Curable silicone compositions containing additives

Abstract

To provide alternative curable compositions based on polyorganosiloxanes which allow use of crosslinkers, release mainly hydroxycarboxylic acid esters (and as possible byproducts hydroxycarboxylic acid amides) during crosslinking, and nevertheless still have good adhesion and excellent storage stability.SOLUTION: The present invention provides curable compositions based on polyorganosiloxanes with special silicon-containing terminal groups, an adhesion promoter, a curing catalyst, and an additive having a ketone functional moiety.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a curable composition based on a polyorganosiloxane having a special silicon-containing end group, an adhesion promoter, a curing catalyst, and an additive having a ketone functional group. These compositions have improved mechanical and adhesive properties, and excellent storage stability. The present invention also relates to its use. [Background technology]

[0002] Polymer systems bearing reactive crosslinkable silyl groups, e.g. alkoxysilyl groups, have been known for a long time. In the presence of atmospheric moisture, these alkoxysilane-terminated polymers can condense with elimination of alkoxy groups. Depending on the amount of alkoxysilane groups and their structure, predominantly long-chain polymers (thermoplastics), relatively wide-meshed three-dimensional networks (elastomers) or highly crosslinked systems (thermosets) are formed.

[0003] Silicone polymers (polyorganosiloxanes), especially polydialkylsiloxanes such as polydimethylsiloxane (PDMS), are of great importance in the manufacture of adhesives, sealing, coatings, and insulation materials. Among these, those that cure at low temperature and ambient conditions constitute a significant share of the market. Typical formulations contain reactive polyorganosiloxanes, especially silanol-terminated polyorganosiloxanes with at least one, preferably two hydroxyl groups bonded to the silicon atoms. This is usually used in combination with a silane-based crosslinker with hydrolyzable groups bonded to the silicon atoms. While the polyorganosiloxane and the crosslinker can be present as separate components, both can also be reacted with each other to form modified polyorganosiloxanes, which can be used in the curable composition. The term endcapping (end group capping) is also used in this respect. This can be optionally carried out in the presence of a catalyst, whereby the catalyst selectively mediates endcapping without simultaneously curing the polyorganosiloxane.

[0004] The uses and potential applications of such silane-terminated polymer systems are similarly diverse. They may be used, for example, in the manufacture of elastomers, sealants, adhesives, elastic adhesive systems, rigid and flexible foams, a wide variety of coating systems, and in the medical field, for example, as impression materials in dentistry. These products may be applied in any form, such as painted, sprayed, cast, pressed, filled, etc.

[0005] A large number of crosslinkers are known in the art that act as end-capping or functionalizing moieties of the respective polymer backbone. In addition to their functionality used for coupling to the polymer backbone, they can be differentiated into acidic, basic, and neutral crosslinkers based on the type of leaving group released during hydrolysis. Typical acidic crosslinkers contain an acid group as a hydrolyzable group and release the corresponding acid, e.g., acetic acid, during crosslinking. Typical basic crosslinkers release an amine during crosslinking. In both cases, aggressive compounds are released during crosslinking, which can corrode or decompose, for example, metals, stones, mortar, etc., and also produce a strong, often unpleasant odor. Therefore, neutral crosslinkers are often used in modern curable silicone compositions. Typical representatives of neutral crosslinkers have hydrolyzable groups that release alcohols, such as methanol or ethanol, or oximes during crosslinking.

[0006] Nevertheless, such alkoxy systems have the drawback that several problems arise in the case of storage stability of the associated curable compositions and the cured products show only poor adhesion to some materials. Oxymosilane crosslinkers, which hydrolyze with the release of alkanone oximes, usually do not have these drawbacks and are therefore widely used. The most common representatives of oximosilane crosslinkers release butan-2-one oxime during crosslinking. However, this compound is suspected of causing cancer, so alternative neutral crosslinkers are urgently needed. Apart from that, the released oximes also have a strong foul odor and working with curable compositions containing such crosslinkers is perceived by users as unpleasant.

[0007] Therefore, silane compounds which release α-hydroxycarboxylic acid esters or α-hydroxycarboxylic acid amides during crosslinking have already been proposed as alternative crosslinking agents.

[0008] The preparation of suitable silane compounds has long been known and is described, for example, by MM Sprung in "Some .alpha.-carbalkoxyalkoxysilanes", J. Org. Chem., 1958, 23 (10), pp. 1530-1534.

[0009] DE 3210337 A1 also discloses related silane compounds and their preparation and use in curable compositions based on polydiorganosiloxanes having condensable end groups.

[0010] Hardeners for silicone rubber materials having three 2-hydroxypropionic acid alkyl ester groups, i.e. lactate alkyl ester groups, are known from EP 2 030 976. In this case, vinyltris(ethyllactato)silane is particularly preferred.

[0011] EP 2 774 672 describes special catalysts for crosslinking silicone rubber materials with crosslinkers based on silane compounds with lactato groups. In this case too, the crosslinkers can be compounds known from EP 2 030 976. However, crosslinkers with only one, two or four 2-hydroxypropionic acid alkyl ester groups are also disclosed. [Prior art documents] [Patent documents]

[0012] [Patent Document 1] DE 3210337 A1 [Patent Document 2] European Patent Application Publication No. 2030976 [Patent Document 3] European Patent Application Publication No. 2774672 [Non-patent literature]

[0013] [Non-Patent Document 1] J. Org. Chem., 1958, 23 (10), pp.1530-1534 Summary of the Invention [Problem to be solved by the invention]

[0014] The use of crosslinkers based on silane compounds bearing lactato or similar α-carbalkoxyalkoxy groups is associated with many advantages, but the resulting formulations may have moderate adhesion to certain difficult substrates such as plastics and concrete. Another challenge is to formulate curable silicone-based compositions containing these crosslinkers that exhibit excellent storage stability, since storage stability may be particularly reduced in the presence of other conventional and often essential components of such compositions, in particular curing catalysts and adhesion promoters.

[0015] Although several formulations exist that address some of these problems, the object of the present invention is to provide an alternative curable composition based on polyorganosiloxanes that allows the use of crosslinkers, releases mainly hydroxycarboxylic acid esters (and possibly by-product hydroxycarboxylic acid amides) during crosslinking, and nevertheless has good adhesion and excellent storage stability. [Means for solving the problem]

[0016] The present invention achieves the above objectives by providing a curable composition based on a particular polyorganosiloxane, i.e., a polyorganosiloxane endcapped with a particular silane group, whereby the composition comprises at least one adhesion promoter, at least one curing catalyst, and an additive having a ketone functionality.

[0017] It has been discovered that the combination of certain endcapped polyorganosiloxanes with the adhesion promoters, catalysts and special additives disclosed herein provides excellent storage stability while retaining good cure and adhesion properties. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] Thus, in a first aspect, the present invention relates to a curable composition comprising or consisting essentially of: (A) at least one polyorganosiloxane containing at least one end group of formula (I): [ka] [In the formula, A is a bond, -O-, or a linear, branched or cyclic divalent group selected from a hydrocarbon group having 1 to 12 carbon atoms, an alkylene, an arylene, an oxyalkylene, an oxyarylene, a siloxane-alkylene, a siloxane-arylene, an ester, an amine, a glycol, an imide, an amide, an alcohol, a carbonate, a urethane, a urea, a sulfide, an ether, or derivatives thereof or combinations thereof; Each R 1 is independently selected from the group consisting of hydrogen, halogen, amino, oxyimino, substituted or unsubstituted alkyl, alkenyl, alkenyloxy, alkynyl, alkynyloxy, alicyclic, alicyclic-O-, aryl, aryloxy, heteroaryl, heteroaryloxy, heteroalicyclic, heteroalicyclicoxy, acyl, acyloxy group or combinations thereof; Each R 2 are independently a group of general formula (2): [ka] [During the ceremony, Y is a substituted or unsubstituted (hetero)aromatic group having 4 to 14 ring atoms, a substituted or unsubstituted saturated or partially unsaturated 4 to 14 membered (hetero)cyclic group, or -(C(R5 )2) O - is; R 4 is a substituted or unsubstituted alkyl, alkenyl, alkynyl, alicyclic, aryl, heteroaryl, and heteroalicyclic group, or combinations thereof; Each R 5 is independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, alicyclic or aryl groups; and o is an integer from 1 to 10. Each R 3 are independently a group of general formula (3): [ka] [During the ceremony, Y is as defined above; R 6 is selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, alicyclic, aryl, heteroaryl, and heteroalicyclic groups or combinations thereof, or R 7 is; R 7 is a group of general formula (4): [ka] (In the formula, R 8 is an alkylene group optionally interrupted by a heteroatom, such as O, N, S or Si; Each R 9 is independently selected from the group consisting of hydrogen, halogen, amino, substituted or unsubstituted alkyl, alkenyl, alkynyl, alicyclic, aryl, heteroaryl, and heteroalicyclic groups, or combinations thereof; Each R 10 is independently selected from the group consisting of substituted or unsubstituted alkyl, alkenyl, alkynyl, or acyl groups; Each p independently represents 0, 1, or 2. m is independently 0, 1 or 2; and n is independently 1, 2, or 3, and the sum of n+m is up to 3]; (B) at least one adhesion promoter; (C) at least one curing catalyst; and (D) at least one additive having a ketone functional group of formula (III): [ka] [In the formula, R 31 is selected from substituted or unsubstituted alkyl, alkoxy, alkenyl, alkenyloxy, alkynyl, alkylnyloxy, alicyclic, alicyclic-O-, aryl, aryloxy, heteroaryl, heteroaryloxy, heteroalicyclic, heteroalicyclicoxy, acyl, acyloxy groups or combinations thereof; and R 32 is selected from hydrogen, halogen, amino, oxyimino, substituted or unsubstituted alkyl, alkoxy, alkenyl, alkenyloxy, alkynyl, alkylnyloxy, alicyclic, alicyclic-O-, aryl, aryloxy, heteroaryl, heteroaryloxy, heteroalicyclic, heteroalicyclicoxy, acyl, acyloxy groups or combinations thereof; or R 31 and R 32 may be combined together with the carbon atom to which they are attached to form a 5- to 20-membered substituted or unsubstituted alicyclic or heteroalicyclic group. The additive of formula (III) here contains up to 24, preferably up to 18, carbon atoms.

[0019] The combination of polyorganosiloxanes end-capped with silyl groups having hydroxycarboxylic acid esters or, to a lesser extent, hydroxycarboxylic acid amides as leaving groups attached to the silicon atoms, which are released only on contact with moisture / water, ensures that the curable compositions have very high storage stability and cure reliably and at a sufficient rate after application even at room temperature (23° C.) and in the presence of atmospheric moisture.

[0020] The present invention further relates to the use of the curable composition of the present invention, or prepared according to the method of the present invention, as an adhesive, sealing or coating material.

[0021] A "curable composition" is understood to be a material or mixture of materials that can be cured by physical or chemical means. In this regard, these chemical or physical means can be, for example, the supply of energy in the form of heat, light, or other electromagnetic radiation, but also simply contact with atmospheric moisture, water, or reactive components. This changes the composition from its original state to a state with higher hardness. In the context of the present invention, "curable" mainly relates to the properties of the condensation product of the terminal silane group of formula (I).

[0022] When referring to the molecular weight of an oligomer or polymer in this application, the amount refers to the weight average, i.e., Mw value, and not to the number average molecular weight, unless otherwise specified. The molecular weight is determined by gel permeation chromatography (GPC) according to DIN 55672-1:2007-08, preferably at 35° C., using tetrahydrofuran (THF) as the eluent. The molecular weight of the monomeric compounds is calculated based on the respective molecular formula and the known molecular weights of the individual atoms.

[0023] As used herein, "at least one" refers to one or more, i.e., 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. With respect to components, the term refers to the type of component and not the absolute number of molecules. Thus, "at least one polymer" means, for example, at least one polymer, i.e., one polymer or a mixture of multiple different polymers may be used. In conjunction with weight data, the term refers to all compounds of a given type contained in a composition / mixture, i.e., the composition does not contain other compounds of this type beyond a given amount of the relevant compound.

[0024] All percentage data provided for the compositions described herein indicate in each case % by weight, based on the relevant mixture, unless expressly stated otherwise.

[0025] As used herein, "consisting essentially of" means that the respective composition is primarily composed of at least 50% by weight, e.g., at least 60, 70 or 80%, of the referenced components, e.g., in the case of the present invention, the recited components (A), (B), (C) and (D), and optionally fillers and / or plasticizers, as described below in the case of the compositions of the present invention.

