LINKABLE MATERIALS BASED ON ORGANYLOXYSILANE TERMINATED POLYMERS

Description

[0001] The invention relates to crosslinkable masses of silane-crosslinking prepolymers, processes for their preparation and their use as adhesives and sealants, in particular for bonding substrates.

[0002] Polymer systems containing reactive alkoxysilyl groups have long been known. Upon contact with water or atmospheric moisture, these alkoxysilane-terminated polymers are capable of condensing with each other, even at room temperature, with the alkoxy groups being eliminated. One of the most important applications of such materials is the production of adhesives.

[0003] Adhesives based on alkoxysilane-curing polymers, for example, exhibit not only good adhesion properties on some substrates when cured, but also very good mechanical properties, as they can be both tear-resistant and highly elastic. Another key advantage of silane-curing systems over numerous other adhesive and sealant technologies (e.g., over isocyanate-curing systems) is the toxicological safety of the prepolymers.

[0004] In many applications, single-component (1K) systems are preferred, which cure upon contact with atmospheric moisture. The key advantage of single-component systems is their ease of application, as they eliminate the need for the user to mix different adhesive components. In addition to saving time and effort and reliably avoiding potential dosing errors, single-component systems also eliminate the need to process the adhesive / sealant within a typically very tight time frame, as is the case with multi-component systems after the two components have been thoroughly mixed.

[0005] A special variant of adhesives based on alkoxysilane-curing polymers is described in DE-A 10 2011 006130 and DE-A 10 2011 081264, which contain phenylsilicone resins in addition to the silane-curing polymers. The corresponding resin additives not only improve adhesion to numerous different substrates, but also lead to adhesives that exhibit significantly improved hardness and tensile shear strength after full curing—particularly at the high resin contents described in DE-A 10 2011 081264.

[0006] However, the systems specifically described in the prior art are limited to materials containing polymers with so-called alpha-alkoxysilane groups, in which the alkoxysilyl group is separated from a heteroatom by only a CH 2 group. This particular type of polymer is characterized by particularly high reactivity, so that the use of highly effective catalysts, such as organotin compounds, amidine, or guanidine derivatives, is not necessary. This is very advantageous in that highly effective catalysts can catalyze exchange reactions in which Si-O-Si bonds of the added phenylsilicone resins react with the Si-OCH 3 groups of the alkoxysilane-functional polymers. Such exchange reactions would lead to the formation of Si-O-Si bonds between the alkoxysilane-functional polymers, which can lead to a drastic increase in viscosity and even complete gelation of the material.The storage stability of the corresponding formulation would no longer be guaranteed.

[0007] A disadvantage of these systems described in the prior art, however, is that almost all commercially available polymer types do not possess the required highly reactive alpha-alkoxysilane groups, but instead possess so-called gamma-alkoxysilane groups, in which the alkoxysilane unit is linked to the nearest heteroatom by a (CH 2 ) 3 spacer. This severely limits the raw material base available, especially since the few commercially available alpha-alkoxysilane-functional polymers also exhibit systemic disadvantages, such as comparatively high manufacturing costs or comparatively poor recovery rates. Many property profiles are therefore not achievable with existing technology.

[0008] The invention relates to crosslinkable compositions containing (A) 100 parts by weight of compounds of the formula Y-[(CR 1< 2 ) 3 -SiR a (OR 2< ) 3-a ] b (I), where Y is an x-valent polymer radical bonded 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 the same or different and represents a hydrogen atom or a monovalent, optionally substituted hydrocarbon radical which can be bonded to the carbon atom via nitrogen, phosphorus, oxygen, sulfur or carbonyl group, R 2< can be the same or different and represents a hydrogen atom or a monovalent, optionally substituted hydrocarbon radical, b is an integer from 1 to 10, preferably 1, 2 or 3, particularly preferably 1 or 2, and a can be the same or different and is 0, 1 or 2, preferably 0 or 1,(B) at least 5 parts by weight of silicone resins containing units of the formula R 3< c (R 4< O) d R 5< SiO (4-cde) / 2 (II), where R 3< can be the same or different and denotes a hydrogen atom, a monovalent, SiC-bonded, optionally substituted aliphatic hydrocarbon radical or a divalent, optionally substituted, aliphatic hydrocarbon radical bridging two units of the formula (II), R 4< can be the same or different and denotes a hydrogen atom or a monovalent, optionally substituted hydrocarbon radical, R 5< can be the same or different and denotes a monovalent, SiC-bonded, optionally substituted aromatic hydrocarbon radical, c is 0, 1, 2 or 3, d is 0, 1, 2 or 3, preferably 0, 1 or 2, particularly preferably 0 or 1, and e is 0, 1 or 2, preferably 0 or 1, is, with the proviso,that the sum of c+d+e is less than or equal to 3 and in at least 40% of the units of formula (II) the sum c+e is equal to 0 or 1, (C1) catalyst selected from metal-containing curing catalysts, guanidines and amidines, and (C2) cocatalyst containing units of the formula D h Si(OR 7< ) g R 6< f O( 4-fgh) / 2 (III), wherein R 6< can be the same or different and denotes a monovalent, optionally substituted SiC-bonded, nitrogen-free organic radical, R 7< can be the same or different and denotes a hydrogen atom or optionally substituted hydrocarbon radicals, D can be the same or different and denotes a monovalent, SiC-bonded radical having at least one nitrogen atom not bonded to a carbonyl group (C=O), f is 0, 1, 2 or 3, preferably 1, g is 0, 1, 2 or 3, preferably 1, 2 or 3, particularly preferably 1 or 3, and h is 0, 1, 2, 3 or 4, preferably 1, with the proviso thatthat the sum of f+g+h is less than or equal to 4 and at least one radical D is present per molecule, wherein the molar ratio of compounds (C1) to radicals D in compounds (C2) is 1:1 to 1:400 and the crosslinkable masses contain components (C1) and (C2) in a total amount of 0.2 to 50 parts by weight based on 100 parts by weight of component (A).

[0009] The invention is based on the surprising discovery that by using the catalyst combination according to the invention comprising catalyst (C1) and cocatalyst (C2), compositions based on the polymers (A) and silicone resins (B) according to the invention can be obtained which not only have sufficient storage stability but also rapidly crosslink and cure upon contact with atmospheric moisture.

[0010] Examples of R radicals 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 n-hexyl radical; heptyl radicals, such as n-heptyl radical; octyl radicals, such as n-octyl, iso-octyl radicals and 2,2,4-trimethylpentyl radical; nonyl radicals, such as n-nonyl radical; decyl radicals, such as n-decyl radical; dodecyl radicals, such as n-dodecyl radical; octadecyl radicals, such as n-octadecyl radical; Cycloalkyl radicals, such as the cyclopentyl, cyclohexyl, cycloheptyl radicals and methylcyclohexyl radicals; alkenyl radicals, such as the vinyl, 1-propenyl and 2-propenyl radicals; aryl radicals, such as the phenyl, naphthyl, anthryl and phenanthryl radicals; 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 β-phenylethyl radicals.

[0011] 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.

[0012] The radical R is preferably a monovalent hydrocarbon radical having 1 to 6 carbon atoms, optionally substituted by halogen atoms, particularly preferably an alkyl radical having 1 or 2 carbon atoms, in particular the methyl radical.

[0013] Examples of radicals R 1< are hydrogen atom, the radicals indicated for R and optionally substituted hydrocarbon radicals bonded to the carbon atom via nitrogen, phosphorus, oxygen, sulfur, carbon or carbonyl group.

[0014] The radical R 1< is preferably a hydrogen atom and a hydrocarbon radical having 1 to 20 carbon atoms, in particular a hydrogen atom.

[0015] Examples of radical R 2< are hydrogen atom or the examples given for radical R.

[0016] The radical R 2< is preferably a hydrogen atom or an alkyl radical having 1 to 10 carbon atoms which is optionally substituted by halogen atoms, particularly preferably an alkyl radical having 1 to 4 carbon atoms, in particular the methyl and ethyl radical.

[0017] For the purposes of the present invention, polymers underlying the polymer radical Y are understood to mean 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.

[0018] Examples of polymer residues Y are polyester, polyether, polyurethane, polyalkylene and polyacrylate residues.

