Silanes and curable compositions containing same

Abstract

The present invention relates to a compound of formula Si(R 1 ) m (R 2 ) 4-m [In the formula, each R 1 each independently represents a substituted or unsubstituted alkyl, alkenyl, or alkynyl group; a substituted or unsubstituted cycloaliphatic or aryl group; a substituted or unsubstituted heteroalicyclic or heteroaryl group; 2 are independently represented by the general formula -O-CHR 3 -C(=O)-OR 4 (In the formula, R 3 independently represent: a substituted or unsubstituted alkenyl group, preferably a vinyl or allyl group; R 4 represents a group represented by the formula: (a) a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocyclyl, or heteroaryl group; and m independently represents 0 or 1, preferably 1. The present invention also relates to curable compositions comprising the silanes and curable polyorganosiloxanes end-capped with such silanes. The silanes act as crosslinkers in the curable compositions and are particularly notable because they can be obtained from renewable resources, providing high overall performance.

Description

[Technical Field]

[0001] The present invention relates to novel silanes containing at least one specific α-hydroxycarboxylic acid ester group, and to curable compositions containing the silanes and polyorganosiloxanes. The silanes are particularly attractive because they act as end-capping and cross-linking agents in the curable compositions and are derived from renewable resources. Furthermore, they offer improved properties compared to existing silane-crosslinked compounds, such as those based on lactate esters. [Background technology]

[0002] Silicone polymers (polyorganosiloxanes), especially polydialkylsiloxanes such as polydimethylsiloxane (PDMS), are of great importance in the production of adhesives, sealants, coatings, and insulating materials. Among these, those that vulcanize at low temperatures and ambient conditions account for a large share of the market. A typical formulation contains a reactive polyorganosiloxane, usually a silanol-terminated polyorganosiloxane, which has at least one, preferably two, hydroxyl groups bonded to the silicon atom. This polymer is used in combination with a silane-based crosslinker that has a hydrolyzable group bonded to the silicon atom. The term curing agent is sometimes used instead of crosslinker. Within the context of this application, the terms crosslinker and curing agent are synonymous. The polyorganosiloxane and crosslinker may exist as separate components. However, polyorganosiloxanes are often selectively reacted with crosslinkers to form modified polyorganosiloxanes, which are then added to the remainder of the curable composition. The term endcapping is also used to describe the process of reacting polyorganosiloxanes with crosslinkers. This can optionally be done in the presence of a catalyst, whereby the catalyst selectively mediates endcapping without simultaneously curing the polyorganosiloxane.

[0003] Numerous silicone crosslinkers are known. These can be classified as acidic, basic, or neutral crosslinkers based on the leaving group released upon hydrolysis. Typical acidic crosslinkers contain an acid group as the 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 metal, stone, or mortar, and also produce a strong, often unpleasant odor. Therefore, neutral crosslinkers are commonly used in modern curable silicone compositions. Representative neutral crosslinkers have hydrolyzable groups that release alcohols or oximes during crosslinking. Alkoxy crosslinkers, however, have the disadvantages of causing several problems with the storage stability of the associated curable compositions, and the cured products exhibit poor adhesion to some materials. Oximosilane crosslinkers, which hydrolyze to release an alkanone oxime, are widely used because they generally do not suffer from these drawbacks. The most common oximosilane crosslinker releases butan-2-one oxime during crosslinking. The substance is suspected to be carcinogenic, which has led to an urgent need to develop alternative neutral crosslinkers. Apart from that, the released oximes have a strong, foul odor, making the use of curable compositions containing the relevant crosslinkers unpleasant for users.

[0004] Silane compounds, particularly lactic acid and lactic acid amide compounds, which release α-hydroxycarboxylic acid esters or α-hydroxycarboxylic acid amides during crosslinking have been proposed as alternative crosslinkers. A curing agent for silicone rubber materials containing three 2-hydroxypropionic acid alkyl ester groups, i.e., lactic acid alkyl ester groups, particularly vinyltris(ethyllactato)silane, is known from EP 2030976. EP 2774672 describes a special catalyst for the crosslinking of silicone rubber materials using a crosslinker based on a silane compound containing lactic acid groups. Further crosslinker compounds are disclosed in EP 2030976, EP 3271421, EP 3271367, and EP 3613803.

[0005] While numerous crosslinked silanes have been described, there is a need in the art for alternative crosslinked silanes that can be obtained at least in part from renewable resources without compromising stability and cure characteristics, and that optimally exhibit improved technical performance. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] European Patent Application Publication No. 2030976 [Patent Document 2] European Patent Application Publication No. 2774672 [Patent Document 3] European Patent Application Publication No. 3271421 [Patent Document 4] European Patent Application Publication No. 3271367 [Patent Document 5] European Patent Application Publication No. 3613803 Summary of the Invention [Problem to be solved by the invention]

[0007] It is therefore an object of the present invention to provide novel silane compounds that can be used as neutral crosslinkers in curable compositions based on polyorganosiloxanes, which are at least partially obtained from renewable resources and have superior properties compared to existing crosslinked silanes. [Means for solving the problem]

[0008] The present invention achieves this objective by providing an inventive silane compound having at least one specific α-hydroxycarboxylic acid ester group derived from a modified glycolic acid ester.

