Curable silicone composition

Abstract

The present invention relates to curable compositions based on polyorganosiloxanes with special silicon-containing end groups, special capped adhesion promoters, and curing catalysts. These compositions have improved adhesive properties and excellent storage stability. The present invention also relates to their use.

Description

[Technical Field]

[0001] The present invention relates to curable compositions based on polyorganosiloxanes with special silicon-containing end groups, special capped adhesion promoters, and curing catalysts. These compositions have improved adhesive properties and excellent storage stability. The present invention also relates to their use. [Background technology]

[0002] It is generally desirable for curable compositions used as adhesives, sealants, and coatings to have excellent adhesion to substrates. To meet this requirement, various adhesion promoters are known in the art. However, many formulations still exhibit undesirable limitations in their overall adhesion profile and properties such as their aging and storage stability. Therefore, there remains a need in the art for formulations that are sufficiently stable over long periods of time while also exhibiting good adhesion profiles.

[0003] Polymer systems containing reactive crosslinkable silyl groups, such as alkoxysilyl groups, have been known for a long time. In the presence of atmospheric moisture, these alkoxysilane-terminated polymers can undergo condensation with the elimination of alkoxy groups. Depending on the amount and structure of the alkoxysilane groups, they form primarily long-chain polymers (thermoplastics), relatively wide-mesh three-dimensional networks (elastomers), or highly crosslinked systems (thermosets).

[0004] Silicone polymers (polyorganosiloxanes), particularly polydialkylsiloxanes such as polydimethylsiloxane (PDMS), are extremely important in the production of adhesives, sealants, coatings, and insulating materials. Among these, those that vulcanize at low temperatures and ambient conditions account for a significant market share. Typical formulations include reactive polyorganosiloxanes, particularly silanol-terminated polyorganosiloxanes with at least one, and preferably two, hydroxyl groups attached to the silicon atoms. These are usually used in combination with silane-based crosslinkers that have hydrolyzable groups attached to the silicon atoms. While the polyorganosiloxane and crosslinker can exist as separate components, they can also be reacted together to form modified polyorganosiloxanes that can be used in curable compositions. The term endcapping (end-group capping) is also used in this regard. This can optionally be carried out in the presence of a catalyst, whereby the catalyst selectively mediates endcapping without simultaneously curing the polyorganosiloxane.

[0005] The uses and potential applications of such silane-terminated polymer systems are equally diverse. They can be used, for example, to produce elastomers, sealants, adhesives, elastic adhesive systems, rigid and flexible foams, a wide variety of coating systems, and impression materials in the medical field, such as dentistry. These products can be applied in any form, such as by painting, spraying, casting, pressing, filling, etc.

[0006] Numerous crosslinkers are known in the art that function as end-capping or partial functionalization agents for the respective polymer backbones. In addition to their function in coupling to the polymer backbone, they can be distinguished 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, such as 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 metals, stone, or mortar, 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 a hydrolyzable group that releases an alcohol or oxime, such as methanol or ethanol, during crosslinking.

[0007] Nevertheless, such alkoxy systems have several drawbacks, including storage stability issues for the associated curable compositions and poor adhesion of the cured products to some materials. Oximosilane crosslinkers, which hydrolyze with the release of an alkanone oxime, generally do not have these drawbacks and are therefore widely used. The most common representatives of oximosilane crosslinkers release butan-2-one oxime upon crosslinking. However, this compound is suspected of causing cancer, and alternative neutral crosslinkers are urgently needed. Apart from this, the released oxime also has a strong, putrid odor, making working with curable compositions containing such crosslinkers unpleasant for users.

[0008] Therefore, silane compounds which release α-hydroxycarboxylic acid esters or α-hydroxycarboxylic acid amides during crosslinking have already been proposed as alternative crosslinkers.

[0009] The preparation of suitable silane compounds has been known for a long time and is described, for example, by MM Sprung in "Some α-carbalkoxyalkoxysilanes," J. Org. Chem., 1958, 23(10), pp. 1530-1534.

[0010] DE-A 3210337 also discloses related silane compounds and their preparation and use in curable compositions based on polydiorganosiloxanes with condensable end groups.

[0011] A curing agent for silicone rubber materials having three 2-hydroxypropionic acid alkyl ester groups, i.e., three lactate alkyl ester groups, is known from EP-A-2 030 976. In this case, vinyltris(ethyllactato)silane is particularly preferred.

[0012] EP 2 774 672 describes a specific catalyst for crosslinking silicone rubber materials with a crosslinker based on a silane compound containing lactic acid groups. In this case, the crosslinker may again be the compound known from EP 2 030 976. However, crosslinkers containing only one, two or four 2-hydroxypropionic acid alkyl ester groups are also disclosed. [Prior art documents] [Patent documents]

[0013] [Patent Document 1] German Patent Application Publication No. 3210337 [Patent Document 2] European Patent Application Publication No. 2030976 [Patent Document 3] European Patent Application Publication No. 2774672 [Non-patent literature]

[0014] [Non-Patent Document 1] MM Sprung, “Some α-carbalkoxyalkoxysilanes,” J. Org. Chem., 1958, 23(10), pp.1530-1534 Summary of the Invention [Problem to be solved by the invention]

[0015] Although the use of crosslinkers based on silane compounds bearing lactic acid groups or similar α-carbalkoxyalkoxy groups is associated with many advantages, the resulting preparations can suffer from only moderate adhesion to certain difficult substrates, such as plastics and concrete. Another challenge is to prepare curable silicone-based compositions containing these crosslinkers that exhibit good storage stability, since storage stability can be particularly poor in the presence of other conventional, often essential, components of such compositions (especially curing catalysts and adhesion promoters).

[0016] 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 that release mainly hydroxycarboxylic acid esters (and hydroxycarboxylic acid amides as possible by-products) during crosslinking, and still have good adhesion and excellent storage stability. [Means for solving the problem]

[0017] The present invention achieves the above objectives by providing a curable composition based on a specific polyorganosiloxane, i.e., a polyorganosiloxane endcapped with specific silane groups, whereby the composition comprises at least one specific adhesion promoter and at least one curing catalyst.

