Crosslinkable composition based on organyloxysilane-terminated polymers

Abstract

The present invention relates to crosslinkable compositions of silane crosslinked prepolymers, methods for producing the same, and their use in adhesives and sealants, particularly in adhesives characterized by a combination of high tear resistance and high elongation at break.

Description

[Technical Field]

[0001] The present invention relates to crosslinkable compositions of silane crosslinked prepolymers, methods for producing them, and their use in adhesives and sealants, particularly in adhesives where the combination of high tensile strength and high elongation at break is noteworthy. [Background technology]

[0002] Polymer systems containing reactive alkoxysilyl groups are well-established. Upon contact with water or moisture in the air, these alkoxysilane-terminated polymers can condense with each other, even at room temperature, while removing the alkoxy groups. One of the most important applications of such materials is the manufacture of adhesives and sealants.

[0003] Therefore, in the cured state, adhesives based on alkoxysilane crosslinked polymers exhibit very good adhesive properties on a wide range of substrates. A further advantage of silane crosslinked systems over many other adhesive and sealing technologies (e.g., isocyanate crosslinked systems) is the relative toxicological safety of the prepolymer.

[0004] Alkoxysilane crosslinked polymers can be used in both one-component and two-component systems (1K and 2K systems). The latter typically contains the curable polymer as one component and water as the curing agent as the second component. Such systems are particularly advantageous when non-porous substrates are to be bonded over a wide area. For most applications, conversely, a one-component system (1K system) that cures upon contact with moisture in the air is preferred. A key advantage of the one-component system is that it is particularly easy to apply, as the user does not need to mix different adhesive components. In addition to saving time / effort and ensuring the avoidance of potential metering errors, one-component systems do not require the adhesive or sealant to be processed within a fairly narrow timeframe after the two components are mixed, as is usually the case with multi-component systems.

[0005] A drawback of many systems corresponding to prior art is the moderate reactivity of the polymer in question to water, which requires aggressive catalysis. Therefore, typically, the mixture in question contains a toxicologically undesirable tin catalyst.

[0006] The advantage here lies in the use of so-called α-silane-terminated prepolymers, which possess reactive alkoxysilyl groups linked to adjacent urethane units via methylene spacers. This class of compounds is highly reactive and does not require tin catalysts or strong acids or bases to achieve high curing rates in contact with air. Commercially available α-silane-terminated prepolymers include GENIOSIL(R)STP-E10 or E30 from Wacker-Chemie AG.

[0007] In addition to their ease of application and favorable adhesion profiles, both conventional binders and α-silane crosslinking binders are noteworthy for their highly attractive mechanical properties. They are particularly well-suited for use in low-modulus sealants with high elasticity, for example. Furthermore, when combined with reinforcing fillers, they can be used to produce so-called elastic adhesives that combine moderate hardness and tensile strength with sustained high elasticity.

[0008] On the other hand, extremely hard adhesives with high lap shear strength or high tensile strength are noteworthy and cannot be manufactured using conventional alkoxysilane crosslinking systems. Typical tensile strengths are between 1 and 3 MPa, and exceeding 4 MPa is virtually impossible, even with a large amount of reinforcing filler. Lap shear strength is similarly affected. This represents a significant limitation on application areas where adhesives with high tensile strength rather than elasticity are required.

[0009] A better example is a specific modification of the adhesive based on the alkoxysilane crosslinked polymer, which is described in WO2013 / 026654. The formulation described therein contains, together with the silane crosslinked polymer, a considerable amount of phenyl silicone resin having methoxy functional groups and therefore being similarly crosslinkable. The addition of these resins results in an adhesive that exhibits significantly improved hardness and lap shear strength after complete curing.

[0010] However, a drawback of these systems is the very low post-curing elasticity of the corresponding resin-containing adhesive systems. For example, in such systems, the elongation at break is far below 200%, and often actually below 50%. The positive benefits of resin addition to hardness and lap shear strength are offset by its negative impact on elasticity.

[0011] While this is not relevant to all applications, adhesives with high tensile strength and high elasticity are still desirable, especially for elastic bonding. One such example is when materials with different thermal expansions are bonded to each other over a wide area, or in numerous adhesive applications in automotive manufacturing, such as bonding body structures or auxiliary components, headlights, or windshields. In these applications, generally speaking, a combination of high tensile strength and high elasticity is required.

[0012] Furthermore, if the modulus is similar, higher elasticity often improves the tensile strength of the corresponding adhesive, as greater elongation is possible before the adhesive breaks. And, naturally, the further technical improvement of elongation at break, described in WO2013 / 026654, is equally desirable for many applications and is often essential in practice, such as in the case of wood adhesives that must meet the standard known as D4.

[0013] One approach to producing silane crosslinked adhesive formulations that exhibit both high tensile strength and high elasticity is described in WO2017 / 137281. In addition to containing silane-terminated polymers and phenyl silicone resins, the adhesive system presented therein also contains carbon black as a third essential component. However, even though this combination represents a considerable improvement, the formulation specifically described in WO2017 / 137281 exhibits a typical tensile strength of 5-6 MPa, with a maximum achievable tensile strength of 6.8 MPa. For many applications, this is insufficient, for example, for the aforementioned D4 wood adhesive, or even for windshield bonding.

[0014] Furthermore, the system described in WO2017 / 137281 contains carbon black and is therefore jet black. Adhesives of different colors, lighter colors, or even transparent colors cannot be produced by this method. This is a major drawback, as the compression of the substrates to be bonded often results in the emergence of small amounts of adhesive from the bonding gaps. Therefore, unless two black substrates happen to be bonded, black adhesives are unsuitable for visually demanding applications. [Prior art documents] [Patent Documents]

[0015] [Patent Document 1] International Publication No. 2013 / 026654 [Patent Document 2] International Publication No. 2017 / 137281 [Overview of the project] [Problems that the invention aims to solve]

[0016] Therefore, an object of the present invention was to provide an improved technical approach that enables access to non-black adhesives that combine high elasticity and high elongation at break.

[0017] For a particularly advantageous achievement of this object, it is furthermore necessary to provide means enabling the manufacturer of the adhesive to produce a transparent or translucent and also substantially colorless adhesive.

Means for Solving the Problem

[0018] The subject of the present invention is (A) 100 parts by weight of a compound (A) of the following formula Y - [(CR 1 2) b -SiR a (OR 2 ) 3-a x (I), (wherein Y is an x-valent polymer group bonded via nitrogen, oxygen, sulfur or carbon, R may be the same or different and is an optionally substituted monovalent SiC-bonded hydrocarbon group, R 1 may be the same or different and is a hydrogen atom or an optionally substituted monovalent hydrocarbon group which may be bonded to a carbon atom via a nitrogen, phosphorus, oxygen, sulfur or carbonyl group, R 2 may be the same or different and is a hydrogen atom or an optionally substituted monovalent hydrocarbon group, x is an integer from 1 to 10, preferably 1, 2 or 3, more preferably 1 or 2, a may be the same or different and is 0, 1 or 2, preferably 0 or 1, and b may be the same or different and is an integer from 1 to 10, preferably 1, 3 or 4, more preferably 1 or 3, and more particularly 1), and (B) more than 10 parts by weight, preferably more than 50 parts by weight, of a silicone resin (B) containing units of the following formula R 3 c (R 4 O) d R 5 e SiO (4-c-d-e) / 2 (II) (In the formula, R 3 These may be the same or different, and are a hydrogen atom, a SiC-bonded, optionally substituted monovalent aliphatic hydrocarbon group, or an optionally substituted divalent aliphatic hydrocarbon group bridging two units of formula (II). R 4 These may be the same or different, and are a hydrogen atom or a monovalent hydrocarbon group optionally substituted. R 5 These may be the same or different, and are SiC-bonded, optionally substituted monovalent aromatic hydrocarbon groups. 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. It contains, however, The sum of c + d + e is 3 or less. In at least 60% of the units of formula (II), the sum of c + e is 0 or 1, preferably in at least 40% of the units of formula (II), e is 1 and c is 0. • All groups R contained in component (A) 2 At least 70 mol%, preferably at least 80 mol%, and more preferably at least 90 mol%, of which are methyl groups. • All groups R contained in silicone resin (B) 4 At least 60 mol%, preferably at least 75 mol%, and more preferably at least 90 mol%, of which are ethyl groups. • All groups R contained in silicone resin (B) 4 The crosslinkable composition (M) is characterized in that up to 30 mol%, preferably up to 20 mol%, and more preferably up to 10 mol%, of the composition is methyl groups.

[0019] The present invention is based on the remarkable discovery that a combination of a methoxy-functionalized silane-terminated polymer (A) and a silicone resin (B) whose alkoxy groups consist mainly of ethoxy groups and contain little to no methoxy groups exhibits significantly better mechanical properties, particularly significantly higher elasticity and, in some cases, higher tensile strength, than combinations of silane-terminated polymers and silicone resins described in, for example, WO2013 / 026654, which lack this specific combination of alkoxy groups contained in polymer (A) and silicone resin (B).

[0020] What makes this discovery even more surprising is that during the curing of the mixture in question, all of the alkoxy groups are removed and volatilized, and therefore no longer present at all in the fully cured mixture. This means that the fully cured mixture consists of exactly the same components, regardless of which alkoxysilyl groups components (A) and (B) originally possessed. Naturally, those skilled in the art would expect that two materials composed of exactly the same components would also have nearly identical properties. However, in the case of the present invention, this expectation proves to be unfounded.

[0021] Examples of group R include alkyl groups, e.g., methyl, ethyl, n-propyl, isopropyl, 1-n-butyl, 2-n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl group; hexyl group, e.g., n-hexyl group; heptyl group, e.g., n-heptyl group; octyl group, e.g., n-octyl group, isooctyl group, and 2,2,4-trimethylpentyl group; nonyl group, e.g., n-nonyl group; decyl group, e.g., n-decyl group; dodecyl group, e.g., n-dodecyl group These include syl groups; octadecyl groups, such as n-octadecyl; cycloalkyl groups, such as cyclopentyl, cyclohexyl, cycloheptyl, and methylcyclohexyl; alkenyl groups, such as vinyl, 1-propenyl, and 2-propenyl; aryl groups, such as phenyl, naphthyl, anthryl, and phenanthryl; alkaryl groups, such as o-, m-, and p-tolyl; xylyl and ethylphenyl; and aralkyl groups, such as benzyl, α-, and β-phenylethyl.