[0009] Thus, in a first aspect, the present invention provides Formula (1): [ka] [In the formula, R 1 is the following: a substituted or unsubstituted alkyl, alkenyl, or alkynyl group; substituted or unsubstituted cycloaliphatic or aryl groups; a substituted or unsubstituted heteroalicyclic or heteroaryl group; represents Each R 2 are independently represented by the general formula (2): [ka] (In the formula, R 3 is the following: a substituted or unsubstituted alkenyl group, preferably a vinyl or allyl group; represents R 4 is the following: substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocyclyl, or heteroaryl groups; (represents represents a group represented by the formula: m is independently 0 or 1, preferably 1. The present invention relates to a silane represented by the formula:

[0010] In yet another aspect, the present invention relates to a curable composition comprising at least one polyorganosiloxane (A) and at least one silane (B) of the present invention, wherein the polyorganosiloxane has at least one hydroxy group bonded to a silicon atom. Optionally, the composition further comprises an end-capping catalyst (C) and / or a curing catalyst (D).

[0011] In a further aspect, the present invention relates to end-capped curable polyorganosiloxanes obtained by reacting the crosslinked silanes disclosed herein with at least one polyorganosiloxane. Such polyorganosiloxanes include: Formula (3): [ka] [In the formula, A is a bond -O- or a linear, branched or cyclic divalent radical 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 or combinations thereof; R 1 is the following: substituted or unsubstituted alkyl, alkenyl, or alkynyl groups; substituted or unsubstituted cycloaliphatic or aryl groups; a substituted or unsubstituted heteroalicyclic or heteroaryl group; represents Each R 2 are independently represented by the general formula (2): [ka] (In the formula, R 3 is the following: a substituted or unsubstituted alkenyl group, preferably a vinyl or allyl group; represents R 4 is the following: substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocyclyl, or heteroaryl groups; (represents represents a group represented by m is independently 0 or 1, preferably 1. and at least one terminal group represented by wherein the polyorganosiloxane is obtained by reacting a polyorganosiloxane (Ia) having at least one reactive group / atom A', preferably at least one hydroxyl group, bonded to a silicon atom with a silane of formula (1), wherein any R of the silane of formula (1) 2 reacts with A' to form said linking group A, optionally in the presence of an (end-capping) catalyst for said reaction. DETAILED DESCRIPTION OF THE INVENTION

[0012] A "hardenable composition" is understood to be a substance or mixture of substances that can be hardened by physical or chemical means. In this regard, these chemical or physical means may be, for example, the supply of energy in the form of heat, light, or other electromagnetic radiation, but may also be simply contact with atmospheric moisture, water, or a reactive component, which changes the composition from its original state to a state with a higher hardness.

[0013] Whenever the molecular weight of an oligomer or polymer is referred to in this application, the value refers to the weight average, i.e., Mw value, and not the number average, unless otherwise specified. Molecular weights can be measured by gel permeation chromatography (GPC) according to DIN 55672-1:2007-08 using tetrahydrofuran (THF) as the eluent, preferably at 35°C. The molecular weight of monomeric compounds is calculated based on the respective molecular formula and the known molecular weights of the individual atoms.

[0014] 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 refers to the type of component, not the absolute number of molecules. "At least one polymer" thus means, for example, at least one polymer, i.e., one type of polymer or a mixture of 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 beyond the given amount of the relevant compound.

[0015] All percentage details provided in relation to the compositions described herein refer in each case to % by weight based on the relevant mixture, unless expressly indicated otherwise.

[0016] 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 used herein, this means that the group, in this case the alkyl group, can have 1 carbon atom, 2 carbon atoms, 3 carbon atoms, or up to 10 carbon atoms.) In particular, alkyl can be a middle 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 atoms and / or hydrogen atoms of the alkyl group have been replaced with a heteroatom or functional group. A heteroalkyl group in which one or more carbon atoms have been replaced with a heteroatom, particularly a heteroatom selected from O, S, N, and Si, is obtained by replacing one or more carbon atoms with a heteroatom. Examples of such heteroalkyl groups include, but are not limited to, methoxymethyl, ethoxyethyl, propoxypropyl, methoxyethyl, isopentoxypropyl, ethylaminoethyl, trimethoxypropylsilyl, etc. Functional groups that can replace hydrogen atoms include, among others, =O, =S, -OH, -SH, -NH2-NO2, -CN, -F, -CL, -Br, -I, -OCN, -NCO, -C 3-8 Cycloalkyl, C 6-14 and selected from aryl, a 5- to 10-membered heteroaryl ring in which 1-4 ring atoms are independently nitrogen, oxygen, or sulfur, and a 5- to 10-membered heteroalicyclic ring in which 1-3 ring atoms are independently nitrogen, oxygen, or sulfur.

[0017] As used herein, "alkenyl" refers to an alkyl group, as defined herein, consisting of at least two carbon atoms and containing 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 preferably have 2 to 10 carbon atoms, e.g., 2 to 6, or 2, 3, or 4 carbon atoms. Alkenyl groups can be substituted or unsubstituted. If substituted, the substituents are as defined above for alkyl.

[0018] As used herein, "alkynyl" refers to an alkyl group, as defined herein, consisting of at least two carbon atoms and containing at least one carbon-carbon triple bond, such as ethynyl (acetylene), propynyl, butynyl, or pentynyl, and their structural isomers as described above. Alkynyl groups can be substituted or unsubstituted. If substituted, the substituents are as defined above for alkyl.

[0019] As used herein, a "cycloaliphatic group" or "cycloalkyl group" refers to a monocyclic or polycyclic group (multiple rings having a carbon atom in common), particularly those having 3 to 8 carbon atoms and rings that do not have fully conjugated π-electron systems, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, and the like. A cycloalkyl group can be substituted or unsubstituted. As used in this context, "substituted" 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, -OCN, -NCO, -C ... 1-10 Alkyl, C 2-10 Alkenyl, C 2-10 Alkynyl, C 3-8 Cycloalkyl, C 6-14and selected from aryl, a 5- to 10-membered heteroaryl ring in which 1-4 ring atoms are independently nitrogen, oxygen, or sulfur, and a 5- to 10-membered heteroalicyclic ring in which 1-3 ring atoms are independently nitrogen, oxygen, or sulfur.

