One-component composition based on epoxy resin

Abstract

The present disclosure relates to a one-component (1K) curable composition comprising, based on the weight of the composition: 50 to 90 wt% of a) at least one epoxy resin which has been modified with a hydrophobic elastomer, the modified epoxy resin having an epoxy equivalent weight of 200 to 1000 g / eq; up to 15 wt% of b) at least one epoxy resin which is different from the modified resin of component a); c) at least one compound providing at least two amine hydrogens reactive towards epoxy groups; and 0.01 to 5 wt% of d) at least one accelerator, wherein the composition is characterized by a molar ratio of epoxy groups to epoxy group reactive groups of 0.5:1 to 1.4:1.

Description

Technical Field

[0001] This invention relates to one-component (1K) curable compositions based on epoxy resins. More specifically, this invention relates to one-component (1K) curable compositions based on elastomer-modified epoxy resins, the cured products of which exhibit effective corrosion resistance and tensile properties. Background Technology

[0002] Epoxy resins have found a wide range of applications, primarily based on the fact that specific choices of resin and crosslinking agent (or curing agent) allow the properties of cured epoxy resins to be tailored to achieve specific performance characteristics.

[0003] This versatility is well-established, and properly cured epoxy resins also possess a variety of other positive properties, including, in particular: excellent chemical resistance, especially to alkaline environments; high tensile and compressive strength; high fatigue strength; low curing shrinkage; and electrical insulation properties and their retention during aging or environmental exposure.

[0004] However, the inventors have recognized that the utility of epoxy resins is somewhat limited in applications where the resin must bond to a metal substrate that has been or will be exposed to industrial manufacturing-related contaminants, particularly oils and greases. Furthermore, the utility of epoxy resins as structural adhesives or sealants is somewhat limited where the components to be adhered or sealed are joined or seamed and / or necessarily subject to bending motion: the requirement for flexibility in adhesives or sealants for such components has historically hindered the use of epoxy resins, which are typically rigid and non-flexible after curing.

[0005] Those skilled in the art will recognize that the aforementioned types of metal substrates and components are particularly common in vehicle manufacturing and repair. Furthermore, the techniques associated with epoxy resins used in this field are considered limited and flawed.

[0006] U.S. Patent No. 5,218,063 A (Kimball) relates to an adhesive composition for use in adhering automotive parts, the composition comprising: (a) a reaction product of at least one epoxy resin and an amine-terminated oligomer; (b) an epoxy adduct of a dimer acid; and (c) a catalyst system present in an amount sufficient to induce homopolymerization of the epoxy resin, wherein the novel composition is characterized by two distinct glass transition temperatures after curing. The presence of these two phases determines the thermomechanical properties of the adhesive, particularly the peel strength at or below room temperature.

[0007] US2014 / 0113983 A1 (Czaplicki et al.) discloses a thermosetting structural adhesive material having, upon curing, an elongation at break of at least 10% and a glass transition temperature (Tg) of at least 80°C. This structural adhesive can be used in automobiles to reduce deformation of bonded joints, particularly during accidents. Furthermore, the structural adhesive material comprises: an epoxy resin; a thermoplastic modifier; a softener; an impact modifier; and a curing agent.

[0008] US 2021 / 0130663 (Koch et al.) describes a one-component epoxy adhesive for bonding substrates in automotive applications, the adhesive comprising a mixture of: a) at least one non-rubber-modified, non-phosphorus-modified epoxy resin that is liquid at 23°C; b) one or more polymers containing reactive urethane groups and / or urea groups, the polymer having a number average molecular weight of up to 35,000, at least one polyether and / or diene rubber segment having a weight of at least 1,000 atomic mass units, and end-capped isocyanate groups; c) at least one epoxy curing catalyst; d) a curing agent; and e) 3.5 to 50% by weight of epoxy resin and an epoxy-containing adduct of phosphoric acid based on the weight of the adhesive, the one-component toughened epoxy adhesive comprising no more than 2 parts by weight of plasticizer (part by weight of component B), and comprising no more than 7% by weight of core-shell rubber particles, and wherein the adhesive exhibits a curing temperature of at least 60°C. Summary of the Invention

[0009] According to a first aspect of the invention, a one-component (1K) curable composition is provided, wherein, based on the weight of the composition, the one-component (1K) curable composition comprises: 50 to 90% by weight of a) at least one epoxy resin that has been modified with a hydrophobic elastomer, wherein the epoxy equivalent weight of the modified epoxy resin is 200 to 1000 g / eq. up to 15% by weight of b) at least one epoxy resin different from component a); c) at least one compound providing at least two amine hydrogens reactive to epoxy groups; and 0.01 to 5% by weight of d) at least one accelerator, The composition is characterized in that the molar ratio of epoxy groups to epoxy reactive groups is from 0.5:1 to 1.4:1.