[0019] Polymer radical Y is preferably an organic polymer radical which, as a 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; polyesters; polyamides; polyacrylates; polymethacrylates; Contain vinyl polymers and polycarbonates and which are preferably linked to the group or via -OC(=O)-NH-, -NH-C(=O)O-, -NH-C(=O)-NH-, -NR'-C(=O)-NH-, NH-C(=O)-NR'-, -NH-C(=O)-, -C(=O)-NH-, -C(=O)-O-, -OC(=O)-, -OC(=O)-O-, -SC(=O)-NH-, -NH-C(=O)-S-, -C(=O)-S-, -SC(=O)-, -SC(=O)-S-, -C(=O)-, -S-, -O-, -NR' -Groups - [(CR 1< 2 ) 3 -SiR a (OR 2< ) 3-a ] are bonded, where R' can be the same or different and has a meaning given for R or stands for a group -CH(COOR")-CH 2 -COOR", in which R" can be the same or different and has a meaning given for R.

[0020] The radical R' is preferably a group -CH(COOR")-CH 2 -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 having 6 to 20 carbon atoms optionally substituted by halogen atoms.

[0021] Examples of radicals R' are cyclohexyl, cyclopentyl, n- and iso-propyl, n-, iso- and t-butyl, the various stereoisomers of the pentyl radical, hexyl radical or heptyl radical as well as the phenyl radical.

[0022] The radicals R" are preferably alkyl groups having 1 to 10 carbon atoms, particularly preferably methyl, ethyl or propyl radicals.

[0023] Component (A) can have the groups - [(CR 1< 2 ) 3 -SiR a (OR 2< ) 3-a ] attached in the manner described at any position in the polymer, such as chain-positioned and / or terminally.

[0024] The radical Y is preferably a polyurethane radical or a polyoxyalkylene radical, particularly preferably a chain-like polyurethane radical or a chain-like polyoxyalkylene radical each having 0 to 3 branching points with terminally attached groups - [(CR 1< 2 ) b -SiR a (OR 2< ) 3-a ], where branching points in the sense of the invention are understood to mean all branches from the main chain having more than one carbon atom and the radicals and indices have the meanings given above.

[0025] In particular, radical Y in formula (I) is a chain-like polyurethane radical or a chain-like polyoxyalkylene radical without branching points with terminally attached groups -[(CR 1< 2 ) b -SiR a (OR 2< ) 3-a] , where the radicals and indices have the meanings given above.

[0026] The polyurethane radicals Y are preferably those whose chain ends are bonded to the group or groups -[(CR 1< 2 ) 3 -SiR a (OR 2< ) 3-a ] via -NH-C(=O)O-, -NH-C(=O)-NH-, -NR'-C(=O)-NH- or -NH-C(=O)-NR'-, in particular via -OC(=O)-NH- or -NH-C(=O)-NR'-, where all radicals and indices have one of the abovementioned meanings. The polyurethane radicals Y can preferably be prepared from linear or branched polyoxyalkylenes, in particular from polypropylene glycols, and di- or polyisocyanates. The radicals Y preferably have average molecular masses M n (number average) of 400 to 30,000 g / mol, preferably of 4,000 to 20,000 g / mol.Suitable processes for producing a corresponding component (A) as well as examples of the component (A) itself are described, inter alia, in EP 1 093 482 B1 (paragraphs

[0014] -

[0023] ,

[0039] -

[0055] 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 content of the present application.

[0027] In the context of the present invention, the number-average molar mass M n is determined 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 Styragel HR3-HR4-HR5-HR5 column set from Waters Corp. USA with an injection volume of 100 μl.

[0028] The polyoxyalkylene radicals Y are preferably linear or branched polyoxyalkylene radicals, particularly preferably polyoxypropylene radicals, whose chain ends are preferably bonded via -OC(=O)-NH- or -O- to the group or groups -[(CR 1< 2 ) 3 -SiR a (OR 2< ) 3-a ], where the radicals and indices have one of the meanings given above. Preferably, at least 85%, particularly preferably at least 90%, in particular at least 95%, of all chain ends are bonded via -OC(=O)-NH- to the group -[(CR 1< 2 ) 3 -SiR a (OR 2< ) 3-a ]. The polyoxyalkylene radicals Y preferably have average molar masses M n of 4,000 to 30,000 g / mol, preferably of 8,000 to 20,000 g / mol.Suitable processes for preparing a corresponding component (A) as well as examples of the component (A) itself are described, inter alia, in EP 1 535 940 B1 (paragraphs

[0005] -

[0025] and Examples 1-3 and Comparative Example 1-4) or EP 1 896 523 B1 (paragraphs

[0008] -

[0047] ), which are to be included in the disclosure content of the present application.

[0029] The end groups of the compounds (A) used according to the invention are preferably those of the general formulas -NH-C (=O)-NR'- (CR 1< 2 ) 3 -SiR a (OR 2< ) 3-a (IV), -OC(=O) -NH- (CR 1< 2 ) 3 -SiR a (OR 2< ) 3-a (V) or -O- (CR 1< 2 ) 3 -SiR a (OR 2< ) 3-a (VI), where the radicals and indices have one of the meanings given above.

[0030] If the compounds (A) are polyurethanes, which is preferred, they preferably have one or more of the following end groups: -NH-C (=O) -NR'- (CH 2 ) 3 -Si(OCH 3 ) 3 , -NH-C (=O)-NR'- (CH 2 ) 3 -Si(OC 2 H 5 ) 3 , -OC(=O)-NH- (CH 2 ) 3 -Si(OCH 3 ) 3 or -OC(=O)-NH- (CH 2 ) 3 -Si(OC 2 H 5 ) 3 , where R' has the meaning given above.

[0031] If the compounds (A) are polypropylene glycols, which is also preferred, they preferably have one or more of the following end groups: -O-(CH 2 ) 3 -Si(CH 3 )(OCH 3 ) 2 , -O-(CH 2 ) 3 -Si(OCH 3 ) 3 , -OC(=O)-NH-(CH 2 ) 3 -Si(OC 2 H 5 ) 3 , -OC(=O)-NH-(CH 2 ) 3 -Si(OCH 3 ) 3 or -OC(=O)-NH-(CH 2 ) 3 -Si(CH 3 )(OCH 3 ) 2 .

[0032] The average molecular weights M n of the compounds (A) are preferably at least 400 g / mol, more preferably at least 4,000 g / mol, in particular at least 10,000 g / mol and preferably at most 30,000 g / mol, more preferably at most 20,000 g / mol, in particular at most 19,000 g / mol.

[0033] 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, in each case measured at 20°C.

[0034] In the context of the present invention, the viscosity is determined after tempering to 23°C using a DV 3 P rotational viscometer from A. Paar (Brookfield Systems), using spindle 5 at 2.5 rpm in accordance with ISO 2555.

[0035] The compounds (A) used according to the invention are commercially available products or can be prepared by processes commonly used in chemistry.

[0036] The preparation of the polymers (A) can be carried out by known processes, such as addition reactions, such as hydrosilylation, Michael addition, Diels-Alder addition or reactions between isocyanate-functional compounds with compounds having isocyanate-reactive groups.

[0037] Component (A) used according to the invention can contain only one type of compound of formula (I) as well as mixtures of different types of compounds of formula (I). Component (A) can contain exclusively compounds of formula (I) in which more than 90%, preferably more than 95% and particularly preferably more than 98% of all silyl groups bonded to the Y radical are identical. However, it is then also possible to use a component (A) which at least partly contains compounds of formula (I) in which different silyl groups are bonded to a Y radical. Finally, mixtures of different compounds of formula (I) in which a total of at least two different types of silyl groups bonded to Y radicals are present, but all silyl groups bonded to a Y radical are identical.

[0038] The compositions according to the invention preferably contain compounds (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.

[0039] 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 15 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 200 parts by weight, particularly preferably at most 60 parts by weight, in particular at most 50 parts by weight, of component (B).

[0040] Component (B) preferably consists of at least 90% by weight of units of formula (II). Component (B) or (B1) particularly preferably consists exclusively of units of formula (II).