[0020] As used herein, "aryl" refers to a monocyclic or polycyclic group (i.e., rings having adjacent carbon atoms in common), particularly 6 to 14 carbon ring atoms having a completely conjugated π-electron system. Examples of aryl groups are phenyl, naphthalenyl, and anthracenyl. Aryl groups can be substituted or unsubstituted. If substituted, the substituents are as defined above for cycloalkyl.

[0021] As used herein, a "heteroaryl" group refers specifically to a monocyclic or polycyclic (i.e., rings sharing adjacent pairs of ring atoms) aromatic ring having from 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, and benzotriazolyl. , 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, or benzoquinolyl. Heteroaryl groups can be substituted or unsubstituted. If substituted, the substituents are as defined above for cycloalkyl.

[0022] As used herein, a "heteroalicyclic group" or "heterocycloalkyl group" refers to a monocyclic or fused ring having 5 to 10 ring atoms and 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 π-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.

[0023] The silanes of the present invention have the formula (1): [ka] It is a silane represented by the formula:

[0024] In this case, each R 1 independently represent a substituted or unsubstituted alkyl, alkenyl, or alkynyl group; a substituted or unsubstituted cycloaliphatic or aryl group; or a substituted or unsubstituted heteroalicyclic or heteroaryl group.

[0025] In various embodiments, each R 1 are each independently an alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, in particular methyl, ethyl, propyl, or isopropyl; an alkenyl group having 2 to 10 carbon atoms, preferably 2 to 4 carbon atoms, in particular vinyl or allyl; or an aryl group having 6 to 10 carbon atoms, in particular phenyl.

[0026] In various preferred embodiments, R 1 independently of one another denote methyl, vinyl or phenyl, very particularly preferably methyl or vinyl, most preferably vinyl.

[0027] In formula (1), each R 2 are each independently represented by the general formula (2): [ka] (In the formula, R 3 represents a substituted or unsubstituted alkenyl group, preferably a vinyl or allyl group, R 4 represents a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocyclyl, or heteroaryl group) represents a group represented by the following formula:

[0028] In various embodiments, each R 2 are each independently a group represented by formula (2), where R 3 represents vinyl or allyl, preferably vinyl, and R 4 represents 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.

[0029] In a preferred embodiment, each R 2 are each independently a group represented by formula (2), where R 3 represents vinyl, and R 4 is methyl or ethyl, preferably methyl.

[0030] In various embodiments, all R 2 The base is the same.

[0031] In formula (1), m can be 0 or 1, but is preferably 1.

[0032] Particularly suitable silanes of formula (1) are those derived from methyl vinyl glycolate (vinyl glycolic acid methyl ester).

[0033] A further aspect of the present invention relates to a curable composition comprising at least one polyorganosiloxane (A) and at least one silane (B) represented by formula (1). The composition may further comprise an (end-capping) catalyst (C) that catalyzes the reaction of the polyorganosiloxane with the silane represented by formula (1), and a curing catalyst (D). When the amounts of each of components (A) to (D) are described below, unless otherwise specified, these refer to the amounts relative to the total amount of (A) to (D).

[0034] Such curable compositions may contain the silane (B) of the present invention in an amount of 1 to 15 wt. %, particularly preferably 3 to 10 wt. %, based on the total weight of the curable composition or the total weight of the polymer (A), crosslinked silane (B), and optional catalysts (C) and (D). When a mixture of silanes represented by formula (1) is used, the amount refers to the total amount of silanes represented by formula (1) in the composition. The amounts listed for components (A), (B), (C), and (D) refer to the total weight of the curable composition or the combined weight of components (A) through (D). When the curable composition contains significant amounts of additives, such as fillers, the amounts listed herein can also refer to the combined weight of components (A) through (D), i.e., the weight excluding additives. However, unless otherwise specified, the amounts can also refer to the total weight of the composition, including all additives, etc.

[0035] At least one polyorganosiloxane (A) may be a polyorganosiloxane having at least one hydroxyl group bonded to a silicon atom. Preferably, the polyorganosiloxane has at least two hydroxyl groups bonded to a silicon atom. Furthermore, it may be preferable that a hydroxyl group or multiple hydroxyl groups are bonded to a terminal silicon atom. If the polyorganosiloxane is branched, it preferably has a hydroxyl group at both ends.

[0036] In such embodiments, at least one hydrogen atom or hydroxy group allows for reaction / endcapping with the silane of formula (1). In the case of a hydroxy group, the silane of formula (1) can react with the polyorganosiloxane in a condensation reaction.

[0037] The at least one polyorganosiloxane (A) is preferably a polydiorganosiloxane, more preferably a polydimethylsiloxane.

[0038] In various embodiments, the polyorganosiloxane used is an α,ω-dihydroxy-terminated polydiorganosiloxane, preferably an α,ω-dihydroxy-terminated polydimethylsiloxane, particularly preferred is an α,ω-dihydroxy-terminated polydimethylsiloxane, which has a kinematic viscosity at 25° C. of 5000 to 120,000 cSt, particularly 10,000 to 100,000 cSt, and particularly preferably 15,000 to 90,000 cSt.

[0039] In various embodiments, the curable composition comprises at least one polyorganosiloxane in an amount of 30 to 95 weight percent, e.g., 40 to 95 weight percent, 40 to 90 weight percent, 40 to 80 weight percent, 40 to 70 weight percent, 50 to 95 weight percent, 60 to 95 weight percent, 70 to 95 weight percent, or 70 to 90 weight percent, based on the total weight of the composition or the sum of components (A) through (D), as detailed above. When a mixture of polyorganosiloxanes is used, the recited amount refers to the total amount of polyorganosiloxane in the composition.

