Room temperature curable composition

Abstract

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

Description

Technical Field

[0001] The present invention relates to a two-component (2K) composition comprising, as a first component, a silicone-based resin containing an epoxy functional group, optionally an epoxy resin and a silicone acrylate oligomer, and, as a second component, a curing agent containing at least one alkoxy-containing amino-functional silicone resin and an aminoalkoxysilane. By reacting the two components of the composition, a cured product is obtained which exhibits processability while maintaining mechanical properties upon curing.

Background Art

[0002] Epoxy compositions are well known as protective and decorative coatings for steel structures in the oil, gas industry and marine applications, including very harsh environmental conditions. Epoxy compositions are known to have excellent adhesion, corrosion resistance and chemical resistance, but have poor UV resistance and weather resistance. These can be improved by introducing silicone into the composition. Silicone is well known for its excellent weather resistance. Silicone epoxy compositions provide excellent UV resistance and weather resistance, but may not provide gloss, may become brittle, and ultimately may form weak bonds that spread corrosion.

Summary of the Invention

Problems to be Solved by the Invention

[0003] The inventors recognize the need to develop a curable composition that provides good processability while maintaining mechanical properties at a sufficient level, particularly the need to simultaneously maintain high levels of gloss, hardness and weather resistance.

Means for Solving the Problems

[0004] According to a first aspect of the present invention, (A) a) at least one silicone-based resin having an epoxy functional group, and, b) optionally, at least one epoxy resin that is not a silicone-based resin; c) Optionally, at least one silicone acrylate oligomer; a first component comprising; (B) d) a curing agent comprising at least one compound having at least two epoxy-reactive groups per molecule, characterized in that it comprises at least one alkoxy-containing amino-functional silicone resin; e) at least one aminoalkoxysilane a second component comprising; not containing a catalyst, 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 a two-component (2K) composition is provided.

[0005] Such a composition solves the above problems, exhibits excellent flexibility, weather resistance, corrosion resistance, gloss retention, and fairly high ultraviolet resistance compared to conventional epoxy systems, and has surface properties that are easy to clean. This composition cures at room temperature without the need for an accelerator / catalyst, providing a long open time that is particularly desirable for larger coating areas with larger volumes.

[0006] In another embodiment of the present invention, the molar ratio of the epoxy-reactive groups provided in component B to the 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.

[0007] In another embodiment, the molar ratio of the silane groups in component B to the carbon double bond, preferably the (meth)acrylate group, is 1.5:1 to 1:1.5, preferably 1.1:1 to 1:1.1, more preferably 1:1.

[0008] In some embodiments, the two-component (2K) composition is A) based on the weight of the first component, 5 to 60% by weight of said at least one silicone epoxy resin a); Optionally, 1 to 50% by weight of said at least one epoxy resin b); Optionally, 1 to 20% by weight of said at least one silicone acrylate oligomer c); A first component comprising; B) Based on the weight of said first component, 50 to 85% by weight, preferably 60 to 80% by weight of said curing agent d), 15 to 50% by weight, preferably 20 to 40% by weight of said at least one aminoalkoxysilane e), A second component comprising, preferably consisting of; Comprising and not containing a catalyst, 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.

[0009] The silicone resin a) containing an epoxy functional group preferably has an epoxy equivalent in the range of 100 to 1500 g / eq, more preferably in the range of 200 to 1000 g / eq, still more preferably in the range of 300 to 700 g / eq.

[0010] Said curing agent d) has at least two amine hydrogen atoms per molecule, an amine hydrogen equivalent of 100 to 1500 g / eq, and a total alkoxy content (AC) based on the number of moles of silicon of 10 to 40 mol%, and contains at least one alkoxy-containing amino-functional silicone resin (C 1 ) and said resin (C 1 ) has 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) [wherein each R is independently a C1-C 18 alkyl group, a C6-C 18 aryl group, or a formula -R 2 NHR 3 or -R 2 NHR 2 NHR 3 amino-functional hydrocarbon group having (each R 2 is independently a C2-C 20 alkylene group, and R 3 is a C1-C6 alkyl group), and is selected from a, b, c and d represent the molar fractions of each unit (i)-(iv) such that a + b + c + d = 1, w, x, y and z represent the molar fractions of the alkoxy groups such that 0 ≦ w < 1, 0 ≦ x < 2, 0 ≦ y < 3, and 0 ≦ z < 4] is preferably included.

[0011] Regarding the alkoxy-containing amino-functional silicone resin (C 1 ), each R is independently a C1-C6 alkyl group, a C6-C 18 aryl group, or a formula -R 1 NHR 2 or -R 1 NHR 1 NHR 2 amino-functional hydrocarbon group having (wherein each R 1 is independently a C2-C8 alkylene group, and R 2 is a C1-C2 alkyl group), and is preferably selected from. Further, when the alkoxy-containing amino-functional silicone resin (C 1 ) has both a methyl group and a phenyl group in R, good results are obtained.

[0012] Although not wishing to be bound by theory, the compositions of the present invention cure in the absence of a catalyst by a dual curing mechanism: the reaction of the amine hydrogen atoms of the alkoxy-containing amino-functional silicone resin hardener with the epoxide groups; and the self-condensation of the reactive alkoxy groups of the curable compound. Further, when carbon-carbon double bonds are present, these can crosslink with the silane functional groups. This curing mechanism is effective under ambient conditions and has been found to result in a highly crosslinked network. Further, it is believed that the open time of this composition does not decrease even in the absence of a catalyst.

[0013] According to a second aspect of the present invention, there is provided a cured product obtained from a two-component (2K) composition as defined hereinabove and also in the appended claims. The present invention further relates to a cured reaction product as a coating, sealant or adhesive.

DETAILED DESCRIPTION OF THE INVENTION

[0014] (Definitions) As used herein, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise.

[0015] As used herein, the terms "comprising", "comprises" and "comprised of" are synonymous with "including", "includes", "containing" or "contains", are inclusive or open-ended and do not exclude additional unrecited members, elements or method steps. When used, the expression "consisting of" is closed and excludes all additional elements. Further, the expression "consisting essentially of" excludes additional material elements but can include immaterial elements that do not substantially change the nature of the invention.

[0016] When amounts, concentrations, dimensions, and other parameters are expressed in the form of ranges, preferred ranges, upper limit values, lower limit values, or preferred upper and lower limit values, it should be understood that any range obtained by combining any upper limit or preferred value with any lower limit or preferred value is specifically disclosed, whether or not the resulting range is explicitly recited in the context.

[0017] The terms “preferred,” “preferably,” “desirably,” and “particularly” and their synonyms are frequently used herein to refer to embodiments of the present disclosure that may provide certain benefits under certain circumstances. However, the recitation of one or more preferred, preferable, desirable, or particular embodiments is not meant to imply that other embodiments are not useful, nor is it intended to exclude those other embodiments from the scope of the present disclosure.

[0018] As used throughout this application, the term “may” is used in a permissive sense, not a mandatory sense, and it means having the possibility.

[0019] As used herein, room temperature is 23°C plus or minus 2°C. As used herein, “ambient conditions” means the temperature and pressure surrounding where the composition is located, or where the coating layer or the substrate of the coating layer is located.

[0020] As used herein, the term “equivalent (eq.)” relates to the relative number of reactive groups present in a reaction, as is customary in chemical notation.

[0021] 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) means the weight (grams) of resin containing 1 equivalent of epoxy. Similarly, "amine hydrogen equivalent weight" (AHEW) means the weight (grams) of an organic amine containing 1 amine hydrogen.

[0022] As used herein, the term "(co)polymer" includes homopolymers, copolymers, block copolymers, and terpolymers.