[0026] As used herein, "alkyl" refers to saturated aliphatic hydrocarbons, including straight-chain and branched-chain groups. The alkyl group preferably has 1-10 carbon atoms (when a numerical range is given herein, e.g., "1-10", this means that the group, in this case the alkyl group, may have up to 10 carbon atoms, 1 carbon atom, 2 carbon atoms, 3 carbon atoms, ... etc.). In particular, the alkyl may be a middle alkyl having 5-6 carbon atoms, or a lower alkyl having 1-4 carbon atoms, e.g., methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, tert-butyl, etc. The alkyl group may be substituted or unsubstituted (not substituted). As used in this context, "substituted" means that one or more carbon and / or hydrogen atoms of the alkyl group are replaced with a heteroatom or a functional group. Functional groups that may replace hydrogen atoms are, in particular, =O, =S, -OH, -SH, -NH2, -N(C 1-10 alkyl)2, e.g. -N(CH3)2, -NO2, -CN, -F, -Cl, -Br, -I, -COOH, -CONH2, -OCN, -NCO, C 3-8 Cycloalkyl, C 6-14aryl, a 5-10 membered heteroaryl ring in which 1-4 ring atoms are independently nitrogen, oxygen, or sulfur, and a 5-10 membered heteroalicyclic ring in which 1-3 ring atoms are independently nitrogen, oxygen, or sulfur. Substituted alkyl includes, for example, alkylaryl groups. Heteroalkyl groups in which one or more carbon atoms are substituted with a heteroatom, particularly selected from O, S, N, and Si, are obtained by replacing one or more carbon atoms with a heteroatom, preferably the substituted carbon does not link the group to the remainder of the molecule. Examples of such heteroalkyl groups include, but are not limited to, methoxymethyl, ethoxyethyl, propoxypropyl, methoxyethyl, isopentoxypropyl, ethylaminoethyl, trimethoxypropylsilyl, and the like. "Alkoxy" refers to an alkyl group (as defined herein) attached to the remainder of the molecule via -O-. Thus, each term includes groups such as methoxy and ethoxy.

[0027] "Alkenyl" refers to an alkyl group, as defined herein, consisting of at least two carbon atoms and at least one carbon-carbon double bond, such as ethenyl, propenyl, butenyl, or pentenyl, and structural isomers thereof, such as 1- or 2-propenyl, 1-, 2-, or 3-butenyl, etc. An alkenyl group may be substituted or unsubstituted. If substituted, the substituents are as defined above for alkyl. "Alkenyloxy" refers to an alkenyl group, as defined herein, attached to the remainder of the molecule through -O-. Thus, each term includes enoxy groups, such as vinyloxy (HC=CH-O-).

[0028] As used herein, "alkynyl" refers to an alkyl group, as defined herein, consisting of at least two carbon atoms and at least one carbon-carbon triple bond, such as ethynyl (acetylene), propynyl, butynyl, or petynyl, and their structural isomers as described above. Alkynyl groups may be substituted or unsubstituted. If they are substituted, the substituents are as defined above for alkyl. "Alkynyloxy" refers to an alkynyl group, as defined herein, attached to the remainder of the molecule via -O-.

[0029] As used herein, "alicyclic group" or "cycloalkyl group" refers specifically to monocyclic or polycyclic groups (several rings having a common carbon atom) of 3 to 8 carbon atoms in which the rings do not have a completely conjugated pi-electron system, e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, and the like. Cycloalkyl groups can be substituted or unsubstituted. "Substituted" as used in this respect means that one or more hydrogen atoms of the cycloalkyl group are replaced by a functional group. Functional groups that may replace hydrogen atoms include, inter alia, =O, =S, -OH, -SH, -NH2, -NO2, -CN, -F, -Cl, -Br, -I, -COOH, -CONH2, -OCN, -NCO, -C, -C-C-H, -C-H ... 1-10 Alkyl, C 2-10 Alkenyl, C 2-10 Alkynyl, C 3-8 Cycloalkyl, C 6-14 and a 5-10 membered heteroaryl ring in which one to four ring atoms are independently nitrogen, oxygen, or sulfur. "Cycloalkyloxy" refers to a cycloalkyl group, as defined herein, attached to the remainder of the molecule through -O-.

[0030] As used herein, "aryl" refers specifically to a monocyclic or polycyclic group (i.e., rings having a common adjacent carbon atom) of 6 to 14 carbon ring atoms having a completely conjugated pi-electron system. Examples of aryl groups are phenyl, naphthalenyl, and anthracenyl. Aryl groups may be substituted or unsubstituted. If substituted, the substituents are as defined above for cycloalkyl. "Aryloxy" refers to an aryl group, as defined herein, attached to the remainder of the molecule via -O-.

[0031] As used herein, a "heteroaryl" group specifically refers to a monocyclic or polycyclic (i.e., rings which share adjacent pairs of ring atoms) aromatic rings having from 5 to 10 ring atoms, in which 1, 2, 3, or 4 ring atoms are nitrogen, oxygen, or sulfur, and the remainder are carbon. Examples of heteroaryl groups include pyridyl, pyrrolyl, furyl, thienyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyrazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, 1,3,4-triazinyl, 1,2,3-triazinyl, benzofuryl, isobenzofuryl, benzothienyl, benzotriazolyl, isobenzothienyl, indolyl, isoindolyl, 3H-indolyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, quinolidinyl, quinazolinyl, phthalazinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, Heteroaryl groups are quinolyl, isoquinolyl, tetrazolyl, 5,6,7,8-tetrahydroquinolyl, 5,6,7,8-tetrahydroisoquinolyl, purinyl, pteridinyl, pyridinyl, pyrimidinyl, carbazolyl, xanthenyl, or benzoquinolyl. Heteroaryl groups can be substituted or unsubstituted. If substituted, the substituents are as defined above for cycloalkyl. "(Hetero)aryl" refers to both aryl and heteroaryl groups as used herein, as defined herein. "Heteroaryloxy" refers to a heteroaryl group as defined herein attached to the remainder of the molecule via -O-.

[0032] A "heteroalicyclic group" or "heterocycloalkyl group" as used herein refers to a monocyclic or fused ring having 5 to 10 ring atoms containing 1, 2, or 3 heteroatoms selected from N, O, and S (the remaining ring atoms are carbon). A "heterocycloalkenyl" group further contains one or more double bonds. However, the ring does not have a completely conjugated pi-electron system. Examples of heteroalicyclic groups are pyrrolidinone, piperidine, piperazine, morpholine, imidazolidine, tetrahydropyridazine, tetrahydrofuran, thiomorpholine, tetrahydropyridine, and the like. A heterocycloalkyl group may be substituted or unsubstituted. If substituted, the substituents are as defined above for cycloalkyl. "Heteroalicyclic" refers to a heteroalicyclic group as defined herein attached to the remainder of the molecule via -O-.

[0033] Combinations of the foregoing groups include, for example, alkylaryl or arylalkyl groups, etc. In such combinations, each group may be substituted or unsubstituted as defined above.

[0034] The curable composition of the present invention contains as component (A) at least one polyorganosiloxane end-capped with a silane group of formula (I). Such a polymer is obtained by providing at least one polyorganosiloxane having at least one hydroxy group bonded to a silicon atom. Preferably, the polyorganosiloxane has at least two hydroxy groups bonded to the silicon atom. Furthermore, hydroxy groups or hydroxy groups bonded to terminal silicon atoms are even more preferred. If the polyorganosiloxane is branched, it preferably has a hydroxy group at each end. Thus, although the present invention is directed to polymers having a silane group of formula (I) at only one end, it is preferred that all polymer chain ends are end-capped with said group, i.e., a linear polymer will have two terminal silane groups. If the polymer is branched, it is preferred that each end is end-capped with a group of formula (I).

[0035] The polyorganosiloxane having at least one hydroxy group bonded to a silicon atom is preferably a polydiorganosiloxane, preferably a polydimethylsiloxane.

[0036] Thus, preferably, α,ω-dihydroxy-terminated polydiorganosiloxanes, in particular α,ω-dihydroxy-terminated polydimethylsiloxanes, are used as polyorganosiloxanes having at least one hydroxy group bonded to a silicon atom. Particularly preferred are α,ω-dihydroxy-terminated polydimethylsiloxanes having a kinematic viscosity at 25° C. of 5000 to 120,000 cSt, in particular 10,000 to 100,000 cSt, and particularly preferably 50,000 to 90,000 cSt.

[0037] The polyorganosiloxane may be attached to the end groups of formula (I) through a variety of different linking groups A. In various embodiments, A is a direct covalent bond, -O-, an oxyalkylene, such as -O-CH- or -O-(CH)-, or a siloxane-alkylene, preferably of the formula -(CH) 1-10 -(Si(Alk)2-O-Si(Alk)2) 1-10 -(CH2) 1-10 Siloxane-alkylene (Alk is C 1-10 A is a linear or branched divalent radical selected from the group consisting of alkyl, preferably methyl, or derivatives thereof. A is a linear or branched divalent radical selected from the group consisting of alkyl, preferably methyl, or derivatives thereof. 1-10 -(Si(Alk)2-O-Si(Alk)2) 1-10 -(CH2) 1-10 When it is a siloxane alkylene, it is preferably selected from -(CH2)2-Si(CH3)2-O-Si(CH3)2-(CH2)2-.

[0038] Alternatively, in various embodiments, the polyorganosiloxane may be -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 A may be linked to the end group of formula (I) through a moiety selected from (=O)-S-, -C(=O)-S-, -SC(=O)-, -SC(=O)-S-, -C(=O)-, -S-, -O-, and -NR'-, where R' may be a hydrocarbon moiety having 1 to 6 carbon atoms, preferably C1-C2 alkyl or hydrogen, optionally substituted with hydrogen or halogen. In such an embodiment, A may consist of the aforementioned groups, preferably -CH2- or -(CH2)3-, optionally substituted, optionally further bonded to a divalent alkylene group having 1 to 10 carbon atoms, optionally interrupted by a heteroatom. When such an alkylene group is present, the orientation is such that the alkylene group is bonded to the silicon atom of the end group of formula (I), while the above functional group is bonded to the terminal silicon atom of the polymer chain, i.e. the complete linker -A- is -OC(=O)-NH-C 1-10 Alkylene- or -OC 1-10 It may be alkylene-.

[0039] To obtain the polymer (A), the polyorganosiloxane having at least one reactive group A'(Ia) may be reacted with a suitable silane crosslinker to produce the desired polymer (A). Typically, the crosslinker is a silane of formula (Ib). [ka] where C is a reactive group that reacts with an end group of the polymer, typically -OH or amino or isocyanate, to produce a linking group -A-. In various embodiments, the reactive group C is a leaving group, preferably R 2 or R 3In a preferred embodiment, C is a leaving group which upon reaction with the terminal reactive group A' of the polyorganosiloxane (Ia) produces the linker group -A-.

[0040] Suitable reactions are known and are also called endcapping. These can be carried out optionally in the presence of a catalyst, which selectively mediates endcapping without simultaneously curing the polyorganosiloxane. Suitable catalysts are, for example, acids, organolithium compounds, amines, inorganic oxides, potassium acetate, organotitanium derivatives, titanium / amine combinations, and carboxylic acid / amine combinations, as described in EP-A-0564253.

[0041] The catalyst can be, in various embodiments, a specific catalyst of formula (Id), whereby the catalyst selectively mediates endcapping without simultaneously curing the polyorganosiloxane.

[0042] The catalyst may be a compound of formula (Id): [ka] During the ceremony, R 11 is an alkylene group, preferably C-C, optionally interrupted by a heteroatom. 10 alkylene, more preferably C1 or C3 alkylene; Each R 12 is independently selected from the group consisting of hydrogen, halogen, amino, substituted or unsubstituted alkyl, alkenyl, alkynyl, alicyclic, aryl, heteroaryl, and heteroalicyclic groups or combinations thereof; Each R 13 is independently selected from the group consisting of substituted or unsubstituted alkyl, alkenyl, alkynyl, or acyl groups; q independently represents 0, 1, or 2; and D is a nitrogen-containing group selected from the group of formula (Ie), (If) or (Ig): [ka] During the ceremony, Each R 14 are independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, alicyclic, aryl, heteroaryl, and heteroalicyclic groups, or combinations thereof; Each R 14a , R 14b , R 14c , R 15 and R 16 is independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, alicyclic, aryl, heteroaryl, and heteroalicyclic groups, or combinations thereof; and r is 1, 2, 3, or 4.