[0010] Ideally, based on the weight of the composition, the one-component (1K) curable composition comprises: 60 to 90% by weight, preferably 65 to 85% by weight of a) at least one epoxy resin that has been modified with a hydrophobic elastomer, wherein the epoxy equivalent weight of the modified epoxy resin is 200 to 1000 g / eq; 1 to 10% by weight, preferably 1 to 5% by weight of b) at least one modified resin different from component a); 1 to 15% by weight, preferably 1 to 10% by weight, of c) at least one compound providing at least two amine hydrogens reactive to epoxy groups; and 0.01 to 2% by weight, preferably 0.01 to 1% by weight of at least one accelerator (d). The characteristic is that the molar ratio of epoxy group to epoxy reactive group is 0.7:1 to 1.2:1, preferably 0.9:1 to 1.0:1.

[0011] In some key embodiments, based on the weight of the composition, the components a) comprise: 60 to 80% by weight of at least one dimer acid-modified epoxy resin; and The resin comprises 0 to 20% by weight of at least one elastomer-modified resin, wherein the elastomer-modified resin is selected from carboxyl-terminated poly(butadiene-acrylonitrile) (CTBN) modified epoxy resin and urethane modified epoxy resin. Each modified resin of component a) is characterized by an epoxy equivalent weight of 200 to 800 g / eq, preferably 250 to 750 g / eq. In particular, good results have been obtained when the dimer acid modified epoxy resin of component ai) or each dimer acid modified epoxy resin is characterized by an epoxy equivalent weight of 500 to 750 g / eq.

[0012] In another important embodiment that is not mutually exclusive with those described above, component d) of the composition comprises or consists of at least one accelerator selected from the group consisting of: tertiary amines; urea derivatives; thiourea derivatives; and amidines.

[0013] In particular, component d) may comprise at least one compound according to formula (I) or formula (II) or consist of at least one compound according to formula (I) or formula (II):

[0014] in: X is O or S; R a R b and R c Independently selected from C1-C 12 Alkyl, C1-C 12Hydroxyalkyl, C3-C 18 cycloalkyl, or C6-C 18 Aryl; and R d It is C6-C 18 aryl or C7-C 18 Alkyl aryl group.

[0015] Compounds of formula (I) or formula (II) have already been used (where: X is O; R is R). a R b and R c Independently selected from C1-C8 alkyl, C1-C8 hydroxyalkyl, C3-C 12 cycloalkyl or C6 aryl; and R d It is C6-C 18 aryl or C7-C 18 Alkyl arylidene groups (ALIs) demonstrated the effective curing of the composition.

[0016] In some embodiments, the composition may further comprise up to 10% by weight of core-shell rubber particles based on the total weight of the composition. Independent of or in addition to this preferred embodiment, it is desirable that the composition is characterized by a 15.5 s [response rate] at 20°C. -1 The viscosity measured by the shear rate is 100 to 500 Pa·s, preferably 200 to 500 Pa·s.

[0017] According to another aspect of the invention, a cured product obtained from a single-component (1K) composition as defined above and in the appended claims is provided. Preferably, the cured product is characterized by an elongation at break greater than 100%. The cured product may also be characterized by a tensile modulus less than 500 MPa, for example less than 200 MPa or even less than 100 MPa. Both the elongation at break and the tensile modulus are determined at room temperature using a type 5A specimen according to ISO EN 527-2.

