Room temperature curable compositions

Abstract

The present invention relates to a two-component (2K) composition comprising, as a first component, a silicone-based resin containing epoxy functional groups, optionally an epoxy resin, and optionally a silicone acrylate oligomer, and, as a second component, a curing agent comprising at least one alkoxy group-containing amino-functional silicone resin and an aminoalkoxysilane: upon curing, the reaction of the two components of the composition provides a cured product that exhibits processability while maintaining mechanical properties.

Description

Technical Field

[0001] The present invention relates to a two-component (2K) composition comprising, as a first component, an epoxy-functional silicone-based resin, an optional epoxy resin and an optional silicone acrylate oligomer, and, as a second component, a curing agent comprising at least one alkoxy-containing amino-functional silicone resin and an aminoalkoxysilane: upon curing, the reaction of the two components of the composition provides a cured product which exhibits processability while retaining mechanical properties. Background Art

[0002] Epoxy compositions are well known as protective and decorative coatings for steel structure protection in the oil and gas industry and marine applications, which include very harsh environmental conditions. Epoxy compositions are known to have excellent adhesion, corrosion resistance, and chemical resistance, but they do not provide longer-lasting UV properties and weathering resistance, which can be addressed by introducing silicones into the composition. Silicones are well known for their excellent weathering resistance. Although silicone-epoxy compositions provide excellent UV properties and weathering resistance, they sometimes do not provide gloss and become brittle, which ultimately creates a weaker link that allows corrosion to spread.

[0003] The present inventors have recognised the need to develop curable compositions which provide good processability while maintaining mechanical properties at a sufficient level, in particular gloss, hardness and weather resistance simultaneously maintained at high levels. Summary of the invention

[0004] According to a first aspect of the present invention, a two-component (2K) composition is provided, the two-component (2K) composition comprising:

[0005] (A) a first component, the first component comprising:

[0006] a) at least one silicone-based resin containing epoxy functional groups, and

[0007] b) optionally at least one epoxy resin which is not a silicone-based resin;

[0008] c) optionally at least one silicone acrylate oligomer;

[0009] (B) a second component, the second component comprising:

[0010] d) a curing agent, the curing agent consisting of at least one compound having at least two epoxy reactive groups per molecule, the curing agent being characterized by comprising at least one alkoxy-containing amino-functional silicone resin,

[0011] e) at least one aminoalkoxysilane,

[0012] The composition is characterized in that it does not contain a catalyst, and preferably the molar ratio of reactive groups provided in component B to reactive groups in component A is 1.5:1 to 1:1.5, preferably 1.1:1 to 1:1.1, more preferably 1:1.

[0013] Such a composition addresses the above needs and exhibits excellent flexibility, weather resistance, corrosion resistance, gloss retention, and relatively high UV resistance, as well as easy-to-clean surface properties compared to conventional epoxy systems. The composition cures at room temperature without any accelerator / catalyst, and it provides a longer open time, which is particularly desirable for larger application areas with larger volumes.

[0014] In another embodiment of the present invention, the molar ratio of epoxy-reactive groups provided in component B to epoxy groups in component A is 1.5:1 to 1:1.5, preferably 1.1:1 to 1:1.1, more preferably 1:1.

[0015] In yet another embodiment, the molar ratio of silane groups to carbon double bonds, preferably (meth)acrylate groups in component B is from 1.5:1 to 1:1.5, preferably from 1.1:1 to 1:1.1, more preferably 1:1.

[0016] In some embodiments, a two-component (2K) composition comprises:

[0017] A) a first component, based on the weight of the first component, the first component comprising:

[0018] 5-60 wt. % of a) at least one silicone epoxy resin a);

[0019] optionally 1 to 50 wt. % of b) at least one epoxy resin b);

[0020] optionally 1 to 20% by weight of c) at least one silicone acrylate oligomer,

[0021] B) a second component, based on the weight of the first component, the second component comprises, preferably consists of:

[0022] 50-85 wt %, preferably 60-80 wt % of d) the curing agent d);

[0023] 15 to 50% by weight, preferably 20 to 40% by weight of e) the at least one aminoalkoxysilane e);

[0024] The composition is characterized in that it does not contain a catalyst, and preferably the molar ratio of reactive groups provided in component B to reactive groups in component A is 1.5:1 to 1:1.5, preferably 1.1:1 to 1:1.1, more preferably 1:1.

[0025] It is preferred that the epoxy functional group-containing silicone-based resin a) has an epoxy equivalent weight of 100-1500 g / eq, preferably 200-1000 g / eq, more preferably 300-700 g / eq.

[0026] Preferably, the curing agent d) comprises at least one alkoxy-containing amino-functional silicone resin (C 1 ), the alkoxy-containing amino-functional silicone resin (C 1 ) has at least two amine hydrogen atoms per molecule, has an amine hydrogen equivalent weight of 100-1500 g / eq, and has a total alkoxy content (AC) of 10-40 mol % based on the moles of silicon, the resin (C 1 ) contains the following units:

[0027] (R3Si(OR') w O (1-w) / 2 ) a (i);

[0028] (R2Si(OR') x O (2-x) / 2 ) b (ii);

[0029] (RSi(OR') y O (3-y) / 2 ) c (iii); and

[0030] (Si(OR') z O (4-z / 2 ) d (iv)

[0031] in:

[0032] Each R is independently selected from C1-C 18 Alkyl, C6-C 18 Aryl, or having the formula -R 2 NHR 3 or -R 2 NHR 2 NHR 3 An amino-functional hydrocarbon group, wherein each R 2 Independently for C2-C 20 Alkylene and R3 is a C1-C6 alkyl group;

[0033] a, b, c and d define the mole fractions of each unit (i) to (iv) respectively, such that a+b+c+d=1; and

[0034] w, x, y, and z define the mole fraction of the alkoxy group such that 0≤w<1, 0≤x<2, 0≤y<3, and 0≤z<4.

[0035] For the alkoxy-containing amino-functional silicone resin (C 1 ), advantageously each R is independently selected from C1-C6 alkyl, C6-C 18 Aryl, or having the formula -R 1 NHR 2 or -R 1 NHR 1 NHR 2 An amino-functional hydrocarbon group, wherein each R 1 are independently C2-C8 alkylene and R 2 is a C1-C2 alkyl group. 1 ) Good results have also been obtained with both methyl and phenyl substitution at R.

[0036] Without intending to be bound by theory, the compositions of the present invention cure in the absence of catalysis by a dual curing mechanism: reaction of the amine hydrogen atoms of the alkoxy-containing amino-functional silicone resin curing agent with epoxy groups; and, self-condensation of the reactive alkoxy groups of the curing agent compound. In addition, if carbon double bonds are present, these can crosslink with the silane functional groups. This curing mechanism has been found to be effective under ambient conditions and produces a highly crosslinked system. In addition, despite the absence of a catalyst, it is believed that the open time of the composition is not degraded.

[0037] According to a second aspect of the present invention there is provided a cured product obtained from a two component (2K) composition as defined herein above and in the appended claims. The present invention also relates to the cured reaction product as a coating, sealant or adhesive.

[0038] definition

[0039] As used herein, the singular forms "a", "an", and "the" include plural referents unless the context clearly dictates otherwise.

[0040] As used herein, the terms "comprising / comprises / comprised of" are synonymous with "including / includes" or "containing / contains," are inclusive or open-ended, and do not exclude additional unrecited members, elements, or method steps. If used, the phrase "consisting of is closed-ended and excludes all additional elements. Furthermore, the phrase "consisting essentially of excludes additional essential elements, but allows for the inclusion of insubstantial elements that do not materially change the nature of the invention.

[0041] When amounts, concentrations, sizes and other parameters are expressed in the form of ranges, preferred ranges, upper values, lower values, or preferred upper and lower values, it should be understood that any range obtainable by combining any upper value or preferred value with any lower value or preferred value is also specifically disclosed, regardless of whether the obtained range is explicitly mentioned in the context.

[0042] The words "preferred / preferably", "desirable", and "particularly / especially" and their synonyms are generally used herein to refer to embodiments of the present disclosure that may provide specific benefits in certain circumstances. However, the recitation of one or more preferred, preferred, desired, or particular embodiments does not mean that other embodiments are not useful, and is not intended to exclude those other embodiments from the scope of the present disclosure.

[0043] As used throughout this application, the words "may" are used in a permissive sense (ie, meaning having the potential to), rather than in a mandatory sense.