[0040] The curable composition can contain the polyorganosiloxane and the silane of formula (1) as separate components. However, it is equally possible for these components to exist in the form of a prepolymer. The prepolymer is the reaction product of the two components. Suitable reactions are known and are also called endcapping. This can optionally be carried out in the presence of a catalyst (C), whereby the catalyst selectively mediates endcapping without simultaneously curing the polyorganosiloxane. Suitable catalysts include, for example, acids, organolithium compounds such as those described in EP 0 564 253 A1, amines, inorganic oxides, potassium acetate, organotitanium derivatives, titanium / amine combinations, and carboxylic acid / amine combinations. In various embodiments, the endcapping catalyst (C) can be lithium hydroxide in an alcohol (e.g., methanol) or an aminosilane (e.g., γ-aminopropyltrimethoxysilane).

[0041] Thus, the curable composition may contain the end-capping catalyst (C) in an amount of typically 0.01 to 2% by weight, preferably 0.05 to 2% by weight, and particularly preferably 0.1 to 0.5% by weight, in each case based on the total weight of the composition or the total weight of components (A) to (D). When a mixture of catalysts is used, the stated amount refers to the total amount of end-capping catalyst in the composition.

[0042] When the polyorganosiloxane and the silane of formula (1) are present as prepolymers, the amounts listed above for the polyorganosiloxane and silane separately are added to obtain the amount of end-capped polyorganosiloxane. Thus, the curable composition preferably contains 31 to 99 wt. % of the prepolymer, particularly preferably 43 to 80 wt. %, in each case based on the total weight of (A) to (D) or the total weight of the composition. When a mixture of prepolymers is used, the amount refers to the total amount of prepolymer in the composition.

[0043] Prepolymers or end-capped polymers also form an aspect of the present invention. These end-capped curable polyorganosiloxanes are prepared by combining a crosslinked silane of formula (1) disclosed herein with a crosslinked silane of formula (3): [ka] [In the formula, A is a bond -O- or a linear, branched or cyclic divalent radical 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 or combinations thereof; R 1 is the following: substituted or unsubstituted alkyl, alkenyl, or alkynyl groups; substituted or unsubstituted cycloaliphatic or aryl groups; a substituted or unsubstituted heteroalicyclic or heteroaryl group; represents Each R 2 are independently represented by the general formula (2): [ka] (In the formula, R 3 is the following: a substituted or unsubstituted alkenyl group, preferably a vinyl or allyl group; represents R 4 is the following: substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocyclyl, or heteroaryl groups; (represents represents a group represented by the formula: m is independently 0 or 1, preferably 1. with at least one polyorganosiloxane containing at least one terminal group represented by the formula:

[0044] The polyorganosiloxane can be obtained by reacting a polyorganosiloxane (Ia) having at least one reactive group / atom A', preferably at least one hydroxy group, bonded to the silicon atom, such as the polyorganosiloxane (A) described above, with a silane of formula (1), where m is 1. In the reaction, any one of the groups R of the silane of formula (1) can be reacted with a silane of formula (1). 2 reacts with A' to form the linking group -A-. This reaction is optionally carried out in the presence of an (end-capping) catalyst for said reaction, particularly one described herein as component (C). In a specific example, A is -O-, m is 1, and R 1 and R 2 is as defined above for the silanes of formula (1). All embodiments disclosed herein for the silanes of formula (1) are equally applicable to these end-capped polyorganosiloxanes, to the extent applicable.

[0045] The present invention also relates to curable compositions comprising such endcapped polyorganosiloxanes, optionally in combination with an endcapping catalyst and / or a cure catalyst, and any one or more of the other ingredients disclosed herein below.

[0046] The composition of the present invention crosslinks in the presence of moisture, forming Si—O—Si bonds as it cures. The curing can be accelerated by adding a suitable curing catalyst.

[0047] Therefore, preferably, the curable composition further comprises at least one curing catalyst (D), such as a tin compound.

[0048] Preferably, the tin compound is an organic tin compound or an inorganic tin salt. The tin in these tin compounds is preferably divalent or tetravalent. Suitable inorganic tin salts are, for example, tin(II) chloride and tin(IV) chloride. However, organic tin compounds are preferably used as the tin compound. Suitable organic tin compounds include, for example, 1,3-dicarbonyl compounds of divalent or tetravalent tin, 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), etc.; dialkyltin(IV) dicarboxylates such as di-n-butyltin dilaurate, di-n-butyltin maleate, etc. 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, such as di-n-butyltin oxide and di-n-octyltin oxide; tin(II) carboxylates, such as tin(II) octoate or tin(II) phenolate.

[0049] Also, for example, tin compounds such as ethyl silicate, dimethyl maleate, diethyl maleate, dioctyl maleate, dimethyl phthalate, diethyl phthalate, and dioctyl phthalate, such as di(n-butyl)tin(IV) di(methyl maleate), di(n-butyl)tin(IV) di(butyl maleate), di(n-octyl)tin(IV) di(methyl maleate), and di(n-octyl)tin(IV) di(butyl maleate), 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 is also appropriate.

[0050] 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.

[0051] Particularly preferably, the tin compound is a dialkyltin(IV) dicarboxylate, especially di-n-butyltin dilaurate or di-n-octyltin dilaurate.

[0052] As an alternative to tin compounds, tin-free curing catalysts can be used.

[0053] Suitable tin-free curing catalysts are, for example, organometallic compounds of iron, for example 1,3-dicarbonyl compounds of iron, such as iron(III) acetylacetonate.