[0022] Examples of substituted groups R include haloalkyl groups, such as 3,3,3-trifluoro-n-propyl, 2,2,2,2',2',2'-hexafluoroisopropyl and heptafluoroisopropyl groups, and haloaryl groups, such as o-, m- and p-chlorophenyl groups.

[0023] The group R preferably comprises a monovalent hydrocarbon group having 1 to 6 carbon atoms and optionally substituted with a halogen atom, more preferably an alkyl group having 1 or 2 carbon atoms, and more specifically a methyl group.

[0024] base R 1 Examples include hydrogen atoms, groups specified for R, and optionally substituted hydrocarbon groups bonded to carbon atoms via nitrogen, phosphorus, oxygen, sulfur, carbon, or carbonyl groups.

[0025] base R 1 It preferably comprises a hydrogen atom and a hydrocarbon group having 1 to 20 carbon atoms, and more specifically, a hydrogen atom.

[0026] base R 2 The example is one that specifies a hydrogen atom or group R.

[0027] base R 2 The group R preferably contains a hydrogen atom or an alkyl group having 1 to 10 carbon atoms and optionally substituted with a halogen atom, more preferably an alkyl group having 1 to 4 carbon atoms, and more specifically a methyl or ethyl group. Here, the group R contained in component (A) 2 At least 70 mol%, preferably at least 80 mol%, and more preferably at least 90 mol%, of which are methyl groups. In one particularly preferred embodiment of the present invention, all groups R contained in component (A) 2 It is a methyl group.

[0028] In the sense of the present invention, the polymers forming the basis of polymer group Y are understood to be any polymer in which at least 50%, preferably 70%, and more preferably at least 90% of all bonds in the main chain are carbon-carbon, carbon-nitrogen, or carbon-oxygen bonds.

[0029] Examples of polymer groups Y include polyester, polyether, polyurethane, polyalkylene, and polyacrylate groups.

[0030] The polymer group Y is preferably, as its polymer chain, polyoxyalkylene, e.g., polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer and polyoxypropylene-polyoxybutylene copolymer; hydrocarbon polymer, e.g., polyisobutylene and copolymer of polyisobutylene and isoprene; polychloroprene; polyisoprene; polyurethane; polyester; polyamide; polyacrylate; polymethacrylate ; vinyl polymer and polycarbonate, and preferably 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'-, one or more groups -[(CR 1 2) b -SiR a (OR 2 ) 3-a The formula includes an organic polymer group that is bonded to (wherein R' may be the same or different and has the specified meaning for R, or the group -CH(COOR")-CH2-COOR") (wherein R") may be the same or different and has the specified meaning for R).

[0031] The group R' preferably includes the group -CH(COOR”)-CH2-COOR” or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, more preferably a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms and optionally substituted with a halogen atom.

[0032] Examples of the R' group include cyclohexyl, cyclopentyl, n- and isopropyl, n-, iso- and t-butyl, various stereoisomers of the pentyl, hexyl, or heptyl group, and the phenyl group.

[0033] The group R'' preferably comprises an alkyl group having 1 to 10 carbon atoms, more preferably a methyl, ethyl, or propyl group.

[0034] Here, component (A) is a group bonded in the described manner at any position in the polymer, such as along the chain and / or at the ends - [(CR 1 2) b -SiR a (OR 2 ) 3-a It may have ].

[0035] In formula (I), the group Y is more preferably a terminally bonded group -[(CR 1 2) b -SiR a (OR 2 ) 3-a It contains polyurethane groups and polyoxyalkylene groups having [ ]. These are preferably linear or have 1 to 3 branching points. More preferably they are linear.

[0036] The polyurethane group Y preferably has one or more groups at its chain end via -NH-C(=O)O-, -NH-C(=O)-NH-, -NR'-C(=O)-NH- or -NH-C(=O)-NR'-, and more specifically via -OC(=O)-NH- or -NH-C(=O)-NR'- -[(CR 1 2) b -SiR a (OR 2 ) 3-aThe polyurethane group Y comprises a group bonded to ] (wherein all groups and subscripts (index) have one of the meanings described above). Here, the polyurethane group Y can be prepared from preferably linear or branched polyoxyalkylene, more specifically from polypropylene glycol and diisocyanate or polyisocyanate. Here, the average molar mass M of group Y is preferably 400 to 30000 g / mol, more preferably 4000 to 20000 g / mol. n It has (numerical mean). A suitable method for preparing such a component (A), and also an example of component (A) itself, is provided in EP1093482B1 (paragraph).

[0037] ~

[0038] ,

[0039] ~

[0040] , and further, Example 1 and Comparative Example 1) or EP1641854B1 (paragraph)

[0041] ~

[0042] Examples 4 and 6, and Comparative Examples 1 and 2) are described in the publication and are counted as part of the disclosures of this application.

[0043] For the purposes of the present invention, the number average molar mass M n This is determined by size exclusion chromatography (SEC) against a polystyrene standard in THF at 60°C and a flow rate of 1.2 ml / min, and detection by RI (refractive index detector) using a Styragel HR3-HR4-HR5-HR5 column set from Waters Corp. USA, with an injection volume of 100 μl.

[0044] The polyoxyalkylene group Y is preferably a linear or branched polyoxyalkylene group, more preferably having one or more groups at the end via -OC(=O)-NH- or -O-[(CR 1 2) b -SiR a (OR 2 )3-a The group contains a polyoxypropylene group (wherein the formula, the group and subscript have one of the meanings described above) preferably bonded to the -OC(=O)-NH- group. Preferably, here, at least 85%, more preferably at least 90%, and more specifically at least 95% of all chain ends are bonded to the -OC(=O)-NH- group-[(CR 1 2) b -SiR a (OR 2 ) 3-a The polyoxyalkylene group Y has an average molar mass M of preferably 4000 to 30000 g / mol, more preferably 8000 to 20000 g / mol. n It has. A suitable method for preparing such component (A), and also an example of component (A) itself, is found in EP1535940B1 (paragraph).

[0045] ~

[0046] , and further, Examples 1-3 and Comparative Examples 1-4) or EP1896523B1 (paragraph)

[0047] ~

[0048] This information is included in publications that include the following, and these are counted as part of the disclosures of this application.

[0049] The terminal group of compound (A) used in the present invention is preferably a group of the general formula. -NH-C(=O)-NR'-(CR 1 2) b -SiR a (OR 2 ) 3-a (III) -OC(=O)-NH-(CR 1 2) b -SiR a (OR 2 ) 3-a (IV) or -O-(CR 1 2) b -SiR a (OR 2 ) 3-a (V) (In the formula, the base and subscript have one of the meanings described above.)

[0050] If compound (A) is preferably polyurethane, they preferably have one or more of the following terminal groups. -NH-C(=O)-NR'-(CH2)3-Si(OCH3)3, -NH-C(=O)-NR'-(CH2)3-Si(OC2H5)3, -OC(=O)-NH-(CH2)3-Si(OCH3)3 or -OC(=O)-NH-(CH2)3-Si(OC2H5)3, (In the formula, R' has the meaning described above.)

[0051] If compound (A) is more preferably polypropylene glycol, they preferably have one or more of the following terminal groups, the latter two being more preferable. -O-(CH2)3-Si(CH3)(OCH3)2, -O-(CH2)3-Si(OCH3)3, -OC(=O)-NH-(CH2)3-Si(OC2H5)3, -OC(=O)-NH-CH2-Si(CH3)(OC2H5)2, -OC(=O)-NH-CH2-Si(OCH3)3, -OC(=O)-NH-CH2-Si(CH3)(OCH3)2 or -OC(=O)-NH-(CH2)3-Si(OCH3)3,

[0052] Average molecular weight M of compound (A) n The amount is preferably at least 400 g / mol, more preferably at least 4000 g / mol, more specifically at least 10000 g / mol, preferably up to 30000 g / mol, more preferably up to 20000 g / mol, and more specifically up to 19000 g / mol.

[0053] The viscosity of compound (A), measured at 20°C in all cases, is preferably at least 0.2 Pas, preferably at least 1 Pas, more preferably at least 5 Pas, and preferably up to 700 Pas, more preferably up to 100 Pas.

[0054] For the purposes of this invention, the viscosity is determined using a DV3P rotational viscometer manufactured by A. Paar (Brookfield Systems) at 2.5 rpm with spindle 5 after being adjusted to 23°C, in accordance with ISO 2555.

[0055] The compound (A) used in the present invention is either commercially available or can be prepared by a method common in chemistry.

[0056] Polymer (A) can be prepared by known methods, such as addition reactions including hydrosilylation, Michael addition, and Diels-Alder addition, or by the reaction of an isocyanate-functional compound with a compound having an isocyanate-reactive group.

[0057] Component (A) used in the present invention may contain only one compound of formula (I), or it may contain a mixture of different types of compounds of formula (I). Here, component (A) may contain only compounds of formula (I) in which more than 90%, preferably more than 95%, and more than 98%, of all silyl groups bonded to group Y are identical. However, it is also possible to use component (A) which contains at least partially compounds of formula (I) in which different silyl groups are bonded to group Y. Finally, it is also possible to use a mixture of different compounds of formula (I) in which a total of at least two different silyl groups are bonded to group Y as component (A). More preferably, in that case, all silyl groups bonded to a particular group Y are identical.

[0058] The composition (M) of the present invention preferably contains compound (A) at a concentration of up to 40% by weight, more preferably up to 30% by weight, and preferably at least 5% by weight, more preferably at least 10% by weight.

[0059] Based on 100 parts by weight of component (A), composition (M) of the present invention preferably contains at least 30 parts by weight, more preferably at least 50 parts by weight, and more specifically at least 80 parts by weight of component (B). Based on 100 parts by weight of component (A), composition (M) of the present invention preferably contains up to 1000 parts by weight, more preferably up to 500 parts by weight, and more specifically up to 300 parts by weight of component (B).

[0060] Component (B) preferably consists of at least 90% by weight of the units of formula (II). More preferably, component (B) consists solely of the units of formula (II).

[0061] base R 3 The example is the aliphatic example shown above for R. Alternatively, the base R 3 This may include a divalent aliphatic group that joins the two silyl groups of formula (II) to each other, such as an alkylene group having 1 to 10 carbon atoms, such as a methylene, ethylene, propylene, or butylene group. A particularly common example of a divalent aliphatic group is the ethylene group.