[0043] In various embodiments, the catalyst (Id) is a compound in which q is 0 or 1, preferably 0.

[0044] R 13 is an unsubstituted alkyl group, preferably C 1-3 It may be an alkyl group, more preferably methyl or ethyl.

[0045] In various embodiments of the catalyst, R 11 is a C1-C6 alkylene which may be branched or linear, preferably a C1 or C3 alkylene, more preferably propylene.

[0046] In various embodiments, D is a group of formula (Ie) and R 14 One of the groups is hydrogen and the other is an unsubstituted alkyl, preferably C 1-4 Alkyl, for example methyl, ethyl, propyl or butyl (including isopropyl and isobutyl).

[0047] In other various embodiments, D is a group of formula (If) and R 14b and R 14cEach of is hydrogen or unsubstituted alkyl, preferably C 1-4 alkyl, such as methyl, ethyl, propyl, or butyl (including isopropyl and isobutyl). In such embodiments, R 14a R may be hydrogen. 14a , R 14b and R 14c When none of are hydrogen, it may be preferred that at least one of these groups contains a CH moiety alpha to the carbon / nitrogen atom to which it is attached.

[0048] In various embodiments, in the group of formula (Ie), R 14 If none of R is hydrogen, then at least one R 14 contains a C-H moiety alpha to the carbon atom to which it is attached.

[0049] In various embodiments, r in the group of formula (Ig) is 1, 2, 3 or 4, preferably 1 or 2.

[0050] The catalyst (Id) may be used in any amount suitable to ensure sufficient formation of the desired polyorganosiloxane of formula (I). Typical amounts range from 0.05 to 1.5% by weight, preferably from 0.1 to 1.0% by weight, or from 0.2 to 0.8% by weight, based on the total amount of polyorganosiloxane (Ia) and compounds of formulae (Ib) and (Ic).

[0051] Various embodiments of the endcapped curable polyorganosiloxanes, optionally obtained by reacting polyorganosiloxane (Ia) with a compound of formula (Ib) in the presence of a catalyst of formula (Id), are described below.

[0052] In the group of formula (I), each R 1 represents independently a substituted or unsubstituted alkyl, alkenyl, or alkynyl group; a substituted or unsubstituted alicyclic or aryl group; or a substituted or unsubstituted heteroalicyclic or heteroaryl group. Alternatively or additionally, one or more R 1may represent hydrogen, halogen, amino, oxyimino, alkenyloxy, alkylnyloxy, alicyclic-O-, aryloxy, heteroaryloxy, heteroalicyclicoxy, acyl, acyloxy, or combinations thereof.

[0053] In various embodiments, each R 1 represent, independently of one another, an alkyl group having 1 to 10 carbon atoms, in particular methyl, ethyl, propyl or isopropyl, an alkenyl group having 2 to 10 carbon atoms, in particular vinyl or allyl, or an aryl group having 6 to 10 carbon atoms, in particular phenyl, or an aryloxy group having 6 to 14 carbon atoms, or an acyloxy group having 2 to 10 carbon atoms, preferably acetoxy, oxyimino, alkenyloxy having 2 to 10 carbon atoms, or amino.

[0054] In certain embodiments, each R 1 independently represents methyl, vinyl, or phenyl, with methyl and vinyl being particularly preferred.

[0055] In formula (I), each R 2 each independently represents a group of general formula (2): [ka] During the ceremony, Y is a substituted or unsubstituted (hetero)aromatic group having 4 to 14 ring atoms, a substituted or unsubstituted saturated or partially unsaturated 4 to 14 membered (hetero)cyclic group, or -(C(R 5 )2) O - is; R 4 is a substituted or unsubstituted alkyl, alkenyl, alkynyl, alicyclic, aryl, heteroaryl, and heteroalicyclic group, or combinations thereof; Each R 5 is independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, alicyclic or aryl groups; and o is an integer of 1 to 10, preferably 1 to 5, and more preferably 1 or 2.

[0056] In various embodiments, each R 2 represent, independently of one another, a group of formula (2), R 4 represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, in particular 1 to 4 carbon atoms, particularly preferably methyl or ethyl. In some embodiments, Y represents a substituted or unsubstituted aromatic group having 6 carbon ring atoms, preferably 1,2-phenylene, or -(C(R 5 )2) o -, o is 1, and R 5 One of the groups is hydrogen and the second R 5 The radical is a substituted or unsubstituted alkyl radical having 1 to 10 carbon atoms, in particular methyl, carboxymethyl or its (alkyl) esters, such as ethylcarboxymethyl.

[0057] In various embodiments, each R 2 represent, independently of one another, a lactate ester, preferably the ethyl ester, or a malic acid mono- or diester, preferably the mono- or diethyl ester.

[0058] In other embodiments, each R 2 is derived from salicylic acid, i.e. Y is 1,2-phenylene. The salicylic acid group is an ester, for example a methyl ester or an ethyl ester, preferably the ethyl ester.

[0059] In various embodiments, each R 3 represent, independently of one another, a radical of the general formula (3): [ka]

[0060] In various embodiments, Y is as defined above; R 6is the group consisting of hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, alicyclic, aryl, heteroaryl, and heteroalicyclic groups or combinations thereof, or R 7 and R 7 is a group of general formula (4): [ka] During the ceremony, R 8 is an alkylene group optionally interrupted by a heteroatom such as O, N, S or Si, preferably C 1-10 or C 1-8 an alkylene group, more preferably a C1-C3 alkylene group, most preferably a methylene (CH2) or propylene ((CH2)3) group; Each R 9 is independently selected from the group consisting of hydrogen, halogen, amino, substituted or unsubstituted alkyl, alkenyl, alkynyl, alicyclic, aryl, heteroaryl, and heteroalicyclic groups, or combinations thereof; Each R 10 is independently selected from the group consisting of a substituted or unsubstituted alkyl, alkenyl, alkynyl, or acyl group, preferably an unsubstituted lower alkyl, more preferably methyl or ethyl; and Each p independently represents 0, 1 or 2, preferably 0 or 1, and more preferably 0.

[0061] In various embodiments, in the radical of formula (3), Y is as defined for the radical of formula (2) above, i.e., Y is a substituted or unsubstituted aromatic group having six carbon ring atoms, preferably 1,2-phenylene or -(C(R 5 )2) o -, where o is 1 and R 5 One of the groups is hydrogen and the second R 5 The radical is a substituted or unsubstituted alkyl radical having 1 to 10 carbon atoms, in particular methyl, carboxymethyl or their (alkyl) esters, such as ethylcarboxymethyl.

[0062] In various embodiments, R 6 represents preferably hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, preferably an unsubstituted alkyl group having 1 to 10 carbon atoms, more preferably an unsubstituted alkyl group having 1 to 6 carbon atoms, even more preferably an unsubstituted alkyl group having 1 to 4 carbon atoms, or hydrogen.

[0063] In various embodiments, R 8 is preferably of the formula -(CH2) 1-8 -, more preferably -(CH2) 1-5 -, even more preferably -(CH2) 1-3 and most preferably an alkylene group of the form -CH2- or -(CH2)3-.

[0064] In various embodiments, each R 9 denote, independently of one another, a substituted or unsubstituted alkyl group, preferably having 1 to 10 carbon atoms, in particular an unsubstituted alkyl group having 1 to 10 carbon atoms, in particular having 1 to 4 carbon atoms, particularly preferably methyl or ethyl.

[0065] In various embodiments, each R 10 denote, independently of one another, a substituted or unsubstituted alkyl radical, preferably having 1 to 10 carbon atoms, in particular an unsubstituted alkyl radical having 1 to 10 carbon atoms, in particular having 1 to 4 carbon atoms, particularly preferably methyl or ethyl, most preferably methyl.

[0066] Preferably, each R 3 represent, independently of each other, a radical of formula (3), where Y is a substituted or unsubstituted aromatic radical having 6 carbon ring atoms, preferably 1,2-phenylene or -C(R 5 )2) o-, o is 1, and R 5 One of the groups is hydrogen and the second R 5 The group is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, in particular methyl, carboxymethyl or its (alkyl) esters, R 6represents hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, in particular 1 to 4 carbon atoms, and R 7 represents a group of formula (4), where R 8 is C 1-10 an alkylene group, preferably a C1 or C3 alkylene group, and each R 9 are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, in particular having 1 to 4 carbon atoms, particularly preferably methyl or ethyl, and each R 10 represent, independently of one another, a substituted or unsubstituted alkyl radical having 1 to 10 carbon atoms, in particular having 1 to 4 carbon atoms, particularly preferably methyl or ethyl; p is 0 or 1, preferably 0.

[0067] In a first embodiment, n and m in formula (I) are selected such that the sum of n+m is 3. In this case, the silane of formula (I) is R 3 It does not contain a group, i.e. it does not contain a hydroxycarboxylic acid amide group.Preferred silane groups of formula (I) in this case are selected from methylbis(ethyllactato)silane, ethylbis(ethyllactato)silane, phenylbis(ethyllactato)silane, vinylbis(ethyllactato)silane, tri(ethyllactato)silane, methylbis(ethylsalicylate)silane, ethylbis(ethylsalicylate)silane, phenylbis(ethylsalicylate)silane, vinylbis(ethylsalicylate)silane, tri(ethylsalicylate)silane, methylbis(diethylmalato)silane, ethylbis(diethylmalato)silane, phenylbis(diethylmalato)silane, vinylbis(diethylmalato)silane, tri(diethylmalato)silane and mixtures thereof.

[0068] In a second embodiment, n and m in formula (I) are selected such that the sum n+m is 2. In this case, the silane of formula (I) contains at least one R 3group, i.e. at least one hydroxycarboxylic acid amide group. Preferred silanes of formula (I) in this case are selected from the compounds obtained by selective amidation of methylbis(ethyllactato)silane, ethylbis(ethyllactato)silane, phenylbis(ethyllactato)silane, vinylbis(ethyllactato)silane, tri(ethyllactato)silane, methylbis(ethylsalicylato)silane, ethylbis(ethylsalicylato)silane, phenylbis(ethylsalicylato)silane, vinylbis(ethylsalicylato)silane, tri(ethylsalicylato)silane, methylbis(diethylmalato)silane, ethylbis(diethylmalato)silane, phenylbis(diethylmalato)silane, vinylbis(diethylmalato)silane, tri(diethylmalato)silane and mixtures thereof with amines of formula (5): [ka] In the formula, p, R 6 , R 8 , R 9 and R 10 have the abovementioned general, preferred and particularly preferred meanings, independently of each other in each case. Particularly preferably, this relates to the amidation products of methylbis(ethyllactato)silane, ethylbis(ethyllactato)silane, phenylbis(ethyllactato)silane, vinylbis(ethyllactato)silane, tri(ethyllactato)silane, methylbis(ethylsalicylate)silane, ethylbis(ethylsalicylate)silane, phenylbis(ethylsalicylate)silane, vinylbis(ethylsalicylate)silane, tri(ethylsalicylate)silane, methylbis(diethylmalato)silane, ethylbis(diethylmalato)silane, phenylbis(diethylmalato)silane, vinylbis(diethylmalato)silane, tri(diethylmalato)silane and mixtures thereof with 3-aminopropyltrimethoxysilane and / or 3-aminopropyltriethoxysilane.

[0069] In various embodiments, the curable composition contains polyorganosiloxane (A) in an amount of 32 to 97% by weight, particularly preferably in an amount of 40 to 70% by weight, in each case based on the total weight of the composition. If a mixture of polyorganosiloxanes is used, the amount relates to the total amount of polyorganosiloxanes in the composition. If such a mixture is used, only one of the polyorganosiloxanes need be a polyorganosiloxane as described herein. However, it is preferred that essentially all of the polyorganosiloxanes used in the composition, i.e. at least 50% by weight, preferably at least 70 or 80% by weight, are as described herein.

[0070] The curable composition contains as component (B) at least one adhesion promoter.