[0054] Boron halides, such as boron trifluoride, boron trichloride, boron tribromide, boron triiodide, or mixtures of boron halides, can also be used as curing catalysts. Preferred are boron trifluoride complexes, such as boron trifluoride diethyl etherate, which are liquids and therefore easier to handle than gaseous boron halides.

[0055] Furthermore, amines, nitrogen heterocycles, and guanidine derivatives are generally suitable as curing catalysts. A well-known suitable catalyst from this group of compounds is 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

[0056] Furthermore, titanium, aluminum, and zirconium compounds, or mixtures thereof, can also be used as catalysts. On the one hand, the use of tin compounds can be avoided in this way, and on the other hand, better adhesion to organic surfaces, such as acrylates, which usually have poor adhesion, can be achieved. Among titanium, aluminum, and zirconium catalysts, titanium catalysts are preferred.

[0057] Suitable titanium catalysts are compounds having hydroxy groups and / or substituted or unsubstituted alkoxy groups, such groups having 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 z The titanium alkoxides may be the same or different. z The group is an acyloxy group -OCOR z Also suitable as titanium catalysts are titanium alkoxides in which one or more alkoxy groups are replaced by hydroxy groups or halogen atoms.

[0058] In various other embodiments, titanium chelate complexes may be used.

[0059] Another alternative is an aluminum catalyst, such as one of the formula: [ka] (In the formula, R z is as defined above, i.e., an organic group, preferably a substituted or unsubstituted hydrocarbon group having 1 to 20 C atoms, and three R z In such aluminum alkoxides, one or more alkoxy groups may be an acyloxy group -OC(O)R z may be substituted with

[0060] Also suitable are aluminum alkoxides in which one or more alkoxy groups are substituted with hydroxy groups or halogen atoms.

[0061] Of the aluminum catalysts mentioned, pure aluminum alcoholates are preferred from the viewpoint of their stability to moisture and the curability of the mixtures to which they are added, and aluminum chelate complexes are also preferred.

[0062] Suitable zirconium catalysts include, but are not limited to, tetramethoxyzirconium or tetraethoxyzirconium.

[0063] Further examples include diisopropoxyzirconium bis(ethylacetoacetate), triisopropoxyzirconium(ethylacetoacetate), and isopropoxyzirconium tris(ethylacetoacetate).

[0064] Also suitable are zirconium acylates, zirconium halide catalysts, and zirconium chelate complexes.

[0065] In various other embodiments, metal carboxylate salts, or mixtures of such salts, can also be used as cure catalysts, and are selected from the following metal carboxylate salts: calcium, vanadium, iron, zinc, titanium, potassium, barium, manganese, nickel, cobalt, and / or zirconium.

[0066] Among the carboxylates, the carboxylates of calcium, vanadium, iron, zinc, titanium, potassium, barium, manganese, and zirconium are preferred because they exhibit particularly high activity. The carboxylates of calcium, vanadium, iron, zinc, titanium, and zirconium are particularly preferred. The carboxylates of iron and titanium are very particularly preferred.

[0067] The curable composition may contain the curing catalyst (D) in an amount of 0.01 to 2% by weight, preferably 0.05 to 2% by weight, and particularly preferably 0.1 to 0.5% by weight, in each case based on the total weight of the curable composition or the total weight of components (A) to (D) of the composition. When a mixture of curing catalysts is used, the stated amount refers to the total amount of curing catalyst in the composition.

[0068] The curable composition may contain one or more ingredients, apart from those mentioned above, that can be used to affect particular properties of the curable composition and / or the cured product.

[0069] These other ingredients may be selected from the group comprising, for example, plasticizers, stabilizers, antioxidants, fillers, reactive diluents, drying agents, adhesion promoters, UV stabilizers, rheological aids, and / or solvents, with particular emphasis being placed on adhesion promoters, plasticizers, fillers, and stabilizers, including antioxidants and UV stabilizers.

[0070] Therefore, preferably the curable composition comprises at least one further component.

[0071] The curable compositions of the present invention may further comprise one or more adhesion promoters, which are understood to be substances that improve the adhesive properties of an adhesive layer on a surface.

[0072] Suitable are silane adhesion promoters, in particular alkoxysilanes which carry (further) functional groups such as amino groups, mercapto groups, epoxy groups, carboxyl groups, vinyl groups, isocyanate groups, isocyanurate groups or halogens. For example, 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-acryloxypropylmethyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, tris(trimethoxysilyl)isocyanurate, and γ-chloropropyltrimethoxysilane.

[0073] In various embodiments, the adhesion promoter is selected from aminosilanes (aminofunctional alkoxysilanes or aminoalkylalkoxysilanes), such as γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-(2-aminoethyl)-3-aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyltriethoxysilane, γ-(2-aminoethyl)aminopropylmethyldiethoxysilane, γ-(2-aminoethyl)aminopropyltriisopropoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzene-γ-aminopropyltrimethoxysilane, and N-vinylbenzyl-γ-aminopropyltriethoxysilane, as well as oligomeric aminosilanes, such as aminoalkyl group-modified alkylpolysiloxanes (Dynasylan 1146) and others.

[0074] In various embodiments, the curable composition comprises the adhesion promoter in an amount of up to 20% by weight, primarily in an amount of 0.05 to 4% by weight, preferably in an amount of 0.1 to 2% by weight, and particularly preferably in an amount of 0.2 to 2% by weight, in each case based on the total weight of the composition including all co-agents.

[0075] The viscosity of the curable composition can be reduced by using a reactive diluent.