[0023] As used herein, the term "epoxide" refers to a compound characterized by the presence of at least one cyclic ether group, i.e., an ether oxygen atom bonded to two adjacent carbon atoms, thereby forming a cyclic structure. This term is intended to encompass monoepoxide compounds, polyepoxide compounds (having two or more epoxy groups), and epoxy-terminated prepolymers. The term "monoepoxide compound" means an epoxide compound having one epoxy group. The term "polyepoxide compound" means an epoxide compound having at least two epoxy groups. The term "diepoxide compound" means an epoxide compound having two epoxy groups.

[0024] Epoxides may be unsubstituted or may be inertly substituted. Exemplary inert substituents include chlorine, bromine, fluorine, and phenyl.

[0025] The silicone-based resin a) containing an epoxy functional group and the optionally elastomer-modified epoxy resin (b) are different substances, and when both are present, one resin cannot act as both a) and b).

[0026] As used herein, "C1-C nThe term "alkyl" refers to a monovalent group containing 1 to n carbon atoms, that is, a group of an alkane, including linear and branched organic groups. Therefore, "C1-C 30 alkyl" refers to a monovalent group containing 1 to 30 carbon atoms, that is, a group of an alkane, including 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 the present invention, such an alkyl group may be unsubstituted or substituted with one or more substituents such as halo, nitro, cyano, amide, amino, sulfonyl, sulfinyl, sulfanyl, urea, thiourea, sulfamoyl, sulfamido, and hydroxy. The above-exemplified halogen derivatives of hydrocarbon radicals can be particularly cited as examples of suitable substituted alkyl groups. However, generally, attention should be paid to the priority of an unsubstituted alkyl group having 1 to 18 carbon atoms (C1-C 18 alkyl), for example, an unsubstituted alkyl group having 1 to 12 carbon atoms (C1-C 12 alkyl), or an unsubstituted alkyl group having 1 to 6 carbon atoms (C1-C6 alkyl).

[0027] The term "C3-C 30 cycloalkyl" is understood to mean a saturated monocyclic, bicyclic or tricyclic hydrocarbon group having 3 to 30 carbon atoms. Generally, attention should be paid to the priority of a cycloalkyl group containing 3 to 18 carbon atoms (C3-C18 cycloalkyl group). Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclophenyl, cyclooctyl, adamantane and norbornane.

[0028] As used herein, "C6-C 18The "aryl" group is used alone or as part of a larger moiety such as an "aralkyl group" and refers to optionally substituted monocyclic, bicyclic and tricyclic systems where the monocyclic system is aromatic or at least one of the rings of the bicyclic or tricyclic system is aromatic. The bicyclic and tricyclic systems include benzo-fused 2- to 3-membered carbocyclic rings. In the present invention, examples of aryl groups include phenyl; indenyl; naphthalenyl, tetrahydronaphthyl, tetrahydroindenyl; tetrahydroanthracenyl; and anthracenyl. Also, priority may be mentioned with respect to the phenyl group.

[0029] As used herein, "C2-C" 20 "alkenyl" refers to a hydrocarbyl group having 2 to 20 carbon atoms and at least one unit of ethylenic unsaturation. The alkenyl group may be straight-chain, branched or cyclic and may optionally be substituted with one or more halogens. The term "alkenyl" also includes groups having "cis" and "trans" configurations, or alternatively "E" and "Z" configurations, as understood by those skilled in the art. However, generally, attention should be paid to the priority of unsubstituted alkenyl groups having 2 to 10 (C 2-10 ) or 2 to 8 (C 2-8 ) carbon atoms. The above C2-C 12Examples 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-cyclopenta-1-enyl; 1-cyclopenta-2-enyl; 1-cyclopenta-3-enyl; 1-cyclohexa-1-enyl; 1-cyclohexa-2-enyl; and 1-cyclohexyl-3-enyl.

[0030] As used herein, "alkylaryl" refers to an alkyl-substituted aryl group, and "substituted alkylaryl" refers to an alkylaryl group further containing one or more substituents as described above.

[0031] As used herein, the term "hetero" refers to a group or moiety containing one or more heteroatoms such as N, O, Si, and S. Thus, for example, "heterocyclic" refers to a cyclic group having, for example, N, O, Si, or S as part of the ring structure. "Heteroalkyl" and "heterocycloalkyl" moieties are, respectively, the alkyl and cycloalkyl groups defined above that contain N, O, Si, or S as part of their structures.

[0032] As used herein, the term "catalytic amount" means a sub-stoichiometric amount of catalyst relative to the reactants, unless expressly stated otherwise. - As used herein, the term "primary amino group" means an NH2 group attached to an organic group, and the term "secondary amino group" means an NH group attached to two organic groups, which may also be part of a ring together. When used, the term "amine hydrogen" refers to the hydrogen atoms of primary and secondary amino groups. - When the term "amine value" is mentioned herein, it can be determined by titration of amine acetate ions with dilute hydrochloric acid, typically 1N hydrochloric acid solution. For pure materials, the amine value can be calculated using the molecular weight of the pure compound and the molecular weight of KOH (56.1 g / mol). An explanatory guide for illustration can be found at: https: / / dowac.custhelp.com / app / answers / detail / a_id / 12987.

[0033] In the context of the present invention, a "two-component (2K) composition" is understood to be a composition in which the binder component (A) and the curing agent component (B) must be stored in separate containers due to their (high) reactivity. The two components are mixed only immediately before application and then react, typically without additional activation, to form a bond, thereby forming a polymer network. Here, a higher temperature can be applied to promote the crosslinking reaction.

[0034] Unless otherwise specified, the viscosity of the coating composition described herein is measured under standard conditions of 20 °C and relative humidity (RH) 50% using a Brookfield viscometer, model RVT. This viscometer is calibrated using silicone oils of known viscosities from 5,000 cps to 50,000 cps. For calibration, a set of RV spindles attached to the viscometer is used. The measurement of the coating composition is carried out for 1 minute at a speed of 20 revolutions per minute using the No. 6 spindle until the viscometer reaches equilibrium. Then, using the calibration, the viscosity corresponding to the equilibrium measurement value is calculated.

[0035] The term "polyol" as used herein includes diols and highly functional hydroxy compounds.

[0036] The hydroxyl value (OH value) used in this specification is measured in accordance with Japanese Industrial Standard (JIS) K-1557, 6.4. The value of the isocyanate content used in this specification is measured in accordance with EN ISO 11909.

[0037] The molecular weight referred to in this specification can be measured by gel permeation chromatography (GPC) using polystyrene calibration standards in accordance with ASTM3536.

[0038] As used in this specification, "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 may not contain water at all. The term "substantially solvent-free" should be analogously understood to mean that the relevant composition contains less than 0.25% by weight of solvent.

[0039] (Detailed Description of the Invention) a) A silicone-based resin containing epoxy functional groups The two-component (2K) composition of the present invention typically should contain, based on the weight of its first component, 5 to 60% by weight, preferably 7 to 40% by weight, of a silicone-based resin containing epoxy functional groups. In another expression of a preferred configuration of the composition of the present invention, although not intended to be mutually exclusive with the above, the composition may contain 2 to 40% by weight, based on the weight of the composition, of the silicone-based resin a) containing epoxy functional groups. For example, the composition of the present invention may contain, based on the weight of the entire composition, 5 to 50% by weight, preferably 5 to 30% by weight, more preferably 5 to 20% by weight of the above-mentioned silicone-based resin a) containing epoxy functional groups.

