Curable composition comprising at least one silane-modified poly (meth) acrylate

Abstract

The present invention relates to a curable composition comprising: I. at least one silane-modified poly (meth) acrylate, II. Surface-treated calcium carbonate, III. At least one aminosilane, IV. Optionally at least one silane-modified polyether, V. Optionally surface-treated silica, VI. Optionally at least one catalyst, V. Optionally at least one silane-modified polyether, V. Optionally at least one silane-modified polyether, V. Optionally at least one silane-modified polyether, V. Optionally at least one silane-modified polyether, V. Optionally at least one silane-modified polyether, V. Optionally at least one silane-modified polyether, V. Optionally at least one silane-modified polyether, V. Optionally at least one silane-modified polyether, and V. Optionally at least one silane-modified polyether. VII. At least one plasticizer having a molecular weight of less than 350 g / mol, preferably less than 300 g / mol, more preferably less than 250 g / mol, in particular less than 200 g / mol. The invention also relates to adhesives, sealants, and / or coatings comprising said composition, and to the use of said composition.

Description

[0001] The present invention relates to a curable composition comprising at least one silane-modified poly(meth)acrylate and optionally a curing catalyst, wherein the composition has excellent mechanical strength. The present invention further relates to an adhesive, a sealant, and / or a coating comprising the composition, and the use of the composition.

[0002] Elastomeric adhesive and sealing materials are used in many different applications ranging from construction and assembly, mobility, and more. These materials can absorb mechanical and thermal stresses and are critical to provide reliability to devices, buildings and vehicles during their lifetime. In particular, in the railway industry, products based on elastomeric polyurethane and silane-modified polymers are used for assembly in the interior as well as in the exterior. The main focus is on the adhesion and sealing of windows (i.e. so-called dgx-type applications).

[0003] Generally, in applications involving elastomeric adhesive and sealing applications, polyurethane-based adhesives (PU) are used in vehicle assembly. They have proven to be reliable, cost-effective, easy to use, and they show very good mechanical properties. However, residual isocyanate in the product is under investigation and is considered problematic in terms of health and safety. Furthermore, polyurethane-based adhesives show weaknesses in terms of UV resistance, coatability, and generally require a primer step.

[0004] On the other hand, the use of silane-modified polymer (SMP)-based adhesives (such as silane-modified poly(meth)acrylate-based adhesives) has also been considered, as they generally do not require a primer step, have increased UV stability compared to PU, a broader working temperature range, and are generally free of residual isocyanate. However, to date, SMPs have not been able to reach comparable adhesive strength (including similar elongation) similar to PU.

[0005] Therefore, it was an object of the present invention to find a possibility to overcome the disadvantages and shortcomings of the conventional materials discussed above. In particular, it was an object of the present invention to provide an adhesive, a sealant, and / or a coating which shows an excellent combination of properties including material reliability, cost-effectiveness, ease of use, excellent mechanical properties, good health and safety characteristics, good UV resistance, good coatability, and which allows for easy implementation in the application.

[0006] The object has been achieved by providing a curable composition according to claim 1. Preferred embodiments of the curable composition are described in the dependent claims. Furthermore, particularly suitable applications of the curable composition are protected by another product independent claim and another use independent claim.

[0007] The present invention provides a curable composition, comprising: I. at least one silane-modified poly(meth)acrylate, II. surface-treated calcium carbonate, III. at least one aminosilane, IV. optionally at least one silane-modified polyether, V. optionally surface-treated silica, VI. optionally at least one catalyst, VII. at least one plasticizer having a molecular weight of less than 350 g / mol, preferably less than 300 g / mol, more preferably less than 250 g / mol, in particular less than 200 g / mol.

[0008] The present invention also relates to an adhesive, a sealant, or a coating comprising the curable composition, and the use of the curable composition as an adhesive, a sealant, or a coating.

[0009] The solution of the present invention is advantageous in several respects. The present invention shows the possibility to overcome the disadvantages and shortcomings of the conventional materials discussed above. In particular, the present invention provides an adhesive, a sealant, and / or a coating which exhibits an excellent combination of properties including: o very good material reliability; o very high cost-effectiveness of the claimed solution; o very easy to use of the claimed solution, application of the inventive material usually does not require a priming step; o low viscosity of < 300 -1 < 300 on an Anton Paar rheometer at 23 °C, 0.5 mm gap, 25 mm plate, 10 s o Excellent mechanical properties, similar to conventional PUs, including excellent Shore A hardness, elongation, and tensile strength of the cured material, preferably below 70 after 7 days curing at 23°C / 50% rH. The material of the claimed invention can be advantageously used to bond substrates to each other with a significantly higher bond strength and elongation than silane-modified adhesives usually have. Typically, a tensile strength of the cured composition of 5 MPa or more, and an elongation of the cured composition of 575% or more is achieved; however, formulations obtained with conventional silane-modified polymers do not show comparable results in terms of tensile strength or elongation; o Very good health and safety properties, since harmful substances (such as residual isocyanate) are reduced and, in the best case, avoided in the inventive material; o Very good resistance to UV irradiation, especially compared to conventional PUs; o Very good coatability.

[0010] Finally, the inventive solution can be easily implemented in applications, in particular due to the excellent curing behavior, as shown by the excellent tack-free time, TFT, and curing depth. The inventive material is particularly suitable for commercial applications in the dgx, window bonding and sealing, internal and external bonding and sealing, especially in the railway and automotive industries.

[0011] The term "curable composition" is to be understood as a substance, or a mixture of substances, which can be cured by physical or chemical measures. In this regard, these chemical or physical measures can be, for example, the supply of energy in the form of heat, light, or other electromagnetic radiation, but also simply the contact with atmospheric moisture, water, or reactive components. Thus, the composition changes from an original state to a state with higher hardness. In a preferred embodiment, the curable composition of the invention is a moisture-curable composition.

[0012] As used herein, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise.

[0013] The term "at least one", as used herein, means one or more (i.e., 1, 2, 3, 4, 5, 6, 7, 8, 9, or more) of. With respect to ingredients, this designation refers to the type of ingredient, not the absolute amount of the molecule. Thus, "at least one polymer" means, for example, at least one type of polymer, i.e., one type of polymer can be used, or a mixture of several different polymers can be used. Together with a weight designation, the designation refers to all of the compounds of the type contained in the composition / mixture, i.e., the composition contains no other compounds of the type in question in addition to the amount of the compound in question.

[0014] The terms "comprising", "comprises" and "comprised of" as used herein are synonymous with "including", "includes" or "containing", "contains", and are inclusive or open-ended and do not exclude additional, unrecited members, elements or method steps. If used, the phrase "consisting of" is a closed term and excludes all additional elements. Additionally, the phrase "consisting essentially of" excludes additional elements not recited, excepting that it does not exclude trace amounts of impurities that would normally be attributed to the ordinary skill in the art, and does not preclude operable incorporation of significant amounts of other elements to the extent these elements do not materially affect the basic and novel characteristics of the composition(s) and / or method(s).

[0015] When expressing equivalent, concentration, size and other parameters in ranges, preferred ranges, upper values, lower values, or preferred upper and lower values, it is understood that any range obtained by combining any upper value with any lower or preferred value, whether or not explicitly mentioned in the context, is also specifically disclosed.

[0016] The term "about" as used herein in connection with a numerical value relates to a variation of ±20%, preferably of ±10% of the respective value.

[0017] The words "preferred," "preferably," "desired," and "particularly," and synonyms thereof, are used herein generally to refer to embodiments of the disclosure that can provide certain benefits under some circumstances. However, the use of these terms does not mean that the disclosure in any way is limited to these embodiments, and the disclosure should not be construed as excluding other embodiments.

[0018] The word "may" as used throughout this application is used in a permissive sense (i.e., meaning having the potential to), rather than in a mandatory sense (i.e., meaning must).

[0019] Room temperature as used herein is 23°C ± 2°C. "Ambient conditions" as used herein means the temperature and pressure of the environment in which a composition is or a coating or the substrate of the coating is.

[0020] Unless otherwise specified, molecular weights are expressed as number average molecular weight (Mn) and are given in Daltons (Da). nAll molecular weight data refer to values ​​obtained by gel permeation chromatography (GPC) performed at 35°C using a Water 2695 HPLC equipped with three Polypore columns and an RI detector. Stable tetrahydrofuran (THF) was used as the eluent at a flow rate of 1 mL / min. The apparatus was calibrated using polystyrene standards.

[0021] As used in this article, "polydispersity" refers to a measure of the molecular weight distribution given in a resin sample. Polydispersity is determined by measuring the weight-average molecular weight (M... w Divide by the number-average molecular weight (M) n It is calculated using ).

[0022] For ease of description of the method of the present invention, the unsaturation provided by the CH2=CH-CH2- terminal group is referred to as "allylic" unsaturation.

[0023] As used herein, the term "hydrocarbon group" is intended to refer to a group or divalent group consisting primarily of carbon and hydrogen atoms. Therefore, the term includes: aliphatic groups such as alkyl, alkenyl, and ynyl groups; aromatic groups such as phenyl groups; and alicyclic groups such as cycloalkyl and cycloalkenyl groups.

[0024] As used herein, “C1-C8 alkyl” refers to a monovalent group containing 1-8 carbon atoms, which is an alkane residue and includes both linear and branched organic groups. Examples of alkyl groups include, but are not limited to: methyl; ethyl; propyl; isopropyl; n-butyl; isobutyl; sec-butyl; tert-butyl; n-pentyl; n-hexyl; n-heptyl; and 2-ethylhexyl. In this invention, such alkyl groups may be unsubstituted or may be substituted with one or more substituents (such as halogen, nitro, cyano, amide, amino, sulfonyl, sulfinyl, sulfanyl, sulfoxy, urea, thiourea, aminosulfonyl, sulfonamide, and hydroxy). The halogenated derivatives of the exemplary hydrocarbon groups listed above are particularly mentioned as examples of suitable substituted alkyl groups. However, it should generally be noted that unsubstituted alkyl groups containing 1-6 carbon atoms (C1-C6 alkyl), such as unsubstituted alkyl groups containing 1-4 carbon atoms (C1-C4 alkyl), are preferred.

[0025] The term "C2-C8alkenyl" as used herein refers to aliphatic hydrocarbon groups containing 2-8 carbon atoms and at least one carbon-carbon double bond, for example, ethenyl (vinyl), propenyl, butenyl, or pentenyl, and structural isomers thereof, such as 1-propenyl, or 2-propenyl, 1-butenyl, 2-butenyl, or 3-butenyl, and the like. Alkenyl groups can be linear or branched, and can be substituted or unsubstituted. If they are substituted, the substituents are as defined above for alkyl groups.