[0076] Preferably, the reactive diluent has at least one functional group that reacts with, for example, moisture or atmospheric oxygen after application. Examples of such groups are silyl groups, isocyanate groups, ethylenically unsaturated groups, and polyunsaturated systems.

[0077] Any compound that can be mixed with other ingredients to provide a viscosity reduction and that has at least one group that is reactive with the polymer can be used as a reactive diluent.

[0078] 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).

[0079] Suitable reactive diluents include, but are not limited to, polyalkylene glycols reacted with isocyanatosilane (e.g., Synalox 100-50B, manufactured by DOW), carbamatopropyltrimethoxysilane, alkyltrimethoxysilanes, alkyltriethoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, and vinyltrimethoxysilane (XL 10, manufactured by Wacker), vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, octyltrimethoxysilane, tetraethoxysilane, vinyldimethoxymethylsilane (XL12, manufactured by Wacker), vinyltriethoxysilane (GF56, manufactured by Wacker), vinyltriacetoxysilane (GF62, manufactured by Wacker), isooctyltrimethoxysilane (IO trimethoxy), isooctyltriethoxysilane (IO triethoxy, manufactured by Wacker), N-trimethoxysilylmethyl-O-methylcarbamate (XL63, manufactured by Wacker), N-dimethoxy(methyl)silylmethyl-O-methylcarbamate (XL65, manufactured by Wacker), hexadecyltrimethoxysilane, 3-octanoylthio-1-propyltriethoxysilane, and partial hydrolysates of the above compounds.

[0080] Additionally, the following polymers manufactured by Kaneka Corporation can also be used as reactive diluents: MS S203H, MS S303H, MS SAT 010, and MS SAX 350.

[0081] Also suitable are silane-modified polyethers, obtained for example from the reaction of isocyanatosilanes with Synalox types.

[0082] Also suitable are polymers that can be prepared from an organic backbone by grafting with vinylsilanes or by reacting polyols, polyisocyanates, and alkoxysilanes.

[0083] Preferably, compounds used as reactive diluents in the context of the present invention have at least one alkoxysilyl group, with di- and trialkoxysilyl groups being preferred.

[0084] 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) ), tetramethylxylylene 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 diisocyanates, Phenylmethane diisocyanates, such as mono-, di-, tri- or tetraalkyldiphenylmethane diisocyanates and their partially or fully hydrogenated cycloalkyl derivatives, 4,4'-diisocyanatophenylperfluoroethane, phthalic acid bisisocyanatoethyl 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.

[0085] For example, tri- or higher hydric isocyanates obtained by oligomerization of diisocyanates, particularly the aforementioned isocyanates, can also be used as polyisocyanates. Examples of such tri- or higher hydric polyisocyanates include triisocyanurates of HDI or IPDI, or mixtures thereof, or mixed triisocyanurates thereof, and polyphenylmethylene polyisocyanates obtained by phosgenation of aniline-formaldehyde condensation products.

[0086] Solvents and / or plasticizers can be used in addition to or in place of reactive diluents to reduce the viscosity of the curable composition.

[0087] Suitable solvents are aliphatic or aromatic hydrocarbons, halogenated hydrocarbons, ketones, ethers, esters, ester alcohols, keto alcohols, keto ethers, keto esters, and ether esters.

[0088] In various embodiments, the compositions disclosed herein may contain a hydrophilic plasticizer. These are used to improve moisture absorption and thereby improve 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 thereof.

[0089] For example, from the group of phthalic acid esters, dioctyl phthalate, dibutyl phthalate, diisoundecyl phthalate or butyl benzyl phthalate are particularly suitable, and from the group of adipic acid esters, dioctyl adipate, diisodecyl adipate, diisodecyl succinate, dibutyl sebacate or butyl oleate are preferred.

[0090] Also suitable as plasticizers are monofunctional, linear or branched C 4-16 They are pure or mixed ethers of alcohols, or mixtures of two or more different ethers of such alcohols, such as dioctyl ether.

[0091] Further suitable plasticizers include end-capped polyethylene glycols, such as polyethylene glycol 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.

[0092] Preferred plasticizers include, but are not limited to, end-capped polyethylene glycols such as polyethylene or polypropylene glycol dialkyl ethers, where the alkyl group has up to four carbon atoms, particularly the dimethyl and diethyl ethers of diethylene glycol and dipropylene glycol. Dimethyl diethylene glycol, in particular, provides good cure even under less favorable application conditions (low humidity, low temperature). Further details on plasticizers are referred to in the relevant technical chemistry literature.

[0093] Also suitable as plasticizers within the scope of the present invention are diurethanes, which can be prepared, for example, by reacting a diol having an OH end group with a monofunctional isocyanate, selecting a stoichiometry such that substantially all free OH groups are reacted.Optionally, excess isocyanate can then be removed from the reaction mixture, for example, by distillation.Another method for preparing diurethanes consists of reacting a monofunctional alcohol with a diisocyanate, thereby reacting as much as possible all NCO groups.

[0094] Preferably, the curable composition comprises at least one plasticizer, in particular a polydimethylsiloxane.

[0095] The curable composition may contain reactive diluents, solvents and / or plasticizers preferably in an amount of 1 to 50% by weight, more preferably 10 to 40% by weight, and particularly preferably 20 to 40% by weight, in each case based on the total weight of the composition. When mixtures of several reactive diluents, solvents and / or plasticizers are used, the stated amounts refer to the total amount of reactive diluents, solvents and / or plasticizers in the composition.

[0096] The curable composition may include one stabilizer selected from an antioxidant, a UV stabilizer, and a drying agent.

[0097] As antioxidants, all conventional antioxidants can be used, which are preferably present in the composition in an amount of up to about 7% by weight, in particular up to about 5% by weight.