[0040] The silicone resin containing an epoxy functional group exhibits the properties of a silicone resin and also contains an epoxy moiety that can be crosslinked by the epoxy curing agent described herein. In particular, the silicone resin containing an epoxy functional group preferably contains an alkoxysilicone moiety. Typically, the silicone resin containing an epoxy functional group is a silicone epoxy elastomer. Such a silicone resin containing an epoxy functional group can be obtained from at least one epoxy resin and at least one alkoxysilicone resin. Typically, they can be obtained by reacting at least one epoxy resin with at least one alkoxysilicone resin, preferably at least one hydroxyl-functional compound. Aliphatic epoxy resins are particularly preferred. Preferably, the silicone resin containing an epoxy functional group is liquid at room temperature and normal pressure. In this regard, the silicone resin containing an epoxy functional group preferably has a viscosity in the range of 500 to 2500 mPas, preferably 800 to 2200 mPas, more preferably 1000 to 2000 mPas, and even more preferably 1200 to 1800 mPas at 25 °C according to ASTM D445. Viscosities higher or lower than this have been found not to be practical within the scope of the present disclosure.

[0041] The silicone resin containing an epoxy functional group generally contains an epoxy moiety that confers the ability to crosslink with the curing agents described herein. With respect to the epoxy moiety present in the silicone resin containing an epoxy functional group, the silicone resin containing an epoxy functional group preferably has an epoxy equivalent in the range of 100 to 1500 g / eq, preferably 200 to 1000 g / eq, and more preferably 300 to 700 g / eq according to ASTM D1652. An example of a silicone resin containing an epoxy functional group advantageously used within the scope of the present disclosure is Silikopon® EF (Evonik Industries).

[0042] b) Epoxy resin The two-component (2K) composition of the present invention can preferably contain an epoxy resin b) in an amount of preferably 1 to 50% by weight, preferably 10 to 40% by weight, based on the weight of its first component. This epoxy resin is different from the resin a) and is not a silicone-based resin. In another expression of a preferred configuration of the composition of the present invention, although not intended to be mutually exclusive with the above, the composition can contain 1 to 50% by weight of epoxy resin a) based on the weight of the composition. For example, the composition of the present invention can contain 5 to 40% by weight, such as 5 to 30% by weight, of the epoxy resin a) based on the weight of the composition.

[0043] The epoxy resins used herein can include monofunctional epoxy resins, polyfunctional epoxy resins, or polyfunctional epoxy resins and combinations thereof. The epoxy resin may be a pure compound, but may also be a mixture of epoxy-functional compounds containing a mixture of compounds with different numbers of epoxy groups per molecule. The epoxy resin can be saturated or unsaturated, aliphatic, alicyclic, aromatic or heterocyclic, and may be substituted. The most preferred epoxy resins are alicyclic or aromatic. Furthermore, the epoxy resin may be a monomer or a polymer.

[0044] Although not intended to limit the present invention, exemplary monoepoxide compounds include alkylene oxides, epoxy-substituted alicyclic hydrocarbons (e.g., cyclohexene oxide, vinylcyclohexene monooxide, (+)-cis-limonene oxide, (+)-cis,trans-limonene oxide, (-)-cis,trans-limonene oxide, cyclooctene oxide, cyclododecene oxide, α-pinene oxide, etc.), epoxy-substituted aromatic hydrocarbons, monoepoxy-substituted alkyl ethers of monohydric alcohols or phenols (e.g., glycidyl ethers of aliphatic, alicyclic and aromatic alcohols, etc.), monoepoxy-substituted alkyl esters of monocarboxylic acids (e.g., glycidyl esters of aliphatic, alicyclic and aromatic monocarboxylic acids, etc.), monoepoxy-substituted alkyl esters of polycarboxylic acids in which other carboxy groups are esterified with alkanols, alkyl and alkenyl esters of epoxy-substituted monocarboxylic acids, epoxyalkyl ethers of polyhydric alcohols in which other OH groups are esterified or etherified with carboxylic acids or alcohols, and monoesters of polyhydric alcohols in which other OH groups are esterified or etherified with carboxylic acids or alcohols and epoxy monocarboxylic acids, etc.

[0045] As an example, the following glycidyl ethers are mentioned as monoepoxide compounds particularly suitable for use in the present invention. 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.

[0046] Preferred monoepoxides include ethylene oxide, 1,2-propylene oxide (propylene oxide), 1,2-butylene oxide, cis-2,3-epoxybutane, trans-2,3-epoxybutane, 1,2-epoxypentane, 1,2-epoxyhexane, 1,2-heptylene oxide, decene oxide, butadiene oxide, isoprene oxide, and styrene oxide.

[0047] Again, without intending to limit the present invention, suitable polyepoxide compounds may be in a liquid, solid, or dissolved in a solvent state. Further, such polyepoxide compounds should have an epoxy equivalent weight of 100 to 700 g / eq, for example 120 to 320 g / eq. And generally, diepoxide compounds with an epoxy equivalent weight of less than 500 g / eq, or less than 400 g / eq are preferred. This is mainly from the perspective of cost, because epoxy resins with a low molecular weight require more limited treatment in purification during production.

[0048] Examples of types or groups of polyepoxide compounds that can be polymerized in the present invention include glycidyl ethers of polyhydric alcohols and polyhydric phenols, glycidyl esters of polycarboxylic acids, and epoxidized polyethylene unsaturated hydrocarbons, esters, ethers, and amides.

[0049] Suitable diglycidyl ether compounds can have aromatic, aliphatic, or alicyclic properties and can thus be derived from dihydric phenols and dihydric alcohols. 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, bisphenol A - based diglycidyl ethers, bisphenol F diglycidyl ethers, diglycidyl o - phthalate, diglycidyl isophthalate, and diglycidyl terephthalate, polyalkylene glycol - based diglycidyl ethers, especially polypropylene glycol diglycidyl ether, and polycarbonate diol - based glycidyl ethers. Other suitable diepoxides include diepoxides of double - unsaturated fatty acid C1 - C18 alkyl esters, butadiene diepoxide, polybutadiene diglycidyl ether, vinylcyclohexene diepoxide, and limonene diepoxide.

[0050] Further exemplary polyepoxide compounds 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.

[0051] The glycidyl esters of polycarboxylic acids useful in the present invention are derived from polycarboxylic acids containing at least two carboxylic acid groups and no other groups reactive with epoxide groups. The polycarboxylic acids can be aliphatic, alicyclic, aromatic and heterocyclic. Preferred polycarboxylic acids contain 18 or fewer carbon atoms per carboxylic acid group, and suitable examples thereof include oxalic acid, sebacic acid, adipic acid, succinic acid, pimelic acid, suberic acid, glutaric acid, dimeric and trimeric acids of unsaturated fatty acids, such as dimeric and trimeric acids of linseed fatty acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, phenylenediacetic acid, chlorendic acid, hexahydrophthalic acid, especially hexahydroorthophthalic acid (1,2-cyclohexanedicarboxylic acid), diphenic acid, naphthalic acid, polyacid terminal esters of dibasic acids and aliphatic polyols, polymers and copolymers of (meth)acrylic acid, and crotonic acid, but are not limited thereto.