[0026] The term "C2-C8alkynyl" as used herein refers to aliphatic hydrocarbon groups containing 2-8 carbon atoms and at least one carbon-carbon triple bond, for example, ethynyl (acetylenyl) (ethyne), propynyl, butynyl, or pentynyl, and structural isomers thereof as described above. Alkynyl groups can be linear or branched, and can be substituted or unsubstituted.

[0027] The term "C3-C 10 Cycloalkyl" is understood to mean saturated monocyclic, bicyclic, or tricyclic hydrocarbon groups having 3-10 carbon atoms. Examples of cycloalkyl groups include: cyclopropyl; cyclobutyl; cyclopentyl; cyclohexyl; cycloheptyl; cyclooctyl; adamantyl; and norbornyl.

[0028] As used herein, "C6-C 18 Aryl" refers to optionally substituted monocyclic ring systems, bicyclic ring systems, and tricyclic ring systems, wherein the monocyclic ring system is aromatic, or at least one of the rings in the bicyclic ring system or tricyclic ring system is aromatic. Bicyclic ring systems and tricyclic ring systems include benzo-fused 2-3 membered carbocyclic rings. Exemplary aryl groups include: phenyl; indenyl; naphthyl; tetrahydronaphthyl; tetrahydroindenyl; tetrahydroanthryl; and anthryl. Additionally, it can be noted that phenyl is preferred.

[0029] "Arylalkyl" as used herein refers to alkyl groups substituted with aryl groups. An example of arylalkyl is benzyl.

[0030] The term "C1-C 60 Alkylene" and "C1-C 20 Alkylene" refers to divalent groups containing 1-60 or 1-20 carbon atoms, respectively, which are the residue of alkanes and include linear, branched, or cyclic groups, which can be substituted or unsubstituted and can optionally be interrupted by at least one heteroatom.

[0031] The term "Alkenylene" as used herein refers to divalent aliphatic hydrocarbon groups having at least one carbon-carbon double bond, which are the residue of alkenes. Alkenylene groups can be linear or branched, and can be substituted or unsubstituted.

[0032] As used herein, the term "alkynylene" refers to a divalent aliphatic hydrocarbon group having at least one carbon-carbon triple bond. The alkynylene group can also have one or more carbon-carbon double bonds. The alkynylene group can be linear or branched, and can be substituted or unsubstituted.

[0033] As used herein, the term "arylene" refers to a divalent group that is a residue of an aryl group. Suitable arylene groups include phenylene, furanylene, piperidylene, and naphthylene.

[0034] As used herein, the term "aralkylene" refers to a divalent group that is a residue of an aralkyl group. The aralkylene group can be represented by the formula -R-Ar-, wherein R is an alkylene group and Ar is an arylene group, i.e., the alkylene group is bonded to the arylene group. Suitable aralkylene groups include xylylene and tolylene.

[0035] The expression "containing at least one heteroatom" when mentioned means that the backbone or side chain of a group comprises at least one atom different from carbon and hydrogen. Preferably, the term "heteroatom" refers to nitrogen, oxygen, silicon, sulfur, phosphor, halogen (such as CI, Br, F). In the context of the present invention, oxygen (O) and nitrogen (N) can be mentioned as typical heteroatoms.

[0036] As used herein, the term "hydrocarbyl" includes saturated or unsaturated hydrocarbyl groups.

[0037] As used herein, the term "heterocyclic compound" refers to a saturated or unsaturated monocyclic, bicyclic, polycyclic, or fused compound containing at least one heteroatom (preferably, O, S, N, and / or P) in the ring structure.

[0038] As used herein, the term "halogen" refers to fluorine, chlorine, bromine, or iodine, and correspondingly, the term "halide" refers to a fluoride anion, a chloride anion, a bromide anion, or an iodide anion.

[0039] The term "pseudohalogen" refers to an inorganic or organic group that, when present in anionic form, exhibits similar chemical properties to halides. Pseudohalogen groups include, but are not limited to, azide (N3), thiocyanate (SCN), and cyanide (CN).

[0040] The curable composition of the present invention comprises at least one silane-modified poly(meth)acrylate (I), i.e., at least one poly(meth)acrylate characterized by at least one hydrolysable silyl group at the end of the corresponding prepoly(meth)acrylate backbone. Preferred silane-modified poly(meth)acrylates include alpha-silane type modified poly(meth)acrylates and gamma-silane type modified poly(meth)acrylates.

[0041] According to a preferred embodiment of the present invention, the curable composition of the present invention comprises at least one compound of formula (I): Y-[(CR 1 2) b -SiR a (OR 2 ) 3-a ] x (I), In equation (I), Y represents an x-valent poly(meth)acrylate group bonded by nitrogen, oxygen, sulfur, or carbon. R is independently selected from monovalent, optionally substituted SiC-bonded hydrocarbon groups. R 1 The hydrocarbon group is independently selected from hydrogen or a monovalent, optionally substituted hydrocarbon group, which may be attached to a carbon atom via a nitrogen, phosphorus, oxygen, sulfur, or carbonyl group. R 2 Independently selected from hydrogen or a monovalent, optionally substituted hydrocarbon group, x is an integer from 1 to 10, preferably 1, 2 or 3, and especially preferably 1 or 2. a is independently selected from 0, 1, and 2, preferably from 0 and 1, and b is an integer independently selected from 1 to 10, preferably selected from 1, 3 and 4, particularly preferably selected from 1 and 3, especially 1.

[0042] Examples of group R are: alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, 1-n-butyl, 2-n-butyl, isobutyl, tert-pentyl, hexyl (e.g., n-hexyl), heptyl (e.g., n-heptyl), octyl (e.g., n-octyl, isooctyl, and 2,2,4-trimethylpentyl), nonyl (e.g., n-nonyl), decyl (e.g., n-decyl), dodecyl (e.g., n-dodecyl), octadecyl (e.g., n-octadecyl); cycloalkyl groups, such as cyclopentyl, cyclohexyl, cycloheptyl, and methylcyclohexyl; alkenyl groups, such as vinyl, 1-propenyl, and 2-propenyl; aryl groups, such as phenyl, 2-propenyl, and 2-propenyl, as well as phenyl, naphthyl, anthracene, and phenanthryl; alkylaryl groups, such as o-tolyl, m-tolyl, p-tolyl, xylyl, and ethylphenyl; and aralkyl groups, such as benzyl, α-phenylethyl, and β-phenylethyl.

[0043] The group R is preferably a monovalent hydrocarbon group having 1 to 6 carbon atoms, optionally substituted with a halogen atom, and particularly preferably an alkyl group having 1 or 2 carbon atoms, especially a methyl group.

[0044] Group R 1 Examples of this include hydrogen atoms; groups indicated by R; and optionally substituted hydrocarbon groups bonded to carbon atoms via nitrogen, phosphorus, oxygen, sulfur, carbon, or carbonyl groups.

[0045] R1 Preferably hydrogen and a hydrocarbon group having 1 to 20 carbon atoms, in particular hydrogen.

[0046] R 2 Examples are hydrogen or the examples given for R.

[0047] The group R 2 Preferably hydrogen or an alkyl group having 1 to 10 carbon atoms, optionally substituted by halogen atoms, in particular an alkyl group having 1 to 4 carbon atoms, in particular methyl and ethyl.

[0048] For the purposes of the present application, the poly(meth)acrylate on which the poly(meth)acrylate group Y is based is all poly(meth)acrylates in which at least 50%, preferably at least 70%, in particular at least 90% of all bonds in the main chain are carbon-carbon bonds, carbon-nitrogen bonds, or carbon-oxygen bonds. The poly(meth)acrylate group Y is preferably an organic polymer group which is a polyacrylate, a polymethacrylate, or a polymer comprising polyacrylate and polymethacrylate moieties, and is preferably bonded to each group -[(CR 1 2) b -SiR a (OR 2 ) 3-a ] x wherein R' can be identical or different and have the meaning as defined for R, or denote the group -CH(COOR'')-CH2-COOR'', wherein R'' can be identical or different and have the meaning as defined for R. Examples of the group R' include cyclohexyl; cyclopentyl; n-propyl and isopropyl; n-butyl, isobutyl and tert-butyl; various stereoisomers of pentyl, hexyl or heptyl; and phenyl. R' is preferably the group -CH(COOR'')-CH2-COOR'', or a hydrocarbon group having 1 to 20 carbon atoms, optionally substituted, in particular preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, optionally substituted by halogen atoms, or an aryl group having 6 to 20 carbon atoms; R'' is preferably an alkyl group having 1 to 10 carbon atoms, in particular methyl, ethyl, or propyl.

[0049] The compounds of the formula (I) can have groups -[(CR 1 2) b -SiR a (OR 2 ) 3-a ] x It is particularly preferred to have the end groups of the compounds according to the formula (I) at the end of the poly(meth)acrylate chain, i.e. as pendant groups of the poly(meth)acrylate main chain.

[0050] The end groups of the compounds according to the formula (I) are preferably those of the formula (II) or (III):

[0051] wherein the radicals and indices are as defined above.

[0052] The average molecular weight M n is preferably at least 400 g / mol, particularly preferably at least 600 g / mol, in particular at least 800 g / mol, and is preferably at most 30000 g / mol, particularly preferably at most 19000 g / mol, in particular at most 13000 g / mol.

[0053] According to various preferred embodiments, the curable composition of the present application comprises at least one poly(meth)acrylate having at least one silane functional group of the formula (IV): -X o -R 3 -Si(R 4 ) k (R 5 ) 3-k (IV), wherein: X is a divalent linking group containing at least one heteroatom; R 3 is selected from divalent hydrocarbon radicals having 1 to 12 carbon atoms; each R 4 is independently of the others selected from hydrocarbon radicals containing 1 to 20 carbon atoms, and each R 5 is independently of the others selected from hydroxyl or hydrolysable groups, wherein R 4 and R 5 are substituents directly bonded to the Si atom, or two of the substituents R 4 and R 5 form a ring together with the Si atom to which they are bonded; k is 0, 1 or 2; and o is 0 or 1.

[0054] In the present context, the divalent bonding group (linking group) X comprising at least one heteroatom shall be understood as a divalent chemical group which links the poly(meth)acrylate backbone of the poly(meth)acrylate to the group R 3 linking.