[0018] It has been discovered that the combination of certain endcapped polyorganosiloxanes disclosed herein with certain adhesion promoters exhibits excellent storage stability while retaining good cure and adhesive properties. DETAILED DESCRIPTION OF THE INVENTION

[0019] Thus, in a first aspect, the present invention relates to a curable composition comprising or consisting essentially of: (A) Formula (I): [ka] [In the formula, A is a bond, -O-, or a linear, branched, or cyclic divalent group selected from a hydrocarbon residue having 1 to 12 carbon atoms, alkylene, arylene, oxyalkylene, oxyarylene, siloxane-alkylene, siloxane-arylene, ester, amine, glycol, imide, amide, alcohol, carbonate, urethane, urea, sulfide, ether, or derivatives thereof, or combinations thereof; Each R 1 are independently selected from the group consisting of hydrogen, halogen, amino, oximino, substituted or unsubstituted alkyl, alkenyl, alkenyloxy, alkynyl, alkylnyloxy, cycloaliphatic, cycloaliphatic-O-, aryl, aryloxy, heteroaryl, heteroaryloxy, heterocycloaliphatic, heterocycloaliphaticoxy, acyl, acyloxy groups or combinations thereof; Each R 2 are independently represented by the 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 - and R 4 is a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloaliphatic, aryl, heteroaryl, and heterocycloaliphatic group or combinations thereof; Each R 5are independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, alicyclic, or aryl groups; o is an integer from 1 to 10. is the basis of Each R 3 are independently represented by the general formula (3): [ka] [During the ceremony, Y is as defined above, R 6 is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl alicyclic, aryl, heteroaryl and heteroalicyclic groups or combinations thereof, or R 7 is selected from the group consisting of R 7 is represented by the general formula (4): [ka] <In the ceremony, R 8 is an alkylene group optionally interrupted by a heteroatom, such as O, N, S or Si, Each R 9 are independently selected from the group consisting of hydrogen, halogen, amino, substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloaliphatic, aryl, heteroaryl, and heterocycloaliphatic groups, or combinations thereof; Each R 10 are independently selected from the group consisting of substituted or unsubstituted alkyl, alkenyl, alkynyl, or acyl groups; each p independently represents 0, 1, or 2; is the basis of m is independently 0, 1, or 2; n is independently 1, 2, or 3, and the sum of n+m is at most 3. at least one polyorganosiloxane containing at least one terminal group of (B) Formula (II): [ka] [In the formula, R 11 is an alkylene group, preferably C-C, optionally interrupted by a heteroatom, such as O, N, S or Si. 10 alkylene, more preferably C1 or C3 alkylene; Each R 12 are independently selected from the group consisting of hydrogen, halogen, amino, substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloaliphatic, aryl, heteroaryl, and heterocycloaliphatic groups, or combinations thereof; Each R 13 are independently selected from the group consisting of substituted or unsubstituted alkyl, alkenyl, alkynyl, or acyl groups; q independently represents 0, 1, or 2; B is expressed by the formula (6): [ka] Formula (7): [ka] or equation (8): [ka] [During the ceremony, Each R 14 , R 14a , R 14b , R 14c , R 15 and R 16 are independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloaliphatic, aryl, heteroaryl, and heterocycloaliphatic groups, or combinations thereof; r is 1, 2, 3, or 4. is a nitrogen-containing group selected from the group at least one capped adhesion promoter of: (C) at least one curing catalyst;

[0020] The combination of a polyorganosiloxane end-capped with silyl groups having hydroxycarboxylic acid esters, or to a lesser extent hydroxycarboxylic acid amides, as leaving groups bonded to the silicon atoms, and an adhesion promoter having a protected amino functionality that is released only upon contact with humidity / moisture ensures that the curable composition has very high storage stability and cures reliably and sufficiently rapidly after application in the presence of atmospheric moisture, even at room temperature (23°C).

[0021] The present invention further relates to the use of the curable composition of the present invention, or of a curable composition prepared according to the method of the present invention, as an adhesive, sealing or coating material.

[0022] A "curable composition" is understood to be a substance or mixture of substances 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, or simply contact with atmospheric humidity, 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, "curability" primarily relates to the properties of the terminal silane groups of formula (I) that condense.

[0023] When referring to the molecular weight of an oligomer or polymer in this application, the amount is the weight average, i.e., M w The molecular weights refer to values, not number average molecular weights. Molecular weights are determined by gel permeation chromatography (GPC) preferably at 35°C according to DIN 55672 1:2007-08 using tetrahydrofuran (THF) as the eluent. The molecular weights of monomeric compounds are calculated based on their respective molecular formulas and the known molecular weights of the individual atoms.

[0024] 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, this term relates to the type of component, not the absolute number of molecules. Thus, for example, "at least one polymer" means that at least one type of polymer can be used, i.e., a mixture of one type of polymer or several different polymers can be used. Together with weight data, this 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 other than the specified amount of the relevant compound.

[0025] All percentage data indicated in connection with the compositions described herein refer to % by weight, based on the mixture concerned in each case, unless otherwise stated.

[0026] As used herein, "consisting essentially of" means that each composition consists primarily, i.e., at least 50% by weight, e.g., at least 60, 70, or 80%, of the recited components (A), (B), and (C) and optionally filler / plasticizer, as described below.

[0027] As used herein, "about" in reference to a numerical value means ±10%, preferably ±5% of the referenced value.

[0028] As used herein, "alkyl" refers to saturated aliphatic hydrocarbons, including straight-chain and branched-chain groups. The alkyl group preferably has 1 to 10 carbon atoms. (When a numerical range, e.g., "1 to 10," is indicated herein, this means that the group (in this case, the alkyl group) can have 1 carbon atom, 2 carbon atoms, 3 carbon atoms, etc., up to 10 carbon atoms.) In particular, alkyl can be a medium alkyl having 5 to 6 carbon atoms, or a lower alkyl having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, tert-butyl, etc. The alkyl group can be substituted or unsubstituted. As used in this context, "substituted" means that one or more carbon and / or hydrogen atoms of the alkyl group are replaced by heteroatoms or functional groups. Functional groups that can replace hydrogen atoms include, inter alia, =O, =S, -OH, -SH, -NH2, -NO2, -CN, -F, -Cl, -Br, -I, -COOH, -CONH2, -OCN, -NCO, -C, and -C. 3-8 Cycloalkyl, C 6-14 The heteroaryl group is selected from aryl, a 5-10-membered heteroaryl ring in which one to four ring atoms are independently nitrogen, oxygen, or sulfur, and a 5-10-membered heteroalicyclic ring in which one to three 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 replaced with heteroatoms, particularly those selected from O, S, N, and Si, are obtained by replacing one or more carbon atoms with heteroatoms. Examples of such heteroalkyl groups include, but are not limited to, methoxymethyl, ethoxyethyl, propoxypropyl, methoxyethyl, isopentoxypropyl, ethylaminoethyl, trimethoxypropylsilyl, and the like.

[0029] As used herein, "alkenyl" refers to an alkyl group, as defined herein, consisting of at least two carbon atoms and at least one carbon-carbon double bond, e.g., ethenyl, propenyl, butenyl, or pentenyl, and structural isomers thereof, e.g., 1- or 2-propenyl, 1-, 2-, or 3-butenyl, etc. Alkenyl groups can 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 via -O-. Thus, each term includes enoxy groups, such as vinyloxy (HC=CH-O-).

[0030] 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 structural isomers thereof, as defined above. Alkynyl groups can 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-.