[0018] The cured reaction product can be used as an adhesive or sealant, particularly as a flexible adhesive or sealant for shaped and joined metal parts. For example, the cured product has been demonstrated as an effective flexible adhesive or sealant for shaped and joined metal parts used in vehicle assembly and repair. The current product is particularly advantageous because it exhibits only slight deformation or no deformation after thermal expansion upon application to a metal substrate. Substrates coated with known products typically exhibit deformation after heat treatment due to the bending CTE (coefficient of thermal expansion) effect. When using the compositions of the present invention, such bending CTE effect is barely observed.

[0019] definition Unless the context clearly specifies otherwise, the singular form used in this document is "One / a kind (a / an) "and" Place The "Including plural referents."

[0020] The term "in this article" Contains (comprising / comprises / comprised of) "and" include (including / includes) "or" Contains "Synonyms, including or open-ended, and do not exclude additional undescribed members, elements, or method steps."

[0021] The term "in this article" Composed of... "Excludes any unspecified elements, components, members, or method steps. For completeness, the term '' is used." Include "covers" Composed of... ".

[0022] Words " Preferred / preferably "", expect "and" Specific / Special / Especially "The term is generally used herein to refer to embodiments of the present disclosure that may provide particular benefits in certain circumstances. However, the description of one or more preferred, preferred, desired or particular embodiments does not imply that other embodiments are unavailable, and is not intended to exclude those other embodiments from the scope of the present disclosure."

[0023] Words " Example "In this text, it is used to mean as an example, illustration, or illustration. It is described in this text as " Example No aspect or design thereof is necessarily to be interpreted as preferred or advantageous over other aspects or designs. Rather, the exemplary use of the word is intended to present the concept in a specific way.

[0024] The term "throughout this application" It is possible / possible / may "It is used in a permissible sense (i.e., it means possible), not in a mandatory sense."

[0025] The term "in this article" Multiple "is defined as two or more."

[0026] When quantities, concentrations, dimensions, and other parameters are expressed in the form of ranges, preferred ranges, upper limits, lower limits, or preferred upper and lower limits, it should be understood that any range that can be obtained by combining any upper or preferred value with any lower or preferred value is also specifically disclosed, whether or not the obtained range is explicitly mentioned in the context.

[0027] Furthermore, according to the standard interpretation, it is represented as " 0-x / 0 to xThe weight range specifically includes 0% by weight: the component or ingredient defined by the range (e.g., a) or b) in this document may be absent from the material or may be present in the material in an amount of up to x% by weight.

[0028] The molecular weights mentioned in this specification can be measured using gel permeation chromatography (GPC) with polystyrene calibration standards, as per ASTM 3536.

[0029] Where mentioned, the calculated glass transition temperature of the polymer or copolymer (“ T g The temperature can be calculated using the Fox equation: 1 / T g,聚合物 ≈ ∑ i w i / T g,i in: T g,聚合物 and T g,i These are the glass transition temperatures of the (co)polymer and the constituent monomer (i), respectively; and w i It is a component i The mass fraction. The glass transition temperatures of some homopolymers can be found in published literature.

[0030] The actual glass transition temperature (T) of the (co-)polymer g It can be based on ASTM E1640 Through dynamic mechanical analysis Standard test method for determining glass transition temperature (DMA) ( Standard Test Method for Assignment of the Glass Transition Temperature By Dynamic Mechanical Analysis(DMA) It is determined by dynamic mechanical analysis (DMA).

[0031] Unless otherwise specified, the viscosity of the materials described herein was measured using an Anton Paar viscometer (model MCR72) at the stated temperature and 50% relative humidity (RH). The viscometer is calibrated annually and inspected by the service department. Calibration is performed using known viscosities from 1 to 50,000 cps (parallel plate PP20, measured in 1 s⁻¹). -1 The shear rate (at 23°C) was measured using a standard liquid. The material according to the invention was measured using parallel plates PP20 at shear rates from 1.5 to 100 s⁻¹. -1 The different shear rates were used.

[0032] The room temperature used in this article was 23℃±2℃.

[0033] The term "in this article" Environmental conditions "This refers to the temperature and pressure of the environment in which the composition is situated, or the coating or the substrate of the coating is situated."

[0034] The term "in this article" hydrophobic "Definition defines a material or component thereof that has a high contact angle with water; the contact angle formed between the surfaces of the material or component thereof is at least 90°."

