WO2022048728A1

WO2022048728A1 - Cross-linkable substances based on organyloxysilane-terminated polymers

Info

Publication number: WO2022048728A1
Application number: PCT/EP2020/074327
Authority: WO
Inventors: Niklas WIENKENHÖVER; Volker Stanjek; Richard Weidner; Lars Zander
Original assignee: Wacker Chemie Ag
Priority date: 2020-09-01
Filing date: 2020-09-01
Publication date: 2022-03-10
Also published as: EP4208492A1

Abstract

The invention relates to cross-linkable substances containing: (A) 100 parts by weight of compounds of formula Y - [ (CR₁2) _b- SiR_a(OR²) _3-a] x (I); (B) 5 to 2000 parts by weight of silicone resins containing units of formula R³ _C (R⁴O)_dSiO _(4-c-d) /2 (II), in which the functional groups and indices have the meanings specified in claim 1, with the proviso that the sum of c+d is less than or equal to 3, in at least 40% of the units of formula (II) c is equal to 0 or 1, and the silicone resin has a polydispersity M_w/M_n of less than 5.0; optionally (C) organosilicon compounds comprising basic nitrogen; optionally (D) fillers; optionally (E) non-reactive plasticisers; optionally (F) catalysts; optionally (G) adhesion promoters; optionally (H) water scavengers; optionally (I) additives; and optionally [J] supplementary substances. The invention also relates to a method for the production thereof and the use thereof as adhesive, sealing and coating substances, in particular for bonding substrates.

Description

Crosslinkable compounds based on organyloxysilane-terminated polymers

The invention preferably relates to one-component, crosslinkable masses of silane-crosslinking prepolymers, processes for their production and their use as adhesives, sealants and coating materials, in particular for bonding substrates.

Polymer systems that have reactive alkoxysilyl groups have been known for a long time. On contact with water or atmospheric moisture, these ^alkoxysilane -terminated polymers are capable of condensing with one another at room temperature, with elimination of the alkoxy groups. One of the most important uses of such materials is in the manufacture of adhesives.

Thus, adhesives based on ^alkoxysilane -crosslinking polymers in the cured state not only have good adhesion properties on many substrates, but also very good mechanical properties, since they can have tear strength sufficient for many applications and high elasticity. Another advantage of silane-crosslinking systems compared to numerous other adhesive and sealant technologies (eg compared to isocyanate-crosslinking systems) is the toxicological harmlessness of the prepolymers.

In many applications, one-component systems (1K systems) are preferred, which harden on contact with atmospheric moisture. The decisive advantages of one-component systems are, above all, their very easy application, as here, unlike with two-component systems, the user does not have to mix different adhesive components. In addition to the time and labor savings and the safe In order to avoid possible dosing errors, with one-component systems there is also no need to process the adhesive or sealant within a mostly very narrow time window, as is the case with multi-component systems after the two components have been mixed.

A special variant of adhesives based on alkoxysilane-crosslinking polymers is described in DE102011081264, which also contain phenyl silicone resins in addition to the silane-crosslinking polymers. The corresponding resin additives also lead to adhesives which, after they have fully cured, have significantly improved hardness and tensile shear strength.

In addition to filled variants, transparent formulations can also be implemented. Until now, only special resins, i.e. pure phenyl silicone resins or phenyl-methyl silicone mixed resins, could be used to obtain transparent formulations in the target applications mentioned. However, other commercial silicone resins, such as conventional methyl silicone resins, could not previously be used because they are not compatible with the usual alkoxysilane-crosslinking polymers. On the one hand, the resulting mixtures are cloudy and, on the other hand, they do not exhibit the excellent properties described in DE102011081264. The use of other silicone resins would be desirable for reasons of availability and - in the case of methyl silicone resins - the expected high hardness of corresponding formulations for certain target applications (e.g. paint applications).

The object of the present invention was therefore to provide hard, crosslinkable compositions based on methyl silicone resins which no longer have the abovementioned restrictions. Surprisingly, it was found that other silicone resins can also be used to produce hard formulations if the polydispersity M _w /M _n of the silicone resin does not exceed a certain limit.

The invention relates to crosslinkable compositions containing (A) 100 parts by weight of compounds of the formula

whereby

Y is an x-valent polymer radical bonded via nitrogen, oxygen, sulfur or carbon, R can be the same or different and is a monovalent hydrocarbon radical optionally substituted with one or more halogen atoms,

R ¹ can be the same or different and represents a hydrogen atom or a monovalent hydrocarbon radical which is optionally substituted by one or more halogen atoms and which can be attached to the carbon atom via nitrogen, phosphorus, oxygen, sulfur or a carbonyl group,

R ² can be the same or different and represents a hydrogen atom or a monovalent hydrocarbon radical optionally substituted by one or more halogen atoms, x is an integer from 1 to 10, preferably 1, 2 or 3, particularly preferably 1 or 2 , a can be the same or different and is 0, 1 or 2, preferably 0 or 1, and b can be the same or different and an integer from 1 to 10, preferably 1, 3 or 4, particularly preferably 1 or 3, in particular 1, is, (B) 5 to 2000 parts by weight of silicone resins containing units of the formula

wherein

R ³ can be the same or different and is a hydrogen atom, a monovalent, SiC-bonded, optionally substituted by halogen atoms C1-C20 hydrocarbon radical or a divalent, optionally substituted by halogen atoms, aliphatic C1-C20 hydrocarbon radical, the two units of Formula (II) bridged, represents,

R ⁴ can be the same or different and is hydrogen or a monovalent C1-C20 hydrocarbon radical optionally substituted with halogen atoms, c is 0, 1, 2 or 3 and d is 0, 1, 2 or 3, with the proviso that that the sum of c+d is less than or equal to 3, c is 0 or 1 in at least 40% of the units of the formula (II) and the silicone resin has a polydispersity M _w /M _n of less than 5.0, optionally (C ) organosilicon compounds containing basic nitrogen, optionally (D) fillers, optionally (E) non-reactive plasticizers, optionally (F) catalysts, optionally (G) adhesion promoters, optionally (H) water scavengers, optionally (I) additives and optionally (J) aggregates. Examples of radicals R are alkyl radicals, such as methyl, ethyl, n-propyl, isopropyl, 1-n-butyl, 2-n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl; 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 radicals and the 2,2,4-triethylpentyl 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 radical; 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 radicals and ethylphenyl radicals; 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 a monovalent C1-C6 hydrocarbon radical which is optionally substituted with at least one halogen atom, the radical R being particularly preferably a C1-C2-alkyl radical, the radical R being very particularly preferably a methyl radical.

Examples of radicals R ¹ are a hydrogen atom, the radicals specified for R and optionally substituted hydrocarbon radicals bonded to the carbon atom via nitrogen, phosphorus, oxygen, sulfur, carbon or a carbonyl group.