[0062] However, preferably base R 3 It comprises a monovalent SiC-bonded aliphatic hydrocarbon group having 1 to 18 carbon atoms and optionally substituted with halogen atoms, more preferably an aliphatic hydrocarbon group having 1 to 6 carbon atoms, and more specifically a methyl group.

[0063] base R 4 The example is one that specifies a hydrogen atom or group R.

[0064] base R 4 Preferably, it comprises a hydrogen atom or an alkyl group having 1 to 10 carbon atoms and optionally substituted with a halogen atom, more preferably an alkyl group having 1 to 4 carbon atoms, and more specifically a methyl or ethyl group. Here, all groups R contained in the silicone resin (B) 4At least 60 mol%, preferably at least 75 mol%, and more preferably at least 90 mol%, of which are ethyl groups, and all groups R contained in the silicone resin (B) 4 Up to 30 mol%, preferably up to 20 mol%, and more preferably up to 10 mol%, of the total is methyl groups.

[0065] base R 5 An example of this is the aromatic group identified above for R.

[0066] base R 5 Preferably, it includes a SiC-bonded aromatic hydrocarbon group having 1 to 18 carbon atoms and optionally substituted with a halogen atom, such as an ethylphenyl, tolyl, xylyl, chlorophenyl, naphthyl, or styryl group, more preferably a phenyl group.

[0067] For use as component (B), all groups R are preferable. 3 It is a silicone resin in which at least 90% are methyl groups.

[0068] For use as component (B), all groups R are preferable. 5 It is a silicone resin in which at least 90% are phenyl groups.

[0069] In the present invention, it is preferable to use a silicone resin (B) having at least 20%, more preferably at least 40%, of the units of formula (II) where c is 0, based on the total number of units of formula (II) in any case.

[0070] In either case, it is preferable to use a silicone resin (B) having at least 30%, more preferably at least 50%, of the units of formula (II) where d has a value of 0 or 1, based on the total number of units of formula (II).

[0071] In any case, based on the total number of units of formula (II), it is preferable to use a silicone resin (B) having at least 20%, more preferably at least 40%, and more particularly at least 50% of the units of formula (II) in which e has a value of 1.

[0072] In a specific embodiment of the present invention, a silicone resin (B) having only the units of formula (II) in which e is 1 is used.

[0073] In a particularly preferred aspect (version) of the present invention, in any case, based on the total number of units of formula (II), a silicone resin (B) having at least 20%, more preferably at least 40%, and more particularly at least 50% of the units of formula (II) in which e has a value of 1 and c has a value of 0 is used.

[0074] In any case, based on the total number of units of formula (II), it is preferable to use a silicone resin (B) having at least 50%, more preferably at least 60%, and more preferably at least 70% of the units of formula (II) in which the sum of c + e is 1.

[0075] Examples of the silicone resin (B) used in the present invention are those in which at least 90% by weight is composed of units of (Q) of formula SiO 4 / 2 , Si(OR 4 )O 3 / 2 , Si(OR 4 )2O 2 / 2 and Si(OR 4 )3O 1 / 2 , units of (T) of formula PhSiO 3 / 2 , PhSi(OR 4 )O 2 / 2 and PhSi(OR 4 )2O 1 / 2 , units of (D) of formula Me2SiO 2 / 2 and Me2Si(OR 4 )O 1 / 2 and further units of (M) of formula Me3SiO 1 / 2 , and are organopolysiloxane resins preferably consisting only of them (where Me is a methyl group, Ph is a phenyl group, and R4 (The meaning of (T) is as described in claim 1 or a preferred or more preferred meaning, wherein the resin preferably has 0 to 2 moles of (Q) units, 0 to 2 moles of (D) units, and 0 to 2 moles of (M) units per mole of (T) units).

[0076] A preferred example of the silicone resin (B) used in the present invention is one in which at least 90% by weight is of the formula PhSiO 3 / 2 PhSi(OR 4 )O 2 / 2 and PhSi(OR 4 )2O 1 / 2 The T units and the formula MeSiO 3 / 2 , MeSi(OR 4 )O 2 / 2 And also MeSi(OR 4 )2O 1 / 2 The organopolysiloxane resin is preferably composed only of units selected from the T units (wherein Me is a methyl group, Ph is a phenyl group, and R 4 (This has the meaning described in claim 1 or a preferred or more preferred meaning). Here, the molar ratio of phenylsilicone units to methylsilicone units is preferably between 0.5 and 5.0, more preferably between 1.0 and 4.0.

[0077] A more preferred example of the silicone resin (B) used in the present invention is one in which at least 90% by weight is of the formula PhSiO 3 / 2 PhSi(OR 4 )O 2 / 2 and PhSi(OR 4 )2O 1 / 2 T units, formula MeSiO 3 / 2 , MeSi(OR 4 )O 2 / 2 and MeSi(OR 4 )2O 1 / 2 The T units, and furthermore, Me2SiO 2 / 2 and Me2Si(OR 4 )O 1 / 2 The organopolysiloxane resin is preferably composed only of units selected from the D units (wherein Me is a methyl group, Ph is a phenyl group, and R 4(This has the meaning described in claim 1 or a preferred or more preferred meaning). Here, the molar ratio of phenyl silicone units to methyl silicone units is preferably between 0.5 and 5.0, more preferably between 1.0 and 4.0. The amount of D units in these silicone resins is preferably less than 15% by weight, more preferably less than 10% by weight.

[0078] A more preferred example of the silicone resin (B) used in the present invention is one in which 80%, preferably 90%, of the formula PhSiO 3 / 2 PhSi(OR 4 )O 2 / 2 and PhSi(OR 4 )2O 1 / 2 More specifically, it is an organopolysiloxane resin consisting only of the T units (wherein Ph is a phenyl group, R 4 (This has the meaning described in claim 1 or a preferred or more preferred meaning).

[0079] The silicone resin (B) used in this invention preferably has an average molar mass (number average) of at least 400 g / mol, more preferably at least 600 g / mol. n It possesses the average molar mass M. n Preferably, the maximum concentration is 400,000 g / mol, more preferably 10,000 g / mol, and more specifically 3,000 g / mol.

[0080] The silicone resin (B) used in the present invention may be either solid or liquid at 23°C and 1000 hPa, and the silicone resin (B) is preferably liquid. The silicone resin (B) preferably has a viscosity of 10 to 100,000 mPas, preferably 50 to 50,000 mPas, and more specifically 100 to 20,000 mPas.

[0081] The silicone resin (B) used in the present invention preferably has a polydispersity of 5 or less, more preferably 3 or less (M w / M n ) holds.

[0082] Number-average molar mass Mn Similarly, the mass-average molar mass M w This is determined by size exclusion chromatography (SEC) against a polystyrene standard in THF at 60°C and a flow rate of 1.2 ml / min, and detection by RI (refractive index detector) using a Styragel HR3-HR4-HR5-HR5 column set from Waters Corp. USA, with an injection volume of 100 μl.

[0083] The silicone resin (B) may be used in pure form or in the form of a mixture with a suitable solvent (BL).

[0084] The solvent (BL) used in this case can be any compound that is inactive with components (A) and (B) at room temperature and has a boiling point of less than 250°C at 10¹³ mbar.

[0085] Examples of solvents (BL) include ethers (e.g., diethyl ether, methyl t-butyl ether, ether derivatives of glycols, THF), esters (e.g., ethyl acetate, butyl acetate, glycol esters), aliphatic hydrocarbons (e.g., pentane, cyclopentane, hexane, cyclohexane, heptane, octane, 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).

[0086] However, it is preferable to use a silicone resin (B) that does not contain organic solvents.

[0087] The silicone resin (B) used in this invention is a product produced by methods common in silicon chemistry. EP1686132 is a publication that describes a suitable method for preparing the corresponding component (B).

[0088] In addition to components (A) and (B) used, composition (M) of the present invention may contain all further substances that have been used in crosslinkable compositions and are different from components (A) and (B), such as organosilicon compounds containing basic nitrogen (C), fillers (D), catalysts (E), adhesion promoters (F), water scavengers (G), additives (H), and adjuvants (K).

[0089] Component (C) preferably comprises an organosilicon compound containing the units of the following formula. D h Si(OR 7 ) g R 6 f O (4-f-g-h) / 2 (VI), (In the formula, R 6 These may be the same or different, and are optionally substituted monovalent SiC bonded organic groups that do not contain basic nitrogen. R 7 These may be the same or different, and are a hydrogen atom or an optionally substituted hydrocarbon group. D may be the same or different, and is a monovalent SiC bond group having a basic nitrogen. f is 0, 1, 2, or 3, preferably 1 or 0. Gi is 0, 1, 2, or 3, preferably 1, 2, or 3, more preferably 2 or 3. h is 0, 1, 2, 3, or 4, preferably 1. However, the sum of f+g+h must be 4 or less, and at least one group D must be present per molecule.

[0090] In a preferred embodiment of the present invention, composition (M) of the present invention contains, in addition to components (A) and (B), at least one further component (C) corresponding to formula (VI). It is worth noting that when components (A) and (B) are used in the present invention in a preferred proportion to each other and are insoluble or sparingly soluble, it is possible to achieve a mostly homogeneous, preferably perfectly homogeneous, mixture by adding component (C).

[0091] The organosilicon compound (C) used optionally in the present invention may include both silanes, i.e., compounds of formula (VI) where f+g+h=4, and siloxanes, i.e., compounds containing units of formula (VI) where f+g+h≦3, and is preferably a silane.

[0092] base R 6 The example shown is an example specified for R.

[0093] base R 6 Preferably, it comprises a hydrocarbon group having 1 to 18 carbon atoms and optionally substituted with halogen atoms, more preferably a hydrocarbon group having 1 to 5 carbon atoms, and more specifically a methyl group.

[0094] Optionally substituted hydrocarbon group R 7 The example is one that specifies hydrogen and also the group R.

[0095] base R 7 Preferably, it comprises a hydrocarbon group having a hydrogen atom and 1 to 18 carbon atoms, optionally substituted with a halogen atom; more preferably, it comprises a hydrocarbon group having a hydrogen atom and 1 to 10 carbon atoms, and more specifically, a methyl and an ethyl group.