[0041] Examples of radicals R 3< are the aliphatic examples given above for R. However, the radical R 3< can also be divalent aliphatic radicals which link two silyl groups of the formula (II) to one another, such as 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 aliphatic hydrocarbon radical having 1 to 18 carbon atoms, particularly preferably an aliphatic hydrocarbon radical having 1 to 6 carbon atoms, in particular the methyl radical.

[0042] Examples of radical R 4< are hydrogen atom or the examples given for radical R.

[0043] The radical R 4< is preferably a hydrogen atom or an alkyl radical having 1 to 10 carbon atoms which is optionally substituted by halogen atoms, particularly preferably an alkyl radical having 1 to 4 carbon atoms, in particular the methyl and ethyl radical.

[0044] Examples of radicals R 5< are the aromatic radicals given above for R.

[0045] The radical R 5< is preferably SiC-bonded aromatic hydrocarbon radicals having 1 to 18 carbon atoms, optionally substituted by halogen atoms, such as ethylphenyl, toluyl, xylyl, chlorophenyl, naphthyl or styryl radicals, particularly preferably the phenyl radical.

[0046] Silicone resins in which at least 90% of all R 3< radicals are methyl radicals are preferably used as component (B).

[0047] Silicone resins in which at least 90% of all radicals R 4< are methyl, ethyl, propyl or isopropyl radicals are preferably used as component (B).

[0048] Silicone resins in which at least 90% of all radicals R 5< are phenyl radicals are preferably used as component (B).

[0049] According to the invention, silicone resins (B) are preferably used which have at least 20%, particularly preferably at least 40%, of units of the formula (II) in which c is 0, in each case based on the total number of units of the formula (II).

[0050] Preference is given to using silicone resins (B) which, based in each case on the total number of units of formula (II), comprise at least 70%, particularly preferably at least 80%, of units of formula (II) in which d is 0 or 1.

[0051] Preferably, silicone resins (B1) are used as component (B) which, in each case based on the total number of units of the formula (II), have at least 20%, particularly preferably at least 40%, in particular at least 50%, units of the formula (II) in which e is 1.

[0052] In a particular embodiment of the invention, silicone resins (B1) are used which exclusively comprise units of the formula (II) in which e is 1,

[0053] In a particularly preferred embodiment of the invention, silicone resins are used as component (B1) which, in each case based on the total number of units of the formula (II), have at least 20%, particularly preferably at least 40%, in particular at least 50%, units of the formula (II) in which e is 1 and c is 0.

[0054] Examples of the silicone resins (B) used according to the invention are organopolysiloxane resins which consist essentially, preferably exclusively, of units selected from (Q) units of the formulas SiO 4 / 2 , Si (OR 4< )O 3 / 2 , Si (OR 4< ) 2 O 2 / 2 and Si (OR 4< ) 3 O 1 / 2 , (T) units of the formulas PhSiO 3 / 2 , PhSi (OR 4< )O 2 / 2 and PhSi (OR 4< ) 2 O 4 / 2 , (D) units of the formulas Me 2 SiO 2 / 2 and Me 2 Si (OR 4< )O 1 / 2 and (M) units of the formula Me 3 SiO 1 / 2 , where Me is methyl, Ph is phenyl and R 4< is hydrogen atom or optionally substituted by halogen atoms alkyl radicals having 1 to 10 carbon atoms, preferably unsubstituted alkyl radicals having 1 to 4 carbon atoms, wherein the resin preferably contains 0-2 mol (Q) units, 0-2 mol (D) units and 0-2 mol (M) units per mol (T) units.

[0055] Preferred examples of the silicone resins (B) used according to the invention are organopolysiloxane resins which consist essentially, preferably exclusively, of units selected from T units of the formulas PhSiO 3 / 2 , PhSi (OR 4< )O 2 / 2 and PhSi(OR 4< ) 2 O 1 / 2 and T units of the formulas MeSiO 3 / 2 , Me-Si(OR 4< )O 2 / 2 and MeSi(OR 4< ) 2 O 1 / 2 , where Me is methyl, Ph is phenyl and R 4< is hydrogen atom or optionally halogen-substituted alkyl radicals having 1 to 10 carbon atoms, preferably unsubstituted alkyl radicals having 1 to 4 carbon atoms.

[0056] Further preferred examples of the silicone resins (B) used according to the invention are organopolysiloxane resins which consist essentially, preferably exclusively, of units selected from T units of the formulas PhSiO 3 / 2 , PhSi(OR 4< )O 2 / 2 and PhSi(OR 4< ) 2 O 1 / 2 , T units of the formulas MeSiO 3 / 2 , MeSi(OR 4< )O 2 / 2 and MeSi(OR 4< ) 2 O 1 / 2 and D units of the formulas Me 2 SiO 2 / 2 and Me 2 Si(OR 4< )O 1 / 2 , where Me is methyl, Ph is phenyl and R 4< is hydrogen atom or optionally halogen-substituted alkyl radicals having 1 to 10 carbon atoms, preferably unsubstituted alkyl radicals having 1 to 4 carbon atoms, with a molar Ratio of phenylsilicone to methylsilicone units from 0.5 to 4.0. The content of D units in these silicone resins is preferably below 10 wt.%.

[0057] Particularly preferred examples of the silicone resins (B1) used according to the invention are organopolysiloxane resins which consist of 80%, preferably 90%, in particular exclusively, of T units of the formulas PhSiO 3 / 2 , PhSi (OR 4< )O 2 / 2 and / or PhSi (OR 4< ) 2 O 1 / 2 , where Ph is phenyl radical and R 4< is hydrogen atom or optionally halogen-substituted alkyl radicals having 1 to 10 carbon atoms, preferably unsubstituted alkyl radicals having 1 to 4 carbon atoms, in each case based on the total number of units.

[0058] The silicone resins (B) used according to the invention preferably have an average molecular weight (number average) M n of at least 400 g / mol, particularly preferably at least 600 g / mol. The average molecular weight M n is preferably at most 400,000 g / mol, particularly preferably at most 10,000 g / mol, in particular at most 3,000 g / mol.

[0059] The silicone resins (B) used according to the invention can be either solid or liquid at 23°C and 1000 hPa, with silicone resins (B) preferably being liquid. The silicone resins (B) preferably have a viscosity of 10 to 100,000 mPas, preferably 50 to 50,000 mPas, in particular 100 to 20,000 mPas.

[0060] The silicone resins (B) preferably have a polydispersity (M w / M n ) of at most 5, preferably of at most 3.

[0061] The mass-average molar mass M w as well as the number-average molar mass M n are determined by 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 Styragel HR3-HR4-HR5-HR5 column set from Waters Corp. USA with an injection volume of 100 µl.

[0062] The silicone resins (B) can be used both in pure form and in the form of a mixture in a suitable solvent (BL).

[0063] All compounds that are non-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).

[0064] Examples of solvents (BL) are ethers (e.g. diethyl ether, methyl t-butyl ether, ether derivatives of glycol, THF), esters (e.g. ethyl acetate, butyl acetate, glycol esters), aliphatic hydrocarbons (e.g. pentane, cyclopentane, hexane, cyclohexane, heptane, octane or longer-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).

[0065] Many commercially available resins (B1), such as SILRES ®< SY 231, SILRES ®< IC 231, SILRES ®< IC 368, or SILRES ®< IC 678 from Wacker Chemie AG (Munich, Germany), are liquid at 23°C and 1013 hPa, but due to their manufacturing process, they nevertheless contain small amounts of solvent (BL), particularly toluene. The resins mentioned above contain approximately 0.1% toluene by weight, based on the total weight of the resin.

[0066] In a preferred embodiment of the invention, component (B1) is used as component (B), which contains 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 aromatic solvents (BL).

[0067] In a particularly preferred embodiment of the invention, component (B1) is used as component (B), which, with the exception of alcohols R 4< OH, contains 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.

[0068] In a very particularly preferred embodiment of the invention, resins (B1) are used as component (B) which, with the exception of alcohols R 4< OH, contain no solvents (BL) at all with R 4< equal to the meaning given above, wherein alcohols R 4< OH can be present in amounts of preferably up to 10% by weight, particularly preferably up to 5% by weight, depending on the preparation.

[0069] The silicone resins (B) or (B1) used according to the invention are commercially available products or can be produced by methods commonly used in silicon chemistry.