The radical R ¹ is preferably a hydrogen atom or a hydrocarbon radical having 1 to 20 carbon atoms, particularly preferably a hydrogen atom. Examples of radical R ² are hydrogen atom and the examples given for radical R. The radical R ² is preferably a hydrogen atom or an alkyl radical having 1 to 10 carbon atoms which is unsubstituted or substituted by halogen atoms, particularly preferably an alkyl radical having 1 to 4 carbon atoms, in particular the methyl and ethyl radical.

For the purposes of the present invention, organic polymers on which the polymer radical Y is based are to be understood as meaning 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.

Examples of polymer residues Y are polyesters, polyethers, polyurethanes, polyalkylenes and polyacrylates.

The polymer radical Y is preferably an organic polymer radical which, as the polymer chain, is polyoxyalkylene, such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer and polyoxypropylene-polyoxybutylene copolymer; hydrocarbon polymers such as polyisobutylene and copolymers of polyisobutylene with isoprene; polychloroprenes; polyisoprenes; polyurethanes; Polyester; polyamides; polyacrylates; polymethacrylates; Contain vinyl polymer or polycarbonate and preferably about

to the group or groups

are bonded, where R' are the same or

can be different and has a meaning given for R or represents a group -CH(COOR")-CH ₂ -COOR" in which R" can be the same or different and has a meaning given for R.

R' is preferably a -CH(COOR")-CH2-COOR" group or an optionally halogen-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 optionally halogen-substituted aryl group having 6 to 20 carbon atoms. Examples of radicals R' are cyclohexyl, cyclopentyl, n-propyl and isopropyl radicals and n-, iso- and t-butyl radicals, the various stereoisomers of the pentyl radical, hexyl radical or heptyl radical and the phenyl radical.

The radicals R" are preferably alkyl groups having 1 to 10 carbon atoms, particularly preferably methyl, ethyl or propyl radicals.

The component (A) can have the groups attached in the manner described

at any point in the polymer, such as chain and/or terminal.

The radical Y in formula (I) is particularly preferably an x-valent organic polymer radical bonded via nitrogen, oxygen, sulfur or carbon and containing polyurethanes or polyoxyalkylenes as the polymer chain, in particular polyurethane radicals with groups attached at the ends

or polyoxyalkylene radicals with groups attached at the ends where the radicals and indices

have the meanings given above. The radicals Y are preferably linear or have 1 to 3 branching points, with particular preference being linear.

The polyurethane radicals Y are preferably those whose chain ends are linked via -NH-C(=0)0-, -NH-C(=0)-NH-,

-NR'-C(=O)-NH- or -NH-C(=O)-NR ⁷ -, in particular via -O-C(=O)-NH- or -NH-C(=O)-NR ⁷ -, to the group or groups

are bound, where all radicals and indices have one of the meanings mentioned above. 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 of 4000 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 1093 482 B1 (paragraphs [0014]-[0023], [0039]-[0055] and example 1 and comparative example

1) or EP 1641 854 B1 (paragraphs [0014]-[0035], examples 4 and 6 and comparative examples 1 and 2), which are included in the disclosure content of the present application.

The polyoxyalkylene radicals Y are preferably linear or branched polyoxyalkylene radicals, particularly preferably polyoxypropylene radicals, whose chain ends are preferably connected to the group or groups via --O--C(=O)--NH-- or --O--

are bound, where the radicals and indices have one of the meanings mentioned above. Preferably at least 85%, particularly preferably at least 90%, in particular at least 95%, of all chain ends are above -0-C(=0)- NH- to the group

bound. The polyoxyalkylene radicals Y preferably have average molar masses M _n of from 4000 to 30000 g/mol, preferably from 8000 to 20000 g/mol. Suitable processes for preparing 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 example 1-4) or EP 1 896 523 B1 (paragraphs [0008]-[0047]), which are part of 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

where the radicals and indices have one of the meanings given above.

If the compounds (A) are polyurethanes, which is preferred, they preferably have one or more end groups

where R' has the meaning given above. If the compounds (A) are polypropylene glycols, which is particularly preferred, they preferably have one or more end groups

the latter two end groups being particularly preferred.

Component (A) preferably has an average molar mass M _n in the range of at least 400 g/mol, particularly preferably at least 4000 g/mol, in particular at least 10000 g/mol, and preferably at most 30000 g/mol, particularly preferably at most 20000 g/mol. mol, in particular at most 19000 g/mol.

Component (A) preferably has a viscosity in the range of at least 0.2 Pa s, preferably at least 1 Pa s, particularly preferably at least 5 Pa s, and preferably at most 700 Pa s, preferably at most 100 Pa s, on, each measured at 23 °C.

The compounds (A) used according to the invention are commercially available products or can be prepared by processes customary in chemistry.

The polymers of component (A) can be prepared by known methods, such as addition reactions, such as hydrosilylation, Michael addition, Diels-Alder addition or reactions between isocyanate-functional compounds with compounds having 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 contain exclusively compounds of the formula (I) in which more than 90%, preferably more than 95% and particularly preferably more than 98% of all the silyl groups bonded to the radical Y are identical. However, it is then also possible to use a component (A) which at least partly contains compounds of the formula (I) in which different silyl groups are bonded to a radical Y. Finally, mixtures of different compounds of the formula (I) can also be used as component (A) in which at least 2 different types of silyl groups bonded to radicals Y are present, but all silyl groups bonded to a radical Y are identical.

The compositions according to the invention preferably contain component (A) in concentrations of at most 60% by weight, particularly preferably at most 40% by weight, and preferably at least 10% by weight, particularly preferably at least 15% by weight.

Based on 100 parts by weight of component (A), the compositions according to the invention preferably contain at least 10 parts by weight, particularly preferably at least 25 parts by weight, particularly preferably at least 50 parts by weight, of component (B). Based on 100 parts by weight of component (A), the compositions according to the invention preferably contain at most 1000 parts by weight, particularly preferably at most 800 parts by weight, in particular at most 400 parts by weight, of component (B). Component (B) preferably consists of at least 90% by weight of units of the formula (II). Component (B) particularly preferably consists exclusively of units of the formula (II). Examples of radicals R ³ are those given above for R

examples. However, radical R ³ can also be a divalent aliphatic radical which connects two units of the formula (II) to one another, such as, for example, alkylene radicals having 1 to 10 carbon atoms, such as methylene, ethylene, propylene or butylene radicals. A particularly common example of a divalent aliphatic radical is the ethylene radical.

However, the radical R ³ is preferably an optionally halogen-substituted, monovalent, SiC-bonded hydrocarbon radical having 1 to 18 carbon atoms, particularly preferably an aliphatic hydrocarbon radical having 1 to 8 carbon atoms, in particular the methyl radical.