[0035] It should be understood that the term " vehicle "Should be interpreted broadly to include any device of motorized transport, such as automobiles, motorcycles, trucks, watercraft, aircraft, trailers, and off-road vehicles. The compositions disclosed herein and the cured products obtained therefrom are considered particularly suitable as adhesives or sealants for use in automobile manufacturing and repair."

[0036] The term "in this article" Equivalent (eq.) "As is usually the case in chemical notation, it refers to the relative number of reactive groups present in the reaction."

[0037] The term "in this article" Equivalent weight "" refers to the molecular weight divided by the number of relevant functional groups. Therefore, " Epoxy Measure weight "(EEW)" refers to the weight (in grams) of a resin containing one equivalent of epoxy groups. Similarly, " Amine hydrogen equivalent weight "(AHEW)" is the weight (in grams) of an organic amine containing one amine hydrogen atom.

[0038] The term "in this article" (co)polymer "Including homopolymers, copolymers, block copolymers and terpolymers."

[0039] The term "in this article" Epoxy compounds "" indicates a compound characterized by the presence of at least one cyclic ether group, i.e., a compound in which the ether oxygen atom is attached to two adjacent carbon atoms to form a cyclic structure. This term is intended to cover monoepoxides, polyepoxides (having two or more epoxy groups), and epoxy-terminated prepolymers. Monoepoxy compound "Intended to refer to an epoxy compound having one epoxy group. The term" Polyepoxides "Intended to refer to epoxy compounds having at least two epoxy groups. The term ' Diepoxide "Intended to refer to epoxy compounds with two epoxy groups."

[0040] Epoxides can be unsubstituted or inertly substituted. Exemplary inert substituents include chlorine, bromine, fluorine, and phenyl.

[0041] The term "in this article" Primary amino"" refers to the NH2 group attached to an organic group, and " secondary amino "" refers to an NH group attached to two organic groups, which can also be part of a ring. In use, the term "" Amine Hydrogen "" refers to the hydrogen atoms of primary and secondary amino groups.

[0042] This article mentions " Amine value The amine value can be determined by titrating the amine acetate ion with a dilute (usually 1N) 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).

[0043] The term "in this article" Latency "This refers to an inert functional group that can be selectively transformed into a reactive functional group at appropriate points in the synthesis sequence: the triggering event for this transformation can be, in particular, moisture, heat, or irradiation."

[0044] The term "in this article" Accelerator "" refers to a chemical agent that has co-reactivity with the curing agent and reduces the curing time of the composition compared to a composition that can be achieved using the curing agent alone under equivalent conditions.

[0045] The term "in this article" C 1 -C n alkyl "" refers to a monovalent group containing 1 to n carbon atoms, which is an alkane group and includes both straight-chain and branched organic groups. Therefore, " C 1 -C 18 alkyl "A group is a monovalent group containing 1 to 18 carbon atoms, which is an alkane group 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 this invention, such alkyl groups may be unsubstituted or may be substituted with one or more halogens. When applicable to a given part (R), the tolerance for one or more non-halogen substituents in the alkyl group will be indicated in the specification."

[0046] The term "in this article" C 1 -C 18 hydroxyalkyl "" refers to a HO-(alkyl) group having 1 to 18 carbon atoms, where alkyl is as defined above.

[0047] “ Alkoxy "" refers to a monovalent group represented by -OA, where A is an alkyl group; non-limiting examples are methoxy, ethoxy, and isopropoxy. The term "" as used herein C 1 -C 18 Alkoxyalkyl "" refers to an alkyl group having an alkoxy substituent as defined above, and wherein a portion thereof ( alkyl-O-alkyl It contains a total of 1 to 18 carbon atoms: such groups include methoxymethyl (—CH2OCH3), 2-methoxyethyl (—CH2CH2OCH3), and 2-ethoxyethyl. Similarly, the term "..." as used herein C 7 -C 18 Alkoxyaryl "Refers to an aryl group having an alkoxy substituent as defined above, and wherein a portion thereof ( Fang alkyl-O-alkyl It contains a total of 7 to 18 carbon atoms.

[0048] The term "in this article" C 2 -C 4 Alkylene It is defined as a saturated divalent hydrocarbon group having 2 to 4 carbon atoms.