[0070] Preferably, the compounds (A) described as preferred or particularly preferred are used in combination with resins (B1) in the stated proportions.

[0071] The catalysts (C1) used in the compositions according to the invention can be any metal-containing curing catalysts, guanidines and amidines known to date.

[0072] The metal-containing curing catalysts (C1) used according to the invention are preferably organic titanium compounds and tin compounds.

[0073] Examples of the metal-containing curing catalysts (C1) are titanic acid esters, such as tetrabutyl titanate, tetrapropyl titanate, tetraisopropyl titanate and titanium tetraacetylacetonate; organotin compounds, such as dibutyltin dilaurate, dibutyltin dimaleate, dibutyltin diacetate, dibutyltin dioctanoate, dibutyltin acetylacetonate, dibutyltin oxides, dibutyltin ethylhexanolate, dibutyltin distearate, dioctyltin dilaurate, dioctyltin maleate, dioctyltin diacetate, dioctyltin dioctanoate, dioctyltin acetylacetonate, dioctyltin oxides, dioctyltin ethylhexanolate or dioctyltin distearate, tin(II) salts, in particular tin(II)carboxylates.

[0074] Furthermore, the catalysts (C1) used according to the invention can be amidines such as 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or guanidines such as 1,3-diphenylguanidine, 1,1,2-trimethylguanidine, 1,2,3-trimethylguanidine, 1,1,3,3-tetramethylguanidine, 1,1,2,3,3-pentamethylguanidine, 2-ethyl-1,1,3,3-tetramethylguanidine, 2-butyl-1,1,3,3-tetramethylguanidine and 1,5,7-triazabicyclo[4.4.0]dec-5-ene as well as the various 7-Alkyl-1,5,7-tri-azabicyclo[4.4.0]dec-5-ene derivatives.

[0075] The catalysts (C1) used according to the invention are preferably titanium-containing compounds, tin-containing compounds, amidines and guanidines, particularly preferably tin-containing compounds, amidines and guanidines, in particular tin-containing compounds.

[0076] The catalysts (C1) to be used according to the invention are commercially available products.

[0077] The cocatalysts (C2) used in the compositions according to the invention can be either silanes, ie compounds of the formula (III) with f+g+h=4, or siloxanes, ie compounds containing units of the formula (III) with f+g+h≤3, wherein they are preferably silanes.

[0078] Examples of radical R 6< are the examples given for R.

[0079] The radical R 6< is preferably a hydrocarbon radical having 1 to 18 carbon atoms, optionally substituted by halogen atoms, particularly preferably a hydrocarbon radical having 1 to 5 carbon atoms, in particular the methyl radical.

[0080] Examples of optionally substituted hydrocarbon radicals R 7< are the examples given for radical R.

[0081] The radicals R 7< are preferably hydrogen atoms and optionally halogen-substituted hydrocarbon radicals having 1 to 18 carbon atoms, particularly preferably hydrogen atoms and hydrocarbon radicals having 1 to 10 carbon atoms, in particular methyl and ethyl radicals.

[0082] Beispiele für Reste D sind Reste der Formeln H 2 N(CH 2 ) 3 -, H 2 N(CH 2 ) 2 NH(CH 2 ) 3 -, H 2 N(CH 2 ) 2 NH(CH 2 ) 2 NH(CH 2 ) 3 -, H 3 CNH(CH 2 ) 3 -, C 2 H 5 NH(CH 2 ) 3 -, C 3 H 7 NH(CH 2 ) 3 -, C 4 H 9 NH(CH 2 ) 3 -, C 5 H 11 NH(CH 2 ) 3 -, C 6 H 13 NH(CH 2 ) 3 -, C 7 H 15 NH(CH 2 ) 3 -, H 2 N(CH 2 ) 4 -, H 2 N-CH 2 -CH(CH3)-CH 2 -, H 2 N(CH 2 ) 5 -, cyclo-C 5 H 9 NH(CH 2 ) 3 -, cyclo-C 6 H 11 NH(CH 2 ) 3 -, Phenyl-NH(CH 2 ) 3 -, (CH 3 ) 2 N(CH 2 ) 3 -, (C 2 H 5 ) 2 N(CH 2 ) 3 -, (C 3 H 7 ) 2 N(CH 2 ) 3 -, (C 4 H 9 ) 2 N(CH 2 ) 3 -, (C 5 H 11 ) 2 N(CH 2 ) 3 -, (C 6 H 13 ) 2 N(CH 2 ) 3 -, (C 7 H 15 ) 2 N(CH 2 ) 3 -, H 2 N(CH 2 )-, H 2 N(CH 2 ) 2 NH(CH 2 )-, H 2 N(CH 2 ) 2 NH(CH 2 ) 2 NH(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 11 NH(CH 2 )-, 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 H 11 NH(CH 2 )-, Phenyl-NH(CH 2 )-, (CH 3 ) 2 N(CH 2 )-, (C 2 H 5 ) 2 N(CH 2 )-, (C 3 H 7 ) 2 N(CH 2 )-,(C 4 H 9 ) 2 N(CH 2 )-, (C 5 H 11 ) 2 N(CH 2 )-, (C 6 H 13 ) 2 N(CH 2 ) (C 7 H 15 ) 2 N(CH 2 )-, (CH 3 O) 3 Si(CH 2 ) 3 NH(CH 2 ) 3 -, (C 2 H 5 O) 3 Si(CH 2 ) 3 NH(CH 2 ) 3 -, (CH 3 O) 2 (CH 3 )Si (CH 2 ) 3 NH(CH 2 ) 3 - and (C 2 H 5 O) 2 (CH 3 )Si (CH 2 ) 3 NH(CH 2 ) 3 - as well as reaction products of the above-mentioned primary amino groups with compounds which have double bonds or contain epoxy groups.,

[0083] Preferably, residue D is the H 2 N(CH 2 ) 3 -, H 2 N(CH 2 ) 2 NH(CH 2 ) 3 - and cyclo-C 6 H 11 NH(CH 2 ) 3 - residue.

[0084] Examples of the silanes of the formula (III) which may be 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-C 6 H 11 NH(CH 2 ) 3 -Si(OCH 3 ) 3 , cyclo-C 6 H 11 NH(CH 2 ) 3 -Si(OC 2 H 5 ) 3 , cyclo-C 6 H 11 NH(CH 2 ) 3 -Si(OCH 3 ) 2 CH 3 , cyclo-C 6 H 11 NH(CH 2 ) 3 -Si(OC 2 H 5 ) 2 CH 3 , cyclo-C 6 H 11 NH(CH 2 ) 3 -Si(OH) 3 , cyclo-C 6 H 11 NH(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-C 6 H 11 NH(CH 2 )-Si (OC 2 H 5 ) 3 , cyclo-C 6 H 11 NH(CH 2 )-Si (OCH 3 ) 2 CH 3 , cyclo-C 6 H 11 NH(CH 2 )-Si (OC 2 H 5 ) 2 CH 3 , cyclo-C 6 H 11 NH(CH 2 )-Si (OH) 3 , cyclo-C 6 H 11 NH(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(OC 2 H 5 ) 2 CH 3 , Phenyl-NH (CH 2 )-Si (OH) 3 und Phenyl-NH(CH 2 )-Si(OH) 2 CH 3 sowie deren Teilhydrolysate, wobei 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-C 6 H 11 NH(CH 2 ) 3 -Si(OCH 3 ) 3 ,cyclo-C 6 H 11 NH(CH 2 ) 3 -Si(OC 2 H 5 ) 3 and cyclo-C 6 H 11 NH(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 H 11 NH(CH 2 ) 3 -Si(OCH 3 ) 3 , cyclo-C 6 H 11 NH(CH 2 ) 3 -Si(OCH 3 ) 2 CH 3 and their partial hydrolysates are particularly preferred.

[0085] The cocatalysts (C2) used according to the invention are commercially available products or can be prepared by processes commonly used in chemistry.

[0086] In the compositions according to the invention, the molar ratio of the compounds (C1) to radicals D in compound (C2) is preferably 1:2 to 1:200, particularly preferably 1:3 to 1:100, in particular 1:10 to 1:80.

[0087] The crosslinkable compositions according to the invention contain components (C1) and (C2) in a total amount of preferably from 0.3 to 35 parts by weight, particularly preferably from 0.6 to 30 parts by weight, in each case based on 100 parts by weight of component (A).