Examples of radical R ⁴ are hydrogen atom and the examples given for radical R.

The radical R ⁴ is preferably a hydrogen atom or an alkyl radical having 1 to 10 carbon atoms which is unsubstituted or substituted by halogen atoms, particularly preferably an alkyl radical having 1 to 4 carbon atoms, in particular the methyl or ethyl radical.

Silicone resins in which at least 90% of all the R ³ radicals are methyl radicals are preferably used as component (B).

In a particularly preferred embodiment, silicone resins in which all the R ³ radicals are methyl radicals are used as component (B). Silicone resins in which at least 90% of all the R ⁴ radicals are methyl, ethyl, propyl or isopropyl radicals are preferably used as component (B).

Silicone resins in which the alkoxy content is at least 5% by weight, particularly preferably at least 10.0% by weight and particularly preferably at least 15.0% by weight, based on the total weight of the resin, are preferably used as component (B). (B) .

In a preferred embodiment, silicone resins are used as component (B) which have a maximum of 40%, particularly preferably a maximum of 20%, particularly preferably 0%, units of the formula (II) in which c is 0, based in each case on the total number of an Units of formula (II).

Silicone resins are preferably used as component (B) which, based in each case on the total number of units of the formula (II), have at least 20%, particularly preferably at least 30%, particularly preferably at least 40%, of units of the formula (II) in which the index d stands for the value 0 or 1. Examples of the silicone resins used as component (B) are organopolysiloxane resins which consist essentially, preferably exclusively, of units selected from (Q) units of the formulas

and

(T)-units of the formulas

and

(D) units of the formulas

and

and (M) units of the formula where Me

represents a methyl radical, and R ⁴ represents a hydrogen atom or an alkyl radical with 1 to 10 which is unsubstituted or substituted with halogen atoms Carbon atoms, particularly preferably unsubstituted alkyl radicals having 1 to 4 carbon atoms, where the resin (B) preferably contains (T) units and per mole of (T) units preferably 0-2 moles of (Q) units, 0-2 mole (D) units and 0-2 mole (M) units.

Preferred examples of the silicone resins (B) used according to the invention are organopolysiloxane resins which essentially, preferably exclusively, consist of units selected from (T) units of the formulas MeSiOg _/ g,

MeSi

and MeSi where Me for methyl radical and R

⁴ are hydrogen atom or optionally halogen-substituted alkyl radicals having 1 to 10 carbon atoms.

Further preferred examples of the silicone resins used as component (B) are organopolysiloxane resins which essentially, preferably exclusively, consist of (T) units of the formulas

and (D)- units of the formulas and consist, where

Me is a methyl radical and R ⁴ is a hydrogen atom or an alkyl radical having 1 to 10 carbon atoms which is unsubstituted or substituted by halogen atoms, preferably unsubstituted alkyl radicals having 1 to 4 carbon atoms. The salary at

(D) units in these silicone resins (B) is preferred

< 10% by weight.

Particularly preferred examples of the silicone resins used as component (B) are organopolysiloxane resins which preferably contain 90%, in particular exclusively, of (T) units of the formulas

exist, where Me is a methyl radical and R ⁴ is a hydrogen atom or optionally halogen-substituted alkyl radicals having 1 to 10 carbon atoms, preferably unsubstituted Alkoxy radicals having 1 to 4 carbon atoms, particularly preferably methyl radicals, based in each case on the total number of units. As already described, the use of silicone resins that have such a high proportion of silicon-bonded methyl groups leads to adhesives with a particularly high level of hardness.

The silicone resins used as component (B) preferably have an average molar mass (number average) M _n of at least 200 g/mol and particularly preferably at least 300 g/mol, the average molar mass M _n preferably being at most 400,000 g/mol, particularly preferably at most 10,000 g/mol, in particular at most 3000 g/mol. Component (B) preferably has a polydispersity (Mw/Mn) of from 1.0 to 4.5, particularly preferably from 1.0 to 4.0, in particular from 1.0 to 3.5.

The silicone resins used as component (B) can be either solid or liquid at 23° C. and 1000 hPa, silicone resins (B) preferably being liquid. The silicone resins (B) preferably have a viscosity in the range from 10 to 100,000 mPa.s, preferably in the range from 20 to 1000 mPa.s, particularly preferably in the range from 50 to 500 mPa.s, in each case at 25.degree.

The silicone resins used as component (B) can be used either in pure form or in the form of a mixture with a suitable solvent (BL).

All compounds which are not reactive towards components (A) and (B) at room temperature and have a boiling point <250° C. at 1013 mbar can be used as solvents (BL). Examples of solvents (BL) that may be used are ethers (eg diethyl ether, methyl t-butyl ether, ether derivatives of glycol, THF), esters (eg ethyl acetate, butyl acetate, glycol ester), aliphatic hydrocarbons (eg pentane, cyclopentane, hexane, cyclohexane, heptane). , Done or long-chain branched and unbranched alkanes), ketones (e.g. acetone, methyl ethyl ketone), aromatics (e.g. toluene, xylene, ethylbenzene, chlorobenzene) or alcohols (e.g. methanol, ethanol, glycol, propanol, isopropanol, glycerol, butanol , isobutanol, t-butanol).

In a preferred embodiment of the invention, silicone resins are used as component (B) which contain less than 0.1% by weight, preferably less than 0.05% by weight, particularly preferably less than 0.02% by weight, in particular less than 0.01% by weight aromatic solvents (BL).

In a particularly preferred embodiment of the invention, silicone resins are used as component (B) which, with the exception of alcohols R ⁴ OH, contain less than 0.1% by weight, preferably less than 0.05% by weight, particularly preferably less than 0.02% by weight, in particular less than 0.01% by weight, of solvent (BL), where R ⁴ has the meaning given above.

In a very particularly preferred embodiment of the invention, resins are used as component (B) which, with the exception of alcohols R ⁴ OH, contain no solvents (BL) at all, where R ⁴ has the meaning given above. The silicone resins used as component (B) are commercially available products or can be prepared by methods customary in silicon chemistry. In addition to the components (A) and (B) used, the compositions according to the invention can contain all other substances which have also been used to date in crosslinkable compositions and which differ from components (A) and (B), such as (C) containing nitrogen organosilicon compounds, (D) fillers, (E) non-reactive plasticizers, (F) catalysts, (G) adhesion promoters, (H) water scavengers, (I) additives, and (J) aggregates.

The optionally used component (C) is preferably an organosilicon compound containing units of the formula

wherein

R ⁶ can be the same or different and is a monovalent, optionally substituted SiC-bonded organic radical free from basic nitrogen,

R ⁷ can be the same or different and is a hydrogen atom or optionally substituted hydrocarbon radicals,

D can be the same or different and is a monovalent, SiC-bonded radical with basic nitrogen, f is 0, 1, 2 or 3, preferably 1, g is 0, 1, 2 or 3, preferably 1, 2 or 3, especially preferably 1 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 can be either silanes, ie compounds of the formula (III) where f+g+h=4, or siloxanes, ie compounds containing units of the formula (III) where it is preferred

is silanes.