[0071] The compositions described herein may contain up to about 20% by weight of conventional adhesion promoters (tackifiers). Suitable as adhesion promoters are, for example, resins, terpene oligomers, coumarone / indene resins, aliphatic petrochemical resins, and modified phenolic resins. Suitable within the context of the present invention are, for example, hydrocarbon resins such as those obtained by polymerization of terpenes, mainly α- or β-pinene, dipentene, or limonene. These monomers are generally polymerized cationically by initiation using Friedel-Crafts catalysts. Terpene resins also include, for example, copolymers of terpenes with other monomers, for example styrene, α-methylstyrene, isoprene, etc. The aforementioned resins are used, for example, as adhesion promoters in contact adhesives and coating materials. Also suitable are terpene-phenolic resins, which are prepared by acid-catalyzed addition of phenols to terpenes or rosins. Terpene-phenolic resins are soluble in most organic solvents and oils and are miscible with other resins, waxes, and natural rubbers. Also suitable as additives in the aforementioned sense within the context of the present invention are rosin resins and their derivatives, for example their esters.

[0072] Also suitable are silane adhesion promoters, especially alkoxysilanes, which have (further) functional groups, such as, for example, amino, mercapto, epoxy, carboxyl, vinyl, isocyanate, isocyanurate groups or halogens. Examples are γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis(2-methoxyethoxy)silane, N-β-(carboxymethyl)aminoethyl-γ-aminopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-acroyloxypropylmethyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, tris(trimethoxysilyl)isocyanurate, and γ-chloropropyltrimethoxysilane.

[0073] In various embodiments, the adhesion promoter is selected from the group consisting of aminosilanes, more preferably 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, aminomethyltrimethoxysilane, aminomethyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, (N-2-aminoethyl)-3-aminopropyltrimethoxysilane, (N-2-aminoethyl)-3-aminopropyltriethoxysilane, diethylenetriaminopropyltrimethoxysilane, phenylaminomethyltrimethoxysilane, phenylaminomethyltrimethoxysilane, phenylaminomethyltriethoxy ... Silanes, (N-2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-(N-phenylamino)propyltrimethoxysilane, 3-piperazinylpropylmethyldimethoxysilane, 3-(N,N-dimethylaminopropyl)aminopropylmethyldimethoxysilane, tri[(3-triethoxysilyl)propyl]amine, tri[(3-trimethoxysilyl)propyl]amine, and their oligomers, 3-(N,N-dimethylamino)propyltrimethoxysilane, 3-(N,N-dimethylamino)propyltrimethoxysilane, Pyrtriethoxysilane, (N,N-dimethylamino)methyltrimethoxysilane, (N,N-dimethylamino)methyltriethoxysilane, 3-(N,N-diethylamino)propyltrimethoxysilane, 3-(N,N-diethylamino)propyltriethoxysilane, (N,N-diethylamino)methyltrimethoxysilane, (N,N-diethylamino)methyltriethoxysilane, bis(3-trimethoxysilyl)propylamine, bis(3-triethoxysilyl)propylamine, 4-amino-3,3-dimethylbutyric acid From the group consisting of 3-aminopropyltri(meth)ethoxysilane, aminomethyltri(meth)ethoxysilane, 3-(N,N-dimethylamino)propyltri(meth)ethoxysilane, (N,N-dimethylamino)methyltri(meth)ethoxysilane, 3-(N,N-diethylamino)propyltri(meth)ethoxysilane, (N,N-diethylamino)methyltri(meth)ethoxysilane, 4-amino-3,3-dimethylbutyltriethoxysilane and mixtures thereof, particularly preferred are 3-aminopropyltri(meth)ethoxysilane, aminomethyltri(meth)ethoxysilane, 3-(N,N-dimethylamino)propyltri(meth)ethoxysilane, (N,N-diethylamino)methyltri(meth)ethoxysilane, 4-amino-3,It may be selected from the group of 3-dimethylbutyltri(methoxy)ethoxysilane and bis(3-tri(meth)ethoxysilyl)propylamine. "(meth)ethoxy" as used herein refers to methoxy and ethoxy. Thus, "aminopropyltri(meth)ethoxysilane" refers to both aminopropyltrimethoxysilane and aminopropyltriethoxysilane.

[0074] In various embodiments, the compositions of the present invention comprise at least one of the aminosilanes described above, particularly one of the tertiary aminosilanes. As used herein, "tertiary aminosilane" refers to an aminosilane in which the nitrogen atom of the amino group is covalently bonded to three non-hydrogen groups. In various embodiments, the aminosilane is selected from the group consisting of tri[(3-tri(meth)ethoxysilyl)propyl]amine and oligomers thereof, 3-(N,N-dimethylamino)propyltri(meth)ethoxysilane, (N,N-dimethylamino)methyltri(meth)ethoxysilane, 3-(N,N-diethylamino)propyltri(meth)ethoxysilane, (N,N-diethylamino)methyltri(meth)ethoxysilane, bis(3-tri(meth)ethoxysilyl)propylamine, and mixtures thereof, particularly preferably from the group of 3-(N,N-dimethylamino)propyltri(meth)ethoxysilane, (N,N-dimethylamino)methyltri(meth)ethoxysilane, 3-(N,N-diethylamino)propyltri(meth)ethoxysilane, and (N,N-diethylamino)methyltri(meth)ethoxysilane.

[0075] In various preferred embodiments, the adhesion promoter used may be a capped adhesion promoter of formula (II): [ka] During the ceremony, R 11 is an alkylene group, preferably C1-C2, optionally interrupted by a heteroatom such as O, N, S or Si. 10 alkylene, more preferably C1 or C3 alkylene; Each R12 is independently selected from the group consisting of hydrogen, halogen, amino, substituted or unsubstituted alkyl, alkenyl, alkynyl, alicyclic, aryl, heteroaryl, and heteroalicyclic groups or combinations thereof; Each R 13 is independently selected from the group consisting of substituted or unsubstituted alkyl, alkenyl, alkynyl or acyl groups, preferably ethyl; q independently represents 0, 1, or 2; and B is a nitrogen-containing group selected from the group of formulas (6), (7), (8) or (9): [ka] In the formula, each R 14 , R 14a , R 14b , R 14c , R 15 and R 16 is independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, alicyclic, aryl, heteroaryl, and heteroalicyclic groups, or combinations thereof; r is 1, 2, 3, or 4; R 17 -Si(R 19 ) 3 are selected; R 18 -Si(R 19 )3, selected from hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, alicyclic, aryl, heteroaryl and heteroalicyclic groups, or combinations thereof; and Each R 19 are independently selected from hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, alicyclic, or aryl groups, or combinations thereof; or R 17 and R 18 are bonded together with the nitrogen atom to which they are attached to form a group of the formula -Si(R 19 )2-C 2-3 Alkylene-Si(R 19 )2-group.

[0076] The terms "blocked" and "capped" in relation to compounds of formula (II) are used interchangeably herein. Additionally, compounds of formula (II) are referred to herein as blocked / capped adhesion promoters. "Blocked," as used herein in relation to compounds of formula (II), refers to the fact that said compounds are derivatized such that the active compound is released only upon contact with water and / or oxygen.

[0077] In various embodiments, in formula (6), one R 14 is hydrogen or methyl, preferably hydrogen, and the other R 14 is an unsubstituted alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, such as isobutyl or methyl, or an unsubstituted aryl group, preferably phenyl.

[0078] In various embodiments, in formula (7), R 14a and R 14b And one R 14c is hydrogen or methyl, preferably hydrogen, and the other R 14c is an unsubstituted alkyl group having 1 to 10 carbon atoms, preferably having 1 to 4 carbon atoms, or an unsubstituted aryl group, preferably phenyl.

[0079] In various embodiments, in formula (8), R 15 and R 16 is hydrogen. In other embodiments, one is hydrogen and the other is alkyl, preferably C-C 10 In another embodiment, R in formula (8) is an alkyl, such as 3-heptyl or 2-propyl, an aryl or an alkylaryl having up to 15 carbon atoms, such as 2-(1-(4-tert)-butyl-phenyl)propyl. 15 and R 16 are not both hydrogen and may preferably be selected from the group described above.

[0080] In formula (8), r is preferably 1 or 2, and more preferably 1.

[0081] In formula (9), R 17 -Si(R 19 )3, and each R 19 are preferably independently hydrogen, unsubstituted alkyl, more preferably C 1-4 R is an alkyl group such as ethyl or methyl, or an alkylene group such as vinyl. 18 is preferably hydrogen, -Si(R 19 )3, alkyl such as propylene or methylene substituted with -Si(R 19 )3, preferably -Si(R 19 ) 3 (each R 19 are independently unsubstituted alkyl, preferably methyl or ethyl, more preferably methyl, or alkylene, such as vinyl. Generally, one R 19 If is hydrogen, then the other R 19 The group is preferably not hydrogen. 17 Preferred groups include, but are not limited to, SiH(CH), Si(CH)(CH=CH), -Si(CH)(CH), and -Si(CH). In such embodiments, q can be 0 or 1, and R 11 is preferably propylene, and R 12 may be methyl, if present, and R 13 may be methyl or ethyl, preferably ethyl.

[0082] In another preferred embodiment, R 17 and R 18 are bonded together with the nitrogen atom to which they are attached to form a compound of the formula -Si(R 19 )2-C 2-3 Alkylene-Si(R 19 )2-, especially -Si(R 19 )2-(CH2)2-Si(R 19 )2- group (R 19 is an unsubstituted alkyl, preferably methyl or ethyl, more preferably methyl, or vinyl.

[0083] In various embodiments, the capped adhesion promoter is a ketimine of formula (II), q is 0, and R 11 is methylene or propylene, preferably propylene, and each R 13 is ethyl and B is a group of formula (6), (i) One R 14 is methyl, and the second R 14 is isobutyl or methyl; or (ii) One R 14 is hydrogen, and the second R 14 is phenyl.

[0084] In various other embodiments, the capped adhesion promoter is a silazane of formula (II), q is 0, and R 11 is methylene or propylene, preferably propylene, and each R 13 is ethyl or methyl, preferably ethyl, B is a group of formula (9), R 17 -Si(R 19 )3, and R 18 is hydrogen, -Si(R 19 )3 substituted alkyl or -Si(R 19 )3, preferably -Si(R 19 ) 3 (each R 19 is independently alkyl, preferably methyl or ethyl, more preferably methyl. In various alternative embodiments, at least one R 19 may be alkylene, preferably vinyl.

[0085] The curable composition preferably contains the capped adhesion promoter in an amount of from about 0.1 to about 5 weight percent, preferably from 0.3 to 2 weight percent, in each case based on the total weight of the composition. When a mixture of capped adhesion promoters is used, the amount refers to the total amount of such capped adhesion promoters in the composition.

[0086] In various embodiments, the amount of uncapped adhesion promoter may be minimized. In contrast to conventional aminosilanes, such capped adhesion promoters are less susceptible to side reactions. Thus, the present invention encompasses embodiments in which no additional adhesion promoter is added beyond the capped adhesion promoter of formula (II).

[0087] The curable composition comprises as component (C) at least one curing catalyst.

[0088] In various embodiments, the curing catalyst may be a tin compound, preferably an organic tin compound or an inorganic tin salt. The tin in these tin compounds is preferably divalent or tetravalent. Component (C) is added to the composition in particular as a crosslinking catalyst. Suitable inorganic tin salts are, for example, tin(II) chloride and tin(IV) chloride. However, organic tin compounds (tin organyls) are preferably used as the tin compounds. Suitable organic tin compounds are, for example, 1,3-dicarbonyl compounds of divalent or tetravalent tin, such as acetylacetonates, such as di(n-butyl)tin(IV) di(acetylacetonate), di(n-octyl)tin(IV) di(acetylacetonate), (n-octyl)(n-butyl)tin(IV) di(acetylacetonate); dialkyltin(IV) dicarboxylates, such as di-n-butyltin dilaurate, di-n-butyltin maleate ... tin(II) carboxylates, such as tin(II) octoate, di-n-butyltin diacetate, di-n-octyltin dilaurate, di-n-octyltin diacetate, or the corresponding dialkoxylates, such as di-n-butyltin dimethoxide; oxides of tetravalent tin, such as dialkyltin oxides, for example di-n-butyltin oxide and di-n-octyltin oxide; and tin(II) carboxylates, such as tin(II) octoate or tin(II) phenolate.

[0089] Further suitable are tin compounds such as ethyl silicate, dimethyl maleate, diethyl maleate, dioctyl maleate, dimethyl phthalate, diethyl phthalate, dioctyl phthalate, for example di(n-butyl)tin(IV) di(methyl maleate), di(n-butyl)tin(IV) di(butyl maleate), di(n-octyl)tin(IV) di(methyl maleate), di(n-octyl)tin(IV) di(maleate), di(isooctyl)tin(IV) maleate; and di(n-butyl)tin(IV) sulfide, (n-butyl)2Sn(SCH2COO), (n-octyl)2Sn(SCH2COO), (n-octyl)2Sn(SCH2CH2COO), (n-octyl)2Sn(SCH2CH2COOCH2CH2OCOCH2S), (n-butyl)2-Sn(SCH2COO-i-CH8H 17 )2, (n-octyl)2Sn(SCH2COO-i-C8H 17 )2, and (n-octyl)2Sn(SCH2COO-n-CH 17 )2.