[0055] In various embodiments, the divalent linking group X in formula (IV) is selected from the group consisting of -0-, -S-, -N(R")-, -R"'-0-, a substituted or unsubstituted amide group, a carbamate group, a urethane group, a urea group, an imino group, a carboxylate group, a carbamoyl group, a guanidinyl group, a carbonate group, a sulfonate group, or a sulfinic acid ester group, wherein R" is hydrogen or a linear or branched, substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms; and R'" is a linear or branched, substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms. The term "substituted" in connection with these groups means that the hydrogen atoms present in these groups can be replaced by non-hydrogen moieties such as alkyl or aryl groups, preferably C 1-12 alkyl or C 6-14 aryl groups.

[0056] In preferred embodiments, the linking group X is a urethane group or a urea group, more preferably a urethane group. A urethane group can be formed, for example, when the poly(meth)acrylate backbone comprises terminal hydroxyl groups and an isocyanatosilane is used as additional component, or vice versa, when a poly(meth)acrylate having terminal isocyanate groups is reacted with an alkoxysilane comprising terminal hydroxyl groups. Similarly, a urea group can be obtained if a primary or secondary amino group at the terminal position (on the silane or on the poly(meth)acrylate) is used which reacts with the terminal isocyanate group present in the respective reactant. This means that an aminosilane is reacted with a poly(meth)acrylate having terminal isocyanate groups, or a poly(meth)acrylate which is substituted with an amino group at the terminal position is reacted with an isocyanatosilane. The urethane group and the urea group advantageously increase the strength of the poly(meth)acrylate chain and of the entire crosslinked poly(meth)acrylate.

[0057] In preferred embodiments, the linking group X is selected from the group consisting of -0-C(=0)-N(R")-, -N(R")-C(=0)0-, -N(R")-C(=0)-N(R")-, -N(R")-C(=0)-, -C(=0)-N(R")-, -C(=0)-0-, -0-C(=0)-, -0-C(=0)-0-, -S-C(=0)-N(R")-, -N(R")-C(=0)-S-, -C(=0)-S-, -S-C(=0)-, -S-C(=0)-S-, -C(=0)-, -S-, -0-, -NR"- and -R'"-0-, wherein R" and R'" are as defined above. In more preferred embodiments, the linking group X is selected from the group consisting of -0-C(=0)-N(R")-, -N(R")-C(=0)0-, -N(R")-C(=0)-N(R")-, -S-, -0-, -N(R")-, or -R'"-0-, wherein R" and R'" are as defined above. In particularly preferred embodiments, the linking group X is selected from the group consisting of -0-C(=0)-N(R")-, -N(R")-C(=0)-N(R")-, -0-, or -R'"-0-, wherein R" and R'" are as defined above, more preferably -0-C(=0)-NH- or -NH-C(=0)-NH-, most preferably -0-C(=0)-NH-.

[0058] The subscript "o" corresponds to 0 (zero) or 1, i.e. the linking group X links the poly(meth)acrylate backbone to the group R 3 linking (o = 1 ), or the poly(meth)acrylate backbone is linked to the group R 3 direct bond or linking (o = 0). In preferred embodiments, o is 1.

[0059] The group R 3 is a divalent hydrocarbon group having 1 to 12 carbon atoms. The hydrocarbon group can be a linear, branched or cyclic alkylene group, and can be substituted or unsubstituted. The hydrocarbon group can be saturated or unsaturated. In preferred embodiments, R 3 is a divalent hydrocarbon group having 1 to 6 carbon atoms. The rate of cure of the composition is influenced by the length of the hydrocarbon group which forms one of the binding links, or the binding link between the poly(meth)acrylate backbone and the silyl group. Particularly preferably, R 3 is methylene, ethylene, or n-propylene, particularly methylene or n-propylene.

[0060] Alkoxysilane-functional compounds having methylene as the binding link to the poly(meth)acrylate backbone (so-called "alpha silanes") have a particularly high silyl reactivity.

[0061] Generally, making the bonding hydrocarbon chain longer leads to a decrease in the reactivity of the poly(meth)acrylates. In particular, "gamma silanes", which comprise an unbranched propylene group as bonding bond, have a balanced ratio between necessary reactivity (acceptable curing time) and delayed curing (open assembly time, possibility of post-adhesion correction).

[0062] R 4 and R 5 are substituents which are directly bonded to the Si atom, or two of the substituents R 4 and R 5 may form a ring together with the Si atom to which they are bonded. In a preferred embodiment, R 4 and R 5 are substituents which are directly bonded to the Si atom.

[0063] each R 4 in formula (IV) is independently of the others selected from a hydrocarbon group containing 1 to 20 carbon atoms, preferably a Ci-C8-alkyl group, more preferably a methyl or ethyl group.

[0064] each R 5 in formula (IV) is independently of the others selected from a hydroxyl group or a hydrolysable group, preferably a Ci-C8-alkoxy group, or a Ci-C8-acyloxy group.

[0065] In a preferred embodiment, each R 5 is independently of the others selected from a Ci-C8-alkoxy group, in particular a methoxy group, an ethoxy group, an isopropoxy group, or an isobutoxy group. Combinations of more than one group are also possible when k is 0 or 1. However, acyloxy groups, such as acetoxy groups -O-CO-CH3, can also be used as hydrolysable groups.

[0066] In a preferred embodiment, k is 0 or 1.

[0067] In a particularly preferred embodiment, the silyl group (i.e. -Si(R 4 ) k (R 5 ) 3-k ) is selected from an alkyl dialkoxymethylsilyl group or a trialkoxymethylsilyl group, preferably from a methyldimethoxymethylsilyl group, an ethyldiethoxymethylsilyl group, a trimethoxymethylsilyl group, or a triethoxymethylsilyl group, most preferably a methyldimethoxymethylsilyl group or a trimethoxymethylsilyl group. Alkoxyl groups are advantageous because no mucosa-irritating substances are released during curing of the composition comprising the alkoxyl group. The alcohol formed by hydrolysis of the group is harmless in terms of the amount released and will evaporate.

[0068] In general, poly(meth)acrylates comprising dialkoxysilyl or trialkoxysilyl groups have high reactivity attachment points which allow fast curing, high crosslinking degree, and thus good final strength. A particular advantage of dialkoxysilyl groups lies in the fact that the corresponding compositions are more elastic, softer and more flexible after curing compared to systems comprising trialkoxysilyl groups. Thus, they are particularly suitable for use as sealants, but also as adhesives. Furthermore, they decompose less alcohol during curing and are thus particularly interesting when the amount of alcohol release is to be reduced.

[0069] On the other hand, with trialkoxysilyl groups a higher crosslinking degree can be achieved which is particularly advantageous when a harder and stronger material after curing is desired. Furthermore, trialkoxysilyl groups are more reactive and thus crosslink more quickly, reducing the amount of catalyst required, and they also have advantages in terms of "cold flow" (i.e. dimensional stability of the corresponding foam under force and possible temperature influences).

[0070] Methoxy and ethoxy groups (as relatively small hydrolysable groups with small steric bulk) are very highly reactive and thus allow fast curing even with low catalyst usage. Thus, they are particularly interesting for systems where fast curing is desired.

[0071] With the combination of the two groups, interesting configuration possibilities also arise. Insofar as a silyl group with only methoxy groups is considered to be too reactive and a silyl group with ethoxy groups is not reactive enough for the intended use, if, for example, R 5 is selected to be methoxy and the other R 5 is selected to be ethoxy, the desired reactivity of the silyl group can be finely adjusted in particular.

[0072] In addition to methoxy and ethoxy groups, of course also larger groups can be used as hydrolysable groups which exhibit lower reactivity in nature. This is particularly interesting if a delayed curing is also to be achieved by means of the configuration of the alkoxysilyl group.

[0073] The silane function of formula (IV) can be a pendant group within the poly(meth)acrylate chain of the corresponding poly(meth)acrylate, or an end group of the corresponding poly(meth)acrylate. In a preferred embodiment, the silane function of formula (IV) is an end group of the poly(meth)acrylate.

[0074] In a preferred embodiment, the poly(meth)acrylate has at least two silane functions of formula (IV). In this case, the poly(meth)acrylate can have at least one lateral silane function of formula (IV) and at least one terminal silane function of formula (IV); or at least two lateral silane functions of formula (IV); or at least two terminal silane functions of formula (IV).

[0075] In a particularly preferred embodiment, the poly(meth)acrylate has at least two terminal silane functions of formula (IV). Thus, each poly(meth)acrylate chain comprises at least two points of attachment at which the condensation of the poly(meth)acrylate can be completed, thereby splitting the hydrolysed groups in the presence of atmospheric moisture. In this way, a regular and fast crosslinking ability is achieved, so that adhesives with good strength can be obtained. Furthermore, by means of the amount and structure of the hydrolysable groups (for example, by using dialkoxysilyl or trialkoxysilyl, methoxy or longer groups), the network configuration (which can be implemented as a long-chain system (thermoplastic), a relatively wide-mesh three-dimensional network (elastomer), or a highly crosslinked system (thermoset)) can be controlled, so that in this way the elasticity, flexibility and heat resistance of the final crosslinked composition can be influenced, in particular.

[0076] In a preferred embodiment, the poly(meth)acrylate backbone of the poly(meth)acrylate is selected from poly(meth)acrylate homopolymers (meth)acrylates and poly(meth)acrylate copolymers, in particular as polyether and poly(meth)acrylate copolymers.

[0077] "Polyether", "polyalkylene oxide", or "polyalkylene glycol", as used interchangeably herein, shall be understood to mean polymers whose organic repeating units in the main chain comprise ether functions C-O-C. Examples of such polymers are polypropylene glycol and polyethylene glycol and copolymers thereof. Polymers with pendant ether groups (such as cellulose ethers, starch ethers and vinyl ether polymers), as well as polyacetals (such as polyoxymethylene (POM)) are not included in polyethers.

[0078] "Poly(meth)acrylate" shall be understood to mean (meth)acrylate-based polymers which thus have the repeating unit structure motif -CH2-CR'(COOR")-, wherein R' denotes a hydrogen atom (acrylate) or a methyl group (methacrylate), and R" denotes a linear alkyl group, a branched alkyl group, a cyclic alkyl group, and / or an alkyl group comprising a functional substituent, for example methyl, ethyl, isopropyl, cyclohexyl, 2-ethylhexyl, or 2-hydroxyethyl.