[0044] As used herein, room temperature is 23° C.±2° C. As used herein, “ambient conditions” means the temperature and pressure of the environment to which a composition is exposed or to which a coating or substrate of the coating is exposed.

[0045] As used herein, the term "equivalent" (eq.) refers, as usual in chemical notation, to the relative quantity of reactive groups present in a reaction.

[0046] As used herein, the term "equivalent weight" refers to the molecular weight divided by the number of relevant functional groups. Thus, "epoxy equivalent weight" (EEW) refers to the weight (in grams) of a resin containing one equivalent of epoxy groups. Similarly, "amine hydrogen equivalent weight" (AHEW) refers to the weight (in grams) of an organic amine containing one amine hydrogen.

[0047] As used herein, the term "(co)polymer" includes homopolymers, copolymers, block copolymers and terpolymers.

[0048] As used herein, the term "epoxide" means a compound characterized by the presence of at least one cyclic ether group, i.e., a compound in which an ether oxygen atom is attached to two adjacent carbon atoms to form a cyclic structure. The term is intended to cover monoepoxides, polyepoxides (having two or more epoxy groups), and epoxy-terminated prepolymers. The term "monoepoxide" is intended to mean an epoxy compound having one epoxy group. The term "polyepoxide" is intended to mean an epoxy compound having at least two epoxy groups. The term "diepoxide" is intended to mean an epoxy compound having two epoxy groups.

[0049] The epoxy compound may be unsubstituted, but may also be inertly substituted. Exemplary inert substituents include chlorine, bromine, fluorine and phenyl.

[0050] The epoxy-functional silicone-based resin a) and the optionally present elastomer-modified epoxy resin b) are different substances; and if both are present, one resin cannot serve as both a) and b) at the same time.

[0051] As used herein, “C1-C n "Alkyl" refers to a monovalent group containing 1-n carbon atoms, which is a radical of an alkane and includes straight-chain and branched organic radicals. Therefore, "C1-C 30 "Alkyl" refers to a monovalent group containing 1 to 30 carbon atoms, which is a radical of an alkane and includes straight-chain 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 the present invention, such alkyl groups may be unsubstituted or may be substituted with one or more substituents such as halogen, nitro, cyano, amido, amino, sulfonyl, sulfinyl, sulfanyl, sulfoxy, urea, thiourea, sulfamoyl, sulfonamide, and hydroxy. Halogenated derivatives of the exemplary hydrocarbon groups listed above may be mentioned as examples of suitable substituted alkyl groups. However, in general, it should be noted that unsubstituted alkyl groups (C1-C12) containing 1 to 18 carbon atoms are preferred. 18 Alkyl), for example, an unsubstituted alkyl group containing 1 to 12 carbon atoms (C1-C 12 alkyl) or an unsubstituted alkyl group containing 1 to 6 carbon atoms (C1-C6 alkyl).

[0052] The term "C3-C 30"Cycloalkyl" should be understood to mean a saturated monocyclic, bicyclic or tricyclic hydrocarbon radical having 3 to 30 carbon atoms. In general, it should be noted that cycloalkyl (C3-C 18 Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantane, and norbornane.

[0053] As used herein, "C6-C8" used alone or as part of a larger moiety (such as in "aralkyl") 18 "Aryl" refers to optionally substituted monocyclic, bicyclic and tricyclic ring systems, wherein the monocyclic ring system is aromatic or at least one of the rings in the bicyclic or tricyclic ring system is aromatic. Bicyclic and tricyclic ring systems include benzo-fused 2-3 membered carbon rings. Exemplary aryl groups include: phenyl; indenyl; naphthyl; tetrahydronaphthyl; tetrahydroindenyl; tetrahydroanthracenyl; and anthracenyl. In addition, it may be noted that phenyl is preferred.

[0054] As used herein, “C2-C 20 "Alkenyl" refers to a hydrocarbon group having 2-20 carbon atoms and at least one ethylenically unsaturated unit. The alkenyl group may be linear, branched or cyclic, and may be optionally substituted. As understood by those of ordinary skill in the art, the term "alkenyl" also includes groups having "cis" and "trans" configurations, or alternatively "E" and "Z" configurations. However, in general, it should be noted that alkenyl groups having 2-10 carbon atoms (C 2-10 ) or contains 2-8 carbon atoms (C 2-8 ) is an unsubstituted alkenyl. 12 Examples of alkenyl groups include, but are not limited to: —CH═CH2; —CH═CHCH3; —CH2CH═CH2; —C(═CH2)(CH3); —CH═CHCH2CH3; —CH2CH═CHCH3; —CH2CH2CH═CH2; —CH═C(CH3)2; —CH2C(═CH2)(CH3); —C(═CH2)CH2CH3; —C(CH3)═CHCH3; —C(CH3)CH═CH2; —CH═CHCH2CH2CH3; —CH2CH ═CHCH2CH3; —CH2CH2CH═CHCH3; —CH2CH2CH2CH═CH2; —C(═CH2)CH2CH2CH3; —C(CH3)═CHCH2CH3; —CH(CH3)CH═CHCH; —CH(CH3)CH2CH═CH2; —CH2CH═C(CH3)2; 1-cyclopent-1-enyl; 1-cyclopent-2-enyl; 1-cyclopent-3-enyl; 1-cyclohex-1-enyl; 1-cyclohex-2-enyl; and 1-cyclohexyl-3-enyl.

[0055] As used herein, "alkylaryl" refers to an aryl group substituted by an alkyl group, and "substituted alkylaryl" refers to an alkylaryl group further bearing one or more substituents as described above.

[0056] As used herein, the term "hetero" refers to a group or moiety that contains one or more heteroatoms such as N, O, Si, and S. Thus, for example, "heterocycle" refers to a cyclic group having, for example, N, O, Si, or S as part of the ring structure. "Heteroalkyl" and "heterocycloalkyl" moieties are alkyl and cycloalkyl groups, respectively, as defined above, containing N, O, Si, or S as part of their structure.

[0057] As used herein, unless expressly stated otherwise, the term "catalytic amount" means a substoichiometric amount of a catalyst (relative to the reactants).

[0058] As used herein, "primary amino" refers to an NH2 group attached to an organic group, and "secondary amino" refers to an NH group attached to two organic groups, which may also be part of a ring together. When used,

[0059] The term "amine hydrogen" refers to the hydrogen atoms of primary and secondary amino groups.

[0060] Where "amine value" is referred to herein, this is determined by titrating the amine acetate ion with a dilute (usually 1 N) HCl solution. For pure substances, the amine value can be calculated using the molecular weight of the pure compound and the molecular weight of KOH (56.1 g / mol). For illustration, a guiding guide can be found at https: / / dowac.custhelp.com / app / answers / detail / a_id / 12987.

[0061] In the context of the present invention, a "two-component (2K) composition" is to be understood as a composition in which the binder component (A) and the hardener component (B) have to be stored in separate containers due to their (high) reactivity. The two components are mixed only shortly before application and then react, usually without additional activation, with bond formation and thus formation of a polymer network. In this context, higher temperatures can be applied in order to accelerate the crosslinking reaction.

[0062] Unless otherwise specified, the viscosity of the coating compositions described herein is measured using a Brookfield viscometer (Model RVT) under standard conditions of 20°C and 50% relative humidity (RH). The viscometer is calibrated using silicone oils of known viscosity, which vary between 5000 cps and 50,000 cps. A set of RV spindles connected to the viscometer are used for calibration. The coating composition measurements are performed using a No. 6 spindle at 20 rpm for 1 minute until the viscometer is balanced. The calibration is then used to calculate the viscosity corresponding to the equilibrium reading.

[0063] As used herein, the term "polyol" shall include diols and higher functionality hydroxy compounds.

[0064] The hydroxyl (OH) values ​​given herein are measured according to Japan Industrial Standard (JIS) K-1557, 6.4. The isocyanate content values ​​given herein are measured according to EN ISO 1 1909.

[0065] Molecular weights referred to in this specification may be measured using gel permeation chromatography (GPC) using polystyrene calibration standards, such as performed according to ASTM 3536.