Examples of radical R ⁶ are the examples given for R.

The radical R ⁶ is preferably an optionally halogen-substituted hydrocarbon radical having 1 to 18 carbon atoms, particularly preferably a hydrocarbon radical having 1 to 5 carbon atoms, in particular the methyl radical.

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

The radicals R ⁷ are preferably a hydrogen atom or a hydrocarbon radical having 1 to 18 carbon atoms which is unsubstituted or substituted by halogen atoms, particularly preferably a hydrogen atom or a hydrocarbon radical having 1 to 10 carbon atoms, in particular a methyl or ethyl radical.

and reaction products of the abovementioned primary amino groups with compounds which contain double bonds or epoxide groups which are reactive towards primary amino groups.

The radical D is preferably the

Examples of the silanes of the formula (III) optionally used according to the invention are

In the compositions according to the invention, the organosilicon compounds (C) can also assume the function of a curing catalyst or cocatalyst.

Furthermore, the organosilicon compounds (C) can act as adhesion promoters and/or as water scavengers.

The organosilicon compounds are commercially available products or can be prepared by processes customary in chemistry.

If the compositions according to the invention contain component (C), the amounts are preferably from 0.1 to 25 parts by weight, particularly preferably from 0.2 to 20 parts by weight, in particular from 0.5 to 15 parts by weight, based in each case on 100 parts by weight of component ( A). The compositions according to the invention preferably contain component (C).

The fillers (D) optionally used in the compositions according to the invention can be any previously known fillers. Examples of fillers (D) 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, zeolite, metal oxide powder such as aluminum, titanium -, Iron or zinc oxides or their mixed oxides, barium sulfate, calcium carbonate, gypsum, silicon nitride, silicon carbide, boron nitride, glass and plastic powders such as polyacrylonitrile powder; reinforcing fillers, ie fillers with a BET surface area of more than 50 m ² / g, such as fumed silica, precipitated

Silicic acid, precipitated chalk and silicon-aluminum mixed oxides with large BET surface; Aluminum trihydrate, carbon black, hollow spherical fillers such as ceramic microspheres, elastic plastic beads, glass beads or fibrous fillers. The fillers mentioned can be made hydrophobic, for example by treatment with organosilanes or. - siloxanes or with stearic acid or by etherification of hydroxyl groups to alkoxy groups.

The optionally used fillers (D) are preferably calcium carbonate, magnesium carbonate and/or calcium-magnesium mixed carbonates, talc, aluminum trihydroxide or silicic acid. Preferred types of calcium carbonate are ground or precipitated and optionally surface-treated with fatty acids such as stearic acid or salts thereof. The preferred silica is preferably pyrogenic silica.

The fillers (D) are preferably additives which are suitable for transparent applications, such as silicate or metal oxide compounds. The preferred fillers for transparent applications are fumed silica or titanium dioxide. Any fillers (D) used have a moisture content of preferably less than 1% by weight, particularly preferably less than 0.5% by weight.

If the compositions according to the invention contain fillers as component (D), the amounts involved are preferably 10 to 1000 parts by weight, particularly preferably 40 to 500 parts by weight, in particular 80 to 300 parts by weight, based in each case on 100 parts by weight of component (A). The compositions according to the invention preferably contain fillers (D).

Any non-reactive plasticizers which have also hitherto been used in crosslinkable organopolysiloxane compositions can be used as optional component (E).

The non-reactive plasticizers optionally used as component (E) are preferably organic compounds selected from the groups of substances consisting of

• fully esterified aromatic or aliphatic carboxylic acids,

• fully esterified derivatives of phosphoric acid,

• fully esterified derivatives sulfonic acids,

• branched or unbranched saturated hydrocarbons,

Polystyrenes, • polybutadienes, polyisobutylenes, • polyesters and • polyethers.

The non-reactive plasticizers optionally used as component (E) are preferably those which do not react with water or with components (A) and (B) at temperatures of < 80°C, are liquid at 20°C and 1013 hPa and have a boiling point of > 250°C at 1013 hPa.

Examples of the carboxylic acid ester (E) are phthalic acid esters such as dioctyl phthalate, diisooctyl phthalate, diisononyl phthalate, diisodecyl phthalate and diundecyl phthalate; perhydrogenated phthalic acid esters such as diisononyl 1,2-cyclohexanedicarboxylate and dioctyl 1,2-cyclohexanedicarboxylate; adipic acid esters such as dioctyl adipate; benzoic acid esters; esters of trimellitic acid, glycol esters; Esters of saturated alkanediols, e.g.

2,2,4-Trimethyl-1,3-pentanediol monoisobutyrate and 2,2,4-Trimethyl-1,3-pentanediol diisobutyrate.

Examples of polyethers (E) are polyethylene glycols, poly-THF and polypropylene glycols with molar masses M _n of preferably 200 to 20,000 g/mol.

Preference is given to using non-reactive plasticizers (E) with molar masses or, in the case of polymeric plasticizers, average molar masses M _n of at least 200 g/mol, particularly preferably greater than 500 g/mol, in particular greater than 900 g/mol. They preferably have molar masses or average molar masses M _n of not more than 20,000 g/mol, particularly preferably not more than 10,000 g/mol, in particular not more than 8000 g/mol.

In a preferred embodiment of the invention, phthalic ester-free plasticizers, such as perhydrogenated phthalic esters, esters of trimellitic acid, polyesters or polyethers, are used as component (E). Component (E) is particularly preferably polyethers, in particular polyethylene glycols, poly-THF and polypropylene glycols, in their entirety particularly preferably polypropylene glycols. The preferred polyethers have molar masses M _n preferably in a range from 400 to 20000 g/mol, particularly preferably in a range from 800 to 12000 g/mol, in particular in a range from 1000 to 8000 g/mol.

If the compositions according to the invention contain non-reactive plasticizers as component (E), the amounts involved are preferably 5 to 300 parts by weight, particularly preferably 10 to 200 parts by weight, in particular 20 to 150 parts by weight, based in each case on 100 parts by weight of component (A). The compositions according to the invention preferably contain non-reactive plasticizers (E).

The catalysts (F) optionally used in the compositions according to the invention can be any previously known catalysts for compositions which cure by silane condensation. Examples of metal-containing curing catalysts (F) 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 dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin dioctanoate,

Dibutyltin acetylacetonate, dibutyltin oxides, and corresponding dioctyltin compounds.