[0079] The silane-modified polymers discussed above are either commercially available products or can be synthesized using known methods and processes, such as addition reactions, for example hydrosilylation, Michael addition, Diels-Alder addition, or reaction between an isocyanate-functional compound and a compound containing isocyanate-reactive groups. In this regard, reference can be made, for example, to EP 1535940 B1 and EP 1896523 B1. Alternative synthesis routes are further disclosed in WO 2013 / 026654 A1.

[0080] Silane-modified poly(meth)acrylates suitable for use in the context of the present application include, but are not limited to, commercially available poly(meth)acrylates and pre-poly(meth)acrylates, a specific example suitable for use according to the present application is Kaneka MS poly(meth)acrylate available from Kaneka Corporation.

[0081] The amount of one or more silane-modified pre-poly(meth)acrylates (i.e. one type of silane-modified pre-poly(meth)acrylate, or different types of silane-modified pre-poly(meth)acrylates (i.e. two or more different types of silane-modified pre-poly(meth)acrylates)) as defined above in the curable composition of the present application, based on the total weight of the curable composition, typically ranges from about 10 to about 95 wt.-%, preferably from about 10 to about 90 wt.-%, even more preferably from about 15 to about 85 wt.-%, for example from about 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85 wt.-%.

[0082] The curable composition according to the claimed application comprises surface-treated calcium carbonate (II).

[0083] The preferred surface-treated calcium carbonate particles comprise a treatment layer on the surface of the calcium carbonate particles, said treatment layer comprising: i. one or more phosphoric acid mono-esters and salty reaction products thereof and / or one or more phosphoric acid di-esters and salty reaction products thereof, and / or ii. at least one saturated aliphatic linear or branched carboxylic acid and salty reaction products thereof, and / or iii. at least one aliphatic aldehyde and / or salty reaction products thereof, and / or iv. at least one mono-substituted succinic anhydride and / or salty reaction products thereof, said mono-substituted succinic anhydride consisting of succinic anhydride mono-substituted by a substituent selected from the group consisting of a substituted group having a total amount of carbon atoms in the substituent of at least C2 to C12,30 Linear, branched, aliphatic and cyclic groups, and / or v. at least one polydialkylsiloxane, and / or vi. A mixture of materials according to i. to v.

[0084] Particularly preferred surface-treated calcium carbonate particles comprise a hydrophobic coating, and are preferably coated with an alkylsilane (e.g., hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octyltriethoxysilane, octyltrimethoxysilane, etc.) containing 4-22 carbon atoms, or an aliphatic carboxylic acid or its salt. For said coating, it is also particularly preferred that it contains 4-22 carbon atoms, more preferably 6-16 carbon atoms, and more preferably 10-12 carbon atoms, of which saturated or unsaturated carboxylic acids are most preferred. In this case, the use of lauric acid and stearic acid, especially stearic acid, is particularly advantageous.

[0085] The curable composition according to the claimed invention comprises at least one aminosilane and / or aminosilane oligomer (III), preferably as an adhesion promoter.

[0086] The additional aminosilane is preferably selected from the group consisting of 3- aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, aminomethyltrimethoxysilane, aminomethyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, (N-2- aminoethyl)-3-aminopropyltrimethoxysilane, (N-2-aminoethyl)-3-aminopropyltriethoxysilane, diethylenetriaminopropyltrimethoxysilane, phenylaminomethyltrimethoxysilane, (N-2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-(N-phenylamino)propyltrimethoxysilane, 3-piperazinylpropylmethyldimethoxysilane, 3-(N,N-dimethylaminopropyl)aminopropylmethyldimethoxysilane, tris[(3- triethoxysilyl)propyl]amine, tris[(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, bis(3- trimethoxysilyl)propylamine, bis(3-triethoxysilyl)propylamine, 4-amino-3,3- dimethylbutyltrimethoxysilane, 4-amino-3,3-dimethylbutyltriethoxysilane, N-(n- butyl)-3-aminopropyltrimethoxysilane, and mixtures thereof; particularly preferably from the group consisting of 3-aminopropyltrimethoxysilane, 3- aminopropyltriethoxysilane, aminomethyltrimethoxysilane, aminomethyltriethoxysilane, 3-(N,N-dimethylamino)propyltrimethoxysilane, 3-(N,N- dimethylamino)propyltriethoxysilane, (N,N-dimethylamino)methyltrimethoxysilane, (N,N-dimethylamino)methyltriethoxysilane, 3-(N,N-diethylamino)propyltrimethoxysilane, 3-(N,N-diethylamino)propyltriethoxysilane, (N,N- diethylamino)methyltrimethoxysilane, (N,N-diethylamino)methyltriethoxysilane, bis(3-trimethoxysilyl)propylamine and bis(3-triethoxysilyl)propylamine, 4-amino-3,3-dimethylbutyltrimethoxysilane, 4-amino-3,3- dimethylbutyltriethoxysilane, or N-(n-butyl)-3-aminopropyltrimethoxysilane, or oligomers obtained from condensation of at least one of the aforementioned aminosilanes, or mixtures thereof.The above amino silane monomers or oligomers can be oligomerized together with alkylalkoxysilanes, alkenylalkoxysilanes, or arylalkoxysilanes (preferably, methyltri(m / eth)oxysilane, ethyltri(m / eth)oxysilane, propyltri(m / eth)oxysilane, vinyltri(m / eth)oxysilane, n-butyltri(m / eth)oxysilane, i-butyltri(m / eth)oxysilane, phenyltri(m / eth)oxysilane, and / or octyltri(m / eth)oxysilane).

[0087] In various embodiments, the curable composition according to the claimed invention comprises at least one tertiary amino silane. As used herein, "tertiary amino silane" means an amino silane in which the nitrogen atom of the amino group is covalently linked to three non-hydrogen groups. tertiary aminosilane "amino silane" means an amino silane in which the nitrogen atom of the amino group is covalently linked to three non-hydrogen groups.

[0088] According to a preferred embodiment, the curable composition of the claimed invention further comprises at least one silane-modified polyether (IV), i.e., at least one polymer characterized by hydrolysable silyl groups at the end of the corresponding prepolymer backbone. Preferred silane-modified polyethers (IV) include alpha-silane type modified polymers and gamma-silane type modified polymers.

[0089] Preferably, the curable composition comprises at least one compound of formula (I'): Y'-[(CR 1 2) b -SiR a (OR 2 ) 3-a ] x (I'), wherein, in formula (I'), Y represents a x-valent polymeric group bonded via nitrogen, oxygen, sulfur or carbon, R is independently selected from the group consisting of monovalent optionally substituted SiC-bonded hydrocarbon radicals, R 1 is independently selected from the group consisting of hydrogen, or a monovalent optionally substituted hydrocarbon radical which can be linked to a carbon atom via nitrogen, phosphorus, oxygen, sulfur, or a carbonyl group, R 2 is independently selected from the group consisting of hydrogen, or a monovalent optionally substituted hydrocarbon radical, x is an integer from 1 to 10, preferably 1, 2 or 3, especially preferably 1 or 2, a is independently selected from the group consisting of 0, 1 and 2, preferably from the group consisting of 0 and 1, and b is independently selected from the group consisting of an integer from 1 to 10, preferably from the group consisting of 1, 3 and 4, particularly preferably from the group consisting of 1 and 3, in particular 1.

[0090] ​Examples of the group R are: alkyl groups such as methyl, ethyl, n-propyl, isopropyl, 1-n-butyl, 2-n-butyl, isobutyl, t-amyl, hexyl (e.g. n-hexyl), heptyl (e.g. n-heptyl), octyl (e.g. n-octyl, isooctyl and 2,2,4-trimethylpentyl), nonyl (e.g. n-nonyl), decyl (e.g. n-decyl), dodecyl (e.g. n-dodecyl), octadecyl (e.g. n-octadecyl); cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl; alkenyl groups such as ethenyl, 1-propenyl and 2-propenyl; aryl groups such as phenyl, 2-propenyl and 2-propenyl, and phenyl, naphthyl, anthryl and phenanthryl; alkaryl groups such as o-, m- and p-tolyl, xylyl and ethylphenyl; and aralkyl groups such as benzyl, α- and β-phenylethyl.

[0091] The group R is preferably a monovalent hydrocarbon group having 1 to 6 carbon atoms which is optionally substituted by a halogen atom, and is particularly preferably an alkyl group having 1 or 2 carbon atoms, in particular methyl.

[0092] Examples of the group R 1 are a hydrogen atom; a group indicated for R; and an optionally substituted hydrocarbon group bonded to a carbon atom via nitrogen, phosphorus, oxygen, sulfur, carbon or carbonyl.

[0093] R 1 is preferably hydrogen and a hydrocarbon group having 1 to 20 carbon atoms, and is particularly hydrogen.

[0094] R 2 is a hydrogen atom; a group indicated for R; and an optionally substituted hydrocarbon group bonded to a carbon atom via nitrogen, phosphorus, oxygen, sulfur, carbon or carbonyl.

[0095] Examples of the group R 2 is preferably hydrogen, or an alkyl group having 1 to 10 carbon atoms which is optionally substituted by a halogen atom, and is particularly preferably an alkyl group having 1 to 4 carbon atoms, in particular methyl and ethyl.

[0096] For the purposes of the present application, the polymers on which the polymer radicals Y' are based are all polymers in which at least 50%, preferably at least 70%, of all the bonds in the main chain are carbon-carbon bonds, carbon-nitrogen bonds or carbon-oxygen bonds. The polymer radicals Y' are preferably organic polymer radicals which are polyalkylene oxides such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polytetramethylene oxide, polyoxyethylene-polyoxypropylene copolymers and polyoxypropylene-polyoxybutylene copolymers as polymer chains and are preferably bonded via -0-C(=0)-NH-, -NH-C(=0)0-, -NH-C(=0)-NH-, -NR'-C(-0)-NH-, NH-C(=0)-NR'-, -NH-C(=0)-, -C(=0)-NH-, -C(=0)-0-, -0-C(=0)-, -0-C(=0)-0-, -S-C(=0)-NH-, -NH-C(=0)-S-, -C(=0)-S-, -S-C(=0)-, -S-C(=0)-S-, -C(-0), -S-, -0-, or -NR'- bonds to each radical -[(CR 1 2) b -SiR a (OR 2 ) 3-a ] x where R' can be identical or different and have the meanings specified for R, or denote the radical -CH(COOR'')-CH2-COOR'', where R'' can be identical or different and have the meanings specified for R. Examples of radicals R' include cyclohexyl; cyclopentyl; n-propyl and isopropyl; n-butyl, isobutyl and tert-butyl; the various stereoisomers of pentyl, hexyl or heptyl; and phenyl. R' is preferably the radical -CH(COOR'')-CH2-COOR'', or an optionally substituted hydrocarbon radical having 1 to 20 carbon atoms, particularly preferably a linear, branched or cyclic alkyl radical having 1 to 20 carbon atoms which is optionally substituted by halogen atoms or an aryl radical having 6 to 20 carbon atoms; R'' is preferably an alkyl radical having 1 to 10 carbon atoms, particularly preferably methyl, ethyl or propyl.