[0066] As used herein, "anhydrous" means that the relevant composition contains less than 0.25% by weight of water. For example, the composition may contain less than 0.1% by weight of water or be completely free of water. The term "substantially free of solvent" should be similarly interpreted to mean that the relevant composition contains less than 0.25% by weight of solvent. DETAILED DESCRIPTION

[0067] a) Silicone-based resins containing epoxy functional groups

[0068] The two-component (2K) composition of the present invention should generally contain a) 5-60% by weight, preferably 7-40% by weight, of an epoxy-functional silicone-based resin, based on the weight of its first component. In an alternative representation of the preferred composition of the composition of the present invention, which is not intended to be mutually exclusive with the above, the composition may contain 2-40% by weight of one or more epoxy-functional silicone-based resins a), based on the weight of the composition. For example, the composition of the present invention may contain 5-50% by weight, preferably 5-30% by weight, more preferably 5-20% by weight of the one or more epoxy-functional silicone-based resins a), based on the weight of the total composition.

[0069] The epoxy-functional silicone-based resin exhibits the characteristics of silicone resins, but also contains epoxy moieties that can be crosslinked by epoxy curing agents as described herein. In particular, it is preferred that the epoxy-functional silicone-based resin contains alkoxy-silicone moieties. Typically, the epoxy-functional silicone-based resin is a silicone-epoxy elastomer. Such epoxy-functional silicone-based resins can be obtained from at least one epoxy resin and at least one alkoxy-silicone resin. Typically, they can be obtained by reacting at least one epoxy resin with at least one alkoxy-silicone resin and preferably at least one hydroxyl-functional compound. Aliphatic epoxy resins are particularly preferred. Preferably, the epoxy-functional silicone-based resin is liquid at ambient temperature and pressure. In this regard, it is preferred that the epoxy-functional silicone-based resin has a viscosity of 500-2500 mPas, preferably 800-2200 mPas, more preferably 1000-2000 mPas, even more preferably 1200-1800 mPas at 25° C. according to ASTM D445. Higher or lower viscosities were not found to be feasible within the scope of the present disclosure.

[0070] The epoxy-functional silicone-based resin generally contains epoxy moieties that provide crosslinking capability with the curing agent described herein. For the epoxy moieties present in the epoxy-functional silicone-based resin, it is preferred that the epoxy-functional silicone-based resin has an epoxy equivalent weight according to ASTM D1652 of 100-1500 g / eq, preferably 200-1000 g / eq, more preferably 300-700 g / eq. Examples of epoxy-functional silicone-based resins that are advantageously used within the scope of the present disclosure are EF (Evonik Industries).

[0071] b) Epoxy resin

[0072] The two-component (2K) composition of the invention may preferably contain an epoxy resin b), preferably in an amount of 1 to 50% by weight, preferably 10 to 40% by weight, based on the weight of its first component. The epoxy resin is different from the resin a) and is not a silicone-based resin. In an alternative formulation of a preferred configuration of the composition of the invention, which is not intended to be mutually exclusive with the above, the composition may contain 1 to 50% by weight of one or more epoxy resins a), based on the weight of the composition. For example, the composition of the invention may contain 5 to 40% by weight, for example 5 to 30% by weight, based on the weight of the composition, of the one or more epoxy resins a).

[0073] Epoxy resins used herein can include monofunctional epoxy resins, multifunctional epoxy resins (multi-orpoly-functional epoxy resins), and combinations thereof. Epoxy resins can be pure compounds, but can also be mixtures of epoxy-functional compounds, including mixtures of compounds with different numbers of epoxy groups per molecule. Epoxy resins can be saturated or unsaturated, aliphatic, alicyclic, aromatic or heterocyclic, and can be substituted. Most preferred epoxy resins are alicyclic or aromatic. In addition, epoxy resins can be monomeric or polymeric.

[0074] Without intending to limit the present invention, exemplary monoepoxides include: alkylene oxides; epoxy-substituted alicyclic hydrocarbons, such as cyclohexene oxide, vinylcyclohexene monooxide, (+)-cis-limonene oxide, (+)-cis,trans-limonene oxide, (-)-cis,trans-limonene oxide, cyclooctene oxide, cyclododecene oxide, and α-pinene oxide; epoxy-substituted aromatic hydrocarbons; monoepoxy-substituted alkyl ethers of monohydric alcohols or phenols, such as glycidyls of aliphatic, alicyclic and aromatic alcohols; ethers; monoepoxy-substituted alkyl esters of monocarboxylic acids, such as glycidyl esters of aliphatic, cycloaliphatic and aromatic monocarboxylic acids; monoepoxy-substituted alkyl esters of polycarboxylic acids, in which one or more other carboxyl groups are esterified with alkanols; alkyl and alkenyl esters of epoxy-substituted monocarboxylic acids; epoxy alkyl ethers of polyols, in which one or more other OH groups are esterified or etherified with carboxylic acids or alcohols; and monoesters of polyols and epoxy monocarboxylic acids, in which one or more other OH groups are esterified or etherified with carboxylic acids or alcohols.

[0075] For example, the following glycidyl ethers can be mentioned as monoepoxy compounds particularly suitable for use herein: methyl glycidyl ether; ethyl glycidyl ether; propyl glycidyl ether; butyl glycidyl ether; pentyl glycidyl ether; hexyl glycidyl ether; cyclohexyl glycidyl ether; octyl glycidyl ether; 2-ethylhexyl glycidyl ether; allyl glycidyl ether; benzyl glycidyl ether; phenyl glycidyl ether; 4-tert-butylphenyl glycidyl ether; 1-naphthyl glycidyl ether; 2-naphthyl glycidyl ether; 2-chlorophenyl glycidyl ether; 4-chlorophenyl glycidyl ether; 4-bromophenyl glycidyl ether; 2,4,6-trichlorophenyl glycidyl ether; 2,4,6-tribromophenyl glycidyl ether; pentafluorophenyl glycidyl ether; o-cresyl glycidyl ether; m-cresyl glycidyl ether; and p-cresyl glycidyl ether.

[0076] Preferred monoepoxides include: ethylene oxide; 1,2-propylene oxide (propylene oxide); 1,2-butylene oxide; cis-2,3-butylene oxide; trans-2,3-butylene oxide; 1,2-pentene oxide; 1,2-hexene oxide; 1,2-heptane oxide; decane oxide; butadiene oxide; isoprene oxide; and styrene oxide.

[0077] Again, without intending to limit the invention, suitable polyepoxides may be liquids, solids, or solutions in solvents. Additionally, such polyepoxides should have an epoxide equivalent weight of 100-700 g / eq, such as 120-320 g / eq. Additionally, typically, diepoxides having an epoxide equivalent weight of less than 500 g / eq or even less than 400 g / eq are preferred: this is primarily from a cost perspective, since lower molecular weight epoxy resins require more limited processing in purification in their production.

[0078] As examples of types or groups of polyepoxides that can be polymerized in the present invention, mention may be made of: glycidyl ethers of polyols and polyphenols; glycidyl esters of polycarboxylic acids; and epoxidized polyethylenically unsaturated hydrocarbons, esters, ethers and amides.

[0079] Suitable diglycidyl ether compounds may be aromatic, aliphatic, or alicyclic in nature and may thus be derived from dihydric phenols and diols. In addition, useful classes of such diglycidyl ethers are: diglycidyl ethers of aliphatic and alicyclic diols such as 1,2-ethanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,12-dodecanediol, cyclopentanediol and cyclohexanediol; diglycidyl ethers based on bisphenol A; bisphenol F diglycidyl ether; diglycidyl phthalate, diglycidyl isophthalate and diglycidyl terephthalate; diglycidyl ethers based on polyalkylene glycols, in particular polypropylene glycol diglycidyl ether; and glycidyl ethers based on polycarbonate diols. Other suitable diepoxides that may also be mentioned include: diunsaturated fatty acids C1-C 18 Alkyl ester diepoxides; butadiene diepoxides; polybutadiene diglycidyl ether; vinyl cyclohexene diepoxides; and limonene diepoxides.

[0080] Additional illustrative polyepoxides include, but are not limited to: glycerol polyglycidyl ether; trimethylolpropane polyglycidyl ether; pentaerythritol polyglycidyl ether; diglycerol polyglycidyl ether; polyglycerol polyglycidyl ether; and sorbitol polyglycidyl ether.

[0081] The glycidyl esters of polycarboxylic acids useful in the present invention are derived from polycarboxylic acids containing at least two carboxylic acid groups and containing no other groups reactive to epoxy groups. The polycarboxylic acids may be aliphatic, alicyclic, aromatic and heterocyclic. Preferred polycarboxylic acids are those containing no more than 18 carbon atoms per carboxylic acid group, suitable examples of which include, but are not limited to: oxalic acid; sebacic acid; adipic acid; succinic acid; pimelic acid; suberic acid; glutaric acid; dimer and trimer acids of unsaturated fatty acids, such as dimer and trimer acids of linseed fatty acids; phthalic acid; isophthalic acid; terephthalic acid; trimellitic acid; trimesic acid; phenylacetic acid; chlorendic acid; hexahydrophthalic acid, in particular hexahydrophthalic acid (1,2-cyclohexanedicarboxylic acid); biphenyl dicarboxylic acid; naphthalene dicarboxylic acid; esters of polyacid-terminated esters of dibasic acids and aliphatic polyols; polymers and copolymers of (meth) acrylic acid; and crotonic acid.