[0088] In addition to the components (A), (B), (C1) and (C2) used, the compositions according to the invention can contain all other substances which have also been used previously in crosslinkable compositions and which are different from components (A), (B), (C1) and (C2), such as non-reactive plasticizers (D), fillers (E), adhesion promoters (F), water scavengers (G), additives (H) and aggregates (I).

[0089] Non-reactive plasticizers (D) in the context of the present invention are all organic compounds which do not react with water or with components (A), (B), (C1) and (C2) at temperatures <80°C, are liquid at 20°C and 1013 hPa, have a boiling point >250°C at 1013 hPa and are selected from the substance groups consisting of fully esterified aromatic or aliphatic carboxylic acids, fully esterified derivatives of phosphoric acid, fully esterified derivatives of sulfonic acids, branched or unbranched saturated hydrocarbons, polystyrenes, polybutadienes, polyisobutylenes, polyesters and polyethers.

[0090] Examples of carboxylic acid esters (D) are phthalic acid esters, such as dioctyl phthalate, diisooctyl phthalate and diundecyl phthalate; perhydrogenated phthalic acid esters, such as 1,2-cyclohexanedicarboxylic acid diisononyl ester and 1,2-cyclohexanedicarboxylic acid dioctyl ester; adipic acid esters, such as dioctyl adipate; benzoic acid esters; esters of trimellitic acid, glycol esters; esters of saturated alkanediols, such as 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate and 2,2,4-trimethyl-1,3-pentanediol diisobutyrate.

[0091] Examples of polyethers (D) are polyethylene glycols, poly-THF and polypropylene glycols with molecular weights of preferably 200 to 20,000 g / mol.

[0092] Preference is given to using plasticizers (D) 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 at most 20,000 g / mol, particularly preferably of at most 10,000 g / mol, in particular of at most 8,000 g / mol.

[0093] Preferably, phthalic acid ester-free plasticizers, such as perhydrogenated phthalic acid esters, esters of trimellitic acid, polyesters or polyethers, are used as component (D).

[0094] Plasticizers (D) are particularly preferably polyethers, in particular polyethylene glycols, polyTHF, and polypropylene glycols, most preferably polypropylene glycols. The preferred polyethers (D) preferably have molecular weights between 400 and 20,000 g / mol, particularly preferably between 800 and 12,000 g / mol, in particular between 1,000 and 8,000 g / mol.

[0095] If the compositions according to the invention contain plasticizers (D), the amounts are preferably from 5 to 300 parts by weight, particularly preferably from 10 to 150 parts by weight, in particular from 26 to 100 parts by weight, based in each case on 100 parts by weight of component (A). The compositions according to the invention preferably contain plasticizers (D).

[0096] The fillers (E) optionally used in the compositions according to the invention may be any fillers known to date.

[0097] Examples of fillers (E) are non-reinforcing fillers, i.e. 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 powders, 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, i.e. fillers with a BET surface area of ​​more than 50 m 2 < / g, such as pyrogenically produced silica, precipitated silica, precipitated chalk, carbon black, such as furnace black and acetylene black and silicon-aluminum mixed oxides with large BET surface areas; Aluminum trihydroxide, hollow spherical fillers such as ceramic microspheres, elastic plastic spheres, glass spheres, or fibrous fillers. These fillers can be hydrophobized, for example, by treatment with organosilanes or-siloxanes or with stearic acid or by etherification of hydroxyl groups to alkoxy groups.

[0098] The optional fillers (E) used are preferably calcium carbonate, talc, aluminum trihydroxide, and silica. Preferred calcium carbonate types are ground or precipitated and optionally surface-treated with fatty acids such as stearic acid or its salts. The preferred silica is preferably fumed silica.

[0099] Optionally used fillers (E) have a moisture content of preferably less than 1 wt.%, particularly preferably less than 0.5 wt.%.

[0100] If the compositions according to the invention contain fillers (E), the amounts are preferably from 10 to 2000 parts by weight, particularly preferably from 40 to 1000 parts by weight, in particular from 80 to 500 parts by weight, based in each case on 100 parts by weight of component (A). The compositions according to the invention preferably contain fillers (E).

[0101] In a particularly preferred embodiment of the invention, the compositions according to the invention contain as fillers (E) a combination of a) silica, in particular fumed silica, and b) calcium carbonate, aluminium trihydroxide and / or talc.

[0102] If the compositions according to the invention contain this particularly preferred combination of different fillers (E), they preferably contain 1 to 50 parts by weight, particularly preferably 5 to 20 parts by weight, of silica, in particular pyrogenic silica, and preferably 10 to 500 parts by weight, particularly preferably 50 to 300 parts by weight, of calcium carbonate, aluminum trihydroxide, talc or mixtures of these materials, in each case based on 100 parts by weight of component (A).

[0103] In a further particularly preferred embodiment of the invention, the compositions according to the invention contain as fillers (E) exclusively calcium carbonate, aluminum trihydroxide and / or talc in amounts of preferably a total of 10 to 500 parts by weight, particularly preferably 50 to 300 parts by weight, in each case based on 100 parts by weight of component (A).

[0104] The adhesion promoters (F) optionally used in the compositions according to the invention can be any adhesion promoters previously described for systems curing by silane condensation.

[0105] Beispiele für Haftvermittler (F) sind Epoxysilane, wie Glycidoxypropyltrimethoxysilane, Glycidoxypropyl-methyldimethoxysilan, Glycidoxypropyltriethoxysilan oder Glycidoxypropyl-methyldiethoxysilan, 2-(3-Triethoxysilylpropyl)-maleinsäureanhydrid, N-(3-Trimethoxysilylpropyl)-harnstoff, N-(3-Triethoxysilylpropyl)-harnstoff, N-(Trimethoxysilylmethyl)-harnstoff, N-(Methyl-dimethoxysilylmethyl)-harnstoff, N-(3-Triethoxysilylmethyl)-harnstoff, N-(3-Methyldiethoxysilylmethyl)harnstoff, O-Methylcarbamatomethyl-methyldimethoxysilan, O-Methylcarbamatomethyltrimethoxysilan, O-Ethylcarbamatomethyl-methyldiethoxysilan, o-Ethylcarbamatomethyl-triethoxysilan, 3-Methacryloxypropyl-trimethoxysilan, Methacryloxymethyl-trimethoxysilan, Methacryloxymethyl-methyldimethoxysilan, Methacryloxymethyl-triethoxysilan, Methacryloxymethyl-methyldiethoxysilan, 3-Acryloxypropyl-trimethoxysilan, Acryloxymethyl-trimethoxysilan, Acryloxymethylmethyldimethoxysilane,Acryloxymethyl-triethoxysilane and acryloxymethyl-methyldiethoxysilane and their partial condensates.,

[0106] If the compositions according to the invention contain adhesion promoters (F), the amounts involved are preferably from 0.5 to 30 parts by weight, particularly preferably from 1 to 10 parts by weight, in each case based on 100 parts by weight of crosslinkable composition.

[0107] The water scavengers (G) optionally used in the compositions according to the invention can be any water scavengers described for systems curing by silane condensation.

[0108] Examples of water scavengers (G) are silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, tetraethoxysilane, O-methylcarbamatomethylmethyldimethoxysilane, O-methylcarbamatomethyltrimethoxysilane, O-ethylcarbamatomethylmethyldiethoxysilane, O-ethylcarbamatomethyltriethoxysilane, and / or their partial condensates and orthoesters such as 1,1,1-trimethoxyethane, 1,1,1-triethoxyethane, trimethoxymethane and triethoxymethane, with vinyltrimethoxysilane being preferred.

[0109] If the compositions according to the invention contain water scavengers (G), the amounts are preferably from 0.5 to 30 parts by weight, particularly 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 (G).

[0110] The additives (H) optionally used in the compositions according to the invention can be any additives known to date that are typical for silane-crosslinking systems.

[0111] The additives (H) optionally used according to the invention are compounds which are different from components (A) to (G), preferably antioxidants, UV stabilizers, such as so-called HALS compounds, fungicides, commercially available defoamers, e.g. from BYK (D-Wesel), commercially available wetting agents, e.g. from BYK (D-Wesel) and pigments.