[0097] In formula (I'), the radical Y' preferably denotes a polyalkylene oxide radical, in particular a polyurethane radical containing polypropylene oxide or a polypropylene oxide radical.

[0098] The compounds of formula (I') can have radicals -[(CR 1 2) b -SiR a (OR 2 ) 3-a ] xat the end or between the ends (i.e. as a side group of the polymer main chain), particularly preferably at the end of the polymer chain.

[0099] End groups of the compounds according to formula (I’) are preferably those of formula (II’) or formula (III’):

[0100] wherein the radicals and indices are defined as above.

[0101] In particular, the compounds according to formula (I’) can represent silane-terminated polyethers, in particular silane-terminated polypropylene glycol, which have a dimethyl- or trimethylsilyl end group bonded via -O-C(=O)-NH-(CR 1 2) b -NH-C(=O)-NR’-(CR 1 2) b dimethoxymethylsilyl, trimethoxysilyl, diethoxymethylsilyl, or triethoxysilyl end group, wherein R’, R 1 and b are defined as above.

[0102] The average molecular weight M n is preferably at least 400 g / mol, particularly preferably at least 600 g / mol, in particular at least 800 g / mol, and is preferably at most 30000 g / mol, particularly preferably at most 19000 g / mol, in particular at most 13000 g / mol.

[0103] The viscosity of the compounds according to formula (I’) is preferably at least 0.2 Pas, preferably at least 1 Pas, particularly preferably at least 5 Pas, and is preferably at most 1000 Pas, preferably at most 700 Pas, each measured at 20°C.

[0104] According to various preferred embodiments, the silane-modified polyether (IV) comprises at least one polymer having at least one silane function of formula (IV’): -X o -R 3 -Si(R 4 ) k (R 5 ) 3-k (IV’), wherein: X is a divalent linking group containing at least one heteroatom; R 3 is selected from divalent hydrocarbon radicals having 1 to 12 carbon atoms; each R 4are independently of each other selected from hydrocarbyl groups having 1 to 20 carbon atoms, and each R 5 are independently of each other selected from hydrocarbyl groups having 1 to 20 carbon atoms, and each R 4 and R 5 are substituents directly bound to the Si atom, or two of the substituents R 4 and R 5 form together with the Si atom to which they are bound a ring; k is 0, 1 or 2; and o is 0 or 1.

[0105] In the present context, the divalent bound group (linker group) X comprising at least one heteroatom shall be understood as a divalent chemical group connecting the polymer backbone of the polymer with the group R 3 of formula (IV’).

[0106] In various embodiments, the divalent linker group X in formula (IV’) is selected from -0-, -S-, -N(R”)-, -R”-0-, a substituted or unsubstituted amido group, a methylaminoate group, a carbamato group, a urea group, an imino group, a carboxylate group, a carbamoyl group, a guanidino group, a carbonate group, a sulfonate group, or a sulfinato group, wherein R” is hydrogen or a linear or branched, substituted or unsubstituted hydrocarbyl group having 1 to 12 carbon atoms; and R’ is a linear or branched, substituted or unsubstituted hydrocarbyl group having 1 to 12 carbon atoms. The term “substituted” in connection with these groups means that the hydrogen atoms present in these groups can be replaced by non-hydrogen moieties, such as alkyl or aryl groups, preferably C 1-12 alkyl or C 6-14 aryl groups.

[0107] In preferred embodiments, the linker group X is a carbamato group or a urea group, more preferably a carbamato group. A carbamato group can be formed, for example, when the polymer backbone comprises terminal hydroxyl groups and an isocyanatosilane is used as further component, or vice versa, when a polymer having terminal isocyanate groups is reacted with an alkoxysilane comprising terminal hydroxyl groups. Similarly, a urea group can be obtained if a primary or secondary amino group at the terminal position (on the silane or on the polymer) is used which reacts with the terminal isocyanate group present in the respective reactant. This means that an aminosilane is reacted with a polymer having terminal isocyanate groups, or a polymer which is substituted with amino groups at the terminal position is reacted with an isocyanatosilane. The carbamato group and the urea group advantageously increase the strength of the polymer chain and of the entire crosslinked polymer.

[0108] In a preferred embodiment, the linking group X is selected from the group consisting of -0-C(=0)-N(R")-, -N(R")-C(=0)0-, -N(R")-C(=0)-N(R")-, -N(R")-C(=0)-, -C(=0)-N(R")-, -C(=0)-0-, -0-C(=0)-, -0-C(=0)-0-, -S-C(=0)-N(R")-, -N(R")-C(=0)-S-, -C(=0)-S-, -S-C(=0)-, -S-C(=0)-S-, -C(=0)-, -S-, -0-, -NR"- and -R'"-0-, wherein R" and R'" are as defined above. In a more preferred embodiment, the linking group X is selected from the group consisting of -0-C(=0)-N(R")-, -N(R")-C(=0)0-, -N(R")-C(=0)-N(R")-, -S-, -0-, -N(R")-, or -R'"-0-, wherein R" and R'" are as defined above. In a particularly preferred embodiment, the linking group X is selected from the group consisting of -0-C(=0)-N(R")-, -N(R")-C(=0)-N(R")-, -0-, or -R'"-0-, wherein R" and R'" are as defined above, more preferably -0-C(=0)-NH- or -NH-C(=0)-NH-, most preferably -0-C(=0)-NH-.

[0109] The subscript "o" corresponds to 0 (zero) or 1, i.e. the linking group X links the polymer backbone to the group R 3 a direct bond or linkage (o = 0). In a preferred embodiment, o is 1. 3 a direct bond or linkage (o = 0). In a preferred embodiment, o is 1.

[0110] The group R 3 is a divalent hydrocarbon group having 1 to 12 carbon atoms. The hydrocarbon group can be a linear, branched or cyclic alkylene group and can be substituted or unsubstituted. The hydrocarbon group can be saturated or unsaturated. In a preferred embodiment, R 3 is a divalent hydrocarbon group having 1 to 6 carbon atoms. The rate of cure of the composition will be influenced by the length of the hydrocarbon group which forms one of the bonding linkages between the polymer backbone and the silyl group. Particularly preferably, R 3 is methylene, ethylene, or n-propylene, particularly methylene or n-propylene.

[0111] Alkoxysilane-functional compounds having methylene as the bonding linkage to the polymer backbone (so-called "alpha silanes") have a particularly high silyl reactivity.

[0112] Generally, making the bonding hydrocarbon chain longer leads to a decrease in the reactivity of the polymer. In particular, "gamma silanes" which contain an unbranched propylene group as bonding bond have a balanced ratio between necessary reactivity (acceptable curing time) and delayed curing (open assembly time, possibility of corrections after adhesion).

[0113] R 4 and R 5 are substituents which are directly bonded to the Si atom, or the substituents R 4 and R 5 together with the Si atom to which they are bonded can form a ring. In a preferred embodiment, R 4 and R 5 are substituents which are directly bonded to the Si atom.

[0114] Each R 4 in formula (IV') is independently of the others selected from a hydrocarbon group containing 1 to 20 carbon atoms, preferably a Ci-C8-alkyl group, more preferably a methyl or ethyl group.

[0115] Each R 5 in formula (IV') is independently of the others selected from a hydroxyl group or a hydrolysable group, preferably a Ci-C8-alkoxy group, or a Ci-C8-acyloxy group.

[0116] In a preferred embodiment, each R 5 is independently of the others selected from a Ci-C8-alkoxy group, in particular a methoxy group, an ethoxy group, an isopropoxy group, or an isobutoxy group. Combinations of more than one group are also possible when k is 0 or 1. However, acyloxy groups such as acetoxy -O-CO-CH3 can also be used as hydrolysable groups.

[0117] In a preferred embodiment, k is 0 or 1.

[0118] In a particularly preferred embodiment, the silyl group (i.e. -Si(R 4 ) k (R 5 ) 3-k ) is selected from an alkyl dialkoxysilyl group or a trialkoxysilyl group, preferably from a methyl dimethoxysilyl group, an ethyl diethoxysilyl group, a trimethoxysilyl group, or a triethoxysilyl group, most preferably a methyl dimethoxysilyl group or a trimethoxysilyl group. Alkoxyl groups are advantageous because no mucosa-irritating substances are released during curing of the composition comprising the alkoxyl group. The alcohol formed by hydrolysis of the group is harmless in terms of the amount released and will evaporate.

[0119] Generally, polymers comprising dialkoxysilyl or trialkoxysilyl groups have high reactivity attachment points which allow fast curing, high crosslinking degree, and thus good final strength. A particular advantage of dialkoxysilyl groups lies in the fact that the corresponding compositions are more elastic, softer and more flexible after curing compared to systems comprising trialkoxysilyl groups. Thus, they are particularly suitable for use as sealants. Furthermore, they decompose less alcohol during curing and are thus particularly interesting when the amount of alcohol release is to be reduced.

[0120] On the other hand, with trialkoxysilyl groups a higher crosslinking degree can be achieved which is particularly advantageous when a harder and stronger material after curing is desired. Furthermore, trialkoxysilyl groups are more reactive and thus crosslink more quickly, reducing the amount of catalyst required, and they also have advantages in terms of "cold flow", i.e. the dimensional stability of the corresponding foam under force and possible temperature influences.

[0121] Methoxy and ethoxy groups, as relatively small hydrolysable groups with small steric bulk, are very highly reactive and thus allow fast curing even with low catalyst usage. Thus, they are particularly interesting for systems where fast curing is desired.

[0122] With the combination of these two groups, interesting configuration possibilities also arise. Insofar as a silyl group with only methoxy groups is considered to be too reactive and a silyl group with ethoxy groups is not reactive enough for the intended use, if, for example, R 5 is selected to be methoxy and the other R 5 is selected to be ethoxy, the desired reactivity of the silyl group can be finely adjusted in particular.

[0123] In addition to methoxy and ethoxy groups, of course also larger groups can be used as hydrolysable groups which exhibit lower reactivity in nature. This is particularly interesting if a delayed curing is also to be achieved by means of the configuration of the alkoxysilyl groups.