[0082] In addition, highly preferred examples of polyepoxides include: bisphenol A epoxy resins, such as DER TM 331、DER TM 383 and Epotec YD 128; bisphenol F epoxy resin, such as DER TM 354; Bisphenol A / F epoxy resin blends, such as DER TM 353; Aliphatic glycidyl ethers, such as DER TM 736; Polypropylene glycol diglycidyl ether, such as DER TM 732; Solid bisphenol A epoxy resin, such as DER TM 661 and DER TM 664UE; Bisphenol A solid epoxy resin solution, such as DER TM 671-X75; Epoxy novolac resin, such as DEN TM 438; Brominated epoxy resins, such as DER TM 542; Castor oil triglycidyl ether, such as ERISYS TM GE-35H; Polyglycerol-3-polyglycidyl ether, such as ERISYS TM GE-38; Sorbitol glycidyl ether, such as ERISYS TM GE-60; and bis(2,3-epoxypropyl)cyclohexane-1,2-dicarboxylate available as Lapox Arch-11.

[0083] c) Silicone acrylate oligomer

[0084] Furthermore, the two-component (2K) composition of the present invention may preferably contain a silicone acrylate oligomer c), preferably in an amount of 1-20% by weight, preferably 2-10% by weight, based on the weight of its first component. In an alternative formulation of the preferred constitution of the composition of the present invention, which is not intended to be mutually exclusive with the above, the composition may contain 0.5-15% by weight of one or more epoxy-functional silicone-based resins a), based on the weight of the composition. For example, the composition of the present invention may contain 1-10% by weight, for example 2-5% by weight, based on the weight of the total composition, of the one or more epoxy-functional silicone-based resins a).

[0085] In the present invention, the silicone acrylate oligomer is an acrylate polymer having a Si-O bond as a main chain structure. The silicone acrylate oligomer preferably has two or more polymerizable functional groups, and specifically, may include one or more of a difunctional oligomer, a trifunctional oligomer, a tetrafunctional oligomer, and a hexafunctional oligomer. Most preferably, the silicone acrylate oligomer has an average of two polymerizable functional groups. The silicone acrylate oligomer can be formed by reacting a silane compound (e.g., polyester dimethylsiloxane diol, polyether dimethylsiloxane diol, polycarbonate dimethylsiloxane diol, etc.) with an acrylate compound (e.g., hydroxyethyl acrylate, hydroxybutyl methacrylate, etc.). Such multifunctional silicone acrylate oligomers are prepared by reacting acrylic monomers (such as alkyl acrylates, alkyl (meth)acrylates) with 3-methacrylopropyltrimethoxysilane (MPTS) having a silicon (Si) functional group, or silicone urethane acrylate polymers or silicone polyester acrylate polymers (which are obtained by modifying urethane acrylate polymers or polyester acrylates with silicon (Si). In addition, the multifunctional silicone acrylate oligomer may be a multifunctional oligomer containing two or more polymerizable functional groups, and specifically, may include one or more of a difunctional oligomer, a trifunctional oligomer, a tetrafunctional oligomer, and a hexafunctional oligomer. In addition, the multifunctional silicone acrylate oligomer may have an average weight average molecular weight (Mw) of 500 to 20,000, and specifically 500 to 30,000, 1,000 to 20,000, or most preferably 2,000 to 10,000.

[0086] c) Curing agent 1

[0087] The curing agent d) necessarily consists of at least one compound having at least two epoxy-reactive groups per molecule, characterized in that it contains at least one alkoxy-containing amino-functional silicone resin. Epoxy-reactive groups are groups that are capable of reacting with epoxy groups. The alkoxy-containing amino-functional silicone resin should be characterized by at least one of the following: i) an amine hydrogen equivalent weight of 80 or 100 to 1500 g / eq, preferably 150-700 g / eq, for example 200-500 g / eq; and ii) a weight average molecular weight (Mw) determined by gel permeation chromatography of 150-10000 g / mol, preferably 150-8000 g / mol, for example 150-5000 g / mol.

[0088] In an important embodiment of the present invention, the curing agent c) comprises at least one alkoxy-containing amino-functional silicone resin (C 1 ) or at least one alkoxy-containing amino-functional silicone resin (C 1 ) is composed of the alkoxy-containing amino-functional silicone resin (C 1 ) has at least two amine hydrogen atoms per molecule, has an amine hydrogen equivalent weight of 100-1500 g / eq, and has a total alkoxy content (AC) of 10-40 mol % based on the moles of silicon, the resin (C 1 ) contains the following units:

[0089] (R3Si(OR') w O (1-w) / 2 ) a (i);

[0090] (R2Si(OR') x O (2-x) / 2 ) b (ii);

[0091] (RSi(OR') y O (3-y) / 2 ) c (iii); and

[0092] (Si(OR') z O (4-z / 2 ) d (iv)

[0093] in:

[0094] Each R is independently selected from C1-C 18 Alkyl, C6-C 18 Aryl, or having the formula -R 2 NHR 3 or -R 2 NHR 2NHR 3 An amino-functional hydrocarbon group, wherein each R 2 Independently for C2-C 20 Alkylene and R 3 is a C1-C6 alkyl group;

[0095] a, b, c and d define the mole fractions of each unit (i) to (iv) respectively, such that a+b+c+d=1; and

[0096] w, x, y and z define the mole fraction of alkoxy groups such that 0≤w<1, 0≤x<2, 0≤y<3, and 0≤z<4, and are selected to satisfy the total alkoxy content (AC) defined above.

[0097] In a preferred embodiment, C 1 Each R in is independently selected from C1-C 12 Alkyl, C6-C 18 Aryl, or having the formula -R 2 NHR 3 or -R 2 NHR 2 NHR 3 An amino-functional hydrocarbon group, wherein each R 2 Independently for C2-C 12 Alkylene and R 3 It is a C1-C4 alkyl group.

[0098] In a particularly preferred embodiment, C 1 Each R in is independently selected from C1-C6 alkyl, C6-C 18 Aryl, or having the formula -R 1 NHR 2 or -R 1 NHR 1 NHR 2 An amino-functional hydrocarbon group, wherein each R 1 are independently C2-C8 alkylene and R 2 Mention may be made of amino-functional silicone resins (C 1 ).

[0099] As noted, the amino-functional silicone resin (C 1) in which the subscripts a, b, c and d describe the mole fractions of the respective units such that a+b+c+d=1. Those mole fractions should satisfy the following conditions: i) the value of a is 0 to 0.40, preferably 0 to 0.20, for example 0 to 0.10; ii) the value of b is ≥ 0.15, preferably 0.15 to 0.8, for example 0.15 to 0.6; iii) c satisfies the condition 0<c<0.85, preferably 0<c<0.80; and iv) the value of d is 0 to 0.20, preferably 0 to 0.10, for example 0 to 0.05.

[0100] Those skilled in the art will recognize that the alkoxy-containing amino-functional silicone resin (C 1 The total alkoxy content (AC) of the resin is represented by the sum of (wa) + (xb) + (yc) + (zd). Desirably, the total alkoxy content should be 10-30 mol % based on the moles of silicon in the resin, and preferably 10-25 mol % or 10-20 mol % on this basis.

[0101] It is not intended to limit the range of alkoxy-containing amino-functional silicone resins (C 1 However, the disclosure of US2012 / 0251729 (Horstman et al.) is instructive for exemplary synthesis processes.

[0102] Without intending to limit the invention, the following may also be mentioned as exemplary alkoxy-containing amino-functional silicone resins which can be used as curing agent c) or in curing agent c): γ-aminopropyltriethoxysilane; γ-aminopropyltriethoxysilane; γ-aminopropyltrimethoxysilane; γ-aminopropylsilsesquioxane; γ-aminopropyltrimethoxysilane; N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane; benzylamino-silane; bis-(γ-triethoxysilylpropyl)amine; bis-(γ-trimethoxysilylpropyl)amine; N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane; and N-ethyl-3-trimethoxysilyl-methylpropamine.