[0096] Examples of base D are formulas H2N(CH2)3-, H2N(CH2)2NH(CH2)3-, H2N(CH2)2NH(CH2)2NH(CH2)3-, H3CNH(CH2)3-, C2H5NH(CH2)3-, C3H7NH(CH2)3-, C4H9NH(CH2)3-, C5H 11 NH(CH2)3-, C6H 13 NH(CH2)3-, C7H 15 NH(CH2)3-, H2N(CH2)4-, H2N-CH2-CH(CH3)-CH2-, H2N(CH2)5-, Cyclo-C5H9NH(CH2)3-, Cyclo-C6H 11NH(CH2)3-, phenyl-NH(CH2)3-, (CH3)2N(CH2)3-, (C2H5)2N(CH2)3-, (C3H7)2NH(CH2)3-, (C4H9)2NH(CH2)3-, (C5H 11 )2NH(CH2)3-,(C6H 13 )2NH(CH2)3-,(C7H 15 )2NH(CH2)3-, H2N(CH2)-, H2N(CH2)2NH(CH2)-, H2N(CH2)2NH(CH2)2NH(CH2)-, H3CNH(CH2)-, C2H5NH(CH2)-, C3H7NH(CH2)-, C4H9NH(CH2)-, C5H 11 NH(CH2)-, C6H 13 NH(CH2)-, C7H 15 NH(CH2)-, Cyclo-C5H9NH(CH2)-, Cyclo-C6H 11 NH(CH2)-, phenyl-NH(CH2)-, (CH3)2N(CH2)-, (C2H5)2N(CH2)-, (C3H7)2NH(CH2)-, (C4H9)2NH(CH2)-, (C5H 11 )2NH(CH2)-,(C6H 13 )2NH(CH2)-,(C7H 15 The reaction product is a reaction between the groups 2NH(CH2)-, (CH3O)3Si(CH2)3NH(CH2)3-, (C2H5O)3Si(CH2)3NH(CH2)3-, (CH3O)2(CH3)Si(CH2)3NH(CH2)3-, and (C2H5O)2(CH3)Si(CH2)3NH(CH2)3-, and further a reaction product of the above primary amino groups with an epoxy group or double bond that is reactive with the primary amino group.

[0097] Group D is preferably H2N(CH2)3- H2N(CH2)2NH(CH2)3- and cyclo-C6H 11 It contains the NH(CH2)3- group.

[0098] Examples of silanes of formula (VI) that can be optionally used in the present invention are: H2N(CH2)3-Si(OCH3)3、H2N(CH2)3-Si(OC2H5)3、H2N(CH2)3-Si(OCH3)2CH3, H2N(CH2)3-Si(OC2H5)2CH3、H2N(CH2)2NH(CH2)3-Si(OCH3)3, H2N(CH2)2NH(CH2)3-Si(OC2H5)3、H2N(CH2)2NH(CH2)3-Si(OCH3)2CH3, H2N(CH2)2NH(CH2)3-Si(OC2H5)2CH3、H2N(CH2)2NH(CH2)3-Si(OH)3, H2N(CH2)2NH(CH2)3-Si(OH)2CH3、H2N(CH2)2NH(CH2)2NH(CH2)3-Si(OCH3)3, H2N(CH2)2NH(CH2)2NH(CH2)3-Si(OC2H5)3、シクロ-C6H 11 NH(CH2)3-Si(OCH3)3, シクロ-C6H 11 NH(CH2)3-Si(OC2H5)3、シクロ-C6H 11 NH(CH2)3-Si(OCH3)2CH3, シクロ-C6H 11 NH(CH2)3-Si(OC2H5)2CH3、シクロ-C6H 11 NH(CH2)3-Si(OH)3, シクロ-C6H 11 NH(CH2)3-Si(OH)2CH3、フェニル-NH(CH2)3-Si(OCH3)3、フェニル-NH(CH2)3-Si(OC2H5)3 、フェニル-NH(CH2)3-Si(OCH3)2CH3、フェニル-NH(CH2)3-Si(OC2H5)2CH3、フェニル-NH(CH2)3 -Si(OH)3, NH(CH2)3-Si(OH)2CH3, HN((CH2)3-Si(OCH3)3)2, HN((CH2)3-Si(OC2H5)3)2, HN((CH2)3-Si(OCH3)2CH3)2, HN((CH2)3-Si(OC2H5)2CH3)2, C6H 11 NH(CH2)-Si(OCH3)3、シクロ-C6H 11NH(CH2)-Si(OC2H5)3, Cyclo-C6H 11 NH(CH2)-Si(OCH3)2CH3, Cyclo-C6H 11 NH(CH2)-Si(OC2H5)2CH3, Cyclo-C6H 11 NH(CH2)-Si(OH)3, Cyclo-C6H 11 NH(CH2)-Si(OH)2CH3, phenyl-NH(CH2)-Si(OCH3)3, phenyl-NH(CH2)-Si(OC2H5)3, phenyl-NH(CH2)-Si(OCH3)2CH3, phenyl-NH(CH2)-Si(OC2H5)2CH3, phenyl-NH(CH2)-Si(OH)3 and phenyl-NH(CH2)-Si(OH)2CH3, and further, partial hydrolysates thereof, including H2N(CH2)2NH(CH2)3-Si(OCH3)3, H2N(CH2)2NH(CH2)3-Si(OC2H5)3, H2N(CH2)2NH(CH2)3-Si(OCH3)2CH3, cyclo-C6H 11 NH(CH2)3-Si(OCH3)3, Cyclo-C6H 11 NH(CH2)3-Si(OC2H5)3 and cyclo-C6H 11 NH(CH2)3-Si(OCH3)2CH3 and, in any case, their partial hydrolysates are preferred, including H2N(CH2)2NH(CH2)3-Si(OCH3)3, H2N(CH2)2NH(CH2)3-Si(OCH3)2CH3, and cyclo-C6H 11 NH(CH2)3-Si(OCH3)3, Cyclo-C6H 11 NH(CH2)3-Si(OCH3)2CH3 and, in any case, their partial hydrolysates are more preferred.

[0099] In the composition (M) of the present invention, the organosilicon compound (C) used optionally in the present invention may also function as a curing catalyst or a curing co-catalyst.

[0100] Furthermore, the organosilicon compound (C) used optionally in the present invention may act as an adhesion promoter and / or a water scavenger.

[0101] The organosilicon compound (C) used optionally in the present invention is commercially available and / or can be prepared by common chemical methods.

[0102] If the composition (M) of the present invention contains component (C), the amount involved is preferably 0.05 to 20 parts by weight, more preferably 0.3 to 5 parts by weight, based on 100 parts by weight of the crosslinkable composition (M).

[0103] The filler (D) optionally used in the composition (M) of the present invention may be any desired filler known to date.

[0104] Examples of fillers (D) are unreinforced fillers, which are preferably up to 50 m 2 Fillers having a BET specific surface area of ​​50m / g, such as quartz, diatomaceous earth, calcium silicate, zirconium silicate, talc, kaolin, zeolite, metal oxide powders, such as oxides and / or mixed oxides of aluminum, titanium, iron or zinc, barium sulfate, calcium carbonate, gypsum, silicon nitride, silicon carbide, boron nitride, glass powder and polymer powders, such as polyacrylonitrile powder; reinforcing fillers, these are 50m 2Fillers having a BET specific surface area greater than / g, such as fumed silica, precipitated silica, precipitated chalk, carbon black, such as furnace black and acetylene black, and mixed silicon-aluminum oxides with a high BET specific surface area; fillers in the form of hollow beads such as aluminum trihydrate and ceramic microbeads, for example, available from 3M Deutschland GmbH in Neuss, Germany under the trade name Zeeospheres®; elastic polymer beads, such as available from AKZO NOBEL in Sundsval, Sweden, under the trade name EXPANCEL® from Expanse; or glass beads; fibrous fillers, such as asbestos and also polymer fibers. The described fillers may be hydrophobized, for example, by treatment with organosilane or organosiloxane, or by treatment with stearic acid, or by etherifying hydroxyl groups to form alkoxy groups.

[0105] The optionally used filler (D) is preferably calcium carbonate, talc, aluminum trihydrate, and silica, with aluminum trihydrate being more preferred. Preferred grades of calcium carbonate may be crushed or precipitated and surface-treated with fatty acids such as stearic acid or their salts. Preferred silica is preferably fumed silica.

[0106] If used, the filler (D) preferably has a water content of less than 1% by weight, more preferably less than 0.5% by weight.

[0107] If the composition (M) of the present invention is an opaque composition, it preferably contains a filler (D). In this case, the composition (M) of the present invention contains the filler (D) in an amount of preferably 5 to 90 parts by weight, more preferably 10 to 80 parts by weight, and more specifically 25 to 70 parts by weight, based on 100 parts by weight of the crosslinkable composition (M).

[0108] In a particular aspect of the present invention, the composition (M) of the present invention is a filler (D) consisting of calcium carbonate, aluminum trihydroxyoxide and / or a) Silica, more specifically fumed silica, b) Calcium carbonate and / or aluminum trihydroxy It contains a combination of these.

[0109] If the composition (M) of the present invention contains this particular combination of different fillers (D), they each contain, in any case, 1 to 30 parts by weight, more specifically 3 to 15 parts by weight of fumed silica, more preferably 10 to 79 parts by weight, more specifically 15 to 67 parts by weight of calcium carbonate and / or aluminum trihydroxyoxide, based on 100 parts by weight of the crosslinkable composition (M).

[0110] If the composition (M) of the present invention is a transparent or translucent composition, it preferably does not contain a filler (D) or contains only fumed silica as the filler (D). If the transparent composition (M) of the present invention contains fumed silica, it preferably contains 1 to 30 parts by weight, more specifically 3 to 20 parts by weight, of fumed silica based on 100 parts by weight of the crosslinkable composition (M).

[0111] The catalyst (E) optionally used in the composition (M) of the present invention may be any desired catalyst known to date for compositions cured by silane condensation.

[0112] Examples of metal-containing curing catalysts (E) are organotitanium and organotin compounds, including titanate esters such as tetrabutyl titanate, tetrapropyl titanate, tetraisopropyl titanate, and titanium tetraacetylacetonate; and tin compounds such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin dioctanoate, dibutyltin acetylacetonate, dibutyltin oxide, and the corresponding dioctyltin compounds.

[0113] Examples of metal-free curing catalysts (E) include basic compounds such as triethylamine, tributylamine, 1,4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]nona-5-ene, 1,8-diazabicyclo[5.4.0]unde-7-ene, N,N-bis(N,N-dimethyl-2-amino-ethyl)methylamine, N,N-dimethylcyclohexylamine, N,N-dimethylphenylamine, and N-ethylmorpholinine.