[0124] The silane function of the formula (IV') can be a pendant group within the polymer chain of the corresponding polymer, or an end group of the corresponding polymer. In a preferred embodiment, the silane function of the formula (IV') is an end group of the polymer.

[0125] In a preferred embodiment, the polymer has at least two silane functions of the formula (IV'). In this case, the polymer can have at least one pendant silane function of the formula (IV') and at least one terminal silane function of the formula (IV'); or at least two pendant silane functions of the formula (IV'); or at least two terminal silane functions of the formula (IV').

[0126] In a particularly preferred embodiment, the polymer has at least two terminal silane functions of the formula (IV'). Thus, each polymer chain comprises at least two points of attachment at which the condensation of the polymer can be completed, thereby splitting the hydrolysed groups in the presence of atmospheric moisture. In this way, a regular and fast crosslinking ability is achieved, so that adhesives with good strength can be obtained. Furthermore, by means of the amount and structure of the hydrolysable groups (for example by using dialkoxysilyl or trialkoxysilyl, methoxy or longer groups), the network configuration (which can be implemented as a long-chain system (thermoplastic), a relatively wide-pored three-dimensional network (elastomer), or a highly crosslinked system (thermoset)) can be controlled, so that in this way the elasticity, flexibility and heat resistance of the final crosslinked composition can be influenced, in particular.

[0127] In a preferred embodiment, the polymer backbone of the polymer is selected from polyethers or copolymers thereof.

[0128] "Polyether", "polyalkylene oxide", or "polyalkylene glycol", as used interchangeably herein, shall be understood to mean polymers whose organic repeating units in the main chain comprise ether functions C-O-C. Examples of such polymers are polypropylene glycol and polyethylene glycol and copolymers thereof. Polymers with pendant ether groups (such as cellulose ethers, starch ethers and vinyl ether polymers), as well as polyacetals (such as polyoxymethylene (POM)) are not included in polyethers.

[0129] In a particularly preferred embodiment, the silane-modified polymer has a polyether main chain. Polyethers have a flexible and elastic structure, which can be utilised to produce compositions with excellent elastic properties. Polyethers are not only flexible in the main chain, but are also strong. Thus, for example, in contrast to, for example, polyesters, polyethers are not eroded or decomposed by water and bacteria.

[0130] The number-average molecular weight M n Preferably, the number-average molecular weight is from 500 to 100000 g / mol (Dalton), more preferably from 500 to 50000 g / mol, particularly preferably from 1000 to 30000 g / mol, in particular from 2000 to 20000 g / mol, most preferably from 8000 to 20000 g / mol. For the polyethers according to the application, it is advantageous for the number-average molecular weight to be at least 500 g / mol, since the corresponding compositions have a balanced viscosity (easy to process), strength and elasticity ratio.

[0131] The silane-modified polymers discussed above are commercially available products or can be synthesized using known methods and processes, such as addition reactions, e.g. hydrosilylation, Michael addition, Diels-Alder addition, or reaction between an isocyanate-functional compound and a compound containing isocyanate-reactive groups. In this regard, reference can be made, for example, to EP 1535940 B1 and EP 1896523 B1. Alternative synthesis routes are further disclosed in WO 2013 / 026654 A1.

[0132] Silane-modified polymers suitable for use in the context of the present application include, but are not limited to, the polymers and prepolymers commercially available under the brand name GENIOSIL®, and specific examples suitable for use according to the present application are the alpha-silane polyether-type prepolymers GENIOSIL® STPE-E10, GENIOSIL® STPE-E15, GENIOSIL® STPE-E30, and GENIOSIL® STPE-E35; the alpha-silane polyether-polyurethane-type prepolymers of the GENIOSIL® XB series, an example of which is GENIOSIL® XB 502; GENIOSIL® XT; GENIOSIL® XM; and GENIOSIL® WP. Further, examples of curable polyoxypropylene resins include various known reactive polyoxypropylene resins, such as the Kaneka MS polymers available from Kaneka Corporation.

[0133] The amount of one or more silane-modified prepolymers (i.e., one type of silane-modified prepolymer, or different types of silane-modified prepolymers (i.e., two or more different types of silane-modified prepolymers)) as defined above in the silane-modified polyether (IV') typically ranges from about 10 to about 95 weight %, preferably from about 10 to about 90 weight %, even more preferably from about 15 to about 85 weight %, for example about 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85 weight %, based on the total weight of the silane-modified polyether (IV').

[0134] In the context of the curable composition of the claimed invention, it will be readily appreciated that in addition to the generally fast curing rate, a significant advantage of the alpha-silane type curable resin composition is that there is no need to include tin catalysts or strong acids or strong bases for the purpose of curing. Thus, according to various documents, the silane-modified polyether (IV) is an alpha-silane type curable resin composition, i.e. a curable resin composition comprising at least one alpha-silane type prepolymer as defined above, in an amount of preferably from about 10 to about 95 wt.%, more preferably from about 10 to about 90 wt.%, such as about 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90 wt.%, based on the total weight of the silane-modified polyether (IV).

[0135] Preferably, the curable composition according to the claimed invention comprises a surface-treated silica (V).

[0136] The BET surface area of the silica is preferably from 5 to 250 m 2 / g. When used, it can additionally increase the viscosity of the curable composition according to the claimed invention to achieve a thixotropic formulation, and it can help to enhance the cured composition.

[0137] It is likewise conceivable to use a silica having a BET surface area advantageously from 100 to 250 m 2 / g, in particular from 110 to 170 m 2 / g, as a filler. Due to the higher BET surface area, the same effect (e.g. enhancing the cured composition) can be achieved at a smaller weight proportion of silicic acid. Thus, other substances can be used to improve the compositions described herein in other requirements.

[0138] According to a preferred embodiment, the curable composition according to the claimed invention comprises at least one curing catalyst (VI), which is preferably selected from tin catalysts, titanium catalysts, aluminum catalysts, or zirconium catalysts, more preferably from tin catalysts, or titanium catalysts, or mixtures thereof.

[0139] In various embodiments, the curing catalyst can be a tin compound, preferably an organotin compound or an inorganic tin salt. The tin in these tin compounds is preferably divalent or tetravalent. The curing catalyst can be added to the composition in particular as a crosslinking catalyst. Suitable inorganic tin salts are, for example, tin (II) chloride and tin (IV) chloride. However, organotin compounds (tin organyles) are preferably used as tin compounds. Suitable organotin compounds are, for example, 1,3-dicarbonyl compounds of divalent tin or tetravalent tin, for example acetylacetonates, such as bis(acetylacetonato)di(n-butyl)tin (IV), bis(acetylacetonato)di(n-octyl)tin (IV), (n-octyl)(n-butyl)tin (IV) acetylacetonate; dialkyltin (IV) dicarboxylates, for example di-n-butyltin dilaurate, di-n-butyltin maleate, di-n-butyltin diacetate, di-n-octyltin dilaurate, di-n-octyltin diacetate, or the corresponding dialkoxides, for example dimethoxydi-n-butyltin; oxides of tetravalent tin, for example 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) phenoxide.

[0140] Furthermore suitable are ethyl silicate, dimethyl maleate, diethyl maleate, dioctyl maleate, dimethyl phthalate, diethyl phthalate, dioctyl phthalate, nonadecanoic acid, tin compounds of myristic acid, for example bis(methylmaleate)di(n-butyl)tin (IV), bis(butylmaleate)di(n-butyl)tin (IV), bis(methylmaleate)di(n-octyl)tin (IV), bis(butylmaleate)di(n-octyl)tin (IV), bis(isooctylmaleate)di(n-octyl)tin (IV); and also bis(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-C8H 17 )2, (n-octyl)2Sn(SCH2COO-i-C8H 17 )2, and (n-octyl)2Sn(SCH2COO-n-C8H 17 )2.

[0141] Preferably, the tin compound is selected from the group consisting of 1,3-dicarbonyl compounds of divalent tin or tetravalent tin, dialkyltin (IV) dicarboxylates, dialkoxylated dialkyltin (IV), dialkyltin (IV) oxides, tin (II) carboxylates, and mixtures thereof.

[0142] Particularly preferred, the tin compound is a dialkyl tin (IV) oxide (e.g. di-n-octyl tin oxide) or a dialkyl tin (IV) dicarboxylate, in particular di-n-butyl tin dilaurate, di-n-butyl tin diacetate, or di-n-octyl tin dilaurate.

[0143] Additionally or alternatively, other metal-based condensation catalysts can be used, including but not limited to: titanium compounds (such as organotitanates or chelates), cerium compounds, zirconium compounds, molybdenum compounds, manganese compounds, copper compounds, aluminium compounds, or zinc compounds, or salts, alkoxides, chelates thereof, or catalytically active compounds of the main groups, or salts of bismuth, lithium, strontium or boron.

[0144] Other suitable (tin-free) curing catalysts are, for example, organometallic compounds of iron, in particular 1,3-dicarbonyl compounds of iron, such as acetylacetone iron (III).

[0145] Halogenated boron compounds (such as boron trifluoride, boron trichloride, boron tribromide, boron triiodide) or mixtures of halogenated boron compounds can also be used as curing catalysts. Particularly preferred are boron trifluoride complexes, such as boron trifluoride diethyl etherate, which are easier to handle as a liquid than as a gaseous halogenated boron compound.

[0146] 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).

[0147] Mixtures of one or more catalysts from one or more of the groups mentioned immediately above can also be used as catalysts.

[0148] Suitable as titanium catalysts are compounds having hydroxyl groups and / or substituted or unsubstituted alkoxy groups, thus titanium alkoxides of the following general formula: Ti(OR z )4, wherein R z is an organic radical, preferably a substituted or unsubstituted hydrocarbon radical having 1 to 20 carbon atoms, and the 4 alkoxy groups -OR z are identical or different. Furthermore, one or more of the -OR z groups can be replaced by acyloxy groups -OCOR z .

[0149] Also suitable as titanium catalysts are titanium alkoxides in which one or more of the alkoxy groups are replaced by hydroxyl groups or halogen atoms.

[0150] Furthermore, titanium chelates can be used.

[0151] Aluminium catalysts can also be used as curing catalysts, for example aluminium alkoxides: Al(OR z )3, wherein R z has the above-mentioned meanings; i.e. it is an organic radical, preferably a hydrocarbon radical having 1 to 20 carbon atoms which is substituted or unsubstituted, and the three R z groups are identical or different. In the case of aluminium alkoxides, one or more of the alkoxy groups can also be replaced by acyloxy groups -OC(O)R z .

