components (Kl) and (K2) used in accordance with the invention and, if appropriate, other components are first mixed with one another and then applied to the surface of at least one substrate, this surface then the second substrate to be bonded is brought into contact, and the mass (K) according to the invention is then allowed to crosslink.

The invention also relates to processes for the manufacture of coatings or potting, in which the components (Kl) and (K2) used according to the invention and, if appropriate, further components are first mixed with one another and then applied to at least one substrate and the composition according to the invention ( K) is then allowed to network.

Examples of this are casting compounds for electronic compo le, the production of molded articles, composite materials with two different substrates such as metal to plastic and composite molded parts. Composite molded parts should be understood here to mean a uniform molded article made from a composite material which is composed of a crosslinking product of the compositions according to the invention and at least one substrate so that there is a solid, permanent connec tion between the two parts.

The compositions (K) according to the invention have the advantage that they are easy to prepare.

The crosslinkable compositions (K) according to the invention have the advantage that they are distinguished by a very high storage stability of the individual components.

The crosslinkable compositions according to the invention have the advantage that after mixing components (Kl) and (K2) and any other components they have a high crosslinking speed and also in great layer thicknesses and / or deep adhesive joints between two substrates impermeable to water and air cure completely.

Furthermore, the crosslinkable compositions according to the invention have the advantage that they have an excellent adhesion profile.

Furthermore, the crosslinkable compositions according to the invention have the advantage that adhesives with high strength, tensile shear strength and hardness can be obtained from them.

The crosslinkable compositions according to the invention have the advantage that the epoxy resins (C) used according to the invention have excellent solubility in component (D), which allows the formulation of a component (K2) that contains the toxicologically favorable but highly viscous or even solid epoxy resins (C) and still have such a lower viscosity shows that it can be mixed with component (Kl) without any problems and that this mixture can then be applied.

Furthermore, the crosslinkable compositions according to the invention have the advantage that the fully cured formulations have excellent mechanical properties which are comparable to the properties of mixtures not according to the invention which contain low molecular weight epoxides as thinners, but which are toxicologically critical, which is why they The masses contained are also not subject to labeling requirements.

In the examples described below, all viscosity data relate to a temperature of 25 ° C. Unless otherwise stated, the following examples are carried out at a pressure of the surrounding atmosphere, i.e. at around 1000 hPa, and at room temperature, i.e. at around 23 ° C, or at a tempera ture that changes when the reactants are combined at room temperature without additional heating or cooling is set, and runs through at a relative humidity of about 50%. Furthermore, all parts and percentages are based on weight, unless otherwise specified.

Production example 1: Production of a component (Kl) for a 2K adhesive formulation (Kl)

123.0 g of a double-sided silane-terminated polypropylene glycol with an average molecular weight (M _n) of 18000 g / mol and end groups of the formula -OC (= 0) -NH- (CH2) 3-Si (OCH3) 3 (available for sale under the Designation GENIOSIL ^® STP-E35 at Wacker Chemie AG, D-Munich) are in a laboratory planetary mixer from PC-Laborsystem, equipped with two bar mixers, at approx. 25 ° C with 1.0 g of a stabilizer mixture (mixture of 20% Irganox ^® 1135 (CAS No. 125643-61-0), 40% Tinuvin ^® 571 (CAS No. 23328-53- 2) and 40% Tinuvin ^® 765 (CAS No. 41556-26-7), commercially available under the name TINUVIN ^® B 75 from BASF SE, Germany) homogenized for 2 minutes at 200 rpm.

Thereafter, 50.0 g of a calcium carbonate coated with stearic acid with an average particle diameter (D50%) of approx. 2.0 mih (available under the name Omyabond 520 from Omya, Cologne, Germany) and 6.0 g of a hydrophobic fumed silica with a BET surface of approx.

200 m ² / g (commercially available under the name ^HDK® H18 from Wacker Chemie AG, D-Munich) digested for one minute with stirring at 600 rpm.

Finally, 10.0 g of 2,4,6-tris (dimethylaminomethyl) phenol (commercially available under the name Accelerator 960-1 from Huntsman, USA-The Woodlands (Texas)) and 10 g of 3-aminopropyl-trimethoxysilane ( commercially available under the be drawing GENIOSIL® ^® GF 96 min mixed at the company. Wacker Chemie AG, D-Munich) for 1 minute at 200 U /. Finally, the mixture is homogenized for 2 minutes at 600 rpm and for 1 minute at 200 rpm at a pressure of 100 mbar and stirred without bubbles.

The finished component (Kl) has a viscosity of 250 Pas.