[0112] If the compositions according to the invention contain additives (H), these are amounts of 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 component (A). The compositions according to the invention preferably contain additives (H).

[0113] The additives (I) optionally used according to the invention, which are different from component (H), are preferably reactive plasticizers, rheology additives, flame retardants and organic solvents.

[0114] Preferred reactive plasticizers (I) are silanes containing alkyl chains with 6 to 40 carbon atoms and possessing a group reactive toward the compounds (A). Examples are isooctyltrimethoxysilane, isooctyltriethoxysilane, N-octyltrimethoxysilane, N-octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, tetradecyltrimethoxysilane, tetradecyltriethoxysilane, hexadecyltrimethoxysilane, and hexadecyltriethoxysilane.

[0115] The rheology additives (I) are preferably compounds that are solid at room temperature and a pressure of 1013 hPa, preferably polyamide waxes, hydrogenated castor oils or stearates.

[0116] All typical flame retardants that are typical for adhesive and sealant systems can be used as flame retardants (I), in particular halogenated compounds and derivatives.

[0117] Examples of organic solvents (I) are the compounds already mentioned above as solvents (BL), preferably alcohols.

[0118] Preferably, no organic solvents (I) are added to the compositions according to the invention.

[0119] If the compositions according to the invention contain one or more components (I), 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, in each case based on 100 parts by weight of component (A).

[0120] The compositions according to the invention are preferably those containing (A) 100 parts by weight of compounds of the formula (I), (B) 5-60 parts by weight of silicone resins containing units of the formula (II), which are preferably resins (B1), (C1) catalyst selected from metal-containing curing catalysts, guanidines and amidines, (C2) cocatalyst containing units of the formula (III), with the proviso that the molar ratio of compounds (C1) to radicals D in compounds (C2) is 1:1 to 1:200 and the crosslinkable masses contain components (C1) and (C2) in a total amount of 0.2 to 50 parts by weight, based on 100 parts by weight of component (A), optionally (D) plasticizer, optionally (E) fillers, optionally (F) adhesion promoters, optionally (G) water scavengers, optionally (H) additives and optionally (I) admixtures.

[0121] The compositions according to the invention are particularly preferably those containing (A) 100 parts by weight of compounds of the formula (I), (B) 5-60 parts by weight of silicone resins consisting of units of the formula (II), which are preferably resins (B1), (C1) catalyst selected from metal-containing curing catalysts, guanidines and amidines, (C2) cocatalyst consisting of units of the formula (III), with the proviso that the molar ratio of compounds (C1) to radicals D in compounds (C2) is 1:2 to 1:200 and the crosslinkable masses contain components (C1) and (C2) in a total amount of 0.3 to 35 parts by weight, based on 100 parts by weight of component (A), (D) 5 to 300 parts by weight of plasticizer, optionally (E) fillers, optionally (F) adhesion promoters, optionally (G) water scavengers, optionally (H) additives and optionally (I) admixtures.

[0122] The compositions according to the invention are most preferably those containing (A) 100 parts by weight of compounds of formula (I), (B) 5-60 parts by weight of silicone resins consisting of units of formula (II), which are preferably resins (B1), (C1) catalyst selected from metal-containing curing catalysts, guanidines and amidines, (C2) cocatalyst consisting of units of formula (III), with the proviso that the molar ratio of compounds (C1) to radicals D in compounds (C2) is 1:2 to 1:200 and the crosslinkable masses contain components (C1) and (C2) in a total amount of 0.3 to 35 parts by weight, based on 100 parts by weight of component (A), (D) 5 to 300 parts by weight of plasticizer, (E) 40 to 1000 parts by weight of fillers, optionally (F) adhesion promoters, optionally (G) water scavengers, optionally (H) additives and optionally (I) Aggregates.

[0123] The compositions according to the invention are most preferably those containing (A) 100 parts by weight of compounds of formula (I) in which Y is a polypropylene oxide residue, (B) 10-50 parts by weight of silicone resins (B1) consisting of units of formula (II), (C1) catalyst selected from tin-containing compounds, (C2) cocatalyst consisting of units of formula (III), with the proviso that the molar ratio of compounds (C1) to residues D in compounds (C2) is 1:2 to 1:200 and the crosslinkable masses contain components (C1) and (C2) in a total amount of 0.3 to 35 parts by weight, based on 100 parts by weight of component (A), (D) 30-150 parts by weight of plasticizer, (E) 60 to 500 parts by weight of fillers, optionally (F) adhesion promoter, (G) 0.5 to 30 parts by weight of water scavenger, (H) 0.1 to 10 parts by weight Additives selected from antioxidants and UV stabilizers, and optionally (I) aggregates.

[0124] The compositions according to the invention preferably contain no further constituents apart from the components (A) to (I) mentioned.

[0125] 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.

[0126] The compositions according to the invention are preferably viscous to pasty compositions with viscosities of preferably 500 to 3 000 000 mPas, particularly preferably 1 500 to 1 500 000 mPas, in each case at 25°C.

[0127] The compositions according to the invention can be prepared by any known method, such as methods and mixing processes customary for the production of moisture-curing compositions. The order in which the various components are mixed together can be varied as desired.

[0128] A further object of the present invention is a process for preparing the composition according to the invention by mixing the individual components in any desired order.

[0129] This mixing can take place at room temperature and the pressure of the surrounding atmosphere, i.e., approximately 900 to 1100 hPa. If desired, this mixing can also take place at higher temperatures, e.g., at temperatures in the range of 30 to 130°C. Furthermore, it is possible to mix temporarily or continuously under reduced pressure, such as 30 to 500 hPa absolute pressure, to remove volatile compounds and / or air.

[0130] The mixing according to the invention is preferably carried out in the absence of moisture.

[0131] The process according to the invention can be carried out continuously or discontinuously.

[0132] The compositions according to the invention are preferably one-component crosslinkable compositions. 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 to a second component.

[0133] The compositions according to the invention can be stored in the absence of water and can be crosslinked in the presence of water.

[0134] The usual water content of air is sufficient for crosslinking the compositions of the invention. Crosslinking of the compositions of the invention preferably takes place at room temperature. If desired, it can also be carried out at temperatures higher or lower than room temperature, e.g., at -5° to 15°C or at 30° to 50°C, and / or using water concentrations that exceed the normal water content of air.

[0135] Preferably, the crosslinking is carried out at a pressure of 100 to 1100 hPa, in particular at the pressure of the ambient atmosphere, i.e. approximately 900 to 1100 hPa.

[0136] The present invention further relates to shaped bodies produced by crosslinking the compositions according to the invention.

[0137] The shaped bodies according to the invention preferably have a tear strength of at least 1 MPa, particularly preferably of at least 1.5 MPa, in particular of at least 2 MPa, each measured according to DIN EN 53504.

[0138] The shaped bodies according to the invention can be any shaped bodies, such as seals, pressed articles, extruded profiles, coatings, impregnations, potting, lenses, prisms, polygonal structures, laminate or adhesive layers.

[0139] Another object of the invention is a process for producing material composites in which the composition according to the invention is applied to at least one substrate and then allowed to crosslink.

[0140] Examples of this include coatings, encapsulation, the production of molded articles, composite materials, and composite molded parts. Composite molded parts are understood here to mean a uniform molded article made of a composite material composed of a crosslinking product of the compositions according to the invention and at least one substrate in such a way that a strong, permanent bond exists between the two parts.

[0141] In the process according to the invention for producing material composites, the composition according to the invention can also be vulcanized between at least two identical or different substrates, such as in adhesive bonds, laminates or encapsulations.

[0142] Examples of substrates that can be bonded or sealed according to the invention are plastics including PVC, concrete, wood, mineral substrates, metals, glass, ceramics and painted surfaces.

[0143] The compositions according to the invention can be used for all purposes for which compositions which can be stored in the absence of water and which crosslink to form elastomers upon exposure to water at room temperature can be used.

[0144] The compositions according to the invention are therefore excellently suitable, for example, as sealing compositions for joints, including vertical joints, and similar empty spaces of, for example, 10 to 40 mm clear width, for example in buildings, land vehicles, water vehicles and aircraft, for sealing surfaces, for example roofs, walls or floors, or as adhesives or putty compositions, for example in window construction or in the manufacture of display cases, and for example for the manufacture of protective coatings, or anti-slip coatings, or of rubber-elastic moldings and for the insulation of electrical or electronic devices.