[0152] In addition, aluminium alkoxides in which one or more of the alkoxy groups are replaced by hydroxyl groups or halogen atoms can also be used.

[0153] Of the aluminium catalysts, pure aluminium alkoxides are preferred in terms of the stability of the pure aluminium alkoxide to moisture and the curing properties of the mixture to which the pure aluminium alkoxide is added. Furthermore, aluminium chelates are preferred.

[0154] Examples of suitable zirconium catalysts are, for example, tetramethoxyzirconium or tetraethoxyzirconium.

[0155] Very particular preference is given to using bis(ethylacetoacetate)diisopropoxyzirconium, (ethylacetoacetate)triisopropoxyzirconium and tri(ethylacetoacetate)isopropoxyzirconium.

[0156] Furthermore, zirconium acylates, zirconium halide catalysts or zirconium chelates can also be used.

[0157] Furthermore, carboxylates of metals, or mixtures of a plurality of such salts, can be used as curing catalysts, wherein these are selected from carboxylates of calcium, vanadium, iron, zinc, titanium, potassium, barium, manganese, nickel, cobalt and / or zirconium.

[0158] Of the carboxylates, calcium carboxylates, vanadium carboxylates, iron carboxylates, zinc carboxylates, titanium carboxylates, potassium carboxylates, barium carboxylates, manganese carboxylates and zirconium carboxylates are preferred, since they exhibit high activity. Calcium carboxylates, vanadium carboxylates, iron carboxylates, zinc carboxylates, titanium carboxylates and zirconium carboxylates are particularly preferred. Iron carboxylates and titanium carboxylates are very particularly preferred (Won and titanium carboxylate).

[0159] Furthermore, phosphorus-containing organic compounds or mixtures thereof can be used as an alternative to metal-based catalysts. Examples are triethyl phosphate or 2- ethylhexyl phosphate.

[0160] Alternatively, strong Brønsted acids, in particular organic acids, such as dodecylbenzenesulphonic acid, can be used as catalysts.

[0161] The curable composition according to the claimed invention can comprise at least one additional auxiliary substance, which is preferably selected from, for example, extenders, stabilizers, antioxidants, fillers, reactive diluents, drying agents, UV stabilizers, rheological aids, thixotropy modifiers, and / or solvents. In general, of particular importance are fillers, thixotropy modifiers, and stabilizers, including antioxidants and UV stabilizers.

[0162] Therefore, preferably, the curable composition according to the claimed invention comprises at least one auxiliary substance.

[0163] It is conceivable that the viscosity of the curable composition according to the claimed invention is too high for certain applications. Therefore, it can generally be reduced in a simple and convenient manner by using a reactive diluent, without any signs of delamination (e.g. migration) occurring in the cured material.

[0164] Suitable solvents can be selected from the group consisting of ethers (e.g. diethyl ether, methyl tert-butyl ether, ether derivatives of ethylene glycol, THF), esters (e.g. ethyl acetate, butyl acetate, glycol esters), hydrocarbons (e.g. pentane, cyclopentane, hexane, cyclohexane, heptane, octane, or long-chain branched and unbranched alkanes), ketones (e.g. acetone, methyl ethyl ketone), aromatic compounds (e.g. toluene, xylene, ethylbenzene, chlorobenzene), and alcohols (e.g. methanol, ethanol, ethylene glycol, propanol, isopropanol, glycerol, butanol, isobutanol, tert-butanol).

[0165] However, due to ecological and / or health considerations, it can be preferred to have a curable composition according to the claimed invention free of organic solvents. In various embodiments, the curable composition according to the claimed invention is thus essentially free of organic solvents.

[0166] In the context of the present invention, the term "essentially free" means a composition comprising less than about 1 wt.%, preferably less than about 0.5 wt.%, more preferably less than about 0.1 wt.% of the respective ingredient. For example, in the context of the present invention, a composition essentially free of organic solvents comprises less than about 1 wt.% of organic solvents.

[0167] According to the present invention, the curable composition comprises at least one plasticizer having a molecular weight of less than 350 g / mol, preferably less than 300 g / mol, more preferably less than 250 g / mol, in particular less than 200 g / mol.

[0168] The curable compositions according to the claimed invention preferably comprise a hydrophilic plasticizer. These are preferably used to improve the moisture absorption and thus the low-temperature reactivity. Suitable for use as plasticizers are, for example: glutarates, abietates, adipates, azelates, benzoates, butyrates, acetates, esters of higher aliphatic acids having from about 8 to about 22 carbon atoms, epoxidized fatty acids, fatty acid esters and alcohols, glycolates, phosphates, phthalates, linear or branched alcohols containing 1 to 12 carbon atoms, propionates, sebacates, sulfonates, thio-butyrates, trimellitates, citrates, and esters based on nitrocellulose and polyvinyl acetate, and mixtures of two or more thereof.

[0169] Particularly preferred plasticizers include esters of dicarboxylic acids, especially methyl and ethyl esters of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, most preferably dimethyl glutarate. Dimethyl glutarate has a molecular weight of 160.17 g / mol.

[0170] Particularly preferred phthalates include dibutyl phthalate and butyl benzyl phthalate, having a molecular weight < 350 g / mol.

[0171] Particularly preferred adipates include dibutyl sebacate and butyl oleate.

[0172] Also suitable as plasticizers are monofunctional, linear or branched C 4-16 pure or mixed ethers of linear or branched alcohols having from 1 to 22 carbon atoms, or mixtures of two or more different ethers of such alcohols, for example dioctyl ether having a molecular weight < 350 g / mol (available as Cetiol OE, BASF, Dusseldorf).

[0173] End-capped polyethylene glycols having a molecular weight < 350 g / mol are also suitable as plasticizers, for example polyethylene glycol or polypropylene glycol di-C 1-4 alkyl ethers, in particular dimethyl or diethyl ethers of diethylene glycol or dipropylene glycol, and mixtures of two or more thereof.

[0174] Suitable plasticizers are end-capped polyethylene glycols, such as polyethylene glycol or polypropylene glycol dialkyl ethers having a molecular weight < 350 g / mol, in which the alkyl groups have up to four carbon atoms, in particular dimethyl and diethyl ethers of diethylene glycol and dipropylene glycol. Acceptable curing is also achieved, in particular with dimethyl diethylene glycol, under less favorable application conditions (low humidity, low temperature). Reference is made to the relevant technical chemical literature for more detailed information on plasticizers.

[0175] Also suitable as plasticizer are diaminocarbonates with a molecular weight < 350 g / mol, which can be prepared, for example, by reacting a diol with hydroxyl end groups with a monofunctional isocyanate and stoichiometrically selected such that essentially all free hydroxyl groups are reacted. Optionally excess isocyanate can then be removed from the reaction mixture, for example, by distillation. Another method for preparing diaminocarbonates consists of reacting a monofunctional alcohol with a diisocyanate, thereby reacting all NCO groups, if possible.

[0176] The curable composition according to the claimed invention can comprise a plasticizer preferably in an amount of > 0 to 40 wt.-%, preferably > 0 to 30 wt.-%, in each case based on the total weight of the curable composition according to the claimed invention.

[0177] If a mixture of plasticizers is used, this amount refers to the total amount of plasticizer in the curable composition according to the claimed invention.

[0178] In a preferred embodiment, the curable composition according to the claimed invention comprises the following components in the weight proportions mentioned: (i) 5 to 70 wt.-%, preferably 15 to 50 wt.-%, based on the total weight of the composition, of the at least one silane-modified (meth)acrylate (co)polymer; and / or (ii) 1 to 80 wt.-%, preferably 20 to 50 wt.-%, based on the total weight of the curable composition, of surface-treated calcium carbonate; and / or (iii) 0.01 to 15 wt.-%, preferably 1 to 7.5 wt.-%, based on the total weight of the curable composition, of at least one aminosilane; (iv) 0 to 70 wt.-%, preferably 15 to 50 wt.-%, based on the total weight of the composition, of at least one silane-modified polyether; and / or (v) 0 to 10 wt.-%, preferably 0.5 to 3 wt.-%, based on the total weight of the curable composition, of surface-treated silicon dioxide; and / or (vi) 0 to 5 wt.-%, preferably 0.05 to 2 wt.-%, based on the total weight of the curable composition, of the at least one catalyst; and / or (vii) > 0 to 50 wt.-%, preferably 5 to 30 wt.-%, based on the total weight of the composition, of at least one plasticizer; wherein the weight proportions add up to 100 wt.-%.

[0179] The statements made above in the description of the individual components apply mutatis mutandis to the preferred representatives of the components and to the preferred use amounts thereof.

[0180] The preparation of the curable composition of the claimed invention can be carried out by simply mixing the at least one silane-modified polymer (I), the surface-treated calcium carbonate (II), and the at least one aminosilane (III), and the optionally present further ingredients described herein. This can be carried out in a suitable dispersing unit, for example a high-speed mixer.

[0181] In this context, it is preferred to note that the curable composition of the invention is as far as possible not in contact with moisture, which would lead to undesired premature curing. Suitable measures are well known and include, for example, operation in an inert atmosphere, possibly under protective gas, and drying / heating of the components before adding them.

[0182] The invention also relates to an adhesive, a sealant, or a coating comprising the curable composition according to the invention.

[0183] The invention also relates to the use of the curable composition according to the invention as an adhesive, a sealant, or a coating.

[0184] Many modifications and other embodiments of the inventions set forth herein will come to mind to one skilled in the art to which these inventions pertain having the benefit of the teachings presented in the foregoing description. Therefore, it is to be understood that the inventions are not to be limited to the specific embodiments disclosed and that modifications and other embodiments are intended to be included within the scope of the appended claims. Moreover, although the foregoing description has been described in the context of certain example embodiments for elements and / or features, it is to be understood that different combinations of elements and / or features can be provided by alternative embodiments without departing from the scope of the appended claims. In this regard, for example, different combinations of elements and / or features can be used as can be specifically adapted to a given implementation of the present invention. Although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.

[0185] The following examples serve to illustrate the invention, but the invention is not limited thereto.

[0186] Example The following examples were carried out at the pressure of the ambient atmosphere, in other words at about 1000 hPa, and at room temperature, in other words at about 23 °C, and / or at the temperature which arises when the components are combined at room temperature without additional heating or cooling, and at a relative atmospheric humidity of about 50%, unless stated otherwise. Furthermore, all numbers of percentage parts are by weight, unless stated otherwise.

[0187] The formulations were prepared as described in the following table.