[0090] Preferably, the tin compound is selected from 1,3-dicarbonyl compounds of divalent or tetravalent tin, dialkyltin(IV) dicarboxylates, dialkyltin(IV) dialkoxylates, dialkyltin(IV) oxides, tin(II) carboxylates, and mixtures thereof.

[0091] Particularly preferably, the tin compound is a dialkyltin(IV) dicarboxylate, in particular di-n-butyltin dilaurate or di-n-octyltin dilaurate.

[0092] Additionally or alternatively, other metal-based condensation catalysts may be used, including, but not limited to, compounds of titanium, such as organotitanates or chelate complexes, cerium compounds, zirconium compounds, molybdenum compounds, manganese compounds, copper compounds, aluminum compounds, or zinc compounds or their salts, alkoxylates, chelate complexes, or catalytically active compounds of main groups, or salts of bismuth, lithium, strontium, or boron.

[0093] Further suitable (tin-free) curing catalysts are, for example, organometallic compounds of iron, in particular 1,3-dicarbonyl compounds of iron, such as, for example, iron(III) acetylacetonate.

[0094] Boron halides, such as boron trifluoride, boron trichloride, boron tribromide, boron triiodide, or mixtures of boron halides, may also be used as curing catalysts. Particularly preferred are boron trifluoride complexes, such as boron trifluoride diethyl etherate, which, as liquids, are easier to handle than gaseous boron halides.

[0095] Furthermore, amines, nitrogen heterocycles, and guanidine derivatives are generally suitable for catalysis. A particularly suitable catalyst from this group is 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

[0096] Titanium, aluminum, and zirconium compounds, or mixtures of one or more catalysts from one or more of the above groups, may also be used as catalysts.

[0097] Suitable titanium catalysts are compounds having hydroxy groups and / or substituted or unsubstituted alkoxy groups, and thus titanium alkoxides of the general formula: Ti(OR Z )4 In the formula, R z is an organic group, preferably a substituted or unsubstituted hydrocarbon group having 1 to 20 C atoms, z are the same or different. In addition, one or more OR z The group is an acyloxy group -OCOR z may be substituted.

[0098] Also suitable as titanium catalysts are titanium alkoxides in which one or more alkoxy groups are replaced by hydroxy groups or halogen atoms.

[0099] Additionally, titanium chelate complexes may be used.

[0100] Aluminum catalysts may also be used as curing catalysts. For example, aluminum alkoxides may be used: Al(OR z )3, In the formula, R z has the above meaning; i.e. an organic radical, preferably a substituted or unsubstituted hydrocarbon radical having 1 to 20 C atoms, with three R z The groups may be the same or different. Similarly, in the case of aluminum alkoxides, one or more of the alkoxy groups may be an acyloxy group -OC(O)R z may be substituted with.

[0101] Additionally, aluminum alkoxides in which one or more alkoxy groups are replaced with hydroxy groups or halogen atoms may be used.

[0102] Of the aluminum catalysts mentioned, the pure aluminum alcoholates are preferred with regard to their stability towards moisture and the curability of the mixtures to which they are added. Furthermore, the aluminum chelate complexes are preferred.

[0103] Suitable zirconium catalysts are, for example, tetramethoxyzirconium or tetraethoxyzirconium.

[0104] Diisopropoxyzirconium bis(ethyl acetoacetate), triisopropoxyzirconium(ethyl acetoacetate) and isopropoxyzirconium tris(ethyl acetoacetate) are very particularly preferably used.

[0105] Additionally, for example, zirconium acylate may be used.

[0106] Zirconium halide catalysts may also be used.

[0107] Additionally, zirconium chelate complexes may also be used.

[0108] Furthermore, metal carboxylates or also mixtures of several such salts may be used as curing catalysts, whereby these are selected from the carboxylates of the metals calcium, vanadium, iron, zinc, titanium, potassium, barium, manganese, nickel, cobalt and / or zirconium.

[0109] Among the carboxylates, calcium, vanadium, iron, zinc, titanium, potassium, barium, manganese and zirconium carboxylates are preferred because they exhibit high activity. Calcium, vanadium, iron, zinc, titanium and zirconium carboxylates are particularly preferred. Iron and titanium carboxylates are particularly preferred.

[0110] The curable composition preferably contains a curing catalyst in an amount of about 0.05 to 2% by weight, preferably 0.1 to 1.5% by weight, in each case based on the total weight of the composition. If a mixture of different catalysts is used, said amount refers to the total amount in said composition.

[0111] The compositions of the present invention crosslink in the presence of moisture and, in so doing, cure with the formation of Si-O-Si bonds.

[0112] In various embodiments, the molar ratio of (capped) adhesion promoter:tin compound may be adjusted so that it is at least 1:1, for example in the range of 1:1 to 50:1. This may help to ensure that the curable composition has, on the one hand, very high storage stability and, on the other hand, cures reliably and at a sufficient rate after application even at room temperature (23°C) in the presence of atmospheric moisture.

[0113] The curable composition further contains as an essential component an additive of formula (III): In the at least one additive having a ketone functionality of formula (III), [ka] R 31is selected from substituted or unsubstituted alkyl, alkenyl, alkenyloxy, alkynyl, alkylnyloxy, alicyclic, alicyclic-O-, aryl, aryloxy, heteroaryl, heteroaryloxy, heteroalicyclic, heteroalicyclicoxy, acyl, acyloxy groups or combinations thereof; and R 32 is selected from hydrogen, halogen, amino, oxyimino, substituted or unsubstituted alkyl, alkenyl, alkenyloxy, alkynyl, alkylnyloxy, alicyclic, alicyclic-O-, aryl, aryloxy, heteroaryl, heteroaryloxy, heteroalicyclic, heteroalicyclicoxy, acyl, acyloxy groups, or combinations thereof; or R 31 and R 32 combine together with the carbon atoms to which they are attached to form a 5- to 18-membered substituted or unsubstituted alicyclic or heteroalicyclic group; Here, the combined R 31 and R 32 contains up to 24, preferably up to 18 carbon atoms.

[0114] In various embodiments, additive (D) has a molecular weight of up to 500 g / mol, preferably up to 300 g / mol.Additive (D) is preferably a monomeric component.

[0115] In various embodiments, the additive (D) is selected from ketones and aldehydes of formula (III), where: (i)R 31 is a substituted or unsubstituted alkyl, aryl, heteroaryl, or combinations thereof, preferably C 1-10 Alkyl, C 6-14 Aryl and C 5-13 R is selected from heteroaryl, more preferably substituted or unsubstituted phenyl, most preferably phenyl or methoxyphenyl; 32 is hydrogen; or (ii)R 31 and R 32are each independently substituted or unsubstituted alkyl, aryl, heteroaryl, or combinations thereof, preferably C 1-10 Alkyl, C 6-14 Aryl and C 5-13 Heteroaryl is selected from the group consisting of aryl, hetero ...

[0116] In various embodiments, the additive (D) is selected from ketones including, but not limited to, 4-(4-hydroxyphenyl)-butan-2-one, cyclohexanone, benzophenone, acetophenone, 1,1,1-trichloroacetone, 2-butanone, 2-pentanone, 3-pentanone, 3-methyl-2-butanone, isopropyl methyl ketone, 2-hexanone, 4-methyl-2-pentanone, isobutyl methyl ketone, 3,3-dimethyl-2-butanone, tert-butyl methyl ketone, 4-heptanone, cyclopentanone, 2,6-dimethyl-4-heptanone, di-iso-butyl ketone, 5-nonanone, di-n-butyl ketone, 2,4-dimethyl-3-pentanone, di-iso-propyl ketone, 2,4-pentanedione, acetylacetone, civetone, carvone, and camphor.

[0117] In various embodiments, the additive (D) is selected from aldehydes including, but not limited to, p-tolualdehyde, vanillin (4-hydroxy-3-methoxybenzaldehyde), valeraldehyde, salicylaldehyde, cinnamaldehyde, butyraldehyde, isovaleraldehyde, n-pentanal, n-hexanal, n-heptanal, 2-ethylhexanal, n-octanal, n-nonanal, n-decanal, n-undecanal, dodecanal, trans-hexene-2-al, benzaldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, and 4-methoxybenzaldehyde.

[0118] In various embodiments, the additive (D) may be an aldehyde that is also used as part of a fragrance or fragrance composition. Such aldehydes have the added advantage that they can improve the odor of the composition and mask or prevent malodors caused by other ingredients. Suitable aldehydes include, but are not limited to, adoxal (2,6,10-trimethyl-9-undecenal), anisaldehyde (4-methoxybenzaldehyde), simal (3-(4-isopropyl-phenyl)-2-methylpropanal), ethyl vanillin, florhydral (3-(3-isopropylphenyl)butanal), helional (3-(3,4-methylenedioxyphenyl)-2-methylpropanal), heliotropin, hydroxycitronellal. , lauraldehyde, lyral (3- and 4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde), methylnonylacetaldehyde, lylial (3-(4-tert-butylphenyl)-2-methylpropanal), phenylacetaldehyde, undecylenal, dehyde, vanillin, 2,6,10-trimethyl-9-undecenal, 3-dodecen-1-al, alpha-n-amylsine Namaldehyde, Melonal (2,6-dimethyl-5-heptenal), 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde (Tripral), 4-Methoxybenzaldehyde, Benzaldehyde, 3-(4-tert-butylphenyl)-propanal, 2-Methyl-3-(para-methoxyphenyl)propanal, 2-Methyl-4-(2,6,6-trimethyl-2(1)-cyclohexen-1-yl)butanal, 3-Phenyl-2-propenal, cis- / trans-3,7-dimethyl-2,6-octadien-1-al, 3,7-dimethyl-6-octen-1-al, [(3,7-dimethyl-6-octenyl)oxy]acetaldehyde, 4-isopropylbenzylaldehyde, 1,2,3,4,5,6,7,8-octahydro-8,8-dimethyl-2-naphthaldehyde, 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde, 2-methyl-3-(isopropylphenyl)propanal, 1-decanal, 2,6-Dimethyl-5-heptenal, 4-(tricyclo[5.2.1.0(2,6)]-decylidene-8)-butanal, octahydro-4,7-methane-1H-indenecarboxaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, para-ethyl-alpha,alpha-dimethylhydrocinnamaldehyde, alpha-methyl-3,4-(methylenedioxy)-hydrocinnamaldehyde, 3,4-methylenedioxybenzaldehyde, alpha-n-hexylcinnamaldehyde, m-cymene-7-carboxaldehyde, ar phenylacetaldehyde, 7-hydroxy-3,7-dimethyloctanal, undecenal, 2,4,6-trimethyl-3-cyclohexene-1-carboxaldehyde, 4-(3)(4-methyl-3-pentyl)-3-cyclohexene-1-carboxaldehyde, 1-dodecanal, 2,4-dimethylcyclohexene-3-carboxaldehyde, 4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde, 7-methoxy-3,7-dimethyloctan-1-al, 2-methylundecanal, 2-Methyldecanal, 1-nonanal, 1-octanal, 2,6,10-trimethyl-5,9-undecadienal, 2-methyl-3-(4-tert-butyl)propanal, dihydrocinnamaldehyde, 1-methyl-4-(4-methyl-3-pentenyl)-3-cyclohexene-1-carboxaldehyde, 5- or 6-methoxyhexahydro-4,7-methanindane-1- or -2-carboxaldehyde, 3,7-dimethyloctan-1-al, 1-undecanal, 10-undecene-1- aldehyde, 4-hydroxy-3-methoxybenzaldehyde, 1-methyl-3-(4-methylpentyl)-3-cyclohexenecarboxaldehyde, 7-hydroxy-3,7-dimethyloctanal, trans-4-decenal, 2,6-nonadienal, para-triracetaldehyde, 4-methylphenylacetaldehyde, 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal, ortho-methoxycinnamaldehyde, 3,5,6-trimethyl-3-cyclohexenecarboxaldehyde, 3,7-Dimethyl-2-methylene-6-octenal, phenoxyacetaldehyde, 5,9-dimethyl-4,8-decadienal, 6,10-dimethyl-3-oxa-5,9-undecadien-1-al, hexahydro-4,7-methanindan-1-carboxaldehyde, 2-methyloctanal, alpha-methyl-4-(1-methylethyl)benzeneacetaldehyde, 6,6-dimethyl-2-norpinen-2-propionaldehyde, para -Methylphenoxyacetaldehyde, 2-methyl-3-phenyl-2-propen-1-al, 3,5,5-trimethylhexanal, hexahydro-8,8-dimethyl-2-naphthaldehyde, 3-propyl-bicyclo-[2.2.1]-hept-5-ene-2-carbaldehyde, 9-decenal, 3-methyl-5-phenyl-1-pentanal, methylnonylacetaldehyde, hexanal and trans-2-hexenal.