Examples of metal-free curing catalysts (F) are basic compounds such as triethylamine, tributylamine, 1,4-diazabicyclo[2.2.2]octane, amidines such as 1,5-diazabicyclo[4.3.0]non-5- en or 1,8-diazabicyclo[5.4.0]undec-7-ene, guanidines such as tetramethylguanidine, N,N-bis(N,N-dimethyl-2-aminoethyl)- methylamine, N,N-dimethylcyclohexylamine, N,N-dimethylphenylamine and N-ethylmorpholinine.

Acidic compounds can also be used as component (F), such as phosphoric acid and its partially esterified derivatives, toluenesulfonic acid, sulfuric acid, nitric acid or else organic carboxylic acids, for example acetic acid and benzoic acid.

If the compositions according to the invention contain catalysts (F), the amounts involved are preferably from 0.01 to 20 parts by weight, particularly preferably from 0.05 to 5 parts by weight, based in each case on 100 parts by weight of component (A).

In one embodiment of the invention, any catalysts (F) used are metal-containing

Curing catalysts, preferably tin-containing catalysts. This embodiment of the invention is particularly preferred when component (A) consists entirely or at least partially, ie at least 90% by weight, preferably at least 95% by weight, of compounds of the formula (I) in which index b is not equal to 1.

In the case of the compositions according to the invention, metal-containing catalysts (F), and in particular tin-containing catalysts, can preferably be dispensed with if component (A) is completely or at least partially, ie at least 10% by weight, preferably at least 20% by weight % by weight, consists of compounds of the formula (I) in which the index b is 1 and the radical R ¹ has the meaning of a hydrogen atom. This embodiment of the invention without metal and in particular without tin-containing catalysts is particularly preferred. The adhesion promoters (G) optionally used in the compositions according to the invention can be any adhesion promoters previously described for systems curing by silane condensation.

Examples of adhesion promoters are epoxysilanes, such as glycidoxypropyltrimethoxysilane, glycidoxypropylmethyldimethoxysilane, glycidoxypropyltriethoxysilane or glycidoxypropylmethyldiethoxysilane, 2-(3-triethoxysilylpropyl)maleic anhydride, N-(3-trimethoxysilylpropyl)urea, N-(3- Triethoxysilylpropyl) urea, N-(trimethoxysilylmethyl) urea, N-(methyldimethoxysilylmethyl) urea, N-(3-triethoxysilylmethyl)urea, N-(3-methyldiethoxysilylmethyl)urea, O-methylcarbamatomethyl- methyldimethoxysilane, O-methylcarbamatomethyl-trimethoxysilane, O-ethylcarbamatomethyl-methyldiethoxysilane, 0-ethylcarbamatomethyl-triethoxysilane, 3-methacryloxypropyl-tri-methoxysilane, methacryloxymethyl-trimethoxysilane, methacryloxy-methyl-methyldimethoxysilane, methacryloxymethyl-triethoxysilane, methacryloxymethyl-methyldiethoxy silane, 3-acryloxypropyl -tri-methoxysilane, acryloxymethyl-trimethoxysilane, acryloxymethyl-methyldimethoxysilane, acryloxymethyl-triethoxysilane and Acryl- oxymethyl-methyldiethoxysilane and their partial condensates.

If the compositions of the invention contain adhesion promoters (G), the amounts involved are preferably from 0.5 to 30 parts by weight, more preferably from 1 to 10 parts by weight, based in each case on 100 parts by weight of crosslinkable composition.

The water scavengers (H) optionally used in the compositions according to the invention can be any water scavengers described for systems curing by silane condensation. Examples of water scavengers (H) are silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, tetraethoxysilane, O-methylcarbamatomethylmethyldimethoxysilane, O-methylcarbamatomethyltrimethoxysilane, 0-ethylcarbamatomethylmethyldiethoxysilane, 0-

Ethylcarbamatomethyl-triethoxysilane and/or their partial condensates and orthoesters such as 1,1,1-trimethoxyethane,

1,1,1-triethoxyethane, trimethoxymethane and triethoxymethane, with vinyltrimethoxysilane being preferred.

If the compositions of the invention contain water scavengers (H), the amounts involved are preferably from 0.5 to 30 parts by weight, more preferably from 1 to 10 parts by weight, based in each case on 100 parts by weight of crosslinkable composition. The compositions according to the invention preferably contain water scavengers (H).

The additives (I) optionally used in the compositions according to the invention can be any additives typical of silane-crosslinking systems known hitherto.

The additives (I) are compounds other than the previously mentioned components, preferably antioxidants, UV stabilizers such as so-called HALS compounds, fungicides, commercially available defoamers, for example from BYK (Wesel, Germany) , commercially available wetting agents, eg from BYK (Wesel, Germany) or pigments.

If the compositions according to the invention contain additives (I), the amounts involved are preferably from 0.01 to 30 parts by weight, particularly preferably from 0.1 to 10 parts by weight, based in each case on 100 parts by weight of component (A). The compositions according to the invention preferably contain additives (I). Any additives (J) used are preferably tetraalkoxysilanes, for example tetraethoxysilane, and/or their partial condensates, reactive plasticizers, rheological additives, flame retardants or organic solvents.

Preferred reactive plasticizers (J) are compounds which contain alkyl chains with 6 to 40 carbon atoms and have a group which is reactive towards the compounds (A).

Examples are isooctyltrimethoxysilane, isooctyltriethoxysilane, N-octyltrimethoxysilane, N-octyltriethoxysilane,

decyltrimethoxysilane, decyltriethoxysilane,

Dodecyltrimethoxysilane, Dodecyltriethoxysilane, Tetradecyltrimethoxysilane, Tetradecyltriethoxysilane,

hexadecyltrimethoxysilane and hexadecyltriethoxysilane.

The rheological additives (J) are preferably polyamide waxes which are solid at room temperature, hydrogenated castor oils or stearates.

Flame retardants (J) which can be used are all typical flame retardants as are typical for adhesive and sealant systems, in particular halogenated compounds and derivatives, in particular (partial) esters, of phosphoric acid.

Examples of organic solvents (J) are the compounds already mentioned above as solvents (BL), preferably alcohols.

Preferably no organic solvents (J) are added to the compositions of the invention. If the compositions according to the invention contain one or more components (J), these are in each case amounts of preferably 0.5 to 200 parts by weight, particularly preferably 1 to 100 parts by weight, in particular 2 to 70 parts by weight, based in each case on 100 parts by weight of component ( A).

The compositions according to the invention are preferably those containing (A) 100 parts by weight of compounds of the formula (I),

(B) 5 to 2000 parts by weight of silicone resins containing units of the formula (II) with a polydispersity M _w /M _n of less than 5.0,

(C) 0.1 to 25 parts by weight of organosilicon compounds containing basic nitrogen, optionally fillers (D), optionally non-reactive plasticizers (E), optionally catalysts (F), optionally adhesion promoters (G), optionally water scavengers (H), optionally additives (I ) and optionally additives (J).