It is filled into an airtight container.

Production example 2: Production of a component (K2) for a 2K adhesive formulation (K2)

38.0 g of phenyltrimethoxysilane (commercially available under the name GENIOSIL ^® XL 70 from Wacker Chemie AG, D-Munich), 152.0 g of an epoxy-phenol novolak resin with an epoxy equivalent weight of about 180 g / mol and a viscosity of 20-50 Pas at 52 ° C (commercially available under the name Aral dite ^® EPN 1180 at the company. Huntsman, USA-the Woodlands (Texas)) and 10.0 g of a hydrophobic pyrogenic silica with a BET surface area of approx. 200 m ² / g (commercially available under the name ^HDK® H18 from Wacker Chemie AG, D-Munich) in a laboratory planetary mixer from PC - Laboratory system, equipped with two bar mixers, mixed at approx. 25 ° C for 60 minutes while stirring for one minute at 200 rpm. 1 g of water is added and the mixture is stirred for 1 minute at 200 rpm at a pressure of 100 mbar and without bubbles.

The finished component (K2) has a viscosity of 160 Pas.

It is filled into an airtight container.

Production example 3 (comparison): Production of a component (K2) for a 2K adhesive formulation (K2-V)

54.0 g of an aromatic mono-epoxy functional Reaktivver thinners having an epoxide equivalent weight of about 180 g / mol and a viscosity of 5-25 Pas at 25 ° C (commercially available under the name Lich Araldite ^® DY-K in Fa . Huntsman, USA-The Woodlands (Texas)), 108.0 g of an epoxy resin based on bisphenol A with an epoxy equivalent weight of approx. 185 g / mol and a viscosity of approx. 11 Pas at 25 ° C (buy Lich available under the name Araldite ^® GY 250 at the company. Huntsman, USA-the Woodlands (Texas)) 28.0 g of a fatty acid with coated precipitated chalk having a central portion chendurchmesser (D50%) of about 0.07 mih (commercially available under the name Hakuenka CCR S10 from Shiraishi Omya GmbH, Aut-Gummern) and 10.0 g of a hydrophobic fumed silica with a BET surface area of approx. 200 m ² / g (commercially available under the name HDK ^® H18 at Wacker Chemie AG, D-Munich) are in a laboratory planetary mixer from PC - Laboratory system, equipped with two bar mixers, mixed at approx. 25 ° C for 5 min with stirring for one minute at 200 rpm. Then 1 g of water is added and it is used for stirred for a further 10 minutes. Finally, the mixture is stirred for 1 minute at 200 rpm at a pressure of 100 mbar and without bubbles.

The finished component (K2-V) has a viscosity of 49 Pas. It is filled into an airtight container.

example 1

50 g of the component K1 prepared above are mixed with 50 g of the component K2 prepared above. The properties of the mass obtained are then determined.

Skin formation time (HBZ)

To determine the skin formation time, the two-component crosslinking compositions obtained are each applied in a 2 mm thick layer to PE film and stored in a standard climate (23 ° C. and 50% relative humidity). During curing, the formation of a skin is tested once per minute. To do this, a dry laboratory spatula is carefully placed on the surface of the sample and pulled upwards. If the sample sticks to the spatula, no skin has yet formed. If the sample no longer sticks to the spatula, a skin has formed and the time is noted. The results can be found in Table 1.

Mechanical properties

The 2-component crosslinking compositions were each spread out on milled Teflon plates with a depth of 2 mm and stored for 2 weeks at 23 ° C, 50 rel. Hardened humidity.

The Shore A hardness is determined in accordance with DIN EN 53505.

The tear strength is determined in accordance with DIN EN 53504-S1.

The elongation at break is determined in accordance with DIN EN 53504-S1.

The 100% modulus is determined in accordance with DIN EN 53504-S1. The results can be found in Table 1.

Comparative example 1

50 g of component K1 are mixed with 50 g of component K2-V. The properties of the mass obtained are then determined.

The results can be found in Table 1. Table 1

It can be seen that both components of the composition according to the invention from Example 1, which does not contain any epoxy compounds with a molar mass below 700 g / mol, have a viscosity which allows good processability. At the same time, it is suitable for providing cured moldings, e.g. adhesives, which have only slightly poorer mechanical properties than conventional systems according to the state of the art, which contain large amounts of toxicologically critical epoxides in component (K2).