[0188] The resulting products were subjected to the following curing performance tests: tensile strength and elongation Tensile strength and elongation at break were determined according to DIN 53504. The samples were cured in a mold for 7 days at room temperature. Type S2 specimens (dog-bone) were used and the speed of the pull head in the tensile testing machine was 200 mm / min.

[0189] surface open time (SOT) Surface dry time (SOT) is defined as the time required for the material to form a non-tacky surface film. The determination of the surface dry time was carried out under standard climatic conditions (temperature 23 + / - 2°C, relative humidity 50 + / - 5%) according to DIN 50014. The temperature of the sealant must be 23 + / - 2°C, where the sealant / adhesive was stored in the laboratory for at least 24 hours in advance. The sealant / adhesive was applied to a paper and spread with a putty knife to form a film (thickness approx. 2 mm, width approx. 7 cm). The stopwatch was started immediately. At regular intervals, the surface was lightly touched with a fingertip and the finger was removed, where, when the surface dry time was reached, a pressure was exerted on the surface sufficient to leave an indentation on the surface. The surface dry time was reached when the sealant compound no longer adhered to the fingertip. The surface dry time (SOT) is indicated in minutes.

[0190] surface tack free time (TFT) In order to determine the surface tackiness of the adhesive sealant material, the above composition was homogenized and applied in a frame (50 x 130 x 2 mm) in the same way as the SOT determination. After 60 minutes, the tackiness of the surface was evaluated by carefully contacting the surface of the polymer film with a tool (150 x 5 mm) having a rounded blade at the tip, "TFT < 60 minutes" means "non-tacky" and "TFT > 60 minutes" means "tacky (including slightly tacky)".

[0191] shore a hardness Shore A hardness was measured according to ISO 868.

[0192] depth of cure (DOC) A strip of material having a height of 10 mm (+ / - 1 mm) and a width of 20 mm (+ / - 2 mm) was applied on a plastic foil (PP) using a Teflon blade. After storing the sample for 24 hours under normal conditions (23 + / - 2°C, relative humidity 50 + / - 5%), a section of the strip was cut off and the thickness of the cured layer was measured with a caliper. The depth of cure after 24 hours is indicated in millimeters.

[0193] viscosityThe viscosity of the polymers was measured by the Casson equation / model on an Anton Paar rheometer MCR 302e at 23 °C, 10

[0194] Table 1

[0195] Table 2

[0196] The comparison of Comparative Example 1 with Examples 6 and 7 shows that much lower (i.e. better) viscosity has been achieved in accordance with the claimed invention. The comparison of Comparative Examples 2 and 3 with Examples 6 and 7 shows that much lower viscosity, as well as higher Shore A hardness and faster curing have been achieved simultaneously for the Examples in accordance with the claimed invention. The comparison of Comparative Example 4 with Example 5 shows that much lower viscosity, as well as higher Shore A hardness and faster curing have been achieved simultaneously for the Examples in accordance with the claimed invention. Furthermore, the mechanical properties (i.e. tensile strength and elongation) have been improved in accordance with the claimed invention.​

Claims

1. A curable composition, said curable composition comprising: I. At least one silane-modified poly(meth)acrylate, II. Surface-treated calcium carbonate, III. At least one aminosilane, IV. At least one silane-modified polyether, optionally present. V. Optional surface-treated silica, VI. At least one catalyst may be present, VII. At least one plasticizer, said plasticizer having a molecular weight of less than 350 g / mol, preferably less than 300 g / mol, more preferably less than 250 g / mol, and particularly less than 200 g / mol.

2. The curable composition according to claim 1, wherein the curable composition comprises at least one compound of formula (I): Y-[(CR 1 2) b -SiR a (OR 2 ) 3-a ] x (I), in: Y represents an x-valent poly(meth)acrylate group bonded by nitrogen, oxygen, sulfur, or carbon. R is independently selected from monovalent, optionally substituted SiC-bonded hydrocarbon groups. R 1 The hydrocarbon group is independently selected from hydrogen or a monovalently substituted hydrocarbon group, which can be attached to a carbon atom via a nitrogen, phosphorus, oxygen, sulfur, or carbonyl group. R 2 Independently selected from hydrogen or a monovalent, optionally substituted hydrocarbon group, x is an integer from 1 to 10, preferably 1, 2 or 3, and especially preferably 1 or 2. a is independently selected from 0, 1, and 2, preferably from 0 and 1, and b is an integer independently selected from 1 to 10, preferably selected from 1, 3 and 4, particularly preferably selected from 1 and 3, especially 1.

3. The curable composition according to claim 2, wherein Y represents an x-valent polyacrylate group, an x-valent polymethacrylate group, or an x-valent copolymer thereof.

4. The curable composition according to claim 2 or 3, wherein the Y is bonded to each group -[(CR)-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)-O-, -OC(=O)-O-, -SC(=O)-NH-, -NH-C(=O)-S-, -C(=O)-S-, -SC(=O)-, -SC(=O)-S-, -C(-O), -S-, -O-, or -NR'-. 1 2) b -SiR a (OR 2 ) 3-a ] x , where R' can be the same or different and has the meaning specified for R, or represents the group -CH(COOR'')-CH2-COOR'', where R'' can be the same or different and has the meaning specified for R.

5. The curable composition according to any one of claims 1-4, wherein the surface-treated calcium carbonate comprises particles, the particles comprising a treatment layer on the surface of the calcium carbonate particles, the treatment layer comprising: i. Phosphate ester blends of one or more phosphate monoesters and their salt reaction products and / or one or more phosphate diesters and their salt reaction products, and / or ii. At least one saturated aliphatic linear or branched carboxylic acid and its salt reaction product, and / or iii. At least one aliphatic aldehyde and / or its salt reaction product, and / or iv. At least one monosubstituted succinic anhydride and / or its salt reaction product, said monosubstituted succinic anhydride being composed of succinic anhydrides monosubstituted with groups selected from: The total number of carbon atoms in the substituents is at least C2 to C3. 30 Linear, branched, aliphatic and cyclic groups, and / or v. at least one polydialkylsiloxane, and / or vi. A mixture of materials according to i. to v.

6. The curable composition according to any one of claims 1-5, wherein at least one aminosilane is selected from: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, aminomethyltrimethoxysilane, aminomethyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, (N-2-aminoethyl)-3-aminopropyltrimethoxysilane, (N-2-aminoethyl)-3-aminopropyltriethoxysilane, diethylenetriaminopropyltrimethoxysilane, phenylaminomethyltrimethoxysilane, (N-2-aminoethyl)-3-aminopropylmethyldiethoxysilane, 3-(N-phenylamino)propyltrimethoxysilane, 3-piperazinylpropylmethyldiethoxysilane, 3-(N,N-dimethylaminopropyl)aminopropylmethyldiethoxysilane, tris[(3-triethoxysilyl)propyl]amine, tris[(3- [Trimethoxysilyl)propyl]amine, 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, 4-amino-3,3-dimethylbutyltriethoxysilane, N-(n-butyl)-3-aminopropyltrimethoxysilane, and oligomers thereof and mixtures thereof.

7. The curable composition according to any one of claims 1-6, wherein the curable composition comprises at least one silane-modified polyether.

8. The curable composition according to claim 7, wherein the curable composition comprises at least one compound of formula (I'): Y'-[(CR 1 2) b -SiR a (OR 2 ) 3-a ] x (I'), in: Y' represents an x-valent polyether group bonded by nitrogen, oxygen, sulfur, or carbon. R is independently selected from monovalent, optionally substituted SiC-bonded hydrocarbon groups. R 1 The hydrocarbon group is independently selected from hydrogen or a monovalently substituted hydrocarbon group, which can be attached to a carbon atom via a nitrogen, phosphorus, oxygen, sulfur, or carbonyl group. R 2 Independently selected from hydrogen or a monovalent, optionally substituted hydrocarbon group, x is an integer from 1 to 10, preferably 1, 2 or 3, and especially preferably 1 or 2. a is independently selected from 0, 1, and 2, preferably from 0 and 1, and b is an integer independently selected from 1 to 10, preferably selected from 1, 3 and 4, particularly preferably selected from 1 and 3, especially 1.

9. The curable composition according to claim 8, wherein Y' represents an x-valent polypropylene glycol group, or an x-valent polyethylene glycol group, or an x-valent copolymer thereof.

10. The curable composition according to claim 8 or 9, wherein the Y' is bonded to each group -[(CR)-, -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)-O-, -OC(=O)-O-, -SC(=O)-NH-, -NH-C(=O)-S-, -C(=O)-S-, -SC(=O)-, -SC(=O)-S-, -C(-O), -S-, -O-, or -NR'-. 1 2) b -SiR a (OR 2 ) 3-a ] x , where R' can be the same or different and has the meaning specified for R, or represents the group -CH(COOR'')-CH2-COOR'', where R'' can be the same or different and has the meaning specified for R.

11. The curable composition according to any one of claims 1-10, wherein the curable composition comprises a BET surface area of ​​5 to 250 m². 2 / g of surface-treated silica.

12. The curable composition according to any one of claims 1-11, wherein the curable composition comprises at least one catalyst selected from tin catalysts, titanium catalysts, aluminum catalysts, or zirconium catalysts, more preferably selected from tin catalysts, or titanium catalysts, or mixtures thereof.

13. The curable composition according to any one of claims 1-12, wherein (i) Based on the total weight of the composition, the amount of the at least one silane-modified (meth)acrylate (co)polymer is from 5% to 70% by weight, preferably from 15% to 50% by weight; and / or (ii) Based on the total weight of the curable composition, the amount of surface-treated calcium carbonate is from 1% to 80% by weight, preferably from 20% to 50% by weight; and / or (iii) Based on the total weight of the curable composition, the amount of the at least one aminosilane is from 0.01% to 15% by weight, preferably from 1% to 7.5% by weight; and / or (iv) Based on the total weight of the composition, the amount of the at least one silane-modified polyether is from 0% to 70% by weight, preferably from 15% to 50% by weight; and / or (v) Based on the total weight of the curable composition, the amount of the surface-treated silica is from 0% to 10% by weight, preferably from 0.5% to 3% by weight; and / or (vi) Based on the total weight of the curable composition, the amount of the at least one catalyst is from 0% to 5% by weight, preferably from 0.05% to 2% by weight; and / or (vii) At least one plasticizer, >0% to 50% by weight, preferably 5% to 30% by weight, based on the total weight of the composition.

14. An adhesive, sealant, or coating comprising a curable composition according to any one of claims 1-13.

15. Use of the curable composition according to any one of claims 1-13 as an adhesive, sealant, or coating.

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