[0114] Other substances that can be used similarly as catalysts (E) include phosphoric acid and its esters, toluenesulfonic acid, sulfuric acid, nitric acid, or acidic compounds such as organic carboxylic acids like acetic acid and benzoic acid.

[0115] If the composition (M) of the present invention contains a catalyst (E), the amount involved is preferably 0.01 to 10 parts by weight, more preferably 0.03 to 3 parts by weight, based on 100 parts by weight of the crosslinkable composition (M).

[0116] In one aspect of the present invention, the optionally used catalyst (E) is a metal-containing curing catalyst, preferably a tin-containing catalyst. This embodiment of the present invention is particularly preferred when component (A) consists entirely or at least partially, i.e., at least 90% by weight, preferably at least 95% by weight, of a compound of formula (I) in which b is not 1.

[0117] In composition (M) of the present invention, if component (A) consists entirely or at least partially, i.e., at least 20% by weight, preferably at least 40% by weight, of a compound of formula (I) where b is 1 and R' means a hydrogen atom, then the metal-containing catalyst (E), and more particularly the tin-containing catalyst, can be preferably omitted. This embodiment of the present invention is preferably free of a metal-containing catalyst, and more particularly, free of a tin-containing catalyst.

[0118] The adhesion promoter (F) optionally used in the composition (M) of the present invention may be any desired adhesion promoter previously described for systems curing by silane condensation.

[0119] Examples of adhesion promoters (F) include epoxysilanes, e.g., glycidoxypropyltrimethoxysilane, glycidoxypropyl-methyldimethoxysilane, glycidoxypropyltriethoxysilane or glycidoxypropyl-methyldiethoxysilane, 2-(3-triethoxysilylpropyl)maleic anhydride, N-(3-trimethoxysilyl-propyl)urea, N-(3-triethoxysilylpropyl)urea, N-(trimethoxysilylmethyl)urea, N-(methyldimethoxysilylmethyl)urea, N-(3-triethoxysilylmethyl)urea, N-(3-methyldiethoxysilylmethyl)urea, O-methylcarbamatomethyl-methyldimethoxysilane, O-methylcarbamatomethyl These include tyl-trimethoxysilane, O-ethylcarbamatomethyl-methyldiethoxysilane, O-ethylcarbamatomethyl-triethoxysilane, 3-methacryloxypropyl-trimethoxysilane, methacryloxymethyl-trimethoxysilane, methacryloxymethyl-methyldimethoxysilane, methacryloxymethyl-triethoxysilane, methacryloxymethyl-methyldiethoxysilane, 3-acryloxypropyl-trimethoxysilane, acryloxymethyl-trimethoxysilane, acryloxymethyl-methyldimethoxysilane, acryloxymethyl-triethoxysilane, and acryloxymethyl-methyldiethoxysilane, as well as partial condensates thereof.

[0120] If the composition (M) of the present invention contains an adhesion promoter (F), the amount involved is preferably 0.5 to 30 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the crosslinkable composition (M).

[0121] The water-scavenging agent (G) optionally used in the composition (M) of the present invention may be any desired water-scavenging agent previously described for systems that harden by silane condensation.

[0122] Examples of water-scavenging agents (G) include silanes and / or partial condensates thereof, such as vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, O-methylcarbamatomethyl-methyldimethoxysilane, O-methylcarbamatomethyl-trimethoxysilane, O-ethylcarbamatomethyl-methyldiethoxysilane, and O-ethylcarbamatomethyl-triethoxysilane, as well as orthoesters such as 1,1,1-trimethoxyethane, 1,1,1-triethoxyethane, trimethoxymethane, and triethoxymethane.

[0123] When the composition (M) of the present invention contains a water-scavenging agent (G), the amount involved is preferably 0.5 to 30 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the crosslinkable composition (M). The composition of the present invention preferably contains a water-scavenging agent (G).

[0124] The additive (H) optionally used in composition (M) of the present invention may be any desired typical additive known to date for silane crosslinking systems.

[0125] The additive (H) used optionally in the present invention is preferably an antioxidant, a UV stabilizer, such as a so-called HALS compound, an antifungal agent, and a pigment.

[0126] If the composition (M) of the present invention contains additive (H), the amount involved is preferably 0.01 to 30 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the crosslinkable composition (M). The composition of the present invention preferably contains additive (H).

[0127] The adjuvant (K) used optionally in the present invention is preferably a tetraalkoxysilane, such as tetraethoxysilane and / or a partial condensate thereof, a plasticizer, a reactive plasticizer, a rheological additive, a flame retardant, and an organic solvent.

[0128] Examples of plasticizers (K) include phthalate esters (e.g., dioctyl phthalate, diisooctyl phthalate, and diundecyl phthalate), perhydrogenated phthalate esters (e.g., diisononyl 1,2-cyclohexane dicarboxylate and dioctyl 1,2-cyclohexane dicarboxylate), adipic acid esters (e.g., dioctyl adipate), benzoic acid esters, 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), phosphate esters, sulfonic acid esters, polyesters, polyethers (e.g., polyethylene glycol and polypropylene glycol having a molar mass of preferably 1,000 to 10,000 daltons), polystyrene, polybutadiene, polyisobutylene, paraffinic hydrocarbons, and high molecular weight branched hydrocarbons, and it is preferable that plasticizers (K) are not used.

[0129] An example of a reactive plasticizer (K) is given by the following formula: R 10 m Si(OR 9 ) l R 8 k O (4-k-l-m) / 2 (VII) (In the formula, R 8 These may be the same or different, and are optionally substituted monovalent SiC bonded hydrocarbon groups having 1 to 2 carbon atoms, preferably methyl. R 9 These may be the same or different, and are a hydrogen atom or an optionally substituted hydrocarbon group. R 10 These are monovalent SiC bonded hydrocarbon groups having 3 to 40 carbon atoms, which may be the same or different, and are optionally substituted. k is 0, 1, 2, or 3, preferably 0 or 1. l is 0, 1, 2, or 3, preferably 2 or 3, more preferably 3. m is 0, 1, 2, 3, or 4, preferably 1. However, the sum of k+l+m is 4 or less, and there is at least one group R per molecule. 10 (Provided that the existence of such a thing exists)

[0130] Optionally substituted hydrocarbon group R 9 The example shown is an example specified for base R.

[0131] base R 9 Preferably, it comprises a hydrocarbon group having a hydrogen atom and 1 to 18 carbon atoms, optionally substituted with a halogen atom; more preferably, it comprises a hydrocarbon group having a hydrogen atom and 1 to 10 carbon atoms, and more specifically, a methyl and an ethyl group.

[0132] Optionally substituted hydrocarbon group R 10 The example is a specified example of a hydrocarbon group having at least three carbon atoms, with group R being the relevant part.

[0133] base R 10 It is preferable that the number of carbon atoms is even.

[0134] base R 10 Preferably, it comprises a hydrocarbon group having 6 to 40 carbon atoms, more preferably a hexyl, isohexyl, isooctyl, octyl, decyl, dodecyl, tetradecyl and hexadecyl group, and very preferably a hexadecyl group.

[0135] Examples of organosilicon compounds (K) of formula (VII) that can be optionally used in the present invention include isooctyltrimethoxysilane, isooctyltriethoxysilane, N-octyltrimethoxysilane, N-octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, tetradecyltrimethoxysilane, tetradecyltriethoxysilane, hexadecyltrimethoxysilane, and hexadecyltriethoxysilane.

[0136] The organosilicon compound (K) of formula (VII) used optionally in this invention is a standard commercial product and / or can be prepared by common chemical methods.

[0137] The rheological additive (K) is preferably a polyamide wax, hydrogenated castor oil, or stearate.

[0138] Examples of organic solvents (K) include the compounds already mentioned above as solvents, preferably alcohols.

[0139] Preferably, no organic solvent (K) is added to composition (M) of the present invention.

[0140] If the composition (M) of the present invention contains one or more components (K), the amount involved in each case is preferably 0.1 to 70 parts by weight, more preferably 0.5 to 50 parts by weight, and more specifically 1 to 30 parts by weight, based on 100 parts by weight of the crosslinkable composition (M).

[0141] The composition (M) of the present invention is preferably a composition containing the following: (A) 100 parts by weight of the compound of formula (I), (B) 60 to 1000 parts by weight of silicone resin containing the units of formula (II), Selectively (C) 0.5 to 10 parts by weight of a compound containing basic nitrogen, Selectively (D) Filler, Selectively (E) Catalyst, Selectively (F) Adhesion promoter, Selectively (G) Water scavenger, Selectively (H) Additives and Selectively (K) Adjuvant

[0142] The composition (M) of the present invention preferably does not contain any further components other than components (A) to (K).

[0143] In any case, the components used in the present invention may be one such component or a mixture of at least two such components.

[0144] The composition (M) of the present invention is preferably, in all cases, a formulation having a viscosity of preferably 500 to 1,000,000 mPas, more preferably 1,000 to 500,000 mPas, and more specifically 1,000 to 20,000 mPas at 25°C.

[0145] The composition (M) of the present invention can be manufactured according to any desired form known in itself, for example, according to conventional methods and mixing methods for producing moisture-curable compositions. The order in which the various components are mixed with each other can be arbitrarily changed.

[0146] A further subject of the present invention is a method for producing composition (M) of the present invention by mixing the individual components in any order.

[0147] This mixing can be carried out at room temperature and ambient pressure, in other words, at approximately 900–1100 hPa. However, if desired, this mixing can be carried out at higher temperatures, for example, in the range of 30–130°C. Furthermore, mixing can be carried out temporarily or continuously under reduced pressure, such as an absolute pressure of 30–500 hPa, for example, to remove volatile compounds and / or air.

[0148] The mixing in this invention is preferably carried out while removing moisture.

[0149] The method of the present invention can be carried out continuously or discontinuously.

[0150] The composition (M) of the present invention is preferably a one-component composition that is storable except for water and crosslinks at room temperature upon the introduction of water. Alternatively, the composition of the present invention may be part of a two-component crosslinking system in which an OH-containing compound such as water is added to the second component.

[0151] Therefore, a further subject of the present invention relates to a one-component crosslinking system comprising at least one crosslinkable composition (M) of the present invention, which hardens upon contact with water, for example, moisture in the air.