Claims

1. Multi-component crosslinkable compositions (K) containing at least one component (Kl) and one component (K2), characterized in that component (Kl)

20 to 250 parts by weight of compounds (A) of the formula

Y - [(CR ¹ _{2) b} -SiR _a (OR ² ) 3- _a ] x (I), where

R can be the same or different and represents a monovalent, optionally substituted hydrocarbon radical, R ^{1 can be} identical or different and represents a hydrogen atom or a monovalent, optionally substituted hydrocarbon radical which is attached to the carbon atom via nitrogen, phosphorus, oxygen, sulfur or carbonyl group can be connected,

R ^{2 can be the} same or different and represent a hydrogen atom or a monovalent, optionally substituted hydrocarbon radical, x is an integer from 1 to 10, a can be identical or different and is 0, 1 or 2 and b can be identical or different and is an integer from 1 to 10, as well

100 parts by weight of an epoxy resin (C) with a number average molar mass M _n of at least 700 g / mol, 0 to 10 parts by weight of water and

R ⁴ _c -Si (OR ³ ) _4-C (II), where

R ^{3 can be} identical or different and represent monovalent hydrocarbon radicals with 1 to 10 carbon atoms, optionally substituted with halogen atoms,

R ^{4 can be the} same or different and denotes a monovalent, optionally substituted hydrocarbon radical, where any substituents present are free of basic nitrogen, and c is 0, 1 or 2, and silicone resins (D2) with a number average molecular weight M _n of a maximum of 4000 g / mol containing units of the formula

R ⁶ _e (R ⁵ 0) SiO (4-de) / 2 (III) wherein

R ^{6 may be the} same or different and denote a monovalent, optionally substituted hydrocarbon radical, where any substituents present do not contain a nitrogen atom, d is 0, 1, 2 or 3 and e is 0, 1, 2 or 3, where the sum of d + e is less than or equal to 3 and at least 50% of the units of the formula (III) e is 0 or 1.

2. Crosslinkable compositions according to claim 1, characterized in that they are two-component compositions consisting of the components (Kl) and (K2).

3. Crosslinkable compositions according to claim 1 or 2, characterized in that accelerators (B) are acids, tertiary amines, Mannich bases, salts of tertiary amines, quaternary ammonium salts, amidines, guanidines, phenols, aldehydes, phosphites or compounds containing mercapto groups.

4. Crosslinkable compositions according to one or more of claims 1 to 3, characterized in that the epoxy resins (C) are reaction products containing epoxy groups from epichlorohydrin with novolak resins.

5. Crosslinkable compositions according to one or more of claims 1 to 4, characterized in that component (D) is silanes (Dl) or mixtures of silanes (Dl) and silicone resins (D2).

6. Crosslinkable compositions according to one or more of claims 1 to 5, characterized in that component (K2) contains water ent.

7. Crosslinkable compositions according to one or more of claims 1 to 6, characterized in that they are those consisting of a component (Kl) containing

20 to 250 parts by weight of compounds (A) of the formula (I), 1 to 50 parts by weight of accelerator (B), optionally silanes (Dl), optionally silicone resins (D2), optionally organosilicon compounds (E) containing basic nitrogen, optionally fillers (F), optionally catalysts (G), optionally non-reactive plasticizers ( H), optionally organic solvents (I), optionally additives (J) and optionally additives (L) and a component (K2) containing 100 parts by weight of epoxy resin (C),

0 to 10 parts of water,

10 to 100 parts by weight of compounds (D) selected from silanes (Dl) and silicone resins (D2), optionally fillers (F), optionally non-reactive plasticizers (H), optionally organic solvents (I), optionally additives (J ) and, if applicable, aggregates (L).

8. Crosslinkable compositions according to one or more of claims 1 to 7, characterized in that the quantitative ratios of (Kl) to (K2) are between 5: 1 and 1: 5, based on the weight.

9. A process for the preparation of the compositions according to one or more of claims 1 to 8 by mixing together the components (Kl) and (K2) and optionally other components, the individual components by mixing them all together separately Components of the respective components have been produced in any order.

10. Moldings produced by crosslinking the compositions according to one or more of claims 1 to 8 or produced according to claim 9.

11. A method for bonding or sealing substrates in which components (Kl) and (K2) and optionally other components are first mixed with one another and then applied to the surface of at least one substrate, this surface then being bonded to the second substrate to be bonded is brought into contact, and the mass according to one or more of claims 1 to 8 or prepared according to claim 9 is then allowed to crosslink.

12. A method for producing coatings or Vergüs sen, in which the components (Kl) and (K2) and, if necessary, further components are first mixed with one another and then applied to at least one substrate and the composition according to one or more of claims 1 to 8 or prepared according to claim 9 is then allowed to crosslink.