[0103] Additionally, the following commercial alkoxy-containing amino-functional silicone resins may also be useful: Silquest A-1130, Silquest A-1387, Silquest Y-19139, Silquest VX 225, and Silquest Y-15744 available from Momentive Performance Materials Inc; and HP2000 available from Wacker Chemie.

[0104] Although it is preferred that the curing agent c) consists of or essentially consists of the one or more alkoxy-containing amino-functional silicones, the present invention does not exclude the presence of additional curing agents in an amount of up to 10 mol % (based on the total moles of the one or more alkoxy-containing amino-functional silicones). In particular, the additional curing agent may include a mercapto compound or at least one polyamine compound, the mercapto compound having at least two mercapto groups reactive toward epoxy groups, the polyamine compound having no alkoxy functional groups.

[0105] When formulating the curable composition, it is preferred that the composition is generally characterized by a molar ratio of epoxy-reactive groups to epoxy groups of 1.5:1 to 1:1.5, such as 1.1:1 to 1:1.1. Notably, a molar ratio of epoxy-reactive groups to epoxy groups of 1:1 is included within these stated ranges and itself represents a highly preferred molar ratio.

[0106] e) Aminoalkoxysilane

[0107] In a preferred embodiment, the aminoalkoxysilane used has the general formula (I):

[0108]

[0109] Where R 1 is hydrogen; R 2 and R 3 are the same or different and are independently selected from linear or branched, substituted or unsubstituted C1-C 20 Alkyl or C6-C 18 Aryl, preferably selected from C1-C8 alkyl, more preferably methyl, ethyl or propyl, which may be interrupted by at least one heteroatom; R 4 Selected from linear or branched, substituted or unsubstituted C1-C 20 Alkylene, preferably C1-C8 alkylene, more preferably methylene, ethylene, 1,3-propylene, 2-methyl-1,3-propylene, or 1,4-butylene, most preferably methylene or 1,3-propylene, which may be interrupted by at least one heteroatom; and n is 0, 1, 2 or 3, preferably 3.

[0110] Examples of aminoalkoxysilanes include, but are not limited to, aminoalkylene alkoxysilanes such as N-cyclohexylaminomethylmethyldiethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-phenylaminomethyltrimethoxysilane, N-cyclohexyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, vinylbenzylaminoethylaminopropyltrimethoxysilane, aminoethylaminopropyltrimethoxysilane (e.g., Dow Corning's Dow Z-6121Silane), aminoethylaminopropylsilanetriol homopolymer (e.g., Dow Corning's Dow Z-6137Silane), bis(3-triethoxysilylpropyl)amine, bis(3-trimethoxysilylpropyl)amine, oligomeric aminosilanes (e.g., Evonik's 1133), aminosilane compositions (e.g., Evonik 1204, AMEO-T, SIVO 210, DAMO-M, DAMO-T), 3-aminopropylmethyldiethoxysilane, 3-aminopropylmethyldiethoxysilane preparations (e.g., Evonik's 1506), 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, VOC-free (i.e., volatile organic compound-free) aqueous siloxanes (e.g., Evonik's HYDROSIL 1151, HYDROSIL 2627, HYDROSIL 2909, HYDROSIL 2929, HYDROSIL 2776), triamino-functional propyltrimethoxysilane (e.g., Evonik's TRIAMO), oligosiloxanes (e.g., Evonik's 1146), N-(n-butyl)-3-aminopropyltrimethoxysilane, cationic benzylamino-functional silane hydrochloride (e.g., Evonik's 1161), 2-aminoethyl-3-aminopropylmethyldimethoxysilane, 2-aminoethyl-3-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, modified aminoorganosilane (e.g., Momentive Performance Materials' A-1108), γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, modified aminoorganosilanes (e.g., Momentive Performance Materials' A-1126 or A-1128), triaminofunctional silanes (e.g., Momentive Performance Materials A-1130), bis-(γ-trimethoxysilylpropyl)amine, polyazamidesilane (e.g., Momentive Performance Materials' A-1387), δ-aminoneohexyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, δ-aminoneohexylmethyldimethoxysilane and N-phenylγ-aminopropyltrimethoxysilane.

[0111] Other amino-functional silanes or amino-functional siloxanes that can be used to form the amine-modified epoxy resin include materials available from Degussa's Sivento division, such as the amino-functional silane composition (known as 1126), oligomeric diaminosilane system (called 1146), N-vinylbenzyl-N'-aminoethyl-e-aminopropyl polysiloxane ( 1175), N-(n-butyl)-3-aminopropyltrimethoxysilane ( 1189), amino-functional silane composition (referred to as 1204), N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane ( 1411), 3-aminopropylmethyldiethoxysilane ( 1505), 3-aminopropylmethyldiethoxysilane ( 1506), 3-aminopropyltriethoxysilane ( AMEO), aminosilane composition (called AMEO-T), 3-aminopropyltrimethoxysilane ( AMMO), N-2-aminoethyl-3-aminopropyltrimethoxysilane ( DAMO), N-(2-aminoethyl)-3-aminopropyltrimethoxysilane ( DAMO-T) and triamino-functional propyltrimethoxysilane (called Most preferably, the aminoalkoxysilane is selected from 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, aminoethylaminopropyltrimethoxysilane, aminoethylaminopropyltriethoxysilane, and / or oligomers thereof, or combinations thereof; more preferably, the aminoalkoxysilane is 3-aminopropyltriethoxysilane.

[0112] Additives and auxiliary ingredients

[0113] The compositions obtained in the present invention will generally also contain adjuvants and additives that can impart improved properties to these compositions. For example, adjuvants and additives can impart one or more of the following: improved elasticity; improved elastic recovery; longer permissible processing time; faster curing time; and lower residual viscosity. Such adjuvants and additives include (which can be included independently of each other in a single component or both components of a two-component (2K) composition): plasticizers, stabilizers (including UV stabilizers, antioxidants), tougheners, fillers, reactive diluents, desiccants, adhesion promoters, bactericides, flame retardants, rheological additives, colored pigments or color pastes, and / or in a small range, additionally optionally present non-reactive diluents.

[0114] For the sake of completeness, it should be noted that auxiliary materials and additives containing epoxy-reactive groups are typically blended into the hardener component of a two-component (2K) composition. Materials containing epoxy groups or reactive toward one or more hardeners are typically formulated into the epoxy-containing component of a two-component (2K) composition. Non-reactive materials may be formulated into either or both of the A and B components.

[0115] A "plasticizer" for the purposes of the present invention is a substance that reduces the viscosity of the composition and thus promotes its processability. In this context, the plasticizer may represent up to 10% by weight or up to 5% by weight, based on the total weight of the composition, and is preferably selected from: polydimethylsiloxane (PDMS); diurethane; monofunctional, linear or branched C4-C 16Ethers of alcohols, such as Cetiol OE (available from Cognis Deutschland GmbH, Düsseldorf); rosin esters, butyrates, thiobutyrates, acetates, propionates and citrates; esters based on nitrocellulose and polyvinyl acetate; fatty acid esters; dicarboxylates; esters of fatty acids with OH groups or epoxidized; glycolates; benzoates; phosphates; sulfonates; trimellitates; epoxidized plasticizers; polyether plasticizers, such as end-capped polyethylene glycols or polypropylene glycols; polystyrene; hydrocarbon plasticizers; chlorinated paraffins; and mixtures thereof. It should be noted that, in principle, phthalates can be used as plasticizers, but these are not preferred due to their toxicological potential. Preferably, the plasticizer comprises or consists of one or more polydimethylsiloxanes (PDMS).

[0116] "Stabilizer" for the purposes of the present invention is understood to be an antioxidant, a UV stabilizer or a hydrolysis stabilizer. In this context, the stabilizer may constitute up to 10% by weight or up to 5% by weight, based on the total weight of the composition. Standard commercial examples of stabilizers suitable for use herein include: sterically hindered phenols; thioethers; benzotriazoles; benzophenones; benzoates; cyanoacrylates; acrylates; hindered amine light stabilizer (HALS) type amines; phosphorus; sulfur; and mixtures thereof.

[0117] Those compositions of the present invention may optionally include toughening rubber in the form of core-shell particles dispersed in an epoxy resin matrix. The term "core-shell rubber" or CSR is used as a shell layer formed by a rubber particle core formed by a polymer (which includes an elastomeric polymer or a rubbery polymer as a main component) and a polymer grafted onto the core according to its standard meaning in the art. The shell layer partially or completely covers the surface of the rubber particle core during the graft polymerization process. By weight, the core should account for at least 50% by weight of the core-shell rubber particles.