[0119] In various embodiments, the additive (D) may be a ketone, which is also used as part of a fragrance or fragrance composition. Such ketones have the added benefit of improving the odor of the composition and masking or preventing malodors caused by other ingredients. Suitable ketones include, but are not limited to, methyl-beta-naphthyl ketone, musk indanone (1,2,3,5,6,7-hexahydro-1,1,2,3,3-pentamethyl-4H-inden-4-one), tonalide (6-acetyl-1,1,2,4,4,7-hexamethyltetralin), alpha-damascone, beta-damascone, delta-damascone, iso-damascone, damascenone, methyl dihydrojasmonate, menthone, carvone, camphor, 3,4,5,6,6-Pentamethylhept-3-en-2-one, fenchone, alpha-ionone, beta-ionone, gamma-methyl-ionone, fluramone (2-heptylcyclopentanone), dihydrojasmone, cis-jasmone, iso-E-super (1-(1,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)-ethan-1-one (and isomers)), methyl cedrenyl ketone, acetophenone, methyl ethylacetophenone, para-methoxyacetophenone, methyl-beta-naphthyl ketone, benzylacetone, benzophenone, para-hydroxyphenylbutanone, 3-methyl-5-propyl-2-cyclohexenone, 6-isopropyldecahydro-2-naphthone, dimethyloctenone, frescomente(2-butan-2-yl-cyclohexan-1-one), 4-(1-ethoxyvinyl)-3,3,5,5-tetramethylcyclohexanone, methylheptenone, 2-(2-(4-methyl-3-cyclohexen-1-yl)propyl)cyclopentanone, 1-(p-menthen-6(2)yl)-1-propanone, 4-(4-hydroxy-3-methoxyphenyl)-2-butanone, 2-acetyl-3,3-dimethylnorbornane, 6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone, 4-damascol (5-methyl-5-phenylhexan-3-one), dulcinyl(4-(1,3-benzodioxol-5-yl)butan-2-one), hexalon (1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-1,6-heptadiene-3-one), isocyclmon E (1-(1,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)ethanone), methyl nonyl ketone, methyl cyclocitron, methyl lavender ketone, orivon (4-tert-amyl-cyclohexanone), 4-tert-butylcyclohexanone, delphon (2-pentyl-cyclopentanone), muscone (CAS 541-91-3), neobutenone (1-(5,5-dimethyl-1-cyclohexenyl)pent-4-en-1-one), plicatone (CAS 41724-19-0), velouton (2,2,5-trimethyl-5-pentylcyclopentan-1-one), 2,4,4,7-tetramethyl-oct-6-en-3-one, and tetrameran (6,10-dimethylundecen-2-one).

[0120] The curable composition may contain one or more components, apart from components (A), (B), (C) and (D), which may be used to selectively affect certain properties of the curable composition and / or the cured product.

[0121] These other ingredients may be selected, for example, from the group comprising plasticizers, extenders, stabilizers, antioxidants, fillers, reactive diluents, drying agents, UV stabilizers, rheological aids, and / or solvents. Of particular interest are typically the plasticizers, fillers and stabilizers (including antioxidants and UV stabilizers).

[0122] Therefore, preferably the hardenable composition contains at least one further component.

[0123] The viscosity of the curable composition is considered too high for certain applications and can be reduced in a simple and expedient manner, usually by using reactive diluents, without any signs of demixing (e.g. migration of plasticizers) occurring in the cured mass.

[0124] Preferably, the reactive diluent has at least one functional group that reacts after application, for example with moisture or atmospheric oxygen. Examples of this type of group are silyl groups, isocyanate groups, vinyl unsaturated groups, and polyunsaturated systems.

[0125] Any compound that reduces the viscosity, can be mixed with the other ingredients, and has at least one group that reacts with the polymer may be used as a reactive diluent.

[0126] The viscosity of the reactive diluent is preferably less than 20,000 mPas, particularly preferably from about 0.1 to 6000 mPas, very particularly preferably from 1 to 1000 mPas (Brookfield RVT, 23° C., spindle 7, 10 rpm).

[0127] For example, the following substances may be used as reactive diluents: polyalkylene glycols reacted with isocyanatosilane (e.g., Synalox 100-50B, DOW), carbamatopropyltrimethoxysilane, alkyltrimethoxysilanes, alkyltriethoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, and vinyltrimethoxysilane (XL 10, Wacker), vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, octyltrimethoxysilane, tetraethoxysilane, vinyldimethoxymethylsilane (XL12, Wacker), vinyltriethoxysilane (GF56, Wacker), vinyltriacetoxysilane (GF62, Wacker), isooctyltrimethoxysilane (IO trimethoxy), isooctyltriethoxysilane (IO triethoxy, Wacker), N-trimethoxysilylmethyl-O-methylcarbamate (XL63, Wacker), N-dimethoxy(methyl)silylmethyl-O-methylcarbamate (XL65, Wacker), hexadecyltrimethoxysilane, 3-octanoylthio-1-propyltriethoxysilane, and partial hydrolysates of the above compounds.

[0128] Additionally, the following polymers from Kaneka Corporation may also be used as reactive diluents: MS S203H, MS S303H, MS SAT 010, and MS SAX 350.

[0129] For example, silane modified polyethers derived from the reaction of isocyanatosilanes with Synalox types may be used as well.

[0130] Additionally, polymers that can be prepared from organic backbones by grafting vinylsilanes or by reacting polyols, polyisocyanates, and alkoxysilanes can be used as reactive diluents.

[0131] A polyol is understood to be a compound which may contain one or more OH groups in the molecule. The OH groups may be both primary and secondary.

[0132] Suitable aliphatic alcohols include, for example, ethylene glycol, propylene glycol, and higher glycols, as well as other polyfunctional alcohols. The polyols may further contain other functional groups, such as, for example, esters, carbonates, or amides.

[0133] To prepare the preferred reactive diluents, the corresponding polyol components are in each case reacted with at least difunctional isocyanates. In principle, any isocyanate having at least two isocyanate groups can be used as the at least difunctional isocyanate. However, within the scope of the present invention, compounds having 2 to 4 isocyanate groups, in particular compounds having 2 isocyanate groups, are generally preferred.

[0134] Preferably, the compound present as reactive diluent has at least one alkoxysilyl group, whereby, of the alkoxysilyl groups, di- and trialkoxysilyl groups are preferred.

[0135] Suitable polyisocyanates for the preparation of the reactive diluents are, for example, ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,4-tetramethoxybutane diisocyanate, 1,6 hexamethylene diisocyanate (HDI), cyclobutane-1,3-diisocyanate, cyclohexane-1,3 and -1,4 diisocyanate, bis(2-isocyanatoethyl) fumarate, and mixtures of two or more thereof, 1 isocyanato-3,3,5-trimethyl- 5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 2,4- and 2,6-hexahydrotoluylene diisocyanate, hexahydro-1,3- or -1,4-phenylene diisocyanate, benzidine diisocyanate, naphthalene-1,5-diisocyanate, 1,6-diisocyanato-2,2,4-trimethylhexane, 1,6 diisocyanato-2,4,4-trimethylhexane, xylylene diisocyanate (XDI), tetramethylxylene diisocyanate, diisocyanate (TMXDI), 1,3- and 1,4-phenylene diisocyanate, 2,4- or 2,6-toluylene diisocyanate (TDI), 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, or 4,4'-diphenylmethane diisocyanate (MDI), or their partially or fully hydrogenated cycloalkyl derivatives, such as fully hydrogenated MDI (H12-MDI), alkyl-substituted diphenyl Methane diisocyanates, such as mono-, di-, tri-, or tetraalkyl diphenylmethane diisocyanates and their partially or fully hydrogenated cycloalkyl derivatives, 4,4'-diisocyanatophenyl perfluoroethane, phthalic acid bis-isocyanatoethyl ester, 1-chloromethylphenyl-2,4- or -2,6-diisocyanate, 1-bromomethylphenyl-2,4- or -2,6-diisocyanate, 3,3-bis-chloromethyl ether-4,4'-diphenyl diisocyanate, sulfur-containing diisocyanates obtained by reacting 2 moles of a diisocyanate with 1 mole of thiodiglycol or dihydroxydihexyl sulfide, diisocyanates and triisocyanates of dimeric and trimeric fatty acids, or mixtures of two or more of the aforementioned diisocyanates.

[0136] Trivalent or higher isocyanates, such as those obtained by oligomerization of diisocyanates, in particular those mentioned above, may also be used as polyisocyanates. Examples of such trivalent or higher polyisocyanates are the triisocyanurates of HDI or IPDI or mixtures thereof or mixed triisocyanurates thereof, as well as polyphenylmethylene polyisocyanates, such as those obtained by phosgenation of aniline-formaldehyde condensation products.

[0137] In addition to, or instead of, the reactive diluents, solvents and / or plasticizers can be used to reduce the viscosity of the curable composition.

[0138] Suitable as solvents are aliphatic or aromatic hydrocarbons, halogenated hydrocarbons, ketones, ethers, esters, ester alcohols, keto alcohols, keto ethers, keto esters and ether esters.

[0139] The compositions described herein may further contain hydrophilic plasticizers. These are used to improve moisture absorption and thereby reactivity at low temperatures. Suitable as plasticizers are, for example, esters of abietic acid, adipic acid esters, azelaic acid esters, benzoic acid esters, butyric acid esters, acetate esters, esters of higher fatty acids having from about 8 to about 44 carbon atoms, epoxidized fatty acids, fatty acid esters and fats, glycolic acid esters, phosphate esters, phthalic acid esters, linear or branched alcohols containing 1 to 12 carbon atoms, propionic acid esters, sebacic acid esters, sulfonic acid esters, thiobutyric acid esters, trimellitic acid esters, citrate esters, and esters based on nitrocellulose, and polyvinyl acetate, as well as mixtures of two or more thereof.

[0140] For example, among phthalic acid esters, dioctyl phthalate, dibutyl phthalate, diisoundecyl phthalate, or butyl benzyl phthalate is suitable, and among adipic acid esters, dioctyl adipate, diisodecyl adipate, diisodecyl succinate, dibutyl sebacate, or butyl oleate is suitable.

[0141] Also suitable as plasticizers are monofunctional, linear or branched C 4-16 These are pure or mixed ethers of alcohols, or mixtures of two or more different ethers of such alcohols, for example dioctyl ether (available as Cetiol OE, Cognis Deutschland GmbH, Düsseldorf).

[0142] Endcapped polyethylene glycols are also suitable as plasticizers, e.g., polyethylene or polypropylene glycol di-C 1-4 -Alkyl ethers, in particular the dimethyl or diethyl ethers of diethylene glycol or dipropylene glycol, and mixtures of two or more thereof.

[0143] Suitable plasticizers are end-capped polyethylene glycols such as polyethylene or polypropylene glycol dialkyl ethers, where the alkyl group has up to 4 C atoms, especially the dimethyl and diethyl ethers of diethylene glycol and dipropylene glycol. Acceptable hardening is achieved even under less favorable application conditions (low humidity, low temperature), especially with dimethyldiethylene glycol. For more information on plasticizers, see the relevant technical chemistry literature.

[0144] Diurethanes that are also suitable as plasticizers can be prepared, for example, by reacting a diol having an OH end group with a monofunctional isocyanate, by selecting the stoichiometry so that substantially all free OH groups are reacted. If necessary, excess isocyanate can then be removed from the reaction mixture, for example by distillation. A further method for preparing diurethanes consists of reacting a monofunctional alcohol with a diisocyanate, whereby, if possible, all NCO groups are reacted.

[0145] In various embodiments, the plasticizer may be a polydimethylsiloxane different from (A), particularly a PDMS that does not have the end groups of formula (I).

[0146] In various embodiments, the hardenable composition includes at least one plasticizer, for example, polydimethylsiloxane.