[0031] As used herein, "alicyclic group" or "cycloalkyl group" refers to a monocyclic or polycyclic group (several rings share carbon atoms), particularly of 3 to 8 carbon atoms, in which the rings do not have a fully conjugated pi-electron system, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, and the like. Cycloalkyl groups can be substituted or unsubstituted. "Substituted," as used in this context, means that one or more hydrogen atoms of the cycloalkyl group have been replaced with a functional group. Functional groups that can replace hydrogen atoms include, among others, =O, =S, -OH, -SH, -NH2, -NO2, -CN, -F, -Cl, -Br, -I, -COOH, -CONH2, -OCN, -NCO, -C ... 1-10Alkyl, 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-.

[0032] As used herein, "aryl" specifically refers to a 6-14 monocyclic or polycyclic group (i.e., rings having a common adjacent carbon atom) having a completely conjugated pi-electron system. Examples of aryl groups are phenyl, naphthalenyl, and anthracenyl. Aryl groups can be substituted or unsubstituted. If they are 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-.

[0033] As used herein, a "heteroaryl" group refers specifically to a monocyclic or polycyclic (i.e., rings which share adjacent pairs of ring atoms) aromatic ring having 5 to 10 ring atoms, where 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, Heteroaryl groups include aryl, isobenzothienyl, indolyl, isoindolyl, 3H-indolyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, quinolizinyl, quinazolinyl, phthalazinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, quinolyl, isoquinolyl, tetrazolyl, 5,6,7,8-tetrahydroquinolyl, 5,6,7,8-tetrahydroisoquinolyl, purinyl, pteridinyl, pyridinyl, pyrimidinyl, carbazolyl, xanthenyl, and benzoquinolyl. Heteroaryl groups can be substituted or unsubstituted. If substituted, the substituents are as defined above for cycloalkyl. As used herein, "(hetero)aryl" refers to both aryl and heteroaryl groups as defined herein. "Heteroaryloxy" refers to a heteroaryl group, as defined herein, attached to the rest of the molecule via -O-.

[0034] As used herein, a "heteroalicyclic group" or "heterocycloalkyl group" refers to a monocyclic or fused ring having 5 to 10 ring atoms containing one, two, or three heteroatoms selected from N, O, and S, whereby 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. Heterocycloalkyl groups can 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-.

[0035] The curable composition of the present invention comprises, as component (A), at least one polyorganosiloxane end-capped with a silane group of formula (I). Such a polymer can be 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, it is preferred that one or more hydroxy groups are bonded to a terminal silicon atom. If the polyorganosiloxane is branched, it preferably has a hydroxy group at each end. Thus, although the present invention extends 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 be end-capped with a group of formula (I).

[0036] The polyorganosiloxane having at least one hydroxy group bonded to a silicon atom is preferably a polydiorganosiloxane, preferably a polydimethylsiloxane.

[0037] Therefore, preferably, α,ω-dihydroxy-terminated polydiorganosiloxanes, especially 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 5,000 to 120,000 cSt, especially 10,000 to 100,000 cSt, and particularly preferably 50,000 to 90,000 cSt.

[0038] 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, wherein Alk is C 1-10 A is a linear or branched divalent group selected from the group consisting of alkyl, preferably methyl, or derivatives thereof. A is a group of formula -(CH2) 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-.

[0039] Alternatively, in various embodiments, the polyorganosiloxane may be selected from the group consisting of -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' can be a hydrocarbon moiety having 1 to 6 carbon atoms, optionally substituted with hydrogen or halogen, and is preferably C-C alkyl or hydrogen. In such embodiments, A may consist of the aforementioned groups further linked to an optionally substituted divalent alkylene group having 1 to 10 carbon atoms (optionally interrupted by a heteroatom), preferably -CH- or (CH)-. 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 full linker -A- is -OC(=O)-NH-C 1-10 Alkylene- or OC 1-10 It can be alkylene-.

[0040] To obtain polymer (A), the polymer may be reacted with a suitable silane crosslinker to produce the desired polymer (A). Generally, the crosslinker has the formula: [ka] [C is a reactive group that reacts with the end group of the polymer, typically -OH or amino or isocyanate, to form the linking group -A-] It is silane.

[0041] Suitable reactions are known, also known as endcapping. These can be carried out optionally in the presence of a catalyst, whereby the catalyst 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 0 564 253 A1.

[0042] In the group of formula (I), each R 1 independently represent 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 in addition, one or more R 1 may represent hydrogen, halogen, amino, oximino, alkenyloxy, alkylnyloxy, cycloaliphatic -O-, aryloxy, heteroaryloxy, heterocycloaliphaticoxy, acyl, acyloxy, or combinations thereof.

[0043] In various embodiments, each R 1 are, 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, oximino, alkenyloxy having 2 to 10 carbon atoms, or amino.

[0044] In certain embodiments, each R 1 independently represent methyl, vinyl or phenyl, with methyl and vinyl being particularly preferred.

[0045] In formula (I), each R 2are independently represented by the general formula (2): [ka] [In the formula, 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 - and R 4 is a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloaliphatic, aryl, heteroaryl, and heterocycloaliphatic group, or combinations thereof; Each R 5 are independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, alicyclic, or aryl groups; o is an integer of 1 to 10, preferably 1 to 5, more preferably 1 or 2. represents a group of

[0046] In various embodiments, each R 2 represent, independently of one another, a group of formula (2), and R 4 represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, particularly 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 - [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 its (alkyl) esters, such as ethylcarboxymethyl.

[0047] In various embodiments, each R 2represent, independently of one another, a lactate ester, preferably the ethyl ester, or a malic acid mono- or diester, preferably the mono- or diethyl ester.

[0048] In other embodiments, each R 2 is derived from salicylic acid, i.e., Y is 1,2-phenylene. The salicylic acid residue is an ester, such as a methyl or ethyl ester, preferably the ethyl ester.

[0049] In various embodiments, each R 3 are each independently represented by the general formula (3): [ka] represents a group of

[0050] In various embodiments, Y is as defined above and R 6 is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloaliphatic, aryl, heteroaryl, and heterocycloaliphatic groups, or combinations thereof, or R 7 R 7 is represented by the 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, preferably a C1-10 or C1-8 alkylene group, more preferably a C1-C3 alkylene group, most preferably a methylene (CH2) or propylene ((CH2)3) group; Each R 9 are independently selected from the group consisting of hydrogen, halogen, amino, substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloaliphatic, aryl, heteroaryl, and heterocycloaliphatic groups, or combinations thereof; Each R 10are independently selected from the group consisting of substituted or unsubstituted alkyl, alkenyl, alkynyl or acyl groups, preferably unsubstituted lower alkyl, more preferably methyl or ethyl; each p independently represents 0, 1 or 2, preferably 0 or 1, more preferably 0. is the basis of

[0051] In various embodiments, in the group of formula (3), Y is as defined above for the group of formula (2), i.e., Y is a substituted or unsubstituted aromatic group having 6 carbon ring atoms, preferably 1,2-phenylene, or -(C(R)) 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 its (alkyl) esters, such as ethylcarboxymethyl.