[0118] The polymer material of the core should have a glass transition temperature (T g ), preferably a glass transition temperature (T ) of -20°C or lower, more preferably -40°C or lower, even more preferably -60°C or lower g The polymer of the shell has a glass transition temperature (T g ) is a non-elastomeric, thermoplastic or thermosetting polymer above room temperature, preferably above 30°C, more preferably above 50°C.

[0119] Without intending to limit the invention, the core may comprise: a diene homopolymer, such as a homopolymer of butadiene or isoprene; a diene copolymer, such as a copolymer of butadiene or isoprene with one or more ethylenically unsaturated monomers such as vinyl aromatic monomers, (meth)acrylonitrile or (meth)acrylates; a polymer based on (meth)acrylate monomers such as polybutyl acrylate; and a polysiloxane elastomer such as polydimethylsiloxane and crosslinked polydimethylsiloxane.

[0120] Similarly, without intending to limit the invention, the shell may comprise a polymer or copolymer of one or more monomers selected from: (meth)acrylates, such as methyl methacrylate; vinyl aromatic monomers, such as styrene;

[0121] Vinyl cyanides, such as acrylonitrile; unsaturated acids and anhydrides, such as acrylic acid; and (meth)acrylamide. The polymers or copolymers used in the shell may have acid groups which are ionically crosslinked by metal carboxylate formation, in particular by formation of salts of divalent metal cations. The shell polymers or copolymers may also be covalently crosslinked by monomers having two or more double bonds per molecule.

[0122] • Preferably, any included core-shell rubber particles have an average particle size (d50) of from 10 nm to 300 nm, such as from 50 nm to 200 nm: the particle size refers to the diameter or largest dimension of a particle in a particle distribution and is measured via dynamic light scattering.

[0123] The present application does not exclude the presence of two types of core-shell rubber (CSR) particles with different particle sizes in the composition to provide a balance of key properties of the resulting cured product, including shear strength, peel strength and resin fracture toughness. In this embodiment, the average particle size of the smaller particles (CSR of type 1) included may be 10-100 nm, and the average particle size of the larger particles (CSR of type 2) included may be 120-300 nm, for example 150-300 nm. On a weight basis, the smaller core-shell rubber particles should generally be used in excess of the larger particles: for example, a weight ratio of smaller CSR particles to larger CSR particles of 3:1 to 5:1 may be used.

[0124] The core-shell rubber may be selected from commercially available products, examples of which include: Paraloid EXL 2650A, EXL 2655 and EXL 2691A available from The Dow Chemical Company; Kane available from Kaneka Corporation; MX series, in particular MX 120, MX 125, MX 130, MX 136, MX 551, MX 553; and METABLEN SX-006 available from Mitsubishi Rayon.

[0125] • The core-shell rubber particles should be included in the composition in an amount of 0-10 wt%, for example 0-5 wt%, based on the total weight of the composition.

[0126] As noted, the composition according to the present invention may also contain fillers. Suitable here are, for example, chalk, lime powder, precipitated silica and / or pyrolytic silica, zeolite, bentonite, magnesium carbonate, diatomaceous earth, aluminum oxide, clay, talc, titanium oxide, iron oxide, zinc oxide, sand, quartz, flint, mica, glass powder and other ground minerals. Organic fillers may also be used, particularly carbon black, graphite, wood fiber, wood powder, sawdust, cellulose, cotton, pulp, cotton, wood chips, chopped straw, husks, ground walnut shells and other chopped fibers. Short fibers may also be added, such as glass fiber, glass filament, polyacrylonitrile, carbon fiber, Kevlar fiber or polyethylene fiber. Aluminum powder is equally suitable as filler.

[0127] The pyrogenic silicic acid and / or precipitated silicic acid advantageously has a molecular weight of 10-90 m 2 When used, they do not cause any additional increase in the viscosity of the composition according to the invention, but do contribute to strengthening the cured composition.

[0128] Likewise, it is conceivable to use materials having a higher BET surface area, advantageously 100-250 m 2 / g, especially 110-170m 2 / g of pyrogenic silicic acid and / or precipitated silicic acid as filler: Due to the larger BET surface area, the effect of reinforcing the cured composition is achieved with a smaller weight proportion of silicic acid.

[0129] Also suitable as fillers are hollow spheres with a mineral shell or a plastic shell. These are available, for example, under the trade name Glass Commercially available hollow glass spheres. Plastic-based hollow spheres (such as or ) can be used and are described in EP 0 520 426 B1: they are made of inorganic or organic substances and each have a diameter of 1 mm or less, preferably 500 μm or less.

[0130] Fillers which impart thixotropy to the composition may be preferred for many applications: such fillers are also described as rheology aids, for example hydrogenated castor oil, fatty acid amides, or expandable plastics such as PVC.

[0131] The total amount of filler present in the composition of the present invention will preferably be 0-70% by weight, more preferably 0-60% by weight, based on the total weight of the composition. The desired viscosity of the curable composition will generally determine the total amount of filler added, and it is believed that in order to be easily extruded from a suitable dispensing device (such as a tube), the curable composition should have a viscosity of 3000 to 150000 mPas, preferably 40000 to 80000 mPas, or even 50000 to 60000 mPas.

[0132] It should be noted that compounds having metal chelating properties may be used in the compositions of the present invention to help enhance the adhesion of the cured adhesive to the substrate surface. Also suitable for use as an adhesion promoter are the acetoacetate functionalized modified resins sold by King Industries under the trade name K-FLEX XM-B301.

[0133] Examples of suitable pigments are titanium dioxide, iron oxide, or carbon black.

[0134] In order to even further increase the shelf life, it is generally recommended to further stabilize the composition of the invention with respect to moisture penetration by using a desiccant. Sometimes it is also necessary to reduce the viscosity of the adhesive or sealant composition according to the invention for a specific application by using one or more reactive diluents. The total amount of reactive diluent present will generally be up to 15 wt %, preferably 0.5-5 wt %, based on the total weight of the composition. Preferably, silanols are present as diluents.

[0135] The presence of solvents and non-reactive diluents in the compositions of the invention is not excluded insofar as they can usefully adjust the viscosity of the composition. For example, but by way of illustration only, the composition may include one or more of the following: xylene; 2-methoxyethanol; dimethoxyethanol; 2-ethoxyethanol; 2-propoxyethanol; 2-isopropoxyethanol; 2-butoxyethanol; 2-phenoxyethanol; 2-benzyloxyethanol; benzyl alcohol; ethylene glycol; ethylene glycol dimethyl ether; ethylene glycol diethyl ether; ethylene glycol dibutyl ether; ethylene glycol diphenyl ether; diethylene glycol; diethylene glycol monomethyl ether; diethylene glycol monoethyl ether; diethylene glycol mono-n-butyl ether; diethylene glycol dimethyl ether; diethylene glycol diethyl ether; diethylene glycol di-n-butyl ether; propylene glycol butyl ether; propylene glycol phenyl ether; dipropylene glycol; dipropylene glycol monomethyl ether; dipropylene glycol dimethyl ether; dipropylene glycol di-n-butyl ether; N-methylpyrrolidone; diphenylmethane; diisopropylnaphthalene; petroleum fractions, such as products (available from Exxon); alkylphenols, such as tert-butylphenol, nonylphenol, dodecylphenol and 8,11,14-pentadecatrienylphenol; styrenated phenols; bisphenols; aromatic hydrocarbon resins, especially those containing phenolic groups, such as ethoxylated or propoxylated phenols; adipates; sebacates; phthalates; benzoates; organic phosphates or sulfonates; and sulfonamides.

[0136] In addition to the above, preferably, the solvent and the non-reactive diluent account for less than 10 wt %, in particular less than 5 wt % or less than 2 wt %, based on the total weight of the composition.

[0137] For the sake of completeness, the composition of the invention may comprise one or more monoamines, such as hexylamine and benzylamine.

[0138] To enhance the physical properties, it is preferred that the two-component (2K) composition further comprises a trialkoxy-functional silicone prepolymer different from the resin a). The prepolymer is condensation curable and can facilitate crosslinking. Preferably, the two-component (2K) composition further comprises a trimethoxy silicone prepolymer. Examples are commercially available under the trade name Silmer TMS (e.g. SilmerTM SDi-400). In a preferred embodiment, the trialkoxy-functional silicone prepolymer is present in an amount of 0.1-5 wt. %, more preferably 0.5-3 wt. %, based on the total weight of the composition.