[0147] The curable composition preferably contains a plasticizer in an amount of 1 to 50% by weight, preferably in an amount of 10 to 40% by weight, particularly preferably in an amount of 20 to 30% by weight, in each case based on the total weight of the composition. If a mixture of plasticizers is used, said amount refers to the total amount of plasticizer in the composition.

[0148] Preferably, the curable composition contains at least one stabilizer selected from antioxidants, UV stabilizers, and drying agents.

[0149] All conventional antioxidants may be used as antioxidants. They are preferably present in an amount of up to about 7% by weight, in particular up to about 5% by weight.

[0150] The compositions herein may contain UV stabilizers, preferably used in amounts up to about 2% by weight, preferably up to about 1% by weight. So-called hindered amine light stabilizers (HALS) are particularly suitable as UV stabilizers. It is preferred within the context of the present invention to use UV stabilizers that have silyl groups and are incorporated into the final product during crosslinking or curing. The products Lowilite 75 and Lowilite 77 (Great Lakes, USA) are particularly suitable for this purpose. In addition, benzotriazoles, benzophenones, benzoates, cyanoacrylates, acrylates, sterically hindered phenols, phosphorus, and / or sulfur may also be added.

[0151] To further enhance storage stability (shelf life), it is often useful to stabilize the composition against penetrating moisture with a desiccant.

[0152] Such improvement in storage property can be achieved, for example, by using desiccant.All compounds that react with water to form groups that are inert to the reactive groups present in the preparation are suitable as desiccant, and thus undergo the smallest possible change in their molecular weight.Furthermore, the reactivity of desiccant to the moisture that penetrates the preparation must be higher than the reactivity of the groups of the silyl group-containing polymer of the present invention present in the preparation.

[0153] For example, isocyanates are suitable as drying agents.

[0154] Advantageously, however, silanes are used as drying agents, for example vinyl silanes, such as 3-vinylpropyltriethoxysilane, oximesilanes, such as methyl-O,O',O''-butan-2-one-trioximosilanes or O,O',O'',O''''-butan-2-one-tetraoximosilanes (CAS numbers 022984-54-9 and 034206-40-1), or benzamidosilanes, such as bis(N-methylbenzamido)methylethoxysilane (CAS number 16230-35-6), or carbamatosilanes, such as carbamatomethyltrimethoxysilane. It is also possible to use methyl, ethyl or vinyltrimethoxysilane, tetramethyl or tetraethylethoxysilane. Vinyltrimethoxysilane and tetraethoxysilane are particularly suitable in terms of cost and efficiency.

[0155] Also suitable as drying agents are the aforementioned reactive diluents, provided that they have a molecular weight (Mn) of less than about 5000 g / mol and have end groups whose reactivity towards penetrating moisture is at least as high as, and preferably higher than, the reactivity of the reactive groups of the polymers used according to the invention.

[0156] Finally, alkyl orthoformates or alkyl orthoacetates may also be used as drying agents, for example methyl or ethyl orthoformate or methyl or ethyl orthoacetate.

[0157] The compositions generally contain from about 0 to about 6% by weight of a desiccant.

[0158] The compositions described herein may further contain a filler. Suitable here are, for example, chalk, lime powder, precipitated and / or pyrogenic (fumed) silica, zeolite, bentonite, magnesium carbonate, diatomaceous earth, alumina, clay, tallow, titanium oxide, iron oxide, zinc oxide, sand, quartz, flint, mica, glass powder, and other ground minerals. Organic fillers may also be used, such as, for example, carbon black, graphite, wood fiber, wood flour, sawdust, cellulose, cotton, pulp, cotton, wood chips, chopped straw, and rice husk. Short fibers, such as glass fiber, glass filament, polyacrylonitrile, carbon fiber, Kevlar fiber, or polyethylene fiber, may also be added. Aluminum powder is also suitable as a filler.

[0159] The pyrogenic (fumed) and / or precipitated silica is preferably 10 to 90 m 2 / g. When they are used, they do not cause a further increase in the viscosity of the compositions of the invention, but contribute to the toughening of the cured compositions.

[0160] Similarly, as a filler, a higher, advantageously 100-250 m 2 / g, especially 110-170m 2 It is conceivable to use pyrogenic and / or precipitated silicas with a BET surface area of ​​1000 / g. Due to the higher BET surface area, the same effect, for example the strengthening of the cured preparation, can be achieved with a smaller weight proportion of silicic acid. Therefore, additional substances can be used to improve the compositions described herein with respect to other requirements.

[0161] Further suitable as fillers are hollow spheres with mineral or plastic shells. These can be, for example, hollow glass spheres commercially available under the trade name Glass Bubbles®. Plastic-based hollow spheres such as Expancel® or Dualite® are described, for example, in EP 0520426. They are composed of inorganic or organic materials and each has a diameter of 1 mm or less, preferably 500 μm or less.

[0162] Fillers that give the preparation thixotropy are preferred for many applications. Such fillers are also described as rheological aids, for example hydrogenated castor oil, fatty acid amides, or swellable plastics such as PVC. In order to be easily squeezed out of a suitable dispensing device (for example a tube), such preparations have a viscosity of 3000 to 15,000 mPas, preferably 40,000 to 80,000 mPas, or 50,000 to 60,000 mPas.

[0163] The fillers are preferably used in an amount of 1 to 80% by weight, particularly preferably 2 to 20% by weight and very particularly preferably 5 to 10% by weight, in each case based on the total weight of the composition. Of course, mixtures of several fillers can also be used. In this case, the quantitative data naturally refer to the total amount of fillers in the composition.

[0164] The preparation of the curable composition can be carried out by simple mixing of the polyorganosiloxane (A), adhesion promoter, catalyst, additive (D) and optionally other components. This can be carried out in a suitable dispersing unit, such as a high-speed mixer. In this case, care is preferably taken to avoid as much as possible contact of the mixture with moisture, as this can lead to undesirable premature curing. Suitable measures are well known and include, for example, working in an inert atmosphere, possibly under a protective gas, and drying / heating the individual components before they are added.

[0165] The compositions of the present invention can be used as adhesives or sealing or coating materials.

[0166] The composition can be used, for example, as an adhesive, sealant, coating and in the production of molded parts. Further fields of application of the composition are the use as a plugging compound, hole filler or crack filler. The use as a sealant is preferred.

[0167] The compositions are particularly suitable for bonding plastics, metals, glass, ceramics, wood, wood-based materials, paper, paper-based materials, rubber and textiles, gluing floors and generally for sealing construction elements, windows, wall and floor coverings and joints, where the materials may bond to themselves or to each other as required. EXAMPLES

[0168] The following examples serve to illustrate the invention without, however, limiting it thereto.

[0169] <Example 1> Comparative composition C1 and composition E1 according to the invention were prepared by mixing the raw materials listed in Table 1. The formulations differ only in that the composition according to the invention further comprises an additive having a ketone functionality, namely benzaldehyde.

[0170] [Table 1]

[0171] Polymer (A) was formed in a previous step from α,ω-dihydroxy-terminated polydimethylsiloxane and vinyltris(ethyllactato)silane using 3-aminopropyltrimethoxysilane (0.4 ppw) as a catalyst in the presence of a plasticizer, and then combined with the siliceous filler, the remaining aminosilane (adhesion promoter), benzaldehyde if used, and a curing catalyst.

[0172] The prepared formulations were subjected to cure performance testing as follows.

[0173] Determination of Skin Over Time (SOT): Skin over time (SOT) is defined as the time required for a material to form a non-tacky surface film. The measurement of the skin over time is carried out according to DIN 50014 at standard climatic conditions (23+ / -2°C, relative humidity 50+ / -5%). The temperature of the sealant must be 23+ / -2°C and the sealant is stored in advance in the laboratory for at least 24 hours. The sealant is applied to a piece of paper and spread with a putty knife to form a skin (approximately 2 mm thick and 7 cm wide). Start a stopwatch immediately. At intervals, lightly touch the surface with your fingertip and pull your finger away. Apply sufficient pressure to the surface so that an impression is left on the surface when the skin formation time is reached. The skin over time is reached when the sealing compound no longer adheres to the fingertips. Skin over time (SOT) is expressed in minutes.

[0174] Measurement of Shore A hardness: Shore A hardness was measured according to ISO868.

[0175] Determination of the depth of cure (DOC): A strip of material 10 mm high (+ / - 1 mm) and 20 mm wide (+ / - 2 mm) was applied to a plastic foil (PP) using a Teflon spatula. After storing the sample for 24 hours under normal conditions (23 + / - 2°C, 50 + / - 5% relative humidity), a part of the strip was cut out and the thickness of the cured layer was measured with a vernier caliper. The depth of cure after 24 hours is expressed in millimeters.

[0176] Evaluation of mechanical properties (tensile tests): The tensile tests determine the breaking force, the elongation at break and the yield stress values ​​(e-module) according to DIN 53504. Deviations from the standard: Dumbbell specimens with the following dimensions were used: thickness 2 + / - 0.2 mm; bar width 10 + / - 0.5 mm; bar length approx. 45 mm; total length 9 cm. The tests were carried out under standard conditions (23 + / - 2 °C, relative humidity 50 + / - 5%). The measurements were carried out after 7 days of curing. Procedure: The prepolymer mixture (formulation) was spread on a uniform surface to form a film with a thickness of 2 mm. After the film was cured for 7 days under standard conditions (see above), dumbbell specimens were punched out. Three specimens were used for each measurement. The tests were carried out under normal conditions. The specimens must be at the same temperature at which the measurements are carried out. Before the measurements, the thickness of the specimens is determined in at least three different positions (center and tip) using a vernier caliper. The average value is introduced into the measurement software. The specimen is clamped in the tensile tester so that its longitudinal axis coincides with the mechanical axis of the tensile tester and constitutes the largest possible surface of the rod head without clamping the middle bar. The dumbbell is then elongated at a rate of 50 mm / min to <0.1 MPa. The force-elongation curve is then recorded at a linear speed of 50 mm / min. Evaluation: The following values ​​are determined: Breaking force [N / mm 2 ], elongation at break [%], and modulus of elasticity at 100% elongation [N / mm 2 ].

[0177] Peel test: If possible and necessary, use an appropriate solvent to clean the substrate (test panel) before application. A strip of material 10mm high (+ / - 1mm) and 20mm wide (+ / - 2mm) was applied onto the substrate using a Teflon spatula. The samples were stored for 7 days at standard conditions (23+ / -2°C, 50+ / -5% relative humidity). The cured material was cut back at least 15mm with a shape blade and the bead was pulled by hand. The failure modes were recorded as follows: JPEG2025000930000017.jpg19125

[0178] [Table 2]

[0179] [Table 3]

[0180] The results show that the compositions of the present invention have better adhesion and higher storage stability compared to the comparative compositions.