[0052] Examples of highly preferred polyepoxide compounds include bisphenol-A epoxy resins (e.g., DER™ 331, DER™ 383, Epotec YD 128, etc.), bisphenol-F epoxy resins (e.g., DER™ 354, etc.), bisphenol-A / F epoxy resin blends (e.g., DER™ 353, etc.), aliphatic glycidyl ethers (e.g., DER™ 736, etc.), polypropylene glycol diglycidyl ether (e.g., DER™ 732, etc.), solid bisphenol-A epoxy resins (e.g., DER™ 661 and DER™ 664UE, etc.), solutions of bisphenol-A solid epoxy resins (e.g., DER™ 671-X75, etc.), epoxy novolac resins (e.g., DEN™ 438, etc.), brominated epoxy resins such as DER™ 542, castor oil triglycidyl ether (e.g., ERISYS™ GE-35H, etc.), polyglycerol-3-polyglycidyl ether (ERISYS™ GE-38, etc.), sorbitol glycidyl ether (e.g., ERISYS™ GE-60, etc.), and bis(2,3-epoxypropyl) cyclohexane-1,2-dicarboxylate (e.g., available as Lapox Arch-11), etc.

[0053] c) silicone acrylate oligomer Furthermore, the two-component (2K) composition of the present invention preferably contains a silicone acrylate oligomer c) in an amount of 1 to 20% by weight, preferably 2 to 10% by weight, based on the weight of the first component. In another expression of a preferred configuration of the composition of the present invention, although not intended to be mutually exclusive with the above, the composition may contain 0.5 to 15% by weight, based on the weight of the composition, of a silicone-based resin a) containing an epoxy functional group. For example, the composition of the present invention may contain 1 to 10% by weight, such as 2 to 5% by weight, of the silicone-based resin a) containing an epoxy functional group, based on the total weight of the composition.

[0054] In the present invention, the silicone acrylate oligomer is an acrylate polymer having a Si—O bond as the main chain structure. The silicone acrylate oligomer preferably has two or more polymerizable functional groups, and specifically, may contain one or more of a bifunctional oligomer, a trifunctional oligomer, a tetrafunctional oligomer, and a hexafunctional oligomer. Most preferably, it is a silicone acrylate oligomer having an average of two polymerizable functional groups. The silicone acrylate oligomer can be formed by reacting a silane compound (for example, polyester dimethyl siloxane diol, polyether dimethyl siloxane diol, polycarbonate dimethyl siloxane diol, etc.) with an acrylate compound (for example, hydroxyethyl acrylate, hydroxybutyl methacrylate, etc.). Such a polyfunctional silicone acrylate oligomer is produced by reacting an acrylic monomer such as an alkyl acrylate, an alkyl (meth) acrylate, 3-methacryloxypropyltrimethoxysilane having a Si-containing functional group (MPTS), or a silicone urethane acrylate polymer or a silicone polyester acrylate polymer obtained by modifying a urethane acrylate polymer or a polyester acrylate with Si. Further, the polyfunctional silicone acrylate oligomer may be a polyfunctional oligomer containing two or more polymerizable functional groups, and specifically, may contain one or more of a bifunctional oligomer, a trifunctional oligomer, a tetrafunctional oligomer, and a hexafunctional oligomer. The average weight average molecular weight (Mw) of the polyfunctional silicone acrylate oligomer is 500 to 20,000, specifically 500 to 30,000, 1000 to 20,000, and most preferably 2000 to 10,000.

[0055] c) Hardener 1 The hardener d) is necessarily composed of at least one compound having at least two epoxy-reactive groups per molecule, and the hardener is characterized by containing at least one alkoxy-containing amino-functional silicone resin. The epoxy-reactive group is a group capable of reacting with an epoxy group. The alkoxy-containing amino-functional silicone resin should be characterized by at least one of the following: i) the amine hydrogen equivalent is 80 or 100 to 1500 g / eq, preferably 150 to 700 g / eq, for example 200 to 500 g / eq, and ii) the weight average molecular weight (Mw) measured by gel permeation chromatography is 150 to 10000 g / mol, preferably 150 to 8,000 g / mol, for example 150 to 5,000 g / mol.

[0056] In an important embodiment of the present invention, the hardener c) has at least two amine hydrogen atoms per molecule, the amine hydrogen equivalent is 100 to 1500 g / eq, and the total alkoxy content (AC) based on the number of moles of silicon is 10 to 40 mol% of at least one alkoxy-containing amino-functional silicone resin (C 1 ), or consists of the same, and the resin (C 1 ) contains 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) [wherein each R is independently a C1-C 18 alkyl group, a C6-C 18 aryl group, or a group of the formula -R 2 NHR 3 or -R 2 NHR 2 NHR3 An amino-functional hydrocarbon group having (each R 2 is independently C2-C 20 is an alkylene group, and R 3 is a C1-C6 alkyl group) and is selected from a, b, c, and d represent the molar fractions of each unit (i)-(iv) such that a + b + c + d = 1. w, x, y, and z represent the molar fractions of the 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.

[0057] In a preferred embodiment, each R of C 1 is independently a C1-C 12 alkyl group, a C6-C 18 aryl group, or a formula -R 2 NHR 3 or -R 2 NHR 2 NHR 3 amino-functional hydrocarbon group having (each R 2 is independently a C2-C 12 alkylene group, and R 3 is a C1-C4 alkyl group) and is selected from

[0058] In a particularly preferred embodiment, each R of C1 is independently a C1-C6 alkyl group, a C6-C 18 aryl group, or a formula -R 1 NHR 2 or -R 1 NHR 1 NHR 2 amino-functional hydrocarbon group having (each R 1 is independently a C2-C8 alkylene group, and R 2 is a C1-C2 alkyl group) and is selected from. An amino-functional silicone resin having both a methyl group and a phenyl group in R (C 1 ) can be said to be determinatively preferred.

[0059] As described above, the amino-functional silicone resin formulated above (C1 ) The subscripts a, b, c, and d therein represent the molar fractions of each unit, and a + b + c + d = 1. These molar fractions need to satisfy the following conditions: i) a is a value from 0 to 0.40, preferably from 0 to 0.20, for example, from 0 to 0.10; ii) b is a value of 0.15 or more, preferably from 0.15 to 0.8, for example, from 0.15 to 0.6; iii) c satisfies the condition 0 < c < 0.85, preferably 0 < c < 0.80; and iv) d is a value from 0 to 0.20, preferably from 0 to 0.10, for example, from 0 to 0.05.

[0060] One skilled in the art will recognize that the total alkoxy content (AC) of the alkoxy-containing amino-functional silicone resin (C 1 ) is represented by the sum of (wa) + (xb) + (yc) + (zd). Desirably, the total alkoxy content should be in the range of 10 to 30 mol% based on the number of moles of silicon in the resin, preferably in the range of 10 to 25 mol% or 10 to 20 mol% based on that criterion.

[0061] There is no intention to limit the method for producing the alkoxy-containing amino-functional silicone resin (C 1 ) defined above. However, the disclosure of US2012 / 0251729 (Horstman et al.) is useful for an exemplary synthesis process.

[0062] While not intended to limit the present invention, examples of alkoxy-containing amino-functional silicone resins useful as hardener c) or in hardener c) also include: γ-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylsilsesquioxane, γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, benzylaminosilane, bis-(γ-triethoxysilylpropyl)amine, bis-(γ-trimethoxysilylpropyl)amine, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, and N-ethyl-3-trimethoxysilylmethylpropanamine.

[0063] Also, the following commercially available 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, and HP2000 available from Wacker Chemie.

[0064] Hardener c) preferably consists of or consists essentially of the alkoxy-containing amino-functional silicone, but the presence of other hardeners in an amount of up to 10 mol% based on the total number of moles of the alkoxy-containing amino-functional silicone is not excluded by the present invention. Auxiliary hardeners may particularly include mercapto compounds having at least two mercapto groups reactive with epoxy groups or at least one polyamine compound having no alkoxy functional groups.