The compositions according to the invention are particularly preferably those containing

(A) 100 parts by weight of compounds of formula (I),

(B) 10 to 1000 parts by weight of silicone resins containing units of the formula (II) with a polydispersity M _w /M _n of less than 4.5, (C) 0.1 to 25 parts by weight of organosilicon compounds containing units of the formula (III), optionally fillers ( D), optionally non-reactive plasticizers (E), optionally catalysts (F), optionally adhesion promoters (G), optionally water scavengers (H), optionally additives (I) and optionally additives (J).

The masses according to the invention are particularly preferably those containing them

(A) 100 parts by weight of compounds of the formula (I), (B) 25 to 800 parts by weight of silicone resins containing units of the formula (II) with a polydispersity M _w /M _n of less than 4.0 and an average molar mass M _n of less than 3000 g /mol,

(C) 0.1 to 25 parts by weight of organosilicon compounds containing units of the formula (III), optionally fillers (D), optionally non-reactive plasticizers (E), optionally catalysts (F), optionally adhesion promoters (G), optionally water scavengers (H), optionally additives (I) and optionally additives (J).

The components used according to the invention can each be one type of such a component or a mixture of at least two types of a respective component.

The compositions according to the invention preferably contain no components other than components (A) to (J).

The materials according to the invention are particularly preferably transparent materials. The masses according to the invention are preferably liquid to pasty masses with viscosities in the range from 500 to 3000,000 mPa.s, particularly preferably in the range from 1000 to 1500,000 mPa.s, in each case at 23.degree.

The compositions according to the invention can be produced in any manner known per se, for example by methods and mixing processes which 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 producing the compositions of the invention by mixing the individual components in any order.

This mixing can take place at room temperature and the pressure of the surrounding atmosphere, ie in a range from about 900 to 1100 hPa. If desired, however, this mixing can also take place at higher temperatures, e.g. at temperatures in the range from 30 to 130 °C. Furthermore, it is possible to mix intermittently or continuously under reduced pressure, such as 30 to 500 hPa absolute pressure, to remove volatile compounds and/or air.

The mixing according to the invention preferably takes place with the exclusion of moisture.

The process according to the invention can be carried out continuously or batchwise. The compositions according to the invention are preferably one-component compositions which can be stored in the absence of water and can be crosslinked at room temperature when exposed to water. However, the compositions according to the invention can also be part of two-component crosslinking systems in which OH-containing compounds, such as water, are added in a second component.

The usual water content of air is sufficient for crosslinking the compositions according to the invention. The compositions according to the invention are preferably crosslinked at room temperature.

If desired, it can also be carried out at temperatures higher or lower than room temperature, e.g. at -5°C to 15°C or at 30°C to 50°C and/or by means of water concentrations exceeding the normal water content of the air.

The crosslinking is preferably carried out at a pressure in the range from 100 to 1100 hPa, in particular at the pressure of the surrounding atmosphere, ie in a range from 900 to 1100 hPa.

Another object of the present invention are moldings produced by crosslinking the compositions of the invention.

The moldings according to the invention preferably have a tear strength of at least 4.0 MPa, particularly preferably at least 5.0 MPa, in particular at least 8.0 MPa, measured in each case according to DIN EN 53504-S1.

The moldings according to the invention can be any moldings, such as seals, pressed articles, extruded profiles, coatings, impregnations, potting, lenses, prisms, polygonal structures, laminate or adhesive layers. Another object of the invention is a method for producing material composites, in which the composition according to the invention is applied to at least one substrate and then crosslinked.

Examples include coatings, potting, the manufacture of molded articles, composite materials, and composite molded parts.

Composite molded parts are to be understood here as meaning a uniform molded article made from a composite material which is composed of a crosslinked product of the compositions according to the invention and at least one substrate such that there is a firm, permanent connection between the two parts.

In the method according to the invention for the production of bonded material, the composition according to the invention can also be vulcanized between at least two identical or different substrates, such as in the case of adhesive bonds, laminates or encapsulations.

Examples of substrates that can be bonded or sealed according to the invention are plastics including PVC, metals, concrete, wood, mineral substrates, glass, ceramics and painted surfaces.

The compositions according to the invention can be used for all purposes for which storage is carried out in the absence of water. capable masses which crosslink to form elastomers when exposed to water at room temperature can be used.

The compositions according to the invention have the advantage that they are easy to produce.

The crosslinkable compositions of the invention have the advantage that they are notable for very high storage stability and a high crosslinking rate.

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

Furthermore, the crosslinkable masses according to the invention have the advantage that they are easy to process.

Unless otherwise stated, all the steps in the examples below are carried out at a pressure of the surrounding atmosphere, i.e. around 1013 hPa, and at room temperature, i.e. around 23° C., or at a temperature which arises when the reactants are combined at room temperature without additional heating or cooling. The masses are crosslinked at a relative atmospheric humidity of about 50%. Furthermore, unless otherwise indicated, all parts and percentages are by weight.

Examples 1 . Educts and measurement methods

1.1 Silane-terminated polyethers a) GENIOSIL ^® STP-E 10: cx-silane-terminated polyether with a dynamic viscosity at 25 °C of approx. 10000 mPa·s, available from Wacker Chemie AG, D-Munich. b) ^GENIOSIL® STP-E 15: γ-silane-terminated polyether with a dynamic viscosity at 25° C. of about 10,000 mPa·s, available from Wacker Chemie AG, D-Munich. c) GENIOSIL ^® STP-E 30: α-silane-terminated polyether with a dynamic viscosity at 25 °C of approx. 30000 mPa·s, available from Wacker Chemie AG, D-Munich. d) ^GENIOSIL® STP-E 35: γ-silane-terminated polyether with a dynamic viscosity at 25° C. of about 30,000 mPa·s, available from Wacker Chemie AG, D-Munich.

1.2 Silicone Resins

SILRES ^® MSE 100: Methoxy-functional methylpolysiloxane resin, available from Wacker Chemie AG, D-Munich, with a kinematic viscosity of 20-35 mm ² /s and a polydispersity of approx. 9.5, measured according to the point 1.4 named Process (Resin VB1).

1 .3 Gel Permeation Chromatography

The mass-average molar mass M _w , like the number-average molar mass M _n , is determined by means of size exclusion chromatography (SEC) against polydimethylsiloxane standards, in toluene, at 35° C., flow rate 0.7 ml/min and detection with RI (refractive index detector ) determined on a column set Meso Pore - Oligo Pore (Agilent, Germany) with an injection volume of 10 μΐ. 1.4 Viscosity

The viscosities of high-viscosity materials (viscosities > 20,000 mPa*s) were measured after heating to 23° C. using a DV 3 P rotational viscometer from A. Paar (Brookfield systems), determined using spindle 5 at 2.5 rpm according to ISO 2555.