Claims

1. (A) at least one polyorganosiloxane containing at least one end group of formula (I): 【Chemistry 1】 [In the formula, A is a bond, -O- or a linear, branched or cyclic divalent group selected from a hydrocarbon group having 1 to 12 carbon atoms, an alkylene, an arylene, an oxyalkylene, an oxyarylene, a siloxane-alkylene, a siloxane-arylene, an ester, an amine, a glycol, an imide, an amide, an alcohol, a carbonate, a urethane, a urea, a sulfide, an ether, or derivatives thereof or combinations thereof; Each R １ is independently selected from the group consisting of hydrogen, halogen, amino, oxyimino, substituted or unsubstituted alkyl, alkenyl, alkenyloxy, alkynyl, alkynyloxy, alicyclic, alicyclic-O-, aryl, aryloxy, heteroaryl, heteroaryloxy, heteroalicyclic, heteroalicyclicoxy, acyl, acyloxy group or combinations thereof; Each R ２ are independently a group of general formula (2): 【Chemistry 2】 [During the ceremony, Y is a substituted or unsubstituted (hetero)aromatic group having 4 to 14 ring atoms, a substituted or unsubstituted saturated or partially unsaturated 4 to 14 membered (hetero)cyclic group, or -(C(R ５ ) ２ ) Ｏ - is; R ４ is a substituted or unsubstituted alkyl, alkenyl, alkynyl, alicyclic, aryl, heteroaryl, and heteroalicyclic group, or combinations thereof; Each R ５ is independently selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl, alkenyl, alkynyl, alicyclic or aryl group; and and o is an integer from 1 to 10. Each R ３ are independently a group of general formula (3): 【Chemistry 3】 [During the ceremony, Y is as defined above; R ６ is selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, alicyclic, aryl, heteroaryl, and heteroalicyclic groups or combinations thereof, or R ７ is; R ７ is a group of general formula (4): 【Chemistry 4】 (In the formula, R ８ is an alkylene group optionally interrupted by a heteroatom; Each R ９ is independently selected from the group consisting of hydrogen, halogen, amino, substituted or unsubstituted alkyl, alkenyl, alkynyl, alicyclic, aryl, heteroaryl, and heteroalicyclic groups, or combinations thereof; Each R １０ is independently selected from the group consisting of a substituted or unsubstituted alkyl, alkenyl, alkynyl, or acyl group; Each p independently represents 0, 1, or 2. m is independently 0, 1 or 2; and n is independently 1, 2, or 3, and the total n+m is up to 3; (B) at least one adhesion promoter; (C) at least one curing catalyst; and (D) at least one additive having a ketone functionality of formula (III): 【Chemistry 5】 [In the formula, R ３１ is selected from substituted or unsubstituted alkyl, alkoxy, alkenyl, alkenyloxy, alkynyl, alkylnyloxy, alicyclic, alicyclic-O-, aryl, aryloxy, heteroaryl, heteroaryloxy, heteroalicyclic, heteroalicyclicoxy, acyl, acyloxy groups or combinations thereof; and R ３２ is selected from hydrogen, halogen, amino, oxyimino, substituted or unsubstituted alkyl, alkoxy, alkenyl, alkenyloxy, alkynyl, alkylnyloxy, alicyclic, alicyclic-O-, aryl, aryloxy, heteroaryl, heteroaryloxy, heteroalicyclic, heteroalicyclicoxy, acyl, acyloxy groups or combinations thereof; or R ３１ and R ３２ are linked together with the carbon atom to which they are attached to form a 5- to 20-membered substituted or unsubstituted alicyclic or heteroalicyclic group. wherein the additive of formula (III) contains up to 24, preferably up to 18, carbon atoms.

1. A curable composition comprising:

2. 2. The curable composition of claim 1, wherein the polyorganosiloxane is a polydiorganosiloxane, preferably polydimethylsiloxane (PDMS).

3. A is a bond, -O-, or a siloxane-alkylene, preferably of the formula -(CH ２ ) １－１０ -(Si(Alk) ２ -O-Si(Alk) ２ ) １－１０ - (CH ２ ) １－１０ [Alk is C １－１０ 3. The curable composition according to claim 1, wherein the siloxane-alkylene is a linear or branched divalent radical selected from the group consisting of siloxane-alkylenes of the formula: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54

4. Each R １ represent, independently of one another, an alkyl group having 1 to 10 carbon atoms, in particular methyl, ethyl, propyl or isopropyl, an alkenyl group having 2 to 10 carbon atoms, in particular vinyl or allyl, or an aryl group having 6 to 10 carbon atoms, in particular phenyl, or an aryloxy group having 6 to 14 carbon atoms, or an acyloxy group having 2 to 10 carbon atoms, preferably acetoxy, oxyimino, alkenyloxy having 2 to 10 carbon atoms or amino; and / or Each R ２ represent, independently of each other, a group of formula (2), in which R ４ represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, in particular 1 to 4 carbon atoms, particularly preferably methyl or ethyl, and Y represents a substituted or unsubstituted aromatic group having 6 carbon ring atoms, preferably 1,2-phenylene, or -(C(R ５ ) ２ ) ｏ - (wherein o is 1 and R ５ One of the groups is hydrogen and the second R ５ The radical is a substituted or unsubstituted alkyl radical having 1 to 10 carbon atoms, in particular methyl, carboxymethyl or their (alkyl) esters, The curable composition according to any one of claims 1 to 3.

5. The curable composition according to any one of claims 1 to 4, wherein the sum n+m is 3.

6. The group Si(R １ ) ｍ (R ２ ) ｎ (R ３ ) ３－（ｍ＋ｎ） The curable composition according to any one of claims 1 to 5, wherein the silane is selected from methyl bis(ethyl lactato) silane, ethyl bis(ethyl lactato) silane, phenyl bis(ethyl lactato) silane, vinyl bis(ethyl lactato) silane, tri(ethyl lactato) silane, methyl bis(ethyl salicylato) silane, ethyl bis(ethyl salicylato) silane, phenyl bis(ethyl salicylato) silane, vinyl bis(ethyl salicylato) silane, tri(ethyl salicylato) silane, methyl bis(diethyl malato) silane, ethyl bis(diethyl malato) silane, phenyl bis(diethyl malato) silane, vinyl bis(diethyl malato) silane, tri(diethyl malato) silane and mixtures thereof.

7. the sum n+m is at most 2, Each R ３ represent, independently of one another, a group of formula (3), in which Y is a substituted or unsubstituted aromatic group having 6 carbon ring atoms, preferably 1,2-phenylene, or -C(R ５ ) ２ ) ｏ - (wherein o is 1 and R ５ One of the groups is hydrogen and the second R ５ The group is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, in particular methyl, carboxymethyl or their (alkyl) esters, R ６ represents hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, in particular 1 to 4 carbon atoms, R ７ represents a group of formula (4), in which R ８ is C １－１０ Alkylene group, preferably C １ Or C ３ is an alkylene group, and each R ９ are each independently a substituted or unsubstituted alkyl radical having 1 to 10 carbon atoms, in particular having 1 to 4 carbon atoms, particularly preferably methyl or ethyl, and each R １０ 5. The curable composition according to claim 1, wherein: independently of one another, represent a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, in particular having 1 to 4 carbon atoms, particularly preferably methyl or ethyl; and p is 0 or 1, preferably 0.

8. The at least one adhesion promoter is preferably selected from the group consisting of aminosilanes, more preferably 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, aminomethyltrimethoxysilane, aminomethyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, (N-2-aminoethyl)-3-aminopropyltrimethoxysilane, (N-2-aminoethyl)-3-aminopropyltriethoxysilane, diethylenetriaminopropyltrimethoxysilane, phenylaminomethyltrimethoxysilane, (N-2-aminoethyl)- 3-aminopropylmethyldimethoxysilane, 3-(N-phenylamino)propyltrimethoxysilane, 3-piperazinylpropylmethyldimethoxysilane, 3-(N,N-dimethylaminopropyl)aminopropylmethyldimethoxysilane, tri[(3-triethoxysilyl)propyl]amine, tri[(3-trimethoxysilyl)propyl]amine, and oligomers thereof, 3-(N,N-dimethylamino)propyltrimethoxysilane, 3-(N,N-dimethylamino)propyltriethoxysilane, (N,N-dimethylamino)methyl trimethoxysilane, (N,N-dimethylamino)methyltriethoxysilane, 3-(N,N-diethylamino)propyltrimethoxysilane, 3-(N,N-diethylamino)propyltriethoxysilane, (N,N-diethylamino)methyltrimethoxysilane, (N,N-diethylamino)methyltriethoxysilane, bis(3-trimethoxysilyl)propylamine, bis(3-triethoxysilyl)propylamine, 4-amino-3,3-dimethylbutyltrimethoxysilane and 4-amino-3,3-dimethylbutyltriethoxysilane. From the group consisting of silanes and mixtures thereof, particularly preferred are 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, aminomethyltrimethoxysilane, aminomethyltriethoxysilane, 3-(N,N-dimethylamino)propyltrimethoxysilane, 3-(N,N-dimethylamino)propyltriethoxysilane, (N,N-dimethylamino)methyltrimethoxysilane, (N,N-dimethylamino)methyltriethoxysilane, 3-(N,N-diethylamino)propyltrimethoxysilane, 3-(N,The curable composition according to any one of claims 1 to 7, comprising a compound selected from the group consisting of (N-diethylamino)propyltriethoxysilane, (N,N-diethylamino)methyltrimethoxysilane, (N,N-diethylamino)methyltriethoxysilane, bis(3-trimethoxysilyl)propylamine, bis(3-triethoxysilyl)propylamine, 4-amino-3,3-dimethylbutyltrimethoxysilane and 4-amino-3,3-dimethylbutyltriethoxysilane.

9. The at least one adhesion promoter is a capped adhesion promoter of formula (II): 【Chemistry 6】 [In the formula, R １１ is an alkylene group optionally interrupted by a heteroatom, preferably C １ -C １０ Alkylene, more preferably C １ Or C ３ is alkylene; Each R １２ is independently selected from the group consisting of hydrogen, halogen, amino, substituted or unsubstituted alkyl, alkenyl, alkynyl, alicyclic, aryl, heteroaryl, and heteroalicyclic groups or combinations thereof; Each R １３ is independently selected from the group consisting of substituted or unsubstituted alkyl, alkenyl, alkynyl, or acyl groups; q independently represents 0, 1, or 2; and B is a group represented by formula (6), (7), (8), or (9): 【Chemistry 7】 [In the formula, each R １４ , R １４ａ , R １４ｂ , R １４ｃ , R １５ and R １６ is independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, alicyclic, aryl, heteroaryl, and heteroalicyclic groups, or combinations thereof; r is 1, 2, 3, or 4; R １７ is -Si(R １９ ) ３ Selected from: R １８ is -Si(R １９ ) ３ , hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, alicyclic, aryl, heteroaryl and heteroalicyclic groups, or combinations thereof; and Each R １９ are independently selected from hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, alicyclic, or aryl groups, or combinations thereof; or R １７ and R １８ are bonded together with the nitrogen atom to which they are bonded to form a group of the formula -Si(R １９ ) ２ -C ２－３ Alkylene-Si(R １９ ) ２ - group is formed. is a nitrogen-containing group selected from the group The curable composition according to any one of claims 1 to 8, comprising:

10. The capped adhesion promoter is (A) a ketimine of formula (II), wherein q is 0 and R １１ is methylene or propylene, preferably propylene, and each R １３ is ethyl or methyl, preferably ethyl, and B is a group of formula (6), in which (i) One R １４ is methyl, and the second R １４ is isobutyl or methyl; or (ii) one R １４ is hydrogen, and the second R １４ is phenyl; or (B) a silane of formula (II), wherein q is 0 and R １１ is methylene or propylene, preferably propylene, and each R １３ is ethyl or methyl, preferably ethyl, and B is a group of formula (9), in which R １７ is -Si(R １９ ) ３ and R １８ is hydrogen, -Si(R １９ ) ３ or -Si(R １９ ) ３ , preferably -Si(R １９ ) ３ and each R １９ is independently alkyl, preferably methyl or ethyl, more preferably methyl The curable composition of claim 9 , wherein

11. (i) the amount of polymer (A) is from about 32 to about 97% by weight, preferably from 40 to 70% by weight, based on the total weight of the composition; and / or (ii) the amount of the capped adhesion promoter (B) is from about 0.1 to about 5 wt. %, preferably from 0.3 to 2 wt. %, based on the total weight of the composition; and / or (iii) the amount of the curing catalyst is about 0.05 to 2% by weight, preferably 0.1 to 1.5% by weight, based on the total weight of the composition; The curable composition according to any one of claims 1 to 10.

12. 12. Curable composition according to any of claims 1 to 11, characterized in that the curing catalyst is a tin compound, preferably an organotin compound, more preferably selected from 1,3-dicarbonyl compounds of divalent or tetravalent tin, diallyltin(IV) dicarboxylates, dialkyltin(IV) dialkoxylates, dialkyltin(IV) oxides, tin(II) carboxylates and mixtures thereof.

13. The additive (D) is selected from ketones and aldehydes of formula (III) (i) R ３１ is a substituted or unsubstituted alkyl, aryl, heteroaryl or combinations thereof, preferably C １－１０ Alkyl, C ６－１４ Aryl and C ５－１３ heteroaryl, more preferably substituted or unsubstituted phenyl, most preferably phenyl or methoxyphenyl; and R ３２ is hydrogen; or (ii) R ３１ and R ３２ are each independently substituted or unsubstituted alkyl, aryl, heteroaryl or combinations thereof, preferably C １－１０ Alkyl, C ６－１４ Aryl and C ５－１３ Heteroaryl, The curable composition according to any one of claims 1 to 12.

14. 14. The curable composition according to any of the preceding claims, further comprising one or more additional components selected from the group consisting of plasticizers, extenders, stabilizers, antioxidants, fillers, reactive diluents, drying agents, UV stabilizers, rheological aids and solvents, preferably plasticizers, fillers, stabilizers, antioxidants and UV stabilizers.

15. Use of the curable composition according to any one of claims 1 to 14 as an adhesive, sealant or coating material.

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