[0139] In addition, a lubricating particulate additive may be added, preferably in component (A). Some examples of suitable lubricating particulate additives are glycerides, waxes and other polymers. In particular, polytetrafluoroethylene, synthetic straight chain hydrocarbons, polyethylene, polypropylene, and combinations thereof are suitable lubricating particulate additives. Most preferred is polytetrafluoroethylene, in particular micronized polytetrafluoroethylene. In a preferred embodiment, the lubricating particulate additive is present in an amount of 0.1-5 wt %, more preferably 0.5-3 wt %, based on the total weight of the composition.

[0140] A preferred embodiment is a two-component (2K) composition comprising:

[0141] (A) a first component, the first component comprising:

[0142] a) at least one silicone-based resin containing epoxy functional groups, and

[0143] b) optionally at least one epoxy resin which is not a silicone-based resin;

[0144] c) optionally at least one silicone acrylate oligomer;

[0145] (B) a second component, the second component comprising:

[0146] d) a curing agent consisting of at least one compound having at least two epoxy-reactive groups per molecule, characterized in that it contains at least one alkoxy-containing amino-functional silicone resin,

[0147] e) at least one aminoalkoxysilane,

[0148] The composition is characterized in that it does not contain a catalyst, and preferably the molar ratio of the reactive groups provided in component B to the reactive groups in component A is 1.5:1 to 1:1.5, preferably 1.1:1 to 1:1.1, more preferably 1:1, and further comprises, preferably in component (A), a trialkoxy-functional silicone prepolymer, a lubricating particle additive and / or a diluent.

[0149] In an even more preferred embodiment, the two-component (2K) composition comprises:

[0150] A) a first component, based on the weight of the first component, the first component comprising:

[0151] 5-60 wt. % of a) at least one silicone epoxy resin a);

[0152] optionally 1 to 50 wt. % of b) at least one epoxy resin b);

[0153] optionally 1 to 20% by weight of c) at least one silicone acrylate oligomer,

[0154] B) a second component, based on the weight of the first component, the second component comprises, preferably consists of:

[0155] 50-85 wt %, preferably 60-80 wt % of d) the curing agent d);

[0156] 15 to 50% by weight, preferably 20 to 40% by weight of e) the at least one aminoalkoxysilane e);

[0157] The composition is characterized in that the composition does not contain a catalyst, and preferably the molar ratio of the reactive groups provided in component B to the reactive groups in component A is 1.5:1 to 1:1.5, preferably 1.1:1 to 1:1.1, more preferably 1:1, and component (A) comprises, each based on the total amount of the composition:

[0158] - 0.5-5% by weight of at least one diluent, preferably a silanol,

[0159] - 0.1 to 5% by weight of at least one trialkoxy-functional silicone prepolymer, preferably a trimethoxy silicone prepolymer, and / or

[0160] - 0.1 to 5% by weight of at least one lubricating particulate additive, preferably polytetrafluoroethylene.

[0161] Methods and Applications

[0162] To obtain a two-component (2K) curable composition, the reactive components are combined and mixed in such a way as to cause hardening thereof: The reactive compounds should be mixed under sufficient shear forces to produce a homogeneous mixture. It is believed that this can be achieved without the need for special conditions or special equipment. That is, suitable mixing devices may include: static mixing devices; magnetic stir bar devices; whipping devices; auger; batch mixer; planetary mixer; CW Brabender or mixers; and high shear mixers, such as blade blenders and rotary mixers.

[0163] For small-scale gasket applications, in which volumes of less than 2 liters will generally be used, the preferred packaging for the two-component (2K) composition will be a side-by-side double cartridge or coaxial cartridge in which two tubular chambers are arranged side by side or nested in one another and sealed with pistons: the actuation of these pistons allows the components to be extruded from the cartridges, advantageously by means of a static or dynamic mixer mounted in close proximity. For larger volume applications, the two components of the composition can advantageously be stored in drums or barrels: in this case, the two components are extruded via a hydraulic press, in particular by means of a follower plate, and supplied via a pipe to a mixing device which can ensure a fine and highly uniform mixing of the hardener and binder components. In any case, it is important for any packaging that the binder component is provided with an airtight and watertight seal so that the two components can be stored for a long time (ideally, 12 months or more).

[0164] The two-component (2K) curable composition should generally be formulated to exhibit an initial viscosity measured immediately after mixing (e.g., up to 2 minutes after mixing) of less than 200,000 mPa·s, for example, less than 100,000 mPa·s at 25° C. Independently or additionally to the viscosity characteristic, the two-component (2K) composition should be formulated to be free of bubbles (foam) after mixing and subsequent curing. Furthermore, the two-component (2K) composition should be formulated to exhibit at least one, desirably at least two, and most desirably all of the following properties: i) a long pot life, typically at least 25 minutes and often at least 60 or 120 minutes, which pot life is to be understood herein as the time after which the viscosity of the mixture at 20° C. rises to more than 50,000 mPas; ii) a maximum exotherm temperature of not more than 120° C., preferably not more than 100° C., more preferably not more than 80° C.; and iii) a Shore A hardness of at least 50, preferably at least 60, more preferably at least 70 after curing and storage for 7 days at room temperature and 50% relative humidity.

[0165] The curing of the composition according to the invention can be carried out at a temperature in the range of -10°C to 120°C, preferably 0°C to 70°C, in particular 20°C to 60°C. Suitable temperatures depend on the specific compounds present and the desired curing rate and can be determined in each case by the person skilled in the art using simple preliminary tests (if necessary). Of course, curing at a temperature of 10°C to 35°C or 20°C to 30°C is particularly advantageous, since it eliminates the need for significantly heating or cooling the mixture from the ambient temperature that usually prevails. However, where applicable, the temperature of the mixture formed from the components of the two-component (2K) composition can be raised to above the mixing temperature and / or application temperature using conventional means (including microwave induction).

[0166] The curable compositions according to the invention can be used in particular in varnishes, inks, binders for fibers and / or particles, coatings for glass, coatings for mineral building materials such as lime and / or cement-bound plasters, gypsum-containing surfaces, fiber cement building materials and concrete, coatings and sealants for wood and wood-based materials such as particleboard, fiberboard and paper, coatings for metal surfaces, coatings for bituminous and asphalt-containing pavements, coatings and sealants for various plastic surfaces, and coatings for leather and textiles.

[0167] In a particularly preferred embodiment, the composition of the present invention is applied to a substrate to produce an adhered, highly wear-resistant coating. The bonding operation can generally be performed at room temperature, and effective wear resistance can be obtained after curing. In addition, when bonded to the surface of a mechanical structure or bonded to a floor or pavement, the coating composition can provide corrosion protection to the surface and can prevent the surface from contacting compounds that are harmful to the operation or efficiency of the particular structure.

[0168] In each of the above applications, the composition can be applied by conventional application methods such as brushing; roller coating, for example, using a 4-application roller device (in the case of a solvent-free composition) or a 2-application roller device (for a solvent-containing composition); blade application; printing methods; and spraying methods, including but not limited to air atomization spraying, air-assisted spraying, airless spraying, and high-volume low-pressure spraying. For coating and adhesive applications, it is recommended that the composition be applied to a wet film thickness of 10-500 μm. The application of thinner layers within this range is more economical and provides the possibility of reducing thick cured areas (which may require grinding for coating applications). However, strict control must be exercised when applying thinner coatings or layers to avoid the formation of discontinuous cured films.

[0169] For the sake of completeness, it should be noted that the present invention does not exclude the preparation of epoxy adhesives in the form of "film adhesives". A prepolymer mixture of epoxy resin, hardener and other desired components is applied as a coating to a polymer film substrate, rolled up and stored at a sufficiently low temperature to inhibit chemical reactions between the components. When needed, the film adhesive is removed from the low temperature environment and applied to a metal or composite part,

[0170] The backing is peeled off and the assembly is completed and cured in an oven or autoclave.

[0171] The following examples illustrate the invention but are not intended to limit the scope of the invention in any way.

[0172] Example:

[0173] The following commercial products were used in the examples:

[0174]

[0175] The following tests were performed in the examples:

[0176] Opening hours : This is measured at room temperature and 50% humidity as the maximum time in which an adhesive bond can form after the composition has been applied to the substrate. For example, if the composition can be applied to a first board and: i) after 5 seconds, another board can still be applied and can still be bonded to the first board; but ii) after 6 seconds, the composition may be too hard and solid to form a bond between the two boards, then the open time is 5 seconds.