[0145] The compositions according to the invention have the advantage that they are easy to produce.

[0146] The crosslinkable compositions according to the invention have the advantage that they are characterized by very high storage stability and a high crosslinking speed.

[0147] Furthermore, the crosslinkable compositions according to the invention have the advantage that they have an excellent adhesion profile.

[0148] Furthermore, the crosslinkable compositions according to the invention have the advantage that they are easy to process.

[0149] Unless otherwise stated, all steps in the following examples are carried out at ambient atmospheric pressure, i.e., approximately 1013 hPa, and at room temperature, i.e., approximately 23°C, or at a temperature that occurs when the reactants are combined at room temperature without additional heating or cooling. The crosslinking of the compounds is carried out at a relative humidity of approximately 50%. Furthermore, all parts and percentages are by weight unless otherwise stated. Example 1

[0150] In a 2-liter four-necked flask equipped with a dropping funnel, Liebig condenser, precision glass stirrer, and thermometer, 1000 g of phenyltrimethoxysilane are placed at room temperature. 20 g of 20% aqueous hydrochloric acid are added while stirring. The mixture is then heated to 65–68°C until a gentle reflux begins. A mixture of 74 g of water and 40 g of methanol is then added evenly over 30 minutes under reflux. After the addition, the mixture is stirred under reflux for another 10 minutes and then cooled to room temperature.

[0151] The reaction mixture is allowed to stand at room temperature for approximately 16 hours. 60 g of sodium bicarbonate are then added with stirring. The mixture is stirred for 30 minutes, and the resulting solid is separated by filtration. Finally, the low-boiling components (mainly methanol) are removed by distillation. Initially, approximately 80-90% of the distillate to be removed is removed at 1013 mbar and a temperature of 120°C. The pressure is then reduced to 10 mbar, and the remaining low-boiling components are distilled off over the next 15-20 minutes.

[0152] A phenylsilicone resin with an average molecular weight Mn of 1200 g / mol, a viscosity of 30 mPas at 23 °C and a methoxy group content of 18% based on the total resin mass is obtained. Example 2

[0153] The procedure is as in Example 1. However, the starting materials and quantities are varied as follows.

[0154] Instead of 1000 g of phenyltrimethoxysilane, a mixture of 700 g of phenyltrimethoxysilane and 300 g of methyltrimethoxysilane is added. After the unchanged hydrochloric acid is added and the mixture is heated to a temperature of 65-68°C, a mixture of 92.5 g of water and 62 g of methanol is added at a steady rate over 30 minutes under reflux, instead of a mixture of 74 g of water and 40 g of methanol. All other process parameters, starting materials, and quantities remain unchanged.

[0155] A phenyl-methyl silicone resin with an average molecular weight Mn of 1100 g / mol, a viscosity of 30 mPas at 23 °C and a methoxy group content of 19% based on the total resin mass is obtained. Example 3 Preparation of an adhesive formulation according to the invention

[0156] 85.6 g of silane-terminated polypropylene glycol with an average molecular weight (M n ) of 18000 g / mol and 2 end groups of the formula -OC(=O)-NH-(CH 2 ) 3 -Si(OCH 3 ) 3 (commercially available under the name GENIOSIL ®< STP-E35 from Wacker Chemie AG, Munich, Germany) and 59.2 g of a polypropylene glycol with an average molecular weight M n of 2000 g / mol are mixed and in a laboratory planetary mixer from PC-Laborsystem, equipped with two bar mixers, at approximately 25°C with 8.0 g of vinyltrimethoxysilane, 54.4 g of a resin prepared according to Example 1 and 2.0 g of a stabilizer mixture (commercially available under the name TINUVIN ®< B 75 from BASF AG (Germany) 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)) for 2 minutes at 200 rpm. Subsequently, 186.0 g of a fatty acid-coated precipitated chalk with an average particle diameter (D50%) of approximately0.07 µm (commercially available under the name Hakuenka ®< CCR S10 from Shiraishi Omya GmbH, AT-Gummern) is dissolved with stirring for one minute at 600 rpm. After incorporating the chalk, 4 g of aminopropyltrimethoxysilane and 0.8 g of dioctyltin dilaurate are mixed in for 1 minute at 200 rpm. Finally, the mixture is homogenized for 2 minutes at 600 rpm and for 1 minute at 200 rpm at a pressure of approximately 100 mbar, and stirred until bubble-free.

[0157] The resulting mass is filled into 310 ml PE cartridges, sealed hermetically and stored at 20°C for 24 hours before testing. Example 4 Preparation of an adhesive formulation according to the invention

[0158] The procedure is as described in Example 3. However, the quantities specified in Example 3 for GENIOSIL ®< STP-E35 and the phenylsilicone resin prepared according to Example 1 are varied.

[0159] For example, 103.6 g of GENIOSIL ®< STP-E35 and 36.4 g of a resin prepared according to Example 1 are used. The quantities of all other raw materials remain unchanged.

[0160] The resulting mass is filled into 310 ml PE cartridges, sealed hermetically and stored at 20°C for 24 hours before testing. Example 5 Preparation of an adhesive formulation according to the invention

[0161] The procedure is as described in Example 3. However, the quantities specified in Example 3 for GENIOSIL ®< STP-E35 and the phenylsilicone resin prepared according to Example 1 are varied.

[0162] For example, 122.0 g of GENIOSIL ®< STP-E35 and 18.0 g of a solvent-free resin prepared according to Example 1 are used. The quantities of all other raw materials remain unchanged.

[0163] The resulting mass is filled into 310 ml PE cartridges, sealed hermetically and stored at 20°C for 24 hours before testing. Comparison example 1 Preparation of an adhesive formulation not according to the invention

[0164] The procedure is as described in Example 3. However, the addition of the phenylsilicone resin prepared according to Example 1 is omitted. Instead, 140 g of GENIOSIL ®< STP-E35 are used instead of 85.6 g.

[0165] The resulting mass is filled into 310 ml PE cartridges, sealed hermetically and stored at 20°C for 24 hours before testing. Comparison example 2 Preparation of an adhesive formulation not according to the invention

[0166] The procedure is as described in Example 3. However, the addition of dioctyltin dilaurate is omitted. Instead, the amount of polypropylene glycol with an average molecular weight M n of 2000 is slightly increased from 59.2 g to 60 g. The amounts of all other raw materials remain unchanged. Example 6

[0167] The compositions obtained in Examples 3 to 5 and Comparative Examples 1 and 2 (C1 and C2) were allowed to crosslink and tested for their skin formation and mechanical properties. The results are shown in Table 1. Skin formation time (HTZ)

[0168] To determine the skin formation time, the crosslinkable materials obtained in the examples are applied in a 2 mm thick layer to PE film and stored under standard conditions (23°C and 50% relative humidity). During curing, the formation of a skin is tested every 5 minutes. 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 finger, a skin has not yet formed. If no sample sticks to the finger, a skin has formed, and the time is recorded. Mechanical properties

[0169] The masses were spread onto milled Teflon plates with a depth of 2 mm and cured for 2 weeks at 23°C and 50% relative humidity.

[0170] Shore A hardness is determined according to DIN 53505.

[0171] Tear strength is determined according to DIN 53504-S1.

[0172] Elongation at break is determined according to DIN 53504-S1. Table 1 Mass from example 3 4 5 V1 V2 Ratio of component (B) to component (A) 0,63 0,35 0,15 0,00 0,63 Catalyst mixture of (C1) and (C2) Yes Yes Yes Yes no Skin formation time [min] 126 94 36 8 >1000 Shore A hardness 63 54 50 50 nb Tensile strength [N / mm 2 ] 4,5 5, 6 4, 1 3,2 nb Elongation at break [%] 612 748 680 418 nb nb: not determinable

[0173] The comparison of Examples 3, 4, 5 and V1 shows that the systems according to the invention which contain phenylsilicone resins (component (B)) not only have significantly better tear strengths but, surprisingly, also significantly better elongations at break than non-inventive compositions without component (B).