[0152] Therefore, a further subject of the present invention relates to a two-component crosslinking system comprising at least one crosslinkable composition (M) of the present invention and a further OH-containing compound, such as water.

[0153] For crosslinking of composition (M) of the present invention, the normal moisture content of air is sufficient. The composition of the present invention is preferably crosslinked at room temperature. Crosslinking may also be carried out at temperatures higher or lower than room temperature, for example, -5° to 15°C or 30° to 50°C, and / or by a water concentration exceeding the normal moisture content of air.

[0154] Crosslinking is preferably carried out at a pressure of 100–1100 hPa, more specifically at the ambient pressure, i.e., about 900–1100 hPa.

[0155] A further subject of the present invention is a molded article produced by crosslinking at least one composition (M) of the present invention. The molded article of the present invention may be any desired molded article, such as a gasket, compression molded article, extruded profile, coating, impregnation, sealing, lens, prism, polygonal structure, laminated layer or adhesive layer.

[0156] The composition (M) of the present invention is preferably used as an adhesive having a combination of high tensile strength and high elasticity after curing. Tensile strength (N / mm 2 The product obtained by multiplying the ) by the elongation at break (%) preferably has a value greater than 500, preferably greater than 1000, and more preferably greater than 1500.

[0157] A further subject of the present invention is a method for bonding or sealing substrates, wherein at least one of the compositions (M) of the present invention is applied to the surface of at least one substrate, and this surface is then brought into contact with and subsequently crosslinked with a second substrate to be bonded.

[0158] Examples of substrates that can be bonded or sealed in this invention include wood, but also plastics such as PVC, concrete, mineral substrates, metals, glass, ceramics, and coated surfaces. The materials bonded together may be the same or different.

[0159] A further subject of the present invention is a method for producing a coating or encapsulation in which at least one of the compositions (M) of the present invention is applied to at least one substrate and subsequently crosslinked.

[0160] Examples include the manufacture of encapsulation compositions, molded articles, composite materials, and molded composite components for LEDs or other electronic components. A molded composite component, in this context, refers to an integral molded article comprising a composite material assembled from crosslinked products of the composition of the present invention and at least one substrate such that a strong and durable bond exists between the two components.

[0161] An advantage of composition (M) of the present invention is that it is easy to manufacture.

[0162] The advantages of the crosslinkable composition (M) of the present invention are its extremely high storage stability and high crosslinking rate, which are noteworthy.

[0163] A further advantage of the crosslinkable composition (M) of the present invention is that it exhibits an excellent adhesion profile.

[0164] Furthermore, an advantage of the crosslinkable compositions (M) of the present invention is that they are easy to process.

[0165] Furthermore, an advantage of the crosslinkable composition (M) of the present invention is that it can be used to obtain an adhesive having a combination of high tensile strength and high elongation at break.

[0166] A further advantage of the composition (M) of the present invention lies in the option of obtaining a composition with low viscosity, i.e., very good workability, without having to add large amounts of solvents and / or plasticizers, which are often undesirable for that purpose, by selecting a low viscosity component (B).

[0167] To avoid unnecessarily extending the number of pages in the description of the present invention, only preferred embodiments of individual features are described.

[0168] However, a knowledgeable reader should understand this type of disclosure as explicitly desired, since all combinations of different levels of preferences are explicitly disclosed.

[0169] However, in the embodiments described below, which are not intended to impose any limitations on the present invention, all viscosity values ​​refer to values ​​at a temperature of 25°C. Unless otherwise indicated, the embodiments described below are carried out at ambient pressure, i.e., about 1000 hPa, room temperature, i.e., about 23°C, or the temperature at which the reactants are brought together at room temperature without additional heating or cooling, and also at a relative humidity of about 50%. Furthermore, all figures in parts and percentages refer to weights unless otherwise indicated. [Examples]

[0170] [Synthesis Example 1] Preparation of non-inventive resins In a 2 L four-necked flask equipped with a dropping funnel, Liebig condenser, KPG stirrer, and thermometer, 1000 g of phenyltrimethoxysilane is introduced at room temperature and mixed with 20 g of 20% aqueous hydrochloric acid while stirring. The temperature is then raised to 65-68°C until gentle reflux begins. Next, under reflux, a mixture of 76 g of water and 20 g of methanol is added at a uniform rate over 30 minutes. After the addition is complete, stirring is continued under reflux for 10 minutes, followed by cooling to room temperature.

[0171] The reaction mixture is left at room temperature for approximately 16 hours, then 60 g of sodium bicarbonate is added while stirring, and the mixture is stirred for 30 minutes. The resulting solid is then separated by filtration. Finally, the low-boiling substance (essentially methanol) is removed by distillation. Here, approximately 80-90% of the recovered distillate is first removed at 1013 mbar and a temperature of 120°C, then the pressure is reduced to 10 mbar, and the remaining low-boiling residue is removed by distillation over the next 15-20 minutes.

[0172] A methoxy-functionalized phenyl silicone resin with an average molar mass of Mn of 1200 g / mol, a viscosity of 50 mPas at 23°C, and a total resin mass of approximately 17% methoxy groups is obtained.

[0173] [Synthesis Example 2] Preparation of the resin of the present invention The procedure is the same as in Example 1, except that 1000 g of phenyltrimethoxysilane is replaced with an equimolar amount, i.e., 1212 g of phenyltriethoxysilane, and 20 g of methanol is replaced with an equimolar amount, i.e., 28.8 g of ethanol. All other parameters (reaction temperature, reaction time, water, and sodium bicarbonate, etc.) remain unchanged.

[0174] A phenylmethyl silicone resin with an average molar mass of Mn of 1100 g / mol, a viscosity of 40 mPas at 23°C, and a total resin mass of 18% methoxy groups is obtained.

[0175] [Synthesis Example 3] Preparation of non-inventive resins Follow the same procedure as in Example 1, except that the materials and their quantities are changed as follows.

[0176] Instead of 1000 g of phenyltrimethoxysilane, a mixture of 700 g of phenyltrimethoxysilane, 250 g of methyltrimethoxysilane, and 50 g of dimethyldimethoxysilane is introduced first. Then, hydrochloric acid is added without modification, and after heating to a temperature of 65-68°C, a mixture of 94.5 g of water and 42 g of methanol is added under reflux at a uniform rate over 30 minutes, instead of a mixture of 76 g of water and 20 g of methanol. All other method parameters, materials, and their amounts remain unchanged.

[0177] [Synthesis Example 4] Preparation of the resin of the present invention The procedure is the same as in Example 3, except that instead of 700 g of phenyltrimethoxysilane, equimolar amounts, i.e., 848.5 g of phenyltriethoxysilane; instead of 250 g of methyltrimethoxysilane, equimolar amounts, i.e., 327.2 g of methyltriethoxysilane; instead of 50 g of dimethyldimethoxysilane, equimolar amounts, i.e., 61.7 g of dimethyldiethoxysilane; and instead of 40 g of methanol, equimolar amounts, i.e., 57.6 g of ethanol are used. All other parameters (reaction temperature, reaction time, water and sodium bicarbonate, etc.) remain unchanged.

[0178] A phenyl silicone resin with an average molar mass of Mn of 1400 g / mol, a viscosity of 60 mPas at 23°C, and a total resin mass of approximately 25% ethoxy group content can be obtained.

[0179] [Synthesis Example 5] Preparation of isocyanatomethyl-trimethoxysilane Isocyanatomethyl-trimethoxysilane is prepared in a thin-film evaporator with a length of 25 cm, an inner diameter of 8 cm, and a wall temperature of 300°C.

[0180] Mix 400 g of N-trimethoxysilylmethyl-O-methylcarbamate (commercially available from Wacker Chemie AG in Munich, Germany as GENIOSIL(R)XL63) with 0.28 g of dioctyltin dilaurate. The mixture is added by weighing at a rate of 110 mL / hour at the top of a thin-film evaporator. A nitrogen stream of 65 L / hour is passed through from bottom to top, i.e., in the opposite direction of the reaction mixture's progress. Under these conditions, efflux at the bottom is only about 10% of the weighed silane added.

[0181] The evaporated product mixture is passed through a 10 cm long Vigreux column insulated with a vacuum jacket, along with a nitrogen stream, and the liquid column reflux is returned to a thin-film evaporator. The overhead temperature of the Vigreux column is 158–164°C. From this gas stream, the pyrolysis silane mixture is selectively condensed at 54°C using a conventional glass condenser. In the second condensation step, methanol is condensed, followed by condensation at 0°C, after which the nitrogen stream passes through a cold trap into the extraction system of a laboratory fume hood containing the entire apparatus. The resulting silane mixture is stored at -20°C.

[0182] A colorless liquid, 1 The analysis is performed by 1H-NMR and gas chromatography. The liquid contains 33.7% isocyanatomethyltrimethoxysilane, 66.4% N-trimethoxysilylmethyl)-O-methylcarbamate, and 0.1% methanol.

[0183] Subsequent fractional distillation yields 75 g of isocyanatomethyltrimethoxysilane with a purity of 98.9%.

[0184] [Synthesis Example 6] Preparation of polypropylene glycol having an α-trimethoxysilylmethyl terminal group In a 2000 mL reaction vessel equipped with stirring, cooling, and heating equipment, an average molar mass of 12000 g / mol M is added. nFirst, 1200.0 g of linear polypropylene glycol containing (commercially available from Covestro AG in Leverkusen, Germany under the name Acclaim 18200) is charged, and this initial charge is dried at 80°C and 1 mbar for 2 hours while stirring.

[0185] After cooling to room temperature, 42.5 g of isocyanatomethyltrimethoxysilane (prepared according to Synthesis Example 5) is added. The mixture is heated to 80°C while stirring. Then, 0.24 g (150 ppm) of bismuth-containing catalyst (commercially available from Borchers GmbH in Langenfeld, Germany under the name Borchi(R)Kat315) is added, and the temperature of the reaction mixture is raised to 83-84°C. The reaction mixture is stirred at 80°C for a further 120 minutes.

[0186] After cooling to 60°C, 21.0 g of polyethylene glycol (with molecular chains having a methoxy-functional chain end on one side and a hydroxy-functional chain end on the other) with a number-average molar mass of 350 g / mol is added, and stirring is continued at 60°C for 30 minutes. In the resulting polymer mixture, isocyanate groups are no longer detectable by IR spectroscopy. The product is a transparent, translucent polymer mixture with a viscosity of 25 Pas at 25°C.