[0098] The composition may further comprise 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. In the context of the present invention, it is preferred to use UV stabilizers that have silyl groups and are incorporated into the final product upon crosslinking or curing. Benzotriazoles, benzophenones, benzoates, cyanoacrylates, acrylates, sterically hindered phenols, phosphorus, and / or sulfur may also be added.

[0099] In order to further improve the shelf life (storage period), it is often useful to stabilize the composition against the penetration of moisture with a desiccant.In principle, any compound that reacts with moisture while forming a group that is inert to the reactive group present in the preparation is suitable as a desiccant, thereby minimizing the change in molecular weight.In addition, the reactivity of the desiccant to the penetration of moisture 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.

[0100] Thus, suitable desiccants include, for example, isocyanates. However, in various preferred embodiments, silanes are used as desiccants, 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 are also possible. Vinyltrimethoxysilane and tetraethoxysilane are particularly preferred in terms of cost and efficiency.

[0101] Also suitable as desiccants are the reactive diluents described above, 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.

[0102] Finally, alkyl orthoformates or alkyl orthoacetates, such as methyl or ethyl orthoformate, methyl orthoacetate or ethyl orthoacetate, can also be used as drying agents.

[0103] The composition generally contains from about 0 to about 6% by weight of a desiccant.

[0104] The compositions described herein may contain fillers. Suitable fillers include, but are not limited to, chalk, lime powder, precipitated and / or pyrogenic silica, zeolite, bentonite, magnesium carbonate, diatomaceous earth, alumina, clay, talc, titanium dioxide, iron oxide, zinc oxide, sand, quartz, flint, mica, glass powder, and other ground mineral substances, as well as carbon black and graphite. Organic fillers may also be used, including, but not limited to, wood fiber, wood flour, sawdust, cellulose, cotton, pulp, cotton, wood chips, shredded straw, and rice husks. 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.

[0105] The pyrogenic and / or precipitated silica is advantageously from 10 to 90 m 2 / g. When used, they do not further increase the viscosity of the compositions of the present invention, but rather contribute to strengthening the cured composition.

[0106] As a filler, a larger BET specific surface area, advantageously 100-250 m 2 / g, especially 110-170m 2 It is also conceivable to use calcined and / or precipitated silicas having a specific surface area of ​​0.1 / g. Due to their larger BET specific surface area, the same effect, for example strengthening of the cured formulation, can be achieved with a smaller weight proportion of silica. Therefore, additional substances can be used to improve the compositions described herein in terms of other requirements.

[0107] Further suitable fillers are hollow spheres with mineral or plastic shells. These are, 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 0 520 426. They are composed of inorganic or organic materials and have a diameter of 1 mm or less, preferably 500 μm or less.

[0108] Fillers that impart thixotropy to the formulation are preferred for many applications. These fillers are also described as rheological adjuvants, such as hydrogenated castor oil, fatty acid amides, or swellable plastics such as PVC. To facilitate easy squeezing from a suitable dispensing device (e.g., a tube), these formulations have a viscosity of 3,000 to 15,000 mPas, preferably 40,000 to 80,000 mPas, and even 50,000 to 60,000 mPas at 20°C.

[0109] The fillers are preferably used in an amount of 1 to 80% by weight, particularly preferably 2 to 50% by weight, 2 to 30% by weight, 2 to 25% by weight, or 2 to 20% 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 stated amount refers to the total amount of fillers in the composition.

[0110] The curable composition can be prepared by simply mixing the polyorganosiloxane having at least one hydroxyl group bonded to the silicon atom of the silane of formula (1) with, optionally, other components. This can be done in a suitable dispersing device, such as a high-speed mixer. Care should preferably be taken to minimize contact of the mixture with moisture, which could lead to undesirable premature curing. Suitable measures are well known and include, for example, working in an inert atmosphere, possibly under protective gas, and drying / heating each component before addition.

[0111] A preferred method of preparation includes mixing a polyorganosiloxane having at least one hydroxy group bonded to a silicon atom with a silane of formula (1) in a first step, whereby this mixing can be carried out in the presence of at least an aminosilane or lithium hydroxide in an alcohol (e.g., methanol) and at least one plasticizer, optionally adding other ingredients except for a curing catalyst in a second step and mixing all the ingredients, and finally adding the curing catalyst and mixing it with the other ingredients in a third step.

[0112] The present invention further relates to the use of the composition of the invention as an adhesive or sealing or coating material.

[0113] The compositions or preparations of the present invention can therefore be used as adhesives, sealants, coatings and in the production of molded parts.

[0114] The compositions and preparations disclosed herein are generally suitable for bonding a variety of materials such as plastics, metals, glass, ceramics, wood, wood-based materials, paper, paper-based materials, rubber, and textiles, bonding floors, building elements, windows, wall and floor coverings, and sealing joints in general.

[0115] The following examples serve to illustrate the invention without, however, limiting it thereto. [Example]

[0116] Example 1: The following compositions were prepared: Ref1 and Ref2 are reference compositions, Ex1 is a composition of the invention.

[0117] [Table 1]

[0118] All three compositions were tested for SOT and TFT as follows: SOT: The aforementioned compositions were homogenized and applied to a frame (50 x 130 x 2 mm). Each mixture was evenly distributed to completely fill the frame, resulting in a thin polymer film. The time it took for these compositions to form a skin (Skin Over Time, or SOT) was measured using a tool with a rounded tip (150 x 5 mm). The tip of the spatula was lightly touched to the surface of the polymer film every 1 to 5 minutes and carefully removed. The SOT was measured when no residue of the formulation remained on the spatula when it was removed from the surface of the polymer film. Any strings that formed should be removed completely from the spatula. The polymer film returned to its original shape. A different portion of the polymer film surface should be used each time the SOT was measured. The test was performed at room temperature (20°C).