[0065] When formulating a hardening composition, as for the whole composition, it is preferable that the molar ratio of the epoxide-reactive group to the epoxide group is 1.5:1 to 1:1.5, for example, 1.1:1 to 1:1.1. In particular, a molar ratio of 1:1 of the epoxide-reactive group to the epoxide group is included within these ranges and represents a very preferable molar ratio by itself.

[0066] e) Aminoalkoxysilane The aminoalkoxysilane used in the preferred embodiment has the general formula (I). TIFF2025521345000001.tif26150Wherein, R 1 is hydrogen, and R 2 and R 3 are the same or different and are independently selected from linear or branched, substituted or unsubstituted C1-C20 alkyl groups or C6-C18 aryl groups, preferably C1-C8 alkyl groups, more preferably methyl, ethyl or propyl groups, and these may be interrupted by at least one heteroatom, R 4 is selected from linear or branched, substituted or unsubstituted C1-C20 alkylene groups, preferably C1-C8 alkylene groups, more preferably methylene group, ethylene group, 1,3-propylene group, 2-methyl-1,3-propylene group, or 1,4-butylene group, most preferably methylene group or 1,3-propylene group, and these may be interrupted by at least one heteroatom, n is 0, 1, 2 or 3, preferably 3.

[0067] Examples of aminoalkoxysilanes include, but are not limited to, aminoalkylene alkoxysilanes (e.g., N-cyclohexylaminomethylmethyldiethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-phenylaminomethyltrimethoxysilane, N-cyclohexyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, vinylbenzylaminoethylaminopropyltrimethoxysilane, aminoethylaminopropyltrimethoxysilane (e.g., Dow Corning Z-6121 Silane from Dow Corning), aminoethylaminopropylsilane triol homopolymer (e.g., Dow Corning Z-6137 Silane from Dow Corning), bis(3-triethoxysilylpropyl)amine, bis(3-trimethoxysilylpropyl)amine, oligoaminosilane (e.g., Dynasylan 1133 from Evonik), aminosilane compositions (e.g., Dynasylan 1204, Dynasylan AMEO-T, Dynasylan SIVO 210, Dynasylan DAMO-M, Dynasylan DAMO-T from Evonik), 3-aminopropylmethyldiethoxysilane, 3-aminopropylmethyldiethoxysilane preparation (e.g., Dynasylan 1506 from Evonik), 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, VOC-free (i.e., volatile organic compound-free) aqueous siloxanes (e.g., Dynasylan HYDROSIL 1151, Dynasylan HYDROSIL 2627, Dynasylan HYDROSIL 2909, Dynasylan HYDROSIL 2929, Dynasylan HYDROSIL2776), triaminofunctional propyltrimethoxysilane (e.g., Dynasylan® TRIAMO from Evonik), oligosiloxane (e.g., Dynasylan® 1146 from Evonik), N-(n-butyl)-3-aminopropyltrimethoxysilane, cationic benzylamino-functional silane hydrochloride (e.g., Dynasylan® 1161 from Evonik), 2-aminoethyl-3-aminopropylmethyldimethoxysilane, 2-aminoethyl-3-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, modified aminoorganosilane (e.g., Silquest® A-1108 from Momentive Performance Materials), γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, modified aminoorganosilane (e.g., Silquest® A-1126 or A-1128 from Momentive Performance Materials), triaminofunctional silane (e.g., Silquest® A-1130 from Momentive Performance Materials), bis-(γ-trimethoxysilylpropyl)amine, polyazamidosilane (e.g., Silquest® A-1387 from Momentive Performance Materials), δ-aminoneohexyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, δ-aminoneohexylmethyldimethoxysilane, and N-phenyl-γ-aminopropyltrimethoxysilane.

[0068] Other amino-functionalized silanes or amino-functionalized siloxanes useful for the formation of amine-modified epoxy resins include materials available from the Sivento division of Degussa, for example, amino-functional silane compositions (referred to as DYNASYLAN® 1126), oligomeric diamino silane-based (referred to as DYNASYLAN® 1146), N-vinylbenzyl-N'-aminoethyl-e-aminopropyl polysiloxane (DYNASYLAN® 1175), N-(n-butyl)-3-aminopropyltrimethoxysilane (DYNASYLAN® 1189), amino-functional silane compositions (referred to as DYNASYLAN® 1204), N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane (DYNASYLAN® 1411), 3-aminopropylmethyldiethoxysilane (DYNASYLAN® 1505), 3-aminopropylmethyldiethoxysilane (DYNASYLAN® 1506), 3-aminopropyltriethoxysilane (DYNASYLAN® AMEO), amino silane composition (referred to as DYNASYLAN® AMEO-T), 3-aminopropyltrimethoxysilane (DYNASYLAN® AMMO), N-2-aminoethyl-3-aminopropyltrimethoxysilane (DYNASYLAN® DAMO), N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (DYNASYLAN® DAMO-T), and triamino-functional propyltrimethoxysilane (referred to as DYNASYLAN® TRIAMO). Aminoolkoxysilanes selected from 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, aminoethylaminopropyltrimethoxysilane, aminoethylaminopropyltriethoxysilane and / or their oligomers or combinations thereof are most preferred, and more preferably, the aminoolkoxysilane is 3-aminopropyltriethoxysilane.

[0069] (Additives and Auxiliary Components) The composition obtained in the present invention may generally further contain auxiliaries and additives that can impart improved properties to these compositions. For example, the auxiliaries and additives may impart one or more of improved elastic properties, improved elastic recovery, longer processing time, faster curing time, and lower residual tack. Such auxiliaries and additives (which may be included independently of each other in one or both components of a two-component (2K) composition) include plasticizers, stabilizers including UV stabilizers, antioxidants, reinforcing agents, fillers, reactive diluents, desiccants, adhesion promoters, bactericides, flame retardants, rheology aids, coloring pigments or coloring pastes, and / or optionally small amounts of non-reactive diluents.

[0070] For completeness, it should be noted that auxiliary materials and additives generally containing epoxy-reactive groups are mixed into the curing agent component of a two-component (2K) composition. Materials containing epoxy groups, or materials that react with the curing agent, are usually incorporated into the epoxy-containing component of a two-component (2K) composition. Non-reactive materials can be incorporated into either or both of Component A and Component B.

[0071] For the purposes of the present invention, a "plasticizer" is a substance that reduces the viscosity of a composition and thereby improves its processability. In the present specification, the plasticizer can constitute up to 10% by weight or up to 5% by weight, based on the total weight of the composition, and preferably is polydimethylsiloxane (PDMS); diurethane; ethers of monofunctional, linear or branched C4-C16 alcohols (e.g., Cetiol OE (available from Cognis Deutschland GmbH, Düsseldorf)); esters of abietic acid, butyric acid, thiobutyric acid, acetic acid, propionic acid esters and citric acid esters; esters based on nitrocellulose and polyvinyl acetate; fatty acid esters; dicarboxylic acid esters; esters of fatty acids having an OH group or epoxidized; glycolic acid esters; benzoic acid esters; phosphate esters; sulfonic acid esters; trimellitic acid esters; epoxidized plasticizers; polyether plasticizers such as end-capped polyethylene or polypropylene glycol; polystyrene; hydrocarbon plasticizers; chlorinated paraffins; and mixtures thereof. In principle, phthalate esters can be used as plasticizers, but it should be noted that they are not preferred because of the potential toxicity. The plasticizer preferably contains or consists of one or more polydimethylsiloxanes (PDMS).

[0072] For the purposes of the present invention, a "stabilizer" is understood to be an antioxidant, a UV stabilizer or a hydrolysis stabilizer. Here, the stabilizer can in total constitute up to 10% by weight or up to 5% by weight, based on the total weight of the composition. Standard commercially available examples of stabilizers suitable for use here include hindered phenols, thioethers, benzotriazoles, benzophenones, benzoates, cyanoacrylates, acrylates, amines of the hindered amine light stabilizer (HALS) type, phosphorus, sulfur, and mixtures thereof.