[0052] 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.

[0053] In various embodiments, R 8 is preferably of the formula -(CH2) 1-8 -, more preferably -(CH2) 1-5 -, even more preferably -(CH2) 1-3 -, most preferably -CH2- or (CH2)3-.

[0054] In various embodiments, preferably, each R 9are each independently 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 4 carbon atoms, particularly preferably methyl or ethyl.

[0055] In various embodiments, preferably, each R 10 are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, preferably an unsubstituted alkyl group having 1 to 10 carbon atoms, in particular an unsubstituted alkyl group having 1 to 4 carbon atoms, particularly preferably methyl or ethyl, most preferably methyl.

[0056] Preferably, each R 3 are each independently of one another represented by the formula (3), wherein 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 group is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, in particular methyl, carboxymethyl or an (alkyl) ester thereof, and R 6 represents hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, particularly 1 to 4 carbon atoms, and R 7 is expressed by the formula (4) [wherein R 8 is a C1-10 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 1 to 4 carbon atoms, particularly preferably methyl or ethyl, and each R 10 are each independently a substituted or unsubstituted alkyl having 1 to 10 carbon atoms, in particular 1 to 4 carbon atoms, particularly preferably methyl or ethyl; and p is 0 or 1, preferably 0.

[0057] In a first embodiment, n and m in formula (1) are selected so that the sum of n+m is 3. In this case, the silane of formula (1) is R 3 In this case, the silane group of formula (1) does not contain a hydroxycarboxylic acid amide group, i.e., does not contain a hydroxycarboxylic acid amide group. Preferred silane groups of formula (1) 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.

[0058] In a second embodiment, n and m in formula (1) are selected so that the sum of n+m is 2. In this case, the silane of formula (1) contains at least one R 3 group, i.e., at least one hydroxycarboxylic acid amide group. Preferred silanes of formula (1) in this case include 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, and silanes of formula (5): [ka] [where p, R 6 , R 8 , R 9 and R 10have in each case independently of one another the general, preferred and particularly preferred meanings given above] 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.

[0059] In various embodiments, the curable composition comprises the polyorganosiloxane (A) in an amount of 32 to 97% by weight, particularly preferably 40 to 70% by weight, in each case based on the total weight of the composition. When a mixture of polyorganosiloxanes is used, the amount relates to the total amount of polyorganosiloxanes in the composition.

[0060] The curable composition comprises, as component (B), a compound of formula (II): [ka] [In the formula, R 11 is an alkylene group, preferably C-C, optionally interrupted by a heteroatom, such as O, N, S or Si. 10 alkylene, more preferably C1 or C3 alkylene; Each R 12are independently selected from the group consisting of hydrogen, halogen, amino, substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloaliphatic, aryl, heteroaryl, and heterocycloaliphatic groups, or combinations thereof; Each R 13 are independently selected from the group consisting of substituted or unsubstituted alkyl, alkenyl, alkynyl, or acyl groups; q independently represents 0, 1, or 2; B is expressed by the formula (6): [ka] Formula (7): [ka] or equation (8): TIFF0007808432000017.tif3582 [In the formula, each R 14 , R 14a , R 14b , R 14c , R 15 and R 16 are independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloaliphatic, aryl, heteroaryl, and heterocycloaliphatic groups, or combinations thereof; r is 1, 2, 3, or 4. is a nitrogen-containing group selected from the group at least one capped adhesion promoter of

[0061] R 11 is an alkylene group interrupted by a heteroatom such as O, N, S or Si, N is NR 13a Si may be Si(R 13a )2[each R 13a is independently selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, cycloaliphatic, aryl, heteroaryl, and heterocycloaliphatic groups, or combinations thereof.

[0062] The terms "blocked" and "capped" are used interchangeably herein with respect to the compound of formula (II) and polymer (A). Additionally, the compound of formula (II) is referred to herein as a blocked / capped adhesion promoter.

[0063] In various embodiments, each R 12 and R 13 is independently selected from methyl and ethyl, and preferably each R 13 is ethyl.

[0064] In various embodiments, R 13 may be alkyl or substituted alkyl, such as aminoalkyl. Preferred (amino)alkyl groups are C1-C6 alkyl groups, preferably straight-chain alkyl groups optionally having a terminal amino group, such as ethyl, n-propyl, n-butyl and n-pentyl, alkylamino or dialkylamino groups, such as N,N-di(C1-C4 alkyl)amino groups, such as N,N-dimethyl- or N,N-diethylamino groups.

[0065] In various embodiments, in formula (6), one R 14 is hydrogen or methyl, preferably hydrogen, and 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.

[0066] In various embodiments, in formula (7), R 14a and R 14b and one R 14c is hydrogen or methyl, preferably hydrogen, and other R 14c is an unsubstituted alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, or an unsubstituted aryl group, preferably phenyl.

[0067] In various embodiments, R in formula (8) 15 and R16 is hydrogen.

[0068] In formula (8), r is preferably 1 or 2, and more preferably 1.

[0069] In various embodiments, the capped adhesion promoter is one in which q is 0 and R 11 is methylene or propylene, preferably propylene, and each R 13 is methyl or ethyl, preferably ethyl, and B is a group represented by the formula (6) [In the formula, (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] is a ketimine of formula (II)

[0070] The curable composition preferably contains the capped adhesion promoter in an amount of about 0.1 to about 5 wt. %, preferably 0.5 to 2 wt. %, 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.

[0071] "Blocked," as used herein in relation to compounds of formula (II), refers to the fact that the compound is derivatized such that the active compound is released only upon contact with water and / or oxygen.

[0072] The curable composition finally comprises as component (C) at least one curing catalyst.

[0073] 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, particularly 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 compound. Suitable organic tin compounds include, for example, 1,3-dicarbonyl compounds of divalent or tetravalent tin, such as acetylacetonates, e.g., 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, e.g., di-n-butyltin dilaurate, di-n-butyltin maleate, and the like. di-n-butyltin 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.

[0074] Also suitable are tin compounds of 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(butyl). di(isooctylmaleate), di(n-octyl)tin(IV) di(isooctylmaleate); 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-CH 17 )2, (n-octyl)2Sn(SCH2COO-i-C8H 17 )2 and (n-octyl)2Sn(SCH2COO-n-CH 17 )2.

[0075] 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.

[0076] Particularly preferably, the tin compound is a dialkyltin(IV) dicarboxylate, in particular di-n-butyltin dilaurate or di-n-octyltin dilaurate.

[0077] Additionally or alternatively, other metal-based condensation catalysts may be used, including, but not limited to, titanium compounds 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 the main group or salts of bismuth, lithium, strontium, or boron.