[0177] Skin formation time: This is determined at 23°C and 50% relative humidity by applying the coating at a wet layer thickness of 75 μm. Skin formation is considered to occur when fingerprints are no longer observable after touching the surface with a clean, dry finger. A timing device is used to measure the tack free time.

[0178] Gloss at 60° : A gloss meter is an instrument used to measure the specular reflection (gloss) of a surface. Gloss is determined by projecting a beam of light onto a surface at a fixed intensity and angle, and measuring the amount of reflected light at an equal but opposite angle.

[0179] Pull of adhesion on GBMS : This is determined by applying the coating on a 250 μm thick blasted panel at 23° C. and 50% relative humidity. The coating is allowed to fully cure for 7 days. The test is determined by ASTM D4541.

[0180] 1000 hours of QUV data : This is determined by applying the coating on a sandblasted panel with a thickness of 250 μm at 23°C and 50% relative humidity. The coating is allowed to fully cure for 7 days. The test is determined by ASTM G154. The following conditions are used: Lamp: UVB-313, Typical irradiance: 0.71 W / (m 2 ·nm), approximate wavelength: 310nm, exposure cycle: 4 hours UV at 60(±3)℃ blackboard temperature; 4 hours condensation at 50(±3)℃ blackboard temperature. Total time: 1000 hours exposure.

[0181] Examples 1-9

[0182] The compositions of the examples are presented in Table 1, and their performance was evaluated by using different resins, hardeners, fillers and additives. Table 1 also describes the different properties of these coating compositions. After mixing the two parts, the resulting compositions were evaluated for tack free time and open time. All these formulations were cured at room temperature and the final properties (such as gloss, hardness and pull-off adhesion strength) were tested after 7 days of full cure. The coating thickness was maintained at around 240-260 μm.

[0183] When using a combination of Hardener 1 and Hardener 2 without a catalyst, the tack free time and open time are within a favorable range. At the same time, the gloss, hardness and pull-off adhesion are within the desired range, with sufficient gloss and pull-off adhesion while being hard enough but not brittle. Without Hardener 1, curing is too fast and results in a brittle coating. Without Hardener 2, the gloss, hardness and pull-off adhesion are too low. By adding epoxy resins and even silicone acrylate oligomers, the results can even be pushed towards more favorable properties.

[0184] Table 1

[0185]

[0186] *Hardener weight (in grams) depends on the combined EEW of the functional groups in Part A

Claims

1. A two-component (2K) composition, comprising: (A) a first component, the first component comprising: a) at least one silicone-based resin containing epoxy functional groups, and b) optionally at least one epoxy resin which is not a silicone-based resin; c) optionally at least one silicone acrylate oligomer; (B) a second component, the second component comprising: d) a curing agent consisting of at least one compound having at least two epoxy-reactive groups per molecule, characterized in that it contains at least one alkoxy-containing amino-functional silicone resin, e) at least one aminoalkoxysilane, The composition is characterized in that it does not contain a catalyst, and preferably the molar ratio of reactive groups provided in component B to reactive groups in component A is 1.5:1 to 1:1.5, preferably 1.1:1 to 1:1.1, more preferably 1:

1.

2. The two-component composition according to claim 1, comprising: A) a first component, based on the weight of the first component, the first component comprising: 5-60 wt. % of a) at least one silicone epoxy resin a); optionally 1 to 50 wt. % of b) at least one epoxy resin b); optionally 1 to 20 wt. % of c) at least one silicone acrylate oligomer; B) a second component, based on the weight of the first component, the second component comprises, preferably consists of: 50-85 wt %, preferably 60-80 wt % of d) the curing agent d); 15 to 50% by weight, preferably 20 to 40% by weight, of e) at least one aminoalkoxysilane e), The composition is characterized in that it contains no catalyst and the molar ratio of reactive groups provided in component B to reactive groups in component A is 1.5:1 to 1:1.5, preferably 1.1:1 to 1:1.1, more preferably 1:

1.

3. The two-component composition according to claim 1 or claim 2, wherein the epoxy-functional silicone-based resin has an epoxy equivalent weight of 100-1500 g / eq, preferably 200-1000 g / eq, more preferably 300-700 g / eq.

4. The two-component composition according to any one of claims 1 to 3, wherein the epoxy resin b) is selected from cycloaliphatic epoxy resins and aromatic epoxy resins.

5. The two-component composition according to any one of claims 1 to 4, wherein the molar ratio of epoxy-reactive groups provided in component B to epoxy groups in component A is 1.5:1 to 1:1.5, preferably 1.1:1 to 1:1.1, more preferably 1:

1.

6. The two-component composition according to any one of claims 1 to 5, wherein the molar ratio of silane groups to carbon double bonds, preferably (meth)acrylate groups in component B is 1.5:1 to 1:1.5, preferably 1.1:1 to 1:1.1, more preferably 1:

1.

7. The two-component composition according to any one of claims 1 to 6, wherein the curing agent c) consists of the following substances: 90-100 mol % of one or more of said alkoxy-containing amino-functional silicone resins; 0-10 mol % of a second epoxy-reactive compound.

8. The two-component composition according to any one of claims 1 to 7, wherein the alkoxy-containing amino-functional silicone resin is characterized by at least one of the following: i) an amine hydrogen equivalent weight of 100-1500 g / eq; and ii) a weight average molecular weight (Mw) of 150-10000 g / mol as determined by gel permeation chromatography.

9. The two-component composition according to any one of claims 1 to 8, wherein the curing agent c) comprises at least one alkoxy-containing amino-functional silicone resin (C1), the alkoxy-containing amino-functional silicone resin (C1) having at least two amine hydrogen atoms per molecule, an amine hydrogen equivalent weight of 100 to 1500 g / eq, and a total alkoxy content (AC) of 10 to 40 mol %, based on the moles of silicon, the resin (C1) comprising the following units: (R3Si(OR’) w O (1-w) / 2 ) a (i); (R2Si(OR’) x O (2-x) / 2 ) b (ii); (RSi(OR') y O (3-y) / 2 ) c (iii); and (Si(OR') z O (4-z / 2 ) d (iv), in: Each R is independently selected from C1-C 18 Alkyl, C6-C 18 Aryl, or having the formula -R 2 NHR 3 or -R 2 NHR 2 NHR 3 An amino-functional hydrocarbon group, wherein each R 2 Independently for C2-C 20 Alkylene and R 3 is a C1-C6 alkyl group; a, b, c and d define the mole fraction of each unit (i) to (iv) respectively, such that a+b+c+d=1; and w, x, y, and z define the mole fraction of the alkoxy group such that 0≤w<1, 0≤x<2, 0≤y<3, and 0≤z<4.

10. The two-component composition according to claim 9, wherein each R in the resin (C1) is independently selected from C1-C6 alkyl, C6-C 18 Aryl, or having the formula -R 1 NHR 2 or -R 1 NHR 1 NHR 2 An amino-functional hydrocarbon group, wherein each R 1 are independently C2-C8 alkylene and R 2 It is a C1-C2 alkyl group. 11 . The two-component composition according to claim 9 , wherein the amino-functional silicone resin (C1) has both methyl and phenyl substitutions at R.

12. The two-component composition according to any one of claims 9 to 11, wherein a in the amino-functional silicone resin (C1) has a value of 0 to 0.10, b has a value of 0.15 to 0.6, c satisfies the condition 0<c<0.85, and d has a value of 0 to 0.

05.

13. The two-component composition according to any one of claims 1 to 12, wherein the aminoalkoxysilane e) has the general formula (I): Where R 1 is hydrogen; R 2 and R 3 are the same or different and are independently selected from linear or branched, substituted or unsubstituted C1-C 20 Alkyl or C6-C 18 Aryl, preferably selected from C1-C8 alkyl, more preferably methyl, ethyl or propyl, which can be interrupted by at least one heteroatom; R 4 Selected from linear or branched, substituted or unsubstituted C1-C 20 Alkylene, preferably C1-C8 alkylene, more preferably methylene, ethylene, 1,3-propylene, 2-methyl-1,3-propylene, or 1,4-butylene, most preferably methylene or 1,3-propylene, which can be interrupted by at least one heteroatom; and n is 0, 1, 2 or 3, preferably 3.

14. A cured product obtained from a two-component (2K) composition as defined in any one of claims 1 to 13.

15. Use of the cured reaction product as defined in claim 14 as a coating, sealant or adhesive.

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