[0073] The composition of the present invention may optionally contain reinforcing rubber in the form of core-shell particles dispersed in an epoxy resin matrix. The term "core-shell rubber" or CSR is used to denote, in accordance with the standard meaning in the art, a rubber particle core formed by a polymer containing an elastomer or rubbery polymer as a main component, and a shell layer formed by a polymer graft-polymerized onto the core. The shell layer partially or completely covers the surface of the rubber particle core in the graft polymerization method. By weight, the core should constitute at least 50% by weight of the core-shell rubber particles. · The polymer material of the core should have a glass transition temperature (Tg) of 0 °C or lower, preferably -20 °C or lower, more preferably -40 °C or lower, and even more preferably -60 °C or lower. The polymer of the shell is a non-elastic, thermoplastic or thermosetting polymer having a glass transition temperature (Tg) of room temperature or higher, preferably 30 °C or higher, more preferably 50 °C or higher. · Without intending to limit the present invention, the core can be composed of a diene homopolymer, such as a homopolymer of butadiene or isoprene; a diene copolymer, such as a copolymer of butadiene or isoprene and one or more ethylenically unsaturated monomers (such as vinyl aromatic monomers, (meth)acrylonitrile or (meth)acrylate); a polymer based on (meth)acrylate monomers, such as polybutyl acrylate; and polysiloxane elastomers such as polydimethylsiloxane and crosslinked polydimethylsiloxane. · Similarly, although not intended to limit the present invention, the shell may be composed of a polymer or copolymer of one or more monomers selected from (meth)acrylates such as methyl methacrylate; vinyl aromatic monomers such as styrene; vinyl cyanides such as acrylonitrile; unsaturated acids and anhydrides such as acrylic acid; and (meth)acrylamide. The polymer or copolymer used for the shell may have acid groups that are ionically crosslinked by the formation of metal carboxylates, particularly the formation of salts of divalent metal cations. The shell polymer or copolymer may be covalently crosslinked by a monomer having two or more double bonds per molecule. · The core-shell rubber particles contained preferably have an average particle diameter (d50) of 10 nm to 300 nm, for example 50 nm to 200 nm. The particle diameter refers to the diameter or the maximum dimension of the particles in the particle distribution and is measured by dynamic light scattering.

[0074] This application does not exclude the presence of two types of core-shell rubber (CSR) particles having different particle sizes in the composition in order to provide a balance of the main properties of the resulting cured product, including shear strength, peel strength, and resin fracture toughness. In this embodiment, the small particles (the first CSR type) contained have an average particle diameter of 10 to 100 nm, and the large particles (the second CSR type) contained have an average particle diameter of 120 to 300 nm, for example 150 to 300 nm. The core-shell rubber particles of the small particles should usually be used in a larger amount than the large particles on a weight basis. For example, the weight ratio of the CSR particles of the small particles to the CSR particles of the large particles can be 3:1 to 5:1. · The core-shell rubber can be selected from commercially available products, examples of which include Paraloid EXL2650A, EXL2655, EXL2691A manufactured by Dow Chemical, Kane Ace (registered trademark) MX series manufactured by Kaneka, particularly MX120, MX125, MX130, MX136, MX551, MX553, and METABLEN SX-006 manufactured by Mitsubishi Rayon. · The core-shell rubber particles should be included in the composition in an amount of 0 to 10% by weight, for example 0 to 5% by weight, based on the total weight of the composition.

[0075] As described above, the composition of the present invention can further contain a filler. Suitable ones here are, for example, chalk, lime powder, precipitated and / or pyrogenic silica, zeolite, bentonite, magnesium carbonate, diatomaceous earth, alumina, clay, talc, titanium oxide, iron oxide, zinc oxide, sand, quartz, flint, mica, glass powder, and other crushed mineral substances. Organic fillers, especially carbon black, graphite, wood fiber, wood flour, sawdust, cellulose, cotton, pulp, cotton, wood chips, chopped straw, rice husks, crushed walnut shells, and other chopped fibers can also be used. Short fibers such as glass fibers, glass filaments, polyacrylonitrile, carbon fibers, Kevlar fibers, or polyethylene fibers can also be added. Aluminum powder is also suitable as a filler in the same way.

[0076] The pyrogenic and / or precipitated silica preferably has a BET specific surface area of 10 to 90 m 2 / g. When these are used, the viscosity of the composition of the present invention does not further increase and contributes to the strengthening of the cured composition.

[0077] Similarly, it is also conceivable to use pyrogenic and / or precipitated silica having a higher BET specific surface area, preferably 100 to 250 m 2 / g, especially 110 to 170 m 2 / g as a filler. Due to the large BET specific surface area, the effect of reducing the weight ratio of silica and strengthening the cured composition can be obtained.

[0078] As fillers, hollow spheres having a mineral shell or a plastic shell are also suitable. These are, for example, hollow glass spheres commercially available under the name Glass Bubbles®. Plastic-based hollow spheres such as Expancel® and Dualite® can also be used, and these are described in EP0520426B1. These are composed of inorganic or organic substances, and each diameter is 1 mm or less, preferably 500 μm or less.

[0079] Fillers that impart thixotropic properties to the composition may be preferred for many applications. Such fillers are also called rheology aids and are, for example, hydrogenated castor oil, fatty acid amides, or swelling plastics such as PVC.

[0080] The total amount of filler present in the composition of the present invention is preferably 0 to 70% by weight, more preferably 0 to 60% by weight, based on the total weight of the composition. The desired viscosity of the curable composition is usually determined by the total amount of filler added, and in order to be easily extrudable from a suitable dispensing device such as a tube, the curable composition should have a viscosity of 3000 to 150,000 mPas, preferably 40,000 to 80,000 mPas, or 50,000 to 60,000 mPas.

[0081] It should be noted that a compound having metal chelate properties can be used in the composition of the present invention to enhance the adhesion of the cured adhesive to the substrate surface. Furthermore, a suitable one for use as an adhesion promoter is an acetoacetate-functionalized modified resin sold by King Industries under the trade name K-FLEX XM-B301.

[0082] Examples of suitable pigments are titanium dioxide, iron oxide or carbon black.

[0083] To further extend the shelf life, it is often recommended to use a desiccant to further stabilize the moisture penetration of the composition of the present invention. Also, depending on the particular application, it may be necessary to lower the viscosity of the adhesive or sealant composition of the present invention by using a reactive diluent. The total amount of reactive diluent present is usually at most 15% by weight, preferably 0.5 to 5% by weight, based on the total weight of the composition. Preferably, silanol is present as the diluent.

[0084] When the viscosity of the composition can be effectively optimized, the presence of a solvent and a non-reactive diluent in the composition of the present invention is not excluded. For example, for illustrative purposes only, the composition may include 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-butyryl 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 Solvesso® products (available from Exxon), alkylphenols such as tert-butylphenol, nonylphenol, dodecylphenol, and 8,11,14-pentadecatrienylphenol, styrenated phenol, bisphenol, aromatic hydrocarbon resins, especially those containing phenolic groups such as ethoxylated or propoxylated phenols, adipic acid esters, sebacic acid esters, phthalic acid esters, benzoic acid esters, organic phosphoric acid esters or sulfonic acid esters, and sulfonamides, and may contain one or more of them.

[0085] Separately from the above, it is preferable that the solvent and the non-reactive diluent together constitute less than 10% by weight, particularly less than 5% by weight or less than 2% by weight, based on the total weight of the composition.