[0078] Further suitable (tin-free) curing catalysts are, for example, organometallic compounds of iron, in particular 1,3-dicarbonyl compounds of iron, such as iron(III) acetylacetonate.

[0079] Boron halides, such as boron trifluoride, boron trichloride, boron tribromide, boron triiodide, or mixtures of boron halides, can 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.

[0080] 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).

[0081] Titanium, aluminum and zirconium compounds or mixtures of one or more catalysts from one or more of the aforementioned groups may also be used as catalysts.

[0082] Suitable titanium catalysts are compounds having hydroxy groups and / or substituted or unsubstituted alkoxy groups, and therefore of the general formula [ka] [In the formula, R z is an organic group, preferably a substituted or unsubstituted hydrocarbon group having 1 to 20 C atoms, and is substituted with four alkoxy groups -ORz are the same or different. In addition, one or more -OR z The group is an acyloxy group -OCOR z can be replaced by It is a titanium alkoxide.

[0083] Also suitable as titanium catalysts are titanium alkoxides in which one or more alkoxy groups are replaced by hydroxy groups or halogen atoms.

[0084] Additionally, titanium chelate complexes can be used.

[0085] Aluminum catalysts, such as aluminum alkoxides [ka] [In the formula, R z has the above meaning; i.e. is an organic group, preferably a substituted or unsubstituted hydrocarbon group having 1 to 20 C atoms, and z The groups may be the same or different. In the case of aluminum alkoxides, one or more alkoxy groups may be replaced by an acyloxy group -OC(O)R z can be replaced by can also be used as a curing catalyst.

[0086] Additionally, aluminum alkoxides in which one or more alkoxy groups are replaced with hydroxy groups or halogen atoms can be used.

[0087] 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, aluminum chelate complexes are preferred.

[0088] Suitable zirconium catalysts are, for example, tetramethoxyzirconium or tetraethoxyzirconium.

[0089] Diisopropoxyzirconium bis(ethylacetoacetate), triisopropoxyzirconium(ethylacetoacetate) and isopropoxyzirconium tris(ethylacetoacetate) are very particularly preferably used.

[0090] Additionally, for example, zirconium acylate can be used.

[0091] Zirconium halide catalysts may also be used.

[0092] Additionally, zirconium chelate complexes may also be used.

[0093] Furthermore, metal carboxylates or mixtures of several such salts can be used as curing catalysts, whereby these are selected from the carboxylates of the following metals: calcium, vanadium, iron, zinc, titanium, potassium, barium, manganese, nickel, cobalt and / or zirconium.

[0094] Among the carboxylates mentioned above, the carboxylates of calcium, vanadium, iron, zinc, titanium, potassium, barium, manganese and zirconium are preferred because they exhibit high activity. Calcium, vanadium, iron, zinc, titanium and zirconium carboxylates are particularly preferred. Iron and titanium carboxylates are very particularly preferred.

[0095] The curable composition preferably comprises a curing catalyst in an amount of about 0.05 to 2% by weight, preferably 0.1 to 1.5 or 0.1 to 0.5% by weight, in each case based on the total weight of the composition. When a mixture of different catalysts is used, the amount refers to the total amount in the composition.

[0096] The compositions of the present invention crosslink in the presence of moisture and, in doing so, cure with the formation of Si-O-Si bonds.

[0097] The molar ratio of the capped adhesion promoter and tin compound may be adjusted in various embodiments so that it is at least 1:1, for example, in the range of 1:1 to 50:1, which may help ensure that the curable composition has very high storage stability on the one hand, and that it cures reliably and quickly after application, even at room temperature (23°C) in the presence of atmospheric moisture on the other hand.

[0098] The curable composition may include one or more components, apart from components (A), (B) and (C), that can be used to selectively affect certain properties of the curable composition and / or the cured product.

[0099] These other ingredients may be selected from the group including, for example, plasticizers, stabilizers, antioxidants, fillers, reactive diluents, drying agents, adhesion promoters other than the capped adhesion promoter of formula (II), UV stabilizers, rheological aids and / or solvents. Of particular interest are the plasticizers, fillers and stabilizers, which typically include antioxidants and UV stabilizers.

[0100] Preferably, therefore, the curable composition comprises at least one further component.

[0101] The compositions described herein may further comprise up to about 20% by weight of a conventional adhesion promoter (tackifier). Suitable adhesion promoters include, for example, resins, terpene oligomers, coumarone / indene resins, aliphatic petrochemical resins, and modified phenolic resins. Within the context of the present invention, suitable resins include hydrocarbon resins such as those obtainable by polymerization of terpenes (primarily α- or β-pinene), dipentene, or limonene. These monomers typically undergo cationic polymerization upon initiation using Friedel-Crafts catalysts. Terpene resins also include copolymers of terpenes with other monomers (e.g., 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 rubber. Also suitable as additives in the aforementioned sense within the context of the present invention are rosin resins and their derivatives, such as their esters.

[0102] Also suitable are silane adhesion promoters, in particular alkoxysilanes which carry (further) functional groups such as amino, mercapto, epoxy, carboxyl, vinyl, isocyanate, isocyanurate groups or halogens. Examples thereof 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.

[0103] Apart from the compound of formula (II), it is further possible to include a further adhesion promoter, said adhesion promoter being an aminosilane, such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, aminomethyltrimethoxysilane, aminomethyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, (N-2-aminoethyl)-3-aminopropyltrimethoxysilane, (N-2-aminoethyl)-3-aminopropyltriethoxysilane, diethylenetriaminopropyltrimethoxysilane, phenylaminomethyltrimethoxysilane, (N-2-aminoethyl)-3-aminopropyl Pyrmethyldimethoxysilane, 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)propyltriethoxysilane, (N,N-di (Methylamino)methyltrimethoxysilane, (N,N-dimethylamino)methyltriethoxysilane, 3-(N,N-diethylamino)propyltrimethoxysilane, 3-(N,N-diethylamino)propyltriethoxysilane, (N,N-diethylamino)methyltrimethoxysilane, (N,N-diethylamino)methyltriethoxysilane, 4-amino-3,3-dimethylbutyltrimethoxysilane, 4-amino-3,3-dimethylbutyltriethoxysilane, bis(3-trimethoxysilyl)propyl Amines, bis(3-triethoxysilyl)propylamine and mixtures thereof, particularly preferably 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,It may be selected from 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.

[0104] In various embodiments, the compositions of the present invention further comprise at least one aminosilane, particularly one of the tertiary aminosilanes described above. 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 residues. In various embodiments, the aminosilane is 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)methyltrimethoxysilane, (N,N-dimethylamino)methyltriethoxysilane, 3-(N,N-diethylamino)propyltrimethoxysilane, 3-(N,N-diethylamino)propyltriethoxysilane, (N,N-diethylamino)methyltrimethoxysilane, (N,N-diethylamino)methyltriethoxysilane Ethoxysilane, bis(3-trimethoxysilyl)propylamine, bis(3-triethoxysilyl)propylamine and mixtures thereof, particularly preferably 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,N-diethylamino)propyltriethoxysilane, (N,N-diethylamino)methyltrimethoxysilane, (N,N-diethylamino)methyltriethoxysilane, 4-amino-3,3-dimethylbutyltrimethoxysilane and 4-amino-3,3-dimethylbutyltriethoxysilane are preferred.