[0187] [Example 1] Manufacturing of transparent 1K adhesive formulations 132.0g, average molar mass (M n)Silane-terminated polypropylene glycol having a molecular weight of 12,000 Daltons and a terminal group of the formula -O-C(=O)-NH-CH2-Si(CH3)(OCH3)2 (commercially available under the name GENIOSIL(R) STP-E10 from Wacker Chemie AG, Munich, Germany) is mixed with 256.0 g of the resin of the present invention from Synthesis Example 2 and 12.0 g of aminopropyltrimethoxysilane at 200 rpm for 1 minute in a laboratory planetary mixer manufactured by PC-Laborsystem with two cross-arm mixers. The mixture is finally homogenized and stirred at 600 rpm for 2 minutes and 200 rpm for 1 minute under a pressure of 100 mbar until the bubbles disappear.

[0188] The formulation is dispensed into 310 mL PE cartridges and stored at 25°C for 1 day before investigation.

[0189] [Comparative Example 1] Production of a transparent one-component adhesive formulation The procedure of Example 1 is repeated, but instead of 256.0 g of the resin of the present invention of Synthesis Example 2, the same amount of the non-invention resin of Synthesis Example 1 is used. All other parameters remain unchanged.

[0190] [[ID=​​​​​​​​​​​​​

[0193] [Comparative Example 2] Manufacturing of transparent 1K adhesive formulations The procedure of Example 2 is repeated, but instead of 216.0 g of the resin of the present invention in Synthesis Example 2, the same amount of the non-inventive resin from Synthesis Example 1 is used. All other parameters remain unchanged.

[0194] Dispense the mixture into 310 mL PE cartridges and store at 25°C for 1 day before the study.

[0195] [Example 3] Determination of the mechanical properties of adhesive formulations The compositions obtained in Examples 1 and 2, as well as Comparative Examples 1 and 2 (C1 and C2), were crosslinked, and their skinning and mechanical properties were investigated. The results are shown in Table 1.

[0196] <Skin Overtime (SOT)> The skin overtime is determined by applying the crosslinkable composition obtained in the examples to a PE film in a 2 mm thick layer and storing the coated film under standard conditions (23°C and 50% relative humidity). During the curing process, skin formation is tested every 5 minutes. For this test, a dry laboratory spatula is carefully placed on the surface of the sample and pulled upwards. If the sample adheres to the finger, skin has not yet formed. If the sample does not adhere to the finger, skin has formed, and the time is recorded.

[0197] <Mechanical properties> Each composition was coated to a depth of 2 mm onto a milled-out Teflon plate and cured at 23°C and 50°C relative humidity for two weeks.

[0198] The Shore A hardness is determined according to DIN 53505.

[0199] The tensile strength is determined according to DIN53504-S1.

[0200] The elongation at break is determined according to DIN53504-S1.

[0201] The advantages of the composition of the present invention over equivalent compositions in the prior art are, in particular, the combination of high tensile strength and high elongation at break. To highlight this advantage, in addition to rows containing pure measurements, Table 1 shows the mathematical product of tensile strength and elongation at break (in units of % × N / mm²). 2 This also includes lines containing ).

[0202] [Table 1]

[0203] [Example 4] Manufacturing of transparent 1K adhesive formulations 210.0g, average molar mass (M n )12,000 Daltons and 172.4 g of silane-terminated polypropylene glycol having the terminal group of formula -OC(=O)-NH-(CH2)3-Si(OCH3)3 (commercially available from Wacker Chemie AG in Munich, Germany under the name GENIOSIL(R)STP-E15) were mixed in a laboratory planetary mixer of PC-Labor-system equipped with two cross-arm mixers to form the resin of the present invention in Synthesis Example 2, CAS number 192268-64-7 (commercially available from BASF SE in Ludwigshafen, Germany under the name Chimassorb(R)2020), a hindered amine photostabilizer (HALS), CAS number 127519-17-9 (BASF SE in Ludwigshafen, Germany) Mix 2.0 g of UV absorber (commercially available from SE under the name Tinuvin(R)384-2), 12.0 g of aminopropyltrimethoxysilane, and 1.6 g of tetramethylguanidine at 200 rpm for 5 minutes. Finally, homogenize the mixture by stirring at 600 rpm for 2 minutes and then at 200 rpm for 1 minute under a pressure of 100 mbar until no bubbles remain.

[0204] Dispense the mixture into 310 mL PE cartridges and store at 25°C for 1 day before the study.

[0205] [Comparative Example 4] Production of a transparent 1K adhesive formulation Repeat the procedure of Example 4, but use the same amount of the resin of the non-invention of Synthesis Example 1 instead of 172.4 g of the resin of the invention of Synthesis Example 2. All other parameters remain unchanged.

[0206] Dispense the formulation into 310 mL PE cartridges and store at 25 °C for 1 day before investigation.

[0207] [Example 5] Production of a transparent 1K adhesive formulation Mix 250.0 g of GENIOSIL(R) STP-E15, 132.4 g of the resin of the invention from Synthesis Example 2, 2.0 g of Chimassorb(R) 2020, 2.0 g of Tinuvin(R) 384-2, 12.0 g of aminopropyltrimethoxysilane and 1.6 g of tetramethylguanidine in a laboratory planetary mixer from PC-Laborsystem equipped with two cross-arm mixers at 200 rpm for 5 minutes. Finally, homogenize the mixture and stir at 600 rpm for 2 minutes and at 200 rpm for 1 minute under a pressure of 100 mbar until no bubbles remain.

[0208] Dispense the formulation into 310 mL PE cartridges and store at 25 °C for 1 day before investigation.

[0209] [Comparative Example 5] Production of a transparent 1K adhesive formulation Repeat the procedure of Example 5, but use the same amount of the resin of the non-invention of Synthesis Example 1 instead of 172.4 g of the resin of the invention of Synthesis Example 2. All other parameters remain unchanged.

[0210] Dispense the formulation into 310 mL PE cartridges and store at 25 °C for 1 day before investigation.

[0211] [Example 6] Determination of the mechanical properties of the adhesive formulation The compositions obtained in Examples 4 and 5, and further in Comparative Examples 4 and 5 (C4 and C5), were crosslinked, and their skinning and mechanical properties were investigated. The results are shown in Table 2.

[0212] The skin overtime and mechanical properties are also determined as described in Example 3. Here again, the mathematical product of tensile strength and elongation at break (unit: % × N / mm) is used in the measured values. 2 ) was added.

[0213] [Table 2]

[0214] [Example 7] Manufacturing of transparent 1K adhesive formulations 170.0 g of GENIOSIL(R)STP-E10 is mixed with 214.0 g of the resin of the present invention from Synthesis Example 4, 4.0 g of a liquid stabilizer mixture containing a hindered amine light stabilizer (HALS) and a UV absorber (commercially available from Wacker Chemie AG in Munich, Germany under the name GENIOSIL(R)STABILIZER T) and 12.0 g of aminopropyltrimethoxysilane at 200 rpm for 1 minute in a laboratory planetary mixer equipped with two cross-arm mixers. Finally, the mixture is homogenized by stirring at 600 rpm for 2 minutes and then at 200 rpm for 1 minute under a pressure of 100 mbar until no bubbles remain. Dispense the mixture into 310 mL PE cartridges and store at 25°C for 1 day before the study.

[0215] [Comparative Example 7] Manufacturing of transparent 1K adhesive formulations The procedure of Example 7 is repeated, but instead of 170.0 g of the present invention resin from Synthesis Example 4, the same amount of the non-inventive resin from Synthesis Example 3 is used. All other parameters remain unchanged.

[0216] Dispense the mixture into 310 mL PE cartridges and store at 25°C for 1 day before the study.

[0217] [Example 8] Manufacturing of transparent 1K adhesive formulations 130.0 g of polypropylene glycol having an α-trimethoxysilyl-methyl terminal group from Synthesis Example 6 was mixed in a laboratory planetary mixer of PC-Laborsystem equipped with two cross-arm mixers, 254.0 g of the resin of the present invention from Synthesis Example 2, 4.0 g of a stabilizer mixture (a mixture of 20% Irganox(R) 1135 (CAS No. 125643-61-0), 40% Tinuvin(R) 571 (CAS No. 23328-53-2), and 40% Tinuvin(R) 765 (CAS No. 41556-26-7) (BASF, Ludwigshafen, Germany) Mix the TINUVIN(R) B75 (commercially available from AG) and 12.0 g of aminopropyltrimethoxysilane at 200 rpm for 1 minute. Finally, homogenize the mixture by stirring at 600 rpm for 1 minute and then at 200 rpm for 1 minute under a pressure of 100 mbar until no bubbles remain.

[0218] Dispense the mixture into 310 mL PE cartridges and store at 25°C for 1 day before the study.

[0219] [Example 9] Determination of the mechanical properties of adhesive formulations The compositions obtained in Examples 7 and 8, as well as Comparative Example 7(C7), were crosslinked, and their skinning and mechanical properties were investigated. The results are shown in Table 3.

[0220] The skin overtime and mechanical properties are also determined as described in Example 3. Here again, the mathematical product of tensile strength and elongation at break (unit: % × N / mm) is used in the measured values. 2 ) was added.

[0221] [Table 3]

[0222] [Example 10] Manufacturing of 1K adhesive formulations with fillers 65.8 g of GENIOSIL(R)STP-E10 is homogenized at approximately 25°C in a laboratory planetary mixer from PC-Laborsystem equipped with two cross-arm mixers, with 122.1 g of the resin of the present invention from Synthesis Example 2, 0.1 g of a 50% citric acid aqueous solution, and 6.0 g of a liquid stabilizer mixture containing a hindered amine light stabilizer (HALS) and a UV absorber (commercially available from Wacker Chemie AG in Munich, Germany, under the name GENIOSIL(R)STABILIZER F) at 200 rpm for 2 minutes. Then, 200.0 g of 3-5 m 2 Aluminum trihydrate (commercially available from Albemarle Corp. under the name "Martinal OL 104") having a BET specific surface area of ​​1 / g and a d50 of 1.7-2.1 μm was incorporated while stirring at 600 rpm for 1 minute. After incorporating the aluminum trihydrate, 6.0 g of 3-aminopropyltrimethoxysilane was mixed at 200 rpm for 1 minute. Finally, the mixture was homogenized and stirred at 600 rpm for 2 minutes and then at 200 rpm for 1 minute under a pressure of 100 mbar until no bubbles remained.