The viscosities of low-viscosity materials (viscosities <20,000 mPa*s) in the context of the present invention after tempering to 25° C. with a Stabinger rotational viscometer SVM3000 from Anton Paar at 25° C

(Default). 1.5 NMR spectroscopy ^H-NMR)

The alkoxy group content was determined by means of ¹ H nuclear magnetic resonance spectroscopy ( ¹ H NMR; Bruker Avance III HD 500 ( ¹ H: 500.2 MHz) spectrometer with BBO 500 MHz S2 probe head; 50 mg of the respective sample in 500 μl CD ₂ CI ₂ ). Here, the signal intensities of the Me-O-Si and Me-Si (=T units) functionalities are determined and compared to one another. Table 1 lists the information on the MeO/T ratio of resins Bl-B7 and VBl-VB5.

2 . Distillative separation of resin VBl

The resin VB1 was fractionated by distillation in a laboratory thin layer. This was done in three consecutive experiments, in which the materials were fractionated at fixed temperatures and pressures in two runs each. In each of the 3 experiments, 2 thin-layer steps were carried out in such a way that the residue from the first thin-layer run was put back into the thin-layer and distilled. The two distillate fractions thus obtained (at the same temperature and pressure) were then combined. All of the analytical data are summarized in Table 1.

2.1 Distillative separation of resin VBl at 80 °C and 40 mbar 725 g of resin VB1 were continuously applied to the thin layer at 80° C. and 40 mbar over a period of four hours. Under the same conditions, the residue obtained was again continuously applied to the thin layer over a period of four hours. The distillate fractions obtained (fraction 1=51.0 g; fraction 2=10.1 g) were combined and are referred to below as resin B1. The viscosity of resin Bl was 2.5 mPa*s. The residue from the second run (referred to below as resin VB2; 662.3 g total mass; viscosity=53.9 mPa*s) was used as starting material for the subsequent experiment according to point 2.2.

2.2. Distillative separation of resin VB2 at 100°C and 1 mbar

555.0 g of the resin VB2 prepared according to point 2.1 were continuously applied to the thin layer at 100° C. and 1 mbar over a period of four hours. The residue now obtained was again continuously added to the thin layer over a period of four hours. The distillate fractions obtained (fraction 1=110.0 g, fraction 2=22.4 g) were combined and are referred to below as resin B2. The viscosity of Resin B2 was 5.7 mPa*s. The residue from the second run of this experiment (referred to below as resin VB3; 418.0 g total mass; viscosity=157.7 mPa*s) was used as starting material for the follow-up experiment according to point 2.3.

2.3. Distillative separation of resin VB3 at 180°C and 1 mbar

300 g of the resin VB3 described in Chapter 2.2 were continuously applied to the thin layer at 180 °C and 1 mbar over a period of four hours. The residue now obtained was again continuously added to the thin layer over a period of four hours. The distillate fractions obtained (fraction 1 = 73.1 g, fraction 2 = 2.2 g) were combined and are hereinafter referred to as resin B3. The viscosity of resin B3 was 20.5 mPa*s. After the second run, a residue remained (hereinafter referred to as resin VB4) with a total amount of 210.5 g and a viscosity of 662.7 mPa*s.

2.4 Distillative separation of resin VB1 at 180° C. and 1 mbar

725 g of resin VB1 were continuously applied to the thin layer at 180° C. and 1 mbar over a period of five hours. The residue obtained was again applied continuously to the thin layer over a period of four hours. The distillate fractions obtained (fraction 1=340.3 g; fraction 2=83.1 g) were combined and are referred to below as resin B4. The viscosity of Resin B4 was 6.1 mPa*s. After the second run, a residue remained (referred to below as resin VB5) with a total amount of 297.7 g and a viscosity of 644.7 mPa*s.

3 . Synthesis of methoxy-functionalized polysiloxane resins

Based on the analytical data of the experiments under point 2, batch syntheses of methoxy-functionalized methylpolysiloxane resins were carried out by cohydrolysis.

3 .1 Synthesis of methoxy-functionalized methylpolysiloxane resin by cohydrolysis of methyltrimethoxysilane

3.1.1 Production of Resin B5

400 g of trimethoxymethylsilane are heated to 50° C. in a 1L three-necked flask equipped with a KPG stirrer, a reflux condenser and a 10 mL dropping funnel with pressure equalization. At this temperature, a mixture of 42.2 g of deionized water and 1.5 g of concentrated hydrochloric acid (32% by weight) is added dropwise over a period of one hour. Afterwards will heated the mixture to reflux for one hour. After the reaction mixture has cooled to room temperature, argon is bubbled through the reaction mixture for 30 minutes. Adhering methanol is then removed on a rotary evaporator at 300 mbar and 40 °C. The material obtained is hereinafter referred to as Resin B5. The analytical data are summarized in Table 2.

3 . 1 .2 Production of Resin B6

1400 g of trimethoxymethylsilane are heated to 50° C. in a 4L three-necked flask equipped with a KPG stirrer, a reflux condenser and a 1L dropping funnel with pressure compensation. At this temperature, a mixture of 182.5 g of deionized water and 5.3 g of concentrated hydrochloric acid (32% by weight) is added dropwise over a period of one hour. The mixture is then heated to reflux for one hour. After the reaction mixture has cooled to room temperature, argon is bubbled through the mixture for 30 minutes. Adhering methanol is then removed on a rotary evaporator at 300 mbar and 40 °C. The material obtained is hereinafter referred to as Resin B6. The analytical data are summarized in Table 2.

3 . 1 .3 Production of Resin B7

200 g of trimethoxymethylsilane are heated to 50° C. in a 1 L three-necked flask equipped with a KPG stirrer, a reflux condenser and a 100 mL dropping funnel with pressure equalization. At this temperature, a mixture of 28.1 g of deionized water and 1.1 g of concentrated hydrochloric acid (32% by weight) is added dropwise over a period of one hour. The mixture is then heated to reflux for one hour. After the reaction mixture has cooled to room temperature, argon is bubbled through the mixture for 30 minutes. clinging Methanol is then removed on a rotary evaporator at 300 mbar and 40°C. The material obtained is hereinafter referred to as Resin B7. The analytical data are summarized in Table 2.

Table 1: Analytical data

Table 2: Analytical data of the materials from 3.1.