[0105] The viscosity of the curable composition is considered too high for certain applications, and therefore, reactive diluents are usually used to reduce the viscosity in a simple and convenient way without any signs of demixing in the cured mass (e.g. migration of plasticizers).

[0106] 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, vinylically unsaturated groups and polyunsaturated systems.

[0107] Any compound that can reduce the viscosity and be mixed with the other ingredients and that has at least one group that reacts with the polymer can be used as a reactive diluent.

[0108] The viscosity of the reactive diluents 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).

[0109] For example, the following substances can 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 these compounds.

[0110] Additionally, the following polymers from Kaneka Corp. can also be used as reactive diluents: MS S203H, MS S303H, MS SAT 010, and MS SAX 350.

[0111] For example, silane-modified polyethers derived from the reaction of isocyanatosilane with Synalox types can be used as well.

[0112] Polymers that can be prepared from an organic backbone by grafting with vinylsilanes or by reacting polyols, polyisocyanates and alkoxysilanes can further be used as reactive diluents.

[0113] Polyols are understood to be compounds which may contain one or more OH groups in the molecule, said OH groups being both primary and secondary.

[0114] 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 esters, carbonates, or amides.

[0115] To prepare the preferred reactive diluents, the corresponding polyol component is in each case reacted with an at least difunctional isocyanate. While any isocyanate having at least two isocyanate groups may in principle be used as the at least difunctional isocyanate, within the scope of the present invention, compounds having 2 to 4 isocyanate groups, in particular 2 isocyanate groups, are generally preferred.

[0116] Preferably, the compound present as reactive diluent has at least one alkoxysilyl group, whereby the alkoxysilyl groups are preferably di- and trialkoxysilyl groups.

[0117] 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-trimethylisocyanate, 1,4-tetramethylisocyanate, 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-trimethylisocyanate, 1,6-hexamethylene di ... 1,6-Diisocyanato-2,2,4-trimethylhexane, 1,6-Diisocyanato-2,4,4-trimethylhexane, Xylylene diisocyanate (XDI), tetramethyl-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), tetramethyl xylene 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 tetraalkyldiphenylmethane diisocyanates and their partially or fully hydrogenated cycloalkyl derivatives, 4,4'-diisocyanatophenylperfluoroethane, phthalic acid bis-isocyanatoethyl ester, 1-chloromethylphenyl-2,4- or 2,6-diisocyanate, 1-bromomethylphenyl-2,4- or 2,6-diisocyanate, 3,3-bis-chloromethylether-4,4'-diphenyl diisocyanate, sulfur-containing diisocyanates (obtainable by reacting 2 moles of a diisocyanate with 1 mole of thiodiglycol or dihydroxydihexyl sulfide), di- and triisocyanates of dimeric and trimeric fatty acids, or mixtures of two or more of the aforementioned diisocyanates.

[0118] Trivalent or higher isocyanates, such as those obtained by oligomerization of diisocyanates, especially the aforementioned isocyanates, can also be used as polyisocyanates. Examples of such trivalent and higher polyisocyanates are the triisocyanurates of HDI or IPDI or mixtures thereof, or mixtures of these triisocyanurates, and polyphenylmethylene polyisocyanates obtained by phosphorylating aniline-formaldehyde condensation products.

[0119] Solvents and / or plasticizers can be used in addition to or in place of reactive diluents to reduce the viscosity of the curable composition.

[0120] Suitable solvents are aliphatic or aromatic hydrocarbons, halogenated hydrocarbons, ketones, ethers, esters, ester alcohols, keto alcohols, keto ethers, keto esters and ether esters.

[0121] The compositions described herein can further include a hydrophilic plasticizer. These are used to improve moisture absorption and thereby reactivity at low temperatures. Suitable plasticizers include, for example, esters of abietic acid, adipates, azelates, benzoates, butyrates, acetates, esters of higher fatty acids having from about 8 to about 44 carbon atoms, epoxidized fatty acids, fatty acid esters and fats, glycolates, phosphates, phthalates, linear or branched alcohols having from 1 to 12 carbon atoms, propionates, sebacates, sulfonates, thiobutyrates, trimellitates, citrates, and esters based on nitrocellulose and polyvinyl acetate, as well as mixtures of two or more of these.

[0122] For example, among the phthalic acid esters, dioctyl phthalate, dibutyl phthalate, diisoundecyl phthalate or butyl benzyl phthalate are suitable, and among the adipates, dioctyl adipate, diisodecyl adipate, diisodecyl succinate, dibutyl sebacate or butyl oleate are suitable.

[0123] 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, such as dioctyl ether (available as Cetiol OE (Cognis Deutschland GmbH, Dusseldorf)).

[0124] End-capped polyethylene glycol, such as 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, are also suitable as plasticizers.

[0125] Suitable plasticizers are end-capped polyethylene glycols such as polyethylene or polypropylene glycol dialkyl ethers (where the alkyl group has up to four carbon atoms), especially the dimethyl and diethyl ethers of diethylene glycol and dipropylene glycol. Acceptable cure is achieved even under less favorable application conditions (low humidity, low temperature), especially with dimethyldiethylene glycol. For further details on plasticizers, see the relevant technical chemistry literature.

[0126] Also suitable as plasticizers are diurethanes, which 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.Another method for preparing diurethanes is to react a monofunctional alcohol with a diisocyanate, thereby reacting, if possible, all NCO groups.

[0127] In various embodiments, the plasticizer may be a polydimethylsiloxane different from (A), in particular a PDMS that does not have the end group of formula (I).

[0128] In various embodiments, the curable composition includes at least one plasticizer, such as polydimethylsiloxane.

[0129] The curable composition preferably comprises a plasticizer in an amount of 1 to 50% by weight, preferably 10 to 40% by weight, particularly preferably 20 to 30% by weight, in each case based on the total weight of the composition. When a mixture of plasticizers is used, the amount refers to the total amount of plasticizer in the composition.

[0130] Preferably, the curable composition comprises at least one stabilizer selected from antioxidants, UV stabilizers and drying agents.

[0131] All conventional antioxidants may be used as antioxidants, which are preferably present in an amount of up to about 7% by weight, in particular up to about 5% by weight.

[0132] The compositions herein may contain a UV stabilizer, preferably used in an amount of 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. Additionally, benzotriazoles, benzophenones, benzoates, cyanoacrylates, acrylates, sterically hindered phenols, phosphorus, and / or sulfur may also be added.