[0086] To achieve perfection, the composition of the present invention may contain one or more monoamines such as hexylamine and benzylamine.

[0087] To enhance the physical properties, the two-component (2K) composition preferably further contains a trialkoxy-functional silicone prepolymer different from resin a). This prepolymer is condensation-curable and can assist in crosslinking. Preferably, the two-component (2K) composition further contains a trimethoxysilicone prepolymer. Examples include those commercially available under the name Silmer TMS such as Silmer TMS Di-400. In a preferred embodiment, the trialkoxy-functional silicone prepolymer is present in an amount of 0.1 to 5% by weight, more preferably 0.5 to 3% by weight, based on the total weight of the composition.

[0088] Furthermore, a lubricating particle additive can be added, preferably to component (A). Examples of suitable lubricating particle additives are glycerides, waxes, and other polymers. Specifically, polytetrafluoroethylene, synthetic linear hydrocarbons, polyethylene, polypropylene, and combinations thereof are suitable lubricating particle additives. Most preferred is polytetrafluoroethylene, especially micronized polytetrafluoroethylene. In a preferred embodiment, the lubricating particle additive is present in an amount of 0.1 to 5% by weight, more preferably 0.5 to 3% by weight, based on the total weight of the composition.

[0089] The two-component (2K) composition of the preferred embodiment is (A) a) at least one silicone-based resin containing an epoxy functional group, and b) optionally, at least one epoxy resin that is not a silicone-based resin, c) optionally, at least one silicone acrylate oligomer comprising a first component, (B) a curing agent comprising 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 comprising a second component, the composition does not contain a catalyst, 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, preferably, component (A) contains a trialkoxy-functional silicone prepolymer, a lubricating particle additive and / or a diluent.

[0090] In a more preferred embodiment, the two-component (2K) composition A) Based on the weight of the first component, 5 to 60% by weight of said at least one silicone epoxy resin a); Optionally, 1 to 50% by weight of said at least one epoxy resin b); Optionally, 1 to 20% by weight of said at least one silicone acrylate oligomer c); comprising a first component, B) Based on the weight of the first component, 50 to 85% by weight, preferably 60 to 80% by weight of said curing agent d), 15 to 50% by weight, preferably 20 to 40% by weight of said at least one aminoalkoxysilane e), comprising a second component, the composition does not contain a catalyst, 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, in component (A), based on the total amount of the composition, · 0.5 to 5% by weight of at least one diluent, preferably silanol, · 0.1 to 5% by weight of at least one trialkoxy-functional silicone prepolymer, preferably trimethoxysilicone prepolymer, and / or, · 0.1 to 5% by weight of at least one lubricating particle additive, preferably polytetrafluoroethylene.

[0091] (Method and Application) In the case of a two-component (2K) curable composition, the reactive components are mixed in a manner that induces curing by bringing them together. The reactive compounds need to be mixed under sufficient shear force to obtain a homogeneous mixture. This is considered achievable without special conditions or special equipment. Suitable mixing devices include static mixing devices, magnetic stir bar devices, wire whisks, augers, batch mixers, planetary mixers, CW Brabender or Banbury (registered trademark) style mixers, and high-shear mixers such as blade-style blenders and rotating impellers.

[0092] In the case of small-scale liner applications where generally a volume of less than 2 liters is used, a preferred package for a two-component (2K) composition is a parallel double cartridge or coaxial cartridge in which two tubular chambers are arranged side by side or one inside the other and sealed with pistons. Driving these pistons allows the components to be extruded from the cartridge, advantageously through a static or dynamic mixer attached in close proximity. For large-volume applications, it may be advantageous to store the two components of the composition in drums or pallets. In this case, the two components are particularly extruded by a hydraulic press via a follower plate and supplied to a mixing device through a pipeline, ensuring a fine and uniform mixing of the hardener and binder components. In any case, in any package, it is important to place the binder component in an airtight and moisture-free sealed state, whereby both components can be stored for a long period, ideally for 12 months or more.

[0093] The two-component (2K) curable composition should generally be prepared such that the initial viscosity measured immediately after mixing, for example within 2 minutes after mixing, is less than 200,000 mPa·s at 25°C, for example less than 100,000 mPa·s. Independently of, or in addition to, the viscosity characteristic, the two-component (2K) composition should be prepared such that no bubbles are generated during mixing and subsequent curing. Further, the two-component (2K) composition should be further prepared to exhibit at least one, desirably at least two, most desirably all of the following characteristics: i) a long pot life, typically at least 25 minutes, generally at least 60 minutes or 120 minutes, where the pot life should be understood as the time until the viscosity of the mixture rises to 50,000 mPa·s or more at 20°C; ii) the maximum exothermic temperature is 120°C or less, preferably 100°C or less, more preferably 80°C or less; and iii) after curing, the Shore A hardness after storage at room temperature and 50% relative humidity for 7 days is at least 50, preferably 60 or more, more preferably at least 70 or more.

[0094] Curing of the composition of the present invention can be carried out at a temperature in the range of -10°C to 120°C, preferably 0°C to 70°C, particularly 20°C to 60°C. The appropriate temperature depends on the specific compounds present and the desired curing rate and can be determined by a skilled person in each case using simple preliminary tests as necessary. Of course, curing at a temperature of 10°C to 35°C or 20°C to 30°C is particularly advantageous since it is not necessary to significantly heat or cool the mixture from the normal ambient temperature. However, where applicable, the temperature of the mixture formed from each component of the two-component (2K) composition can be made higher than the mixing temperature and / or the application temperature using conventional means including microwave induction.

[0095] The curable composition according to the present invention is particularly useful as a coating for varnishes, inks, binders for fibers and / or particles, glass coatings, lime and / or cement-bonded plasters, gypsum-containing surfaces, fiber cement building materials and mineral building materials such as concrete; coatings and sealants for wood and wood-based materials such as chipboard, fiberboard and paper; coatings for metal surfaces, coatings for asphalt and bitumen-containing pavements, coatings and sealants for various plastic surfaces, and coatings for leather and fibers.

[0096] In a particularly preferred embodiment, the composition of the present invention is applied to a substrate to form a coating having high adhesiveness and excellent abrasion resistance. The adhesion operation is often carried out at room temperature, and effective abrasion resistance can be obtained after curing. Further, when adhering to the surface of a mechanical structure or a floor or pavement, the coating composition provides a corrosion prevention effect on the surface and can prevent the surface from coming into contact with compounds that adversely affect the operation or efficiency of a specific structure.

[0097] In each of the above applications, the composition can be applied by conventional coating methods, such as brush coating, for example, roll coating using a four-roll roll coater when the composition is solvent-free and a two-roll coater when the composition contains a solvent, doctor blade coating, printing methods, and spray methods including, but not limited to, air atomizing spray, air-assisted spray, airless spray, and high volume low pressure spray. For coating and adhesive applications, the composition is preferably applied with a wet film thickness of 10 to 500 μm. Applying a thinner layer within this range is more economical and less likely to result in a thick cured area that may require sanding in the case of coating applications. However, when applying a thinner coating or layer, sufficient control must be exercised to avoid the formation of a discontinuous cured film. Note that in order to achieve perfection, it is not excluded to prepare an epoxy adhesive in the form of a "film adhesive". A prepolymer mixture of an epoxy resin, a curing agent, and other desired components is applied as a coating onto a polymer film substrate, wound up, and stored at a low temperature sufficient to suppress the chemical reaction between the components. When needed, the film adhesive is taken out of the low-temperature environment and applied to a metal or composite member, the backing is peeled off to complete the assembly, and it is cured in an oven or an autoclave.