[0119] TFT: To measure surface tack from adhesive sealants, the aforementioned composition was homogenized and applied to a frame (50 x 130 x 2 mm) in the same manner as for SOT measurement. After 60 minutes, a tool with a rounded tip (150 x 5 mm) was carefully touched to the surface of the polymer film to evaluate the surface tack. A TFT of "<60 minutes" indicates "not tacky," and a TFT of ">60 minutes" indicates "tacky (including slightly tacky)."

[0120] The Shore A hardness was measured according to the method described in DIN EN ISO 868:2003.

[0121] The results are shown in Table 2.

[0122] [Table 2]

[0123] The results show that the compositions of the present invention have significantly shorter SOT and TFT than the prior art compositions Ref1 and Ref2, which use known silane crosslinkers. The Shore A hardness is comparable among all the compositions tested.

Claims

1. Formula (1): 【Chemical 1】 [In the formula, Each R １ are, independently, the following: a substituted or unsubstituted alkyl, alkenyl, or alkynyl group; a substituted or unsubstituted cycloaliphatic or aryl group; a substituted or unsubstituted heteroalicyclic or heteroaryl group; represents Each R ２ are independently represented by the general formula (2): 【Chemistry 2】 (In the formula, R ３ are independently the following: a substituted or unsubstituted alkenyl group, preferably a vinyl or allyl group; represents R ４ Below: substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocyclyl, or heteroaryl groups; (represents represents a group represented by m independently represents 0 or 1, preferably 1. Silane, denoted by

2. Each R １ 2. Silanes according to claim 1, characterized in that: are, independently of one another, an alkyl group having 1 to 10 carbon atoms, in particular methyl, ethyl, propyl or isopropyl, or an alkenyl group having 2 to 10 carbon atoms, in particular vinyl or allyl.

3. Each R ２ are each independently a group represented by formula (2), where R ３ 3. Silane according to claim 1 or 2, characterized in that represents an unsubstituted alkenyl group having 2 to 4 carbon atoms, in particular vinyl.

4. R ４ 4. Silane according to claim 1, wherein 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.

5. R ２ The silane according to any one of claims 1 to 4, wherein are all the same.

6. m is 1, and R １ is vinyl, and R ３ is vinyl or allyl, preferably vinyl, and R ４ A silane according to any one of claims 1 to 5, wherein is methyl or ethyl, preferably methyl.

7. Formula (3): 【Chemistry 3】 [In the formula, A is a bond -O- or a linear, branched, or cyclic divalent radical 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 or combinations thereof; R １ Below: a substituted or unsubstituted alkyl, alkenyl, or alkynyl group; a substituted or unsubstituted cycloaliphatic or aryl group; a substituted or unsubstituted heteroalicyclic or heteroaryl group; represents Each R ２ are independently represented by the general formula (2): 【Chemistry 4】 (In the formula, R ３ Below: a substituted or unsubstituted alkenyl group, preferably a vinyl or allyl group; represents R ４ Below: substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocyclyl, or heteroaryl groups; (represents represents a group represented by m is independently 0 or 1, preferably 1. A polyorganosiloxane comprising at least one terminal group represented by The polyorganosiloxane is obtained by reacting a polyorganosiloxane (Ia) having at least one reactive group / atom A', preferably at least one hydroxyl group, bonded to a silicon atom with a silane of formula (1) according to any one of claims 1 to 6, wherein any R of the silane of formula (1) ２ is a polyorganosiloxane which reacts with A' to form a linking group -A-, optionally in the presence of an (end-capping) catalyst for said reaction.

8. (A) at least one polyorganosiloxane having at least one hydroxy group bonded to a silicon atom; (B) at least one crosslinked silane, wherein the crosslinked silane is a silane according to any one of claims 1 to 6.

1. A curable composition comprising:

9. 10. The curable composition of claim 8, further comprising (C) at least one end-capping catalyst.

10. 10. The curable composition of claim 8 or 9, further comprising (D) at least one curing catalyst, preferably a tin compound.

11. The curable composition contains, based on the total weight of the curable composition or the total amount of components (A) to (D), (1) at least one polyorganosiloxane having at least one hydroxy group bonded to a silicon atom (A) in an amount of 30 to 95 weight percent; (2) at least one silane of formula (1) (B) in an amount of 1 to 15% by weight, preferably in an amount of 3 to 10% by weight; (3) optionally, at least one end-capping catalyst (C) in an amount of 0.01 to 2 wt. %, preferably 0.05 to 2 wt. %, and particularly preferably 0.1 to 0.5 wt. %; and / or (4) optionally containing at least one curing catalyst (D) in an amount of 0.01 to 2% by weight, preferably in an amount of 0.05 to 2% by weight, particularly preferably in an amount of 0.1 to 0.5% by weight; The curable composition according to any one of claims 8 to 10.

12. 8. A curable composition comprising at least one polyorganosiloxane according to claim 7, optionally further comprising (C) at least one end-capping catalyst and / or (D) at least one curing catalyst, preferably a tin compound.

13. The curable composition of any one of claims 8 to 12, wherein the curable composition comprises any one or more additional components selected from the group consisting of plasticizers, stabilizers, antioxidants, fillers, reactive diluents, drying agents, adhesion promoters, UV stabilizers, rheology aids, and solvents.

14. The curable composition according to any one of claims 8 to 13, wherein the curable composition is an adhesive, sealant or coating composition.

15. Use of the curable composition according to any one of claims 8 to 13 as an adhesive, sealant or coating.

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