[0133] To further enhance storage stability (shelf life), it is often useful to stabilize the composition with respect to penetrating moisture by a desiccant.

[0134] Such improvement in storage stability can be achieved, for example, by using desiccant.All compounds that react with water to form inert groups to the reactive groups present in composition are suitable as desiccant, and thereby minimize the change in molecular weight as much as possible.In addition, the reactivity of desiccant to the moisture that penetrates into the preparation must be higher than the reactivity of the group of the silyl group-containing polymer of the present invention present in the preparation.

[0135] For example, isocyanates are suitable as drying agents.

[0136] However, silanes are preferably used as drying agents. For example, vinylsilanes such as 3-vinylpropyltriethoxysilane, oximesilanes such as methyl-O,O',O''-butan-2-one-trioximosilane or O,O',O'',O''''-butan-2-one-tetraoximosilane (CAS Nos. 022984-54-9 and 034206-40-1), benzamidosilanes such as bis(N-methylbenzamido)methylethoxysilane (CAS No. 16230-35-6), or carbamatosilanes such as carbamatomethyltrimethoxysilane. Methyl-, ethyl-, or vinyltrimethoxysilane, tetramethyl-, or tetraethylethoxysilane can also be used. Vinyltrimethoxysilane and tetraethoxysilane are particularly suitable in terms of cost and efficiency.

[0137] Also suitable as desiccants are the reactive diluents described above, except that they have a molecular weight (M) of less than about 5000 g / mol. n ) and has terminal groups whose reactivity towards the permeated moisture is at least the same as (and preferably higher than) the reactivity of the reactive groups of the polymer used according to the invention.

[0138] Finally, alkyl orthoformates or alkyl orthoacetates, such as methyl or ethyl orthoformate or methyl or ethyl orthoacetate, can also be used as drying agents.

[0139] The composition generally contains from about 0 to about 6% by weight of a desiccant.

[0140] The compositions described herein may further comprise fillers. Suitable fillers include, for example, chalk, lime powder, precipitated and / or calcined (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 mineral substances. Organic fillers, such as carbon black, graphite, wood fiber, wood flour, sawdust, cellulose, cotton, pulp, cotton, wood chips, chopped straw, and rice husks, can also be used. Short fibers, such as glass fiber, glass filament, polyacrylonitrile, carbon fiber, Kevlar fiber, or polyethylene fiber, can also be added. Aluminum powder is also suitable as a filler.

[0141] The calcined (fumed) and / or precipitated silica is preferably 10 to 90 m 2 / g. When used, they do not cause a further increase in the viscosity of the compositions of the present invention, but contribute to the toughening of the cured composition.

[0142] Similarly, a larger BET surface area, advantageously 100-250 m 2 / g, especially 110-170m 2 It is conceivable to use pyrogenic and / or precipitated silica as a filler, having a BET surface area of ​​1 / g. Due to the larger BET surface area, the same effect (e.g., 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.

[0143] Further suitable fillers are hollow spheres with mineral or plastic shells. These may be, for example, hollow glass spheres commercially available under the trade name GlassBubbles®. Plastic hollow spheres, such as Expancel® or Dualite®, are described, for example, in EP 0520426. They are composed of inorganic or organic materials and have a diameter of 1 mm or less, preferably 500 μm or less.

[0144] Fillers that impart thixotropy to the formulation are preferred for many applications. Such fillers, also referred to as rheological additives, are, for example, hydrogenated castor oil, fatty acid amides, or swellable plastics, such as PVC. To ensure easy squeezability from a suitable dispensing device (e.g., a tube), such formulations have a viscosity of 3,000 to 15,000, preferably 40,000 to 80,000 mPas, or 50,000 to 60,000 mPas.

[0145] 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, based in each case on the total weight of the composition. Naturally, 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.

[0146] The curable composition can be prepared by simply mixing the polyorganosiloxane (A), the capped adhesion promoter, the catalyst, and optionally other components. This can be done in a suitable dispersion unit, such as a high-speed mixer. In this case, care is preferably taken to minimize contact of moisture with the mixture, which could lead to undesired premature curing. Suitable measures are well known and include, for example, working in an inert atmosphere (possibly under protective gas) and drying / heating the individual components before adding them.

[0147] The compositions of the present invention can be used as adhesives or sealing or coating materials.

[0148] The composition can be used, for example, as an adhesive, a sealant, a coating, and for the production of molded parts. Further application areas of the composition are as a plugging compound, a hole filler, or a crack filler. The use as a sealant is preferred.

[0149] 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 sealing construction elements, windows, wall and floor coverings, and general joints, where the materials can be bonded to themselves or to each other as needed.

[0150] The following examples serve to illustrate the invention without, however, limiting it thereto. [Example]

[0151] Example 1: Comparative compositions C1 and C2 and compositions E1 and E2 according to the invention were prepared by mixing the raw materials listed in Table 1. The preparations differ in the type of adhesion promoter used. Polyorganosiloxane (A) was obtained in a first step by mixing polydimethylsiloxane with vinyltris(ethyllactato)silane to obtain polymer (A).

[0152] [Table 1]

[0153] Polymer (A) was formed in a previous step from α,ω-dihydroxy-terminated polydimethylsiloxane and vinyltris(ethyllactato)silane, and then combined with an adhesion promoter containing a ketimine and a curing catalyst.

[0154] The prepared formulations were subjected to the following curing performance tests.

[0155] Skin Over Time (SOT) Measurement: Skin over time (SOT) is defined as the time required for a material to form a non-tacky surface film. Skin over time measurements are carried out according to DIN 50014 under standard climatic conditions (23 + / - 2°C, 50 + / - 5% relative humidity). The sealant temperature must be 23 + / - 2°C and the sealant must have been stored in the laboratory for at least 24 hours beforehand. The sealant is applied to a piece of paper and spread with a putty knife to form a film (approximately 2 mm thick and 7 cm wide). A stopwatch is immediately started. At intervals, the surface is lightly touched with the tip of a finger and then removed; sufficient pressure is applied to the surface to leave a mark until the skin formation time is reached. The skin over time is reached when the sealing compound no longer adheres to the fingertip. Skin over time (SOT) is expressed in minutes.

[0156] Measurement of Shore A hardness: Shore A hardness was measured according to ISO 868.

[0157] Determination of 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 section of the strip was cut out and the thickness of the cured layer was measured with a caliper. The depth of cure after 24 hours is expressed in millimeters.