[0174] At the same time, a comparison of the same examples shows that the skin formation time is surprisingly significantly extended by the addition of phenylsilicone resins (component (B)). Without the combined use of components (C1) and (C2), practical curing times cannot be achieved (see Comparative Example 2). Example 7 Preparation of an adhesive formulation according to the invention

[0175] 160.0 g of silane-terminated polypropylene glycol with an average molecular weight (M n ) of 18000 g / mol and 2 end groups of the formula - OC(=O)-NH-(CH 2 ) 3 -Si(OCH 3 ) 3 (commercially available under the name GENIOSIL ®< STP-E35 from Wacker Chemie AG, Munich, Germany) are homogenized in a laboratory planetary mixer from PC-Laborsystem, equipped with two bar mixers, at approx. 25°C with 42.0 g of a solvent-free resin produced according to Example 1 and 2.0 g of a stabilizer mixture (commercially available under the name TINUVIN ®< B 75 from BASF AG, Germany) for 2 minutes at 200 rpm. Then, 189.6 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.) are digested for one minute at 600 rpm while stirring.After incorporating the filler, 6 g of aminopropyltrimethoxysilane and 0.4 g of dioctyltin dilaurate are mixed in for 1 minute at 200 rpm. Finally, the mixture is homogenized for 2 minutes at 600 rpm and for 1 minute at 200 rpm at a pressure of approximately 100 mbar, and stirred until bubble-free.

[0176] The resulting mass is filled into 310 ml PE cartridges, sealed hermetically and stored at 20°C for 24 hours before testing. Example 8 Preparation of an adhesive formulation according to the invention

[0177] The procedure is as described in Example 7. However, instead of 0.4 g of dioctyltin dilaurate, 0.4 g of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, commercially available under the name Lupragen ®< N 700 from BASF AG, Germany) is used.

[0178] The resulting mass is filled into 310 ml PE cartridges, sealed hermetically and stored at 20°C for 24 hours before testing. Example 9 Preparation of an adhesive formulation according to the invention

[0179] The procedure is as described in Example 7. However, instead of 0.4 g of dioctyltin dilaurate, 0.4 g of diisopropoxytitanium ethyl acetoacetate (commercially available under the name "Tyzor®< IBAY" from Dorf Ketal Chemicals Pvt. Ltd., Stafford, USA) is used.

[0180] The resulting mass is filled into 310 ml PE cartridges, sealed hermetically and stored at 20°C for 24 hours before testing. Comparison example 3 Preparation of an adhesive formulation not according to the invention

[0181] The procedure is as described in Example 7. However, the addition of 0.4 g of dioctyltin dilaurate is omitted.

[0182] The resulting mass is filled into 310 ml PE cartridges, sealed hermetically and stored at 20°C for 24 hours before testing. Example 10

[0183] The compositions obtained in Examples 7 to 9 and Comparative Example 3 (C3) were allowed to cure and tested for their skin formation and mechanical properties. The results are shown in Table 2. Skin formation time (HTZ)

[0184] The skin formation time is determined as described in Example 6. Mechanical properties

[0185] The tensile shear strength is determined as described in DIN EN 204. To determine the tensile shear strength, the respective compound is applied to both pieces of beech wood to be glued, which are then scraped off using a 100 µm doctor blade. The two pieces of wood are then bonded over an area of ​​1 x 2 cm with a contact pressure of 5 kg. After 24 hours of pressing, the pieces are stored in a standard climate. To determine the D1 value, the storage time is 7 days. The tensile shear strength of the two bonded pieces of wood is then measured directly. For the D4 measurement, the storage time in a standard climate is 21 days, followed by an additional six hours of storage in boiling water. The pieces are then removed from the water, dried and stored at room temperature for one hour. The tensile shear strength is then determined. Table 2 Mass from example 7 8 9 V3 HBZ [min] 97 60 336 1165 D1 measurement [MPa] 5,7 5,1 5,4 3,8 D4 measurement [MPa] 2,3 2,1 2,0 1,6 Example 11 Preparation of an adhesive formulation according to the invention

[0186] The procedure is as described in Example 5. However, instead of 18 g of phenylsilicone resin prepared according to Example 1, 18 g of phenylmethylsilicone resin prepared according to Example 2 are used. All other process parameters, starting materials, and quantities remain unchanged.

[0187] The resulting mass is filled into 310 ml PE cartridges, sealed hermetically and stored at 20°C for 24 hours before testing.

[0188] When determining skin formation time and mechanical properties according to the procedure described in Example 6, the following values ​​are determined. Skin formation time: 21 minutes Shore A hardness: 49 Tear resistance: 3.6 N / mm 2 Elongation at break: 486%

Claims

1. Crosslinkable compositions comprising (A) 100 parts by weight of compounds of formula         Y-[(CR12)3-SiRa(OR2)3-a]b     (I), where Y is a polyurethane radical or polyoxyalkylene radical, R may be identical or different and is a monovalent, optionally substituted hydrocarbon radical, R1 may be identical or different and is hydrogen atom or a monovalent optionally substituted hydrocarbon radical, which may be attached via nitrogen, phosphorus, oxygen, sulfur or carbonyl group to the carbon atom, R2 may be identical or different and is hydrogen atom or a monovalent, optionally substituted hydrocarbon radical, b is an integer from 1 to 10, preferably 1, 2 or 3, more preferably 1 or 2, and a may be identical or different and is 0, 1 or 2, preferably 0 or 1, (B) at least 15 and at most 50 parts by weight of silicone resins composed exclusively of units of the formula         R3c(R4O)dR5eSiO(4-c-d-e) / 2     (II), where R3 may be identical or different and is hydrogen atom, a monovalent, SiC-bonded, optionally substituted aliphatic hydrocarbon radical or a divalent, optionally substituted, aliphatic hydrocarbon radical which bridges two units of the formula (II), R4 may be identical or different and is hydrogen atom or a monovalent, optionally substituted hydrocarbon radical, R5 may be identical or different and is a monovalent, SiC-bonded, optionally substituted aromatic hydrocarbon radical, c is 0, 1, 2 or 3, d is 0, 1, 2 or 3, preferably 0, 1 or 2, more preferably 0 or 1, and e is 0, 1 or 2, preferably 0 or 1, with the proviso that the sum of c+d+e is less than or equal to 3 and in at least 40% of the units of the formula (II) the sum c+e is 0 or 1, characterized in that use is made as component (B) of silicone resins (B1) which, based in each case on the total number of units of the formula (II), have at least 20% of units of the formula (II) in which e is 1, (C1) catalyst selected from metal-containing curing catalysts, guanidines, and amidines, and (C2) cocatalyst comprising units of the formula         DhSi(OR7)gR6fO(4-f-g-h) / 2     (III), in which R6 may be identical or different and is a monovalent, optionally substituted SiC-bonded, nitrogen-free organic radical, R7 may be identical or different and is hydrogen atom or optionally substituted hydrocarbon radicals, D may be identical or different and is a monovalent, SiC-bonded radical having at least one nitrogen atom not bonded to a carbonyl group (C=O), f is 0, 1, 2 or 3, preferably 1, g is 0, 1, 2 or 3, preferably 1, 2 or 3, more 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 per molecule there is at least one radical D present, where the molar ratio of compounds (C1) to radicals D in compounds (C2) is 1:1 to 1:400 and the crosslinkable compositions comprise components (C1) and (C2) in a total amount of 0.2 to 50 parts by weight per 100 parts by weight of component (A).

2. Crosslinkable compositions according to Claim 1, characterized in that plasticizers (D) are present in amounts of 5 to 300 parts by weight per 100 parts by weight of component (A).

3. Crosslinkable compositions according to either of Claims 1 and 2, characterized in that the catalysts (C1) are tin-containing compounds.

4. Crosslinkable compositions according to one or more of Claims 1 to 3, characterized in that the molar ratio of the compounds (C1) to radicals D in compound (C2) is 1:2 to 1:200.

5. Process for producing the composition according to one or more of Claims 1 to 4 by mixing the individual components in any order.

6. Shaped article produced by crosslinking the compositions according to one or more of Claims 1 to 4.

7. Process for producing composite materials, wherein the composition according to one or more of Claims 1 to 4 is applied to at least one substrate and then allowed to crosslink.