4. Mixture experiments

Examples 1 to 26 and Comparative Examples 1 to 20

With the illustrated resins B1 to B7 and VB1 to VB5, individual mixing experiments with the commercial available silane-terminated polyethers GENIOSIL ^® STP-E 10, GENIOSIL ^® STP-E 15, GENIOSIL ^® STP-E 30 and GENIOSIL ^® STP-E 35. For this purpose, in individual experiments, the sample containers "Becher PP30-60mL" (Hauschild, diameter: 4 cm) with 20 g of the respective resins with 10 g of the respective

Weighed silane-terminated polyether. The mixture was filled into a PP30-60mL sample container (Hauschild) and homogenized at 2500 revolutions per minute for 5 minutes in a SpeedMixer DAC 150 (Hauschild). It was then checked whether an optically perceptible turbidity of the homogenized mixture was present. The results of this investigation are summarized for the examples in Table 3 (comprising resins B1-B7) and for the comparative examples in Table 4 (comprising resins VB1-VB5).

Table 3 :

Table 4 :

5. General Instructions for the Production of the 1K Adhesive Formulations Examples 27 to 29

150 g of GENIOSIL ^® STP-E10 are mixed in a laboratory planetary mixer from PC-LaborSystem, equipped with two bar mixers, at approx. 25°C with 150 g of the respective resins B4 and B5 and 6 g of stabilizer (commercially available under the name TINUVIN ^® 123 at BASF AG, Germany; GAS NO: 129757-67-1) for 2 minutes at 200 rpm. Thereafter, 284.5 g of aluminum trihydroxide with a BET surface area of 3-5 m ² /g and a d50 value of 1.7-2.1 μm (commercially available under the name “Martinal OL 104” from Albemarie Corp.) with stirring for one minute at 600 rpm. After the aluminum trihydroxide has been incorporated, 6 g of N-(2-aminoethyl)-3-aminopropyl-methyl-dimethoxysilane are mixed in for 1 minute at 200 rpm. Finally, for 2 Minutes at 600 rpm and for 1 minute at 200 rpm at a pressure of 100 mbar and stirred without bubbles.

The formulation is filled into 310 ml PE cartridges and stored at 25° C. for one day before the examination.

The compositions were each spread out to a depth of 2 mm on milled Teflon plates and cured for 2 weeks at 23° C. and 50% relative atmospheric humidity. For smaller sample quantities (resin B3), the above mixing procedure was scaled down as follows, while observing the mass ratios used above. 20 g of GENIOSIL ^® STP-E10 were mixed in a DAG speed mixer

600.1 VAC-P from Hauschild, at approx. 25°C with 20 g of resin B3 and 0.8 g of stabilizer (commercially available under the name TINUVIN ^® 123 from BASF AG, Germany; CAS NO: 129757-67 -1) homogenized for 30 seconds at 2000 rpm. Thereafter, 37.9 g of aluminum trihydroxide with a BET surface area of 3-5 m ² /g and a d50 value of 1.7-2.1 μm (commercially available under the name "Martinal OL 104" from Albemarle Corp.) with stirring for 60 seconds at 2000 rpm After the aluminum trihydroxide has been incorporated, 0.8 g of N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane are mixed in for one minute at 2000 rpm. Finally, the mixture is homogenized for one minute at 1350 rpm and for 30 seconds at 800 rpm at a pressure of 100 mbar and stirred without bubbles.

The formulation is filled into a 55 ml PE cartridge and stored at 25° C. for one day before the examination.

The mass was spread out onto a milled Teflon plate to a depth of 2 mm and cured at 23° C. and 50% relative atmospheric humidity for 2 weeks.

The Shore A hardness, the tensile strength and the elongation at break were determined for each of the specimens shown (presented using the laboratory planetary mixer or speed mixer).

The Shore A hardness was determined according to DIN 53505, the tensile strength according to DIN 53504-S1 and the elongation at break according to DIN 53504-S1. The assignments of the test specimens are in Table 5, the application data of the moldings are summarized in Table 6.

Table 5 :

Table 6 :

Claims

patent claims

1. Containing crosslinkable masses

(A) 100 parts by weight of compounds of formula

whereby

Y is an x-valent polymer radical bonded via nitrogen, oxygen, sulfur or carbon,

R can be the same or different and is a monovalent hydrocarbon radical optionally substituted by one or more halogen atoms,

R ² can be the same or different and represents a hydrogen atom or a monovalent hydrocarbon radical optionally substituted with one or more halogen atoms, x is an integer from 1 to 10, a can be the same or different and is 0, 1 or 2 and b may be the same or different and is an integer from 1 to 10,

(B) 5 to 2000 parts by weight of silicone resins containing units of the formula

wherein R ³ can be the same or different and is a hydrogen atom, a monovalent, SiC-bonded, optionally substituted by halogen atoms C1-C20 hydrocarbon radical or a divalent, optionally substituted by halogen atoms, aliphatic C1-C20 hydrocarbon radical, the two units of Formula (II) bridged, represents,

R ⁴ can be the same or different and is a hydrogen atom or a monovalent C1-C20 hydrocarbon radical optionally substituted with halogen atoms, c is 0, 1, 2 or 3 and d is 0, 1, 2 or 3, with the proviso that that the sum of c+d is less than or equal to 3, c is 0 or 1 in at least 40% of the units of the formula (II) and the silicone resin has a polydispersity M _w /M _n of less than 5.0, optionally (C ) organosilicon compounds containing basic nitrogen, optionally (D) fillers, optionally (E) non-reactive plasticizers, optionally (F) catalysts, optionally (G) adhesion promoters, optionally (H) water scavengers, optionally (I) additives and optionally (J) aggregates.

2. Crosslinkable compositions according to Claim 1, characterized in that the radical Y in formula (I) is a polyurethane radical or polyoxyalkylene radical.

3. Crosslinkable compositions according to claim 1 or 2, characterized in that the end groups of the compounds (A) are those of the general formulas

is, where the radicals and indices have one of the meanings given above.

4. Crosslinkable compositions as claimed in one or more of claims 1 to 3, characterized in that they contain at least 10 parts by weight of component (B) per 100 parts by weight of component (A).

5. Crosslinkable compositions according to one or more of Claims 1 to 4, characterized in that the silicone resins (B) have a polydispersity (Mw/ _Mn ) of from 1.0 to 4.5.

6. Crosslinkable compositions according to one or more of Claims 1 to 5, characterized in that R ³ of the silicone resin (B) is exclusively methyl groups.

7. Crosslinkable compositions as claimed in one or more of claims 1 to 4, characterized in that they are containing

(A) 100 parts by weight of compounds of formula (I),

(C) 0.1 to 25 parts by weight of organosilicon compounds containing basic nitrogen, optionally fillers (D), optionally non-reactive plasticizers (E), optionally catalysts (F), optionally adhesion promoters (G), optionally water scavengers (H), optionally additives (I) and optionally aggregates (J).

8. Crosslinkable compositions according to one or more of claims 1 to 7, characterized in that they are transparent compositions.

9. A process for preparing the composition according to one or more of claims 1 to 8 by mixing the individual components 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 process for the production of material composites, in which the masses according to one or more of claims 1 to 8 or produced according to claim 9 are applied to at least one substrate and then crosslinked.