[0158] Evaluation of mechanical properties (tensile test): The breaking strength, elongation at break, and yield stress values ​​(e-module) are determined in a tensile test 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 approximately 45 mm; total length 9 cm. Tests were performed under normal conditions (23 + / - 2 °C, 50 + / - 5% relative humidity). Measurements were performed 7 days after curing. Procedure: The prepolymer mixture (preparation) was spread on a uniform surface to form a 2 mm thick film. After 7 days of curing under normal conditions (see above), dumbbell specimens were punched out. Three specimens were used for each measurement. Tests were performed under normal conditions. The specimens must be at the same temperature as the measurements. Prior to the measurement, the thickness of the specimen was measured at least three different positions (center and both ends) using a vernier caliper. The average value was entered 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 includes as large a surface area as possible of the rod head without clamping the middle bar. The dumbbell is then pulled to <0.1 MPa at a rate of 50 mm / min. A force-extension curve is then recorded at a linear speed of 50 mm / min. Evaluation: The following values ​​are determined: [N / mm 2 ], breaking strength in [%] and breaking elongation in [N / mm 2 ]Modulus of elasticity at 100% elongation.

[0159] Peel test: If possible and necessary, the substrate (test panel) is cleaned before application using an appropriate solvent. A strip of material 10 mm high (+ / - 1 mm) and 20 mm wide (+ / - 2 mm) was applied to the substrate using a Teflon spatula. The samples were stored for 7 days under normal conditions (23 + / - 2°C, 50 + / - 5% relative humidity). The cured material was cut to at least 15 mm with a shape blade and the bead was pulled by hand. The failure mode was recorded as follows:

[0160] [Table 2]

[0161] [Table 3]

[0162] [Table 4]

[0163] The results show that the compositions of the present invention have better adhesion and significantly higher storage stability compared to the comparative compositions.

Claims

1. (A) Formula (I): 【Chemistry 1】 [In the formula, A is a bond, -O-, or a linear, branched, or cyclic divalent group selected from a hydrocarbon residue having 1 to 12 carbon atoms, alkylene, arylene, oxyalkylene, oxyarylene, siloxane-alkylene, siloxane-arylene, ester, amine, glycol, imide, amide, alcohol, carbonate, urethane, urea, sulfide, ether, or derivatives thereof, or combinations thereof; Each R １ are independently selected from the group consisting of hydrogen, halogen, amino, oximino, substituted or unsubstituted alkyl, alkenyl, alkenyloxy, alkynyl, alkylnyloxy, cycloaliphatic, cycloaliphatic-O-, aryl, aryloxy, heteroaryl, heteroaryloxy, heterocycloaliphatic, heterocycloaliphaticoxy, acyl, acyloxy groups or combinations thereof; Each R ２ are independently represented by the 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 - and R ４ is a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloaliphatic, aryl, heteroaryl, and heterocycloaliphatic group or combinations thereof; Each R ５ are 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. is the basis of Each R ３ are independently represented by the general formula (3): 【Transformation 3】 [During the ceremony, Y is as defined above, R ６ is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl alicyclic, aryl, heteroaryl and heteroalicyclic groups or combinations thereof, or R ７ is selected from the group consisting of R ７ is represented by the general formula (4): 【Chemistry 4】 <During the ceremony, R ８ is an alkylene group optionally interrupted by a heteroatom, Each R ９ are independently selected from the group consisting of hydrogen, halogen, amino, substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloaliphatic, aryl, heteroaryl, and heterocycloaliphatic groups, or combinations thereof; Each R １０ are independently selected from the group consisting of substituted or unsubstituted alkyl, alkenyl, alkynyl, or acyl groups; each p is independently 0, 1, or 2; is the basis of m is independently 0, 1 or 2; n is independently 1, 2, or 3, and the sum of n and m is up to 3. at least one polyorganosiloxane containing at least one end group of (B) Formula (II): 【Transformation 5】 [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 are independently selected from the group consisting of hydrogen, halogen, amino, substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloaliphatic, aryl, heteroaryl, and heterocycloaliphatic groups, or combinations thereof; Each R １３ are independently selected from the group consisting of substituted or unsubstituted alkyl, alkenyl, alkynyl, or acyl groups; q independently represents 0, 1, or 2; B is represented by the formula (6): 【Transformation 6】 Formula (7): 【Transformation 7】 Or formula (8): 【Transformation 8】 [During the ceremony, Each R １４ , R １４ａ , R １４ｂ , R １４ｃ , R １５ and R １６ are independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloaliphatic, aryl, heteroaryl, and heterocycloaliphatic groups, or combinations thereof; r is 1, 2, 3 or 4. is a nitrogen-containing group selected from the group at least one capped adhesion promoter of (C) at least one curing catalyst 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 siloxane-alkylene, preferably of the formula —(CH ２ ) １－１０ -(Si(Alk) ２ -O-Si(Alk) ２ ) １－１０ - (CH ２ ) １－１０ wherein Alk is C １－１０ 3. The curable composition according to claim 1, wherein R is a linear or branched divalent group selected from the group consisting of alkyl, preferably methyl, and derivatives thereof.

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, oximino, alkenyloxy having 2 to 10 carbon atoms, or amino; and / or Each R ２ are each independently a group represented by the formula (2) [wherein 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 4. The curable composition according to claim 1, wherein the group is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, in particular methyl, carboxymethyl or an (alkyl) ester thereof.

5. The curable composition according to any one of claims 1 to 4, wherein the sum of n and 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 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.

7. the sum of n+m is at most 2; Each R ３ are each independently represented by the formula (3), wherein 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 group is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, in particular methyl, carboxymethyl or an (alkyl) ester thereof, and R ６ represents hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, in particular 1 to 4 carbon atoms, and R ７ is represented by formula (4) [wherein R ８ is a C1-10 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 1 to 4 carbon atoms, particularly preferably methyl or ethyl, and each R １０ are each independently 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 p is 0 or 1, preferably 0.

8. The capped adhesion promoter is a ketimine of formula (II), where q is 0 and R １１ is methylene or propylene, preferably propylene, and each R １３ is ethyl, and B is a compound of formula (6): [In the formula, (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] The curable composition according to any one of claims 1 to 7, wherein the group is

9. (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 0.5 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 wt. %, preferably 0.1 to 0.5 wt. %, based on the total weight of the composition; The curable composition according to any one of claims 1 to 8.

10. 10. The curable composition according to any one of claims 1 to 9, characterized in that the curing catalyst is selected from tin compounds, preferably organotin compounds, more preferably 1,3-dicarbonyl compounds of divalent or tetravalent tin, diallyltin(IV) dicarboxylates, dialkyltin(IV) dialkoxylates, dialkyltin(IV) oxides, tin(II) carboxylates and mixtures thereof.

11. 11. The curable composition of any of claims 1 to 10, further comprising one or more additional components selected from the group consisting of a plasticizer, a filler, a base, and an adhesion promoter different from the capped adhesion promoter (B).

12. 12. The curable composition of claim 11, wherein the composition further comprises at least one adhesion promoter different from the capped adhesion promoter, the additional adhesion promoter preferably being selected from the group consisting of 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,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.

13. Use of the curable composition according to any one of claims 1 to 12 as an adhesive, sealing or coating material.

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