[0223] Dispense the mixture into 310 mL PE cartridges and store at 25°C for 1 day before the study.

[0224] [Comparative Example 10] Manufacturing of 1K adhesive formulations with fillers The procedure of Example 10 is repeated, but instead of 122.2 g of the present invention resin from Synthesis Example 2, the same amount of the non-inventive resin from Synthesis Example 1 is used. All other parameters remain unchanged.

[0225] Dispense the mixture into 310 mL PE cartridges and store at 25°C for 1 day before the study.

[0226] [Example 11] Manufacturing of 1K adhesive formulations with fillers 93.1 g of GENIOSIL(R)STP-E10 is homogenized at approximately 25°C in a laboratory planetary mixer manufactured by PC-Laborsystem with two cross-arm mixers, at 200 rpm for 2 minutes with 172.8 g of the resin of the present invention from Synthesis Example 2, 0.1 g of a 50% citric acid aqueous solution, and 6.0 g of a liquid stabilizer mixture containing a hindered amine light stabilizer (HALS) and a UV absorber (commercially available from Wacker Chemie AG in Munich, Germany, under the name GENIOSIL(R)STABILIZER F). Subsequently, 108.0 g of powdered marble with an average particle size (D50%) of approximately 5 μm (commercially available from Shiraishi Omya GmbH in Gumann, Austria, under the name Omyacarb5-GU) and a BET specific surface area of ​​approximately 200 m². 2 12.0 g of hydrophobic fumed silica (commercially available from Wacker Chemie AG in Munich, Germany under the name HDK H18(R)) was incorporated while stirring at 600 rpm for 1 minute. Then, 8.0 g of aminopropyltrimethoxysilane was mixed in at 200 rpm for 1 minute. Finally, the mixture was homogenized and stirred at 600 rpm for 2 minutes and then at 200 rpm for 1 minute under a pressure of approximately 100 mbar until no bubbles remained.

[0227] Dispense the mixture into 310 mL PE cartridges and store at 25°C for 1 day before the study.

[0228] [Comparative Example 11] Manufacturing of 1K adhesive formulations with fillers The procedure of Example 11 is repeated, but instead of 172.9 g of the present invention resin from Synthesis Example 2, the same amount of the non-inventive resin from Synthesis Example 1 is used. All other parameters remain unchanged.

[0229] Dispense the mixture into 310 mL PE cartridges and store at 25°C for 1 day before the study.

[0230] [Example 12] Determination of the mechanical properties of adhesive formulations The compositions obtained in Examples 10 and 11, and in Comparative Examples 10 and 11 (C10 and C11), were crosslinked, and their skinning and mechanical properties were investigated. The results are shown in Table 4.

[0231] The skin overtime and mechanical properties are also determined as described in Example 3. Here again, the mathematical product of tensile strength and elongation at break (unit: % × N / mm) is used in the measured values. 2 ) was added.

[0232] [Table 4]

Claims

1. (A) 100 parts by weight of the compound (A) of the following formula Y-[(CR １ ２ ) ｂ -SiR ａ (OR ２ ) ３－ａ ] ｘ (I)、 (In the formula, Y is an x-valent polymer group bonded via nitrogen, oxygen, sulfur, or carbon. R may be the same or different, and is a monovalent SiC bonded hydrocarbon group that is optionally substituted. R １ These are either the same or different monovalent hydrocarbon groups that are optionally substituted and bonded to a carbon atom via a hydrogen atom, or a nitrogen, phosphorus, oxygen, sulfur, or carbonyl group. R ２ may be the same or different and is a hydrogen atom or an optionally substituted monovalent hydrocarbon group, x is an integer between 1 and 10. a may be the same or different, and is 0, 1 or 2. b may be the same or different integers, and is an integer between 1 and 10. (B) Silicone resin (B) containing more than 10 parts by weight of the following units: R ３ ｃ (R ４ O) ｄ R ５ ｅ SiO （４－ｃ－ｄ－ｅ）／２ (-I) (In the formula, R ３ These may be the same or different, and are a hydrogen atom, a SiC-bonded, optionally substituted monovalent aliphatic hydrocarbon group, or an optionally substituted divalent aliphatic hydrocarbon group bridging the two units of formula (II). R ４ These may be the same or different, and are a hydrogen atom or a monovalent hydrocarbon group optionally substituted. R ５ These may be the same or different, and are SiC-bonded, optionally substituted monovalent aromatic hydrocarbon groups. c is 0, 1, 2, or 3. d is 0, 1, 2, or 3, preferably 0, 1, or 2, more preferably 0 or 1. e is 0, 1, or 2, preferably 0 or 1. It contains, however, The sum of c + d + e is 3 or less. - In at least 60% of the units of formula (II) above, the sum of c + e is 0 or 1. • All bases R contained in component (A) ２ At least 70 mol% of it is methyl groups, - All groups R contained in the silicone resin (B) ４ At least 60 mol% of it is ethyl groups, - All groups R contained in the silicone resin (B) ４ The maximum percentage of methyl groups is 30 moles. A crosslinkable composition (M) subject to the following conditions.

2. The group R comprises a monovalent hydrocarbon group having 1 to 6 carbon atoms and optionally substituted with a halogen atom, preferably an alkyl group having 1 or 2 carbon atoms, more particularly a methyl group, and / or group R １ However, it is a hydrocarbon group having a hydrogen atom and 1 to 20 carbon atoms, more specifically a hydrogen atom, and / or group R ２ However, it contains a hydrogen atom or an alkyl group having 1 to 10 carbon atoms and optionally substituted with a halogen atom, preferably an alkyl group having 1 to 4 carbon atoms, more specifically a methyl or ethyl group, where all groups R contained in component (A) ２ At least 70 mol% of it is a methyl group, and / or The polymer group Y is a polyester, polyether, polyurethane, polyalkylene, or polyacrylate group, and the group Y in formula (I) is more specifically a terminally bonded group -[(CR １ ２ ) ｂ -SiR ａ (OR ２ ) ３－ａ The crosslinkable composition (M) according to claim 1, comprising a polyurethane group having ] and a polyoxyalkylene group.

3. The crosslinkable composition (M) according to claim 1 or 2, wherein the terminal group of compound (A) is a group of the following general formula. -NH-C(=O)-NR’-(CR １ ２ ) ｂ -SiR ａ (OR ２ ) ３－ａ (III)、 -O-C(=O)-NH-(CR １ ２ ) ｂ -SiR ａ (OR ２ ) ３－ａ (IV) or -O-(CR １ ２ ) ｂ -SiR ａ (OR ２ ) ３－ａ (V)、 (In the formula, the base and subscript have one of the above definitions.)

4. The crosslinkable composition (M) according to any one of claims 1 to 3, wherein the silicone resin (B) used is a liquid and has a viscosity of 50 to 50,000 mPas, preferably 100 to 20,000 mPas, and the viscosity for the purposes of the present invention is measured using a DV3P rotational viscometer manufactured by A. Paar (Brookfield system) at 2.5 rpm with a spindle 5 in accordance with ISO 2555 after being adjusted to 23°C.

5. group R ３ The crosslinkable composition (M) according to any one of claims 1 to 4, comprising a monovalent SiC-bonded aliphatic hydrocarbon group having 1 to 18 carbon atoms and optionally substituted with a halogen atom, preferably an aliphatic hydrocarbon group having 1 to 6 carbon atoms, more particularly a methyl group.

6. group R ４ However, it contains a hydrogen atom or an alkyl group having 1 to 10 carbon atoms and optionally substituted with a halogen atom, preferably an alkyl group having 1 to 4 carbon atoms, more specifically a methyl or ethyl group, and all groups R contained in the silicone resin (B) ４ At least 60 mol% of the group is an ethyl group, and all the groups R contained in the silicone resin (B) ４ A crosslinkable composition (M) according to any one of claims 1 to 5, wherein up to 30 mol% of the composition is methyl groups.

7. group R ５ The crosslinkable composition (M) according to any one of claims 1 to 6, comprising a SiC bonded aromatic hydrocarbon group having 1 to 18 carbon atoms and optionally substituted with a halogen atom, for example, an ethylphenyl, tolyl, xylyl, chlorophenyl, naphthyl or styryl group, more preferably a phenyl group.

8. A crosslinkable composition (M) according to any one of claims 1 to 7, further comprising the following: (C) at least one compound (C) containing basic nitrogen, and / or (D) at least one filler (D), and / or (E) at least one catalyst (E), and / or (F) at least one adhesion promoter (F), and / or (G) at least one water-scavenging agent (G), and / or (H) at least one additive (H), and / or (K) at least one adjuvant (K).

9. A crosslinkable composition (M) according to any one of claims 1 to 8, comprising at least one compound (C) containing basic nitrogen, which is an organosilicon compound containing units of the following formula. ｈ Si ( OR ７ ) ｇ R ６ ｆ O （４－ｆ－ｇ－ｈ）／２ (VI), (In the formula, R ６ These may be the same or different, and are optionally substituted monovalent SiC bonded organic groups that do not contain basic nitrogen. R ７ These may be the same or different, and are a hydrogen atom or an optionally substituted hydrocarbon group. D may be the same or different, and is a monovalent SiC bond group having a basic nitrogen. f is 0, 1, 2, or 3. g is 0, 1, 2 or 3, and h is 0, 1, 2, 3 or 4, However, the sum of f + g + h must be 4 or less, and at least one group D must be present per molecule.

10. A one-component crosslinking system comprising a crosslinkable composition (M) according to at least one of claims 1 to 9, which hardens upon contact with water, for example, moisture in the air.

11. A two-component crosslinking system comprising a crosslinkable composition (M) according to at least one of claims 1 to 9 and a further OH-containing compound, such as water.

12. A method for producing a crosslinkable composition (M) according to any one of claims 1 to 9 by mixing the individual components in any order.

13. A molded article manufactured by crosslinking at least one one-component crosslinking system according to claim 10 or at least one two-component crosslinking system according to claim 11.

14. A method for bonding or sealing a substrate, wherein at least one one-component crosslinking system according to claim 10 or at least one two-component crosslinking system according to claim 11 is applied to the surface of at least one substrate, and this surface is then brought into contact with and subsequently crosslinked with a second substrate to be bonded.

15. A method for producing a coating or seal, wherein at least one one-component crosslinking system according to claim 10 or at least one two-component crosslinking system according to claim 11 is applied to and subsequently crosslinked on at least one substrate.

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