[0098] The following examples illustrate the present invention and do not limit the scope of the present invention in any way.

Example

[0099] In the examples, the following commercially available products were used.

[0100] TIFF2025521345000002.tif77153

[0101] In the examples, the following tests were conducted.

[0102] <Open time> The open time was measured at room temperature and 50% humidity as the maximum time after applying the composition to the substrate during which an adhesive bond can be formed. For example, if the composition is applied to the first piece of cardboard, i) after 5 seconds, another piece of cardboard can still be applied and adhered to the first piece of cardboard, but ii) after 6 seconds, the composition has become too hard to form an adhesion between the two pieces of cardboard, the open time is 5 seconds.

[0103] <Film formation time> The film formation time was measured by applying a coating with a wet layer thickness of 75 μm at 23 °C and a relative humidity of 50%. After touching the surface with a dry and clean finger, the point at which no fingerprints were observed was regarded as film formation. The film formation time was measured using a timing device.

[0104] <Gloss at 60°> A gloss meter is a device used to measure the specular reflection (gloss) of a surface. Gloss is determined by projecting a light beam onto the surface at a certain intensity and angle and measuring the amount of light reflected at an equal but opposite angle.

[0105] <Pull-off adhesion to GBMS> Measured by applying to a blasted panel with a thickness of 250 microns under the conditions of 23°C and 50% relative humidity. The coating was allowed to cure completely for 7 days. This test was measured in accordance with ASTM D4541.

[0106] <QUV data for 1000 hours> Measured by applying to a blasted panel with a thickness of 250 microns under the conditions of 23°C and 50% relative humidity. The coating was allowed to cure completely for 7 days. This test was measured in accordance with ASTM G154. The following conditions were used: Lamp: UVB-313, Standard irradiance: 0.71 W / (m2·nm), Approximate wavelength: 310 nm, Exposure cycle: UV for 4 hours at a black panel temperature of 60 (±3)°C; Condensation for 4 hours at a black panel temperature of 50 (±3)°C, Total time: Exposure for 1000 hours.

[0107] <Examples 1 to 9> The compositions of the examples are shown in Table 1, and their performance was evaluated using different resins, curing agents, fillers, and additives. Also, various properties of these coating compositions are described in Table 1. After mixing the two components, the film-forming time and open time of the resulting composition were evaluated. All these preparations were cured at room temperature, and the final properties such as gloss, hardness, and pull-off adhesion strength were tested after 7 days of complete curing. The thickness of the coating was maintained at approximately 240 - 260 microns.

[0108] When using a combination of hardeners 1 and 2 without a catalyst, the film formation time and open time are within a preferable range. At the same time, the gloss, hardness, and pull-off adhesion are within a desirable range, having sufficient gloss and pull-off adhesion while having sufficient hardness but not being brittle. Without hardener 1, the curing is too fast and the coating becomes brittle. Without hardener 2, the gloss, hardness, and adhesion are too low. By adding an epoxy resin and a silicone acrylate oligomer, the results can be enhanced to more advantageous properties.

[0109]

Table 1

Claims

1. (A)a) At least one silicone-based resin having an epoxy functional group, and, b) Optionally, at least one epoxy resin that is not a silicone-based resin; c) Optionally, at least one silicone acrylate oligomer; A first component comprising, (B)d) A curing agent comprising at least one compound having at least two epoxy-reactive groups per molecule, characterized in that it comprises at least one alkoxy-containing amino-functional silicone resin, e) At least one aminoalkoxysilane A second component comprising, Without a catalyst, 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, A two-component (2K) composition.

2. A) Based on the weight of the first component, 5 to 60% by weight of the at least one silicone epoxy resin a); Optionally, 1 to 50% by weight of the at least one epoxy resin b); Optionally, 1 to 20% by weight of the at least one silicone acrylate oligomer c); A first component comprising, B) Based on the weight of the first component, 50 to 85% by weight, preferably 60 to 80% by weight of the curing agent d), 15 to 50% by weight, preferably 20 to 40% by weight of the at least one aminoalkoxysilane e), A second component comprising, preferably consisting of, Including, without a catalyst, 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, The two-component composition according to claim 1.

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

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

5. The molar ratio of the epoxy-reactive groups provided in Component B to the 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. The two-component composition according to any one of Claims 1 to 4.

6. The molar ratio of the silane groups in Component B to the carbon double bonds, preferably (meth)acrylate groups, is 1.5:1 to 1:1.5, preferably 1.1:1 to 1:1.1, more preferably 1:

1. The two-component composition according to any one of Claims 1 to 5.

7. The curing agent c) is 90 to 100 mol% of the alkoxy-containing amino-functional silicone resin; 0 to 10 mol% of a second epoxy-reactive compound The two-component composition according to any one of Claims 1 to 6.

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

9. The curing agent c) contains at least one alkoxy-containing amino-functional silicone resin (C1) having at least two amine hydrogen atoms per molecule, an amine hydrogen equivalent of 100 to 1500 g / eq, and a total alkoxy content (AC) based on the number of moles of silicon of 10 to 40 mol%. The resin (C1) has the following units: (R3Si(OR')wO(1 - w) / 2)a (i); (R2Si(OR')xO(2 - x) / 2)b (ii); (RSi(OR')yO(3 - y) / 2)c (iii); and, (Si(OR')zO(4 - z / 2))d (iv) [wherein each R is independently selected from a C1 - C18 alkyl group, a C6 - C18 aryl group, or an amino-functional hydrocarbon group having the formula -R2NHR3 or -R2NHR2NHR3 (each R2 is independently a C2 - C20 alkylene group and R3 is a C1 - C6 alkyl group), a, b, c, and d represent the molar fractions of each unit (i) to (iv) such that a + b + c + d = 1, w, x, y, and z represent the molar fractions of the alkoxy groups such that 0 ≤ w < 1, 0 ≤ x < 2, 0 ≤ y < 3, and 0 ≤ z < 4] The two-component composition according to any one of Claims 1 to 8.

10. In the resin (C1), each R is independently selected from a C1-C6 alkyl group, a C6-C18 aryl group, or an amino group-containing hydrocarbon group having the formula -R1NHR2 or -R1NHR1NHR2 (each R1 is independently a C2-C8 alkylene group and R2 is a C1-C2 alkyl group), the two-component composition according to claim 9.

11. The amino-functional silicone resin (C1) has both a methyl group and a phenyl group in R, the two-component composition according to claim 9 or claim 10.

12. The value of a in the amino-functional silicone resin (C1) is 0 to 0.10, the value of b is 0.15 to 0.6, c satisfies the condition 0 < c < 0.85, and the value of d is 0 to 0.05, the two-component composition according to any one of claims 9 to 11.

13. The aminoalkoxysilane e) has the general formula (I): [wherein, R １ is hydrogen, R ２ and R ３ are the same or different and independently of one another are selected from linear or branched, substituted or unsubstituted C1-C20 alkyl groups or C6-C18 aryl groups, preferably C1-C8 alkyl groups, more preferably methyl, ethyl or propyl groups, which may be interrupted by at least one heteroatom, R ４ is selected from linear or branched, substituted or unsubstituted C1-C20 alkylene groups, preferably C1-C8 alkylene groups, more preferably methylene group, ethylene group, 1,3-propylene group, 2-methyl-1,3-propylene group, or 1,4-butylene group, most preferably methylene group or 1,3-propylene group, which may be interrupted by at least one heteroatom, n is 0, 1, 2 or 3, preferably 3] The two-component composition according to any one of claims 1 to 12.

14. A cured product obtained from the two-component (2K) composition according to any one of claims 1 to 13.

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

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