[0049] the term" C 3 -C 18 cycloalkyl "Should be understood to mean a saturated monocyclic or polycyclic hydrocarbon group having 3 to 18 carbon atoms. In this invention, such cycloalkyl groups may be unsubstituted or may be substituted with one or more halogens. When applied to a given part (R), the specification will indicate the tolerance for one or more non-halogen substituents in the cycloalkyl group. Examples of cycloalkyl groups include: cyclopropyl; cyclobutyl; cyclopentyl; cyclohexyl; cycloheptyl; cyclooctyl; adamantane; and norbornane."

[0050] The term "in this article" C 2 -C 18 alkenyl "Alkenyl" refers to a hydrocarbon group having 2 to 18 carbon atoms and at least one alkene-bonded unsaturated unit. The alkenyl group can be linear, branched, or cyclic, and may optionally be substituted with one or more halogens. When applied to a given part (R), the specification will indicate the tolerance for one or more non-halogen substituents in the alkenyl group. As understood by those skilled in the art, the term "alkenyl" alkenyl It also includes those with " Cis "Configuration and" trans "Configuration, or alternatively" E "Configuration and" Z "The configuration group. The C2-C" 20 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-cyclohexyl-1-enyl; 1-cyclohexyl-2-enyl; and 1-cyclohexyl-3-enyl.

[0051] As used in this article, either alone or as part of a larger portion (such as in "...") Aryl groups (in Chinese) C 6 -C 18 Aryl "A group refers to a monocyclic, bicyclic, or tricyclic cyclic system, wherein the monocyclic system is aromatic, or at least one ring in the bicyclic or tricyclic system is aromatic. Bicyclic and tricyclic systems comprise benzofused 2- to 3-membered carbon rings. In this invention, such aryl groups may be unsubstituted or may be substituted with one or more halogens. When applied to a given part (R), the specification will indicate tolerances for one or more non-halogen substituents in the aryl group. Exemplary aryl groups include: phenyl; (C1-C4)alkylphenyl, such as tolyl and ethylphenyl; 1,1'-biphenyl; indenyl; naphthyl, tetrahydronaphthyl, tetrahydroindenyl; tetrahydroanthrayl; and anthracel. Note that phenyl is preferred."

[0052] The term "in this article" C 6 -C 18 Aspartic"Arylidene" refers to a divalent group having 6 to 18 carbon atoms, derived from monocyclic, bicyclic, and tricyclic systems, wherein the monocyclic system is aromatic, or at least one ring in the bicyclic or tricyclic system is aromatic. The arylidene may be substituted with at least one halogen substituent, but the aromatic moiety of the arylidene contains only carbon atoms. Example " C 6 -C 18 Aspartic "Including phenylene and naphthalene-1,8-dimethyl."

[0053] The term "in this article" Aryl groups "" refers to alkyl groups substituted with aryl groups as defined above. Furthermore, the term "" as used herein... alkylaryl "" refers to an aryl group substituted with an alkyl group, both groups being defined as above. Additionally, the term " alkylene aryl "" indicates a divalent aryl group substituted with an alkyl group, wherein a hydrogen atom at any position on the alkyl carbon backbone is replaced by another binding site. Examples of alkylene aryl groups include methylphenylene, ethylphenylene, and methyldiphenylene.

[0054] The term "in this article" miscellaneous "" refers to a group or part containing one or more heteroatoms (such as N, O, Si, and S). Therefore, for example, " Heterocyclic "Refers to cyclic groups having, for example, N, O, Si, or S as part of a ring structure." Heteroalkyl "", Heterocyclic alkyl "and" heteroaryl The “parts” are alkyl, cycloalkyl, and aryl groups as defined above, which contain N, O, Si, or S as part of their structure.

[0055] More specifically, the term " C 1 -C 9 heteroaryl "Aromatic group" refers to an aromatic group having 1 to 9 carbon atoms and 1 to 4 heteroatoms. This group may be linked via a nitrogen atom (if feasible) or via a carbon atom. Exemplary C1-C9 heteroaryl groups include imidazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, furanyl, pyrazolyl, isoxazolyl, tetrazolyl, and quinolinyl. All carbon atoms of this group may optionally be substituted with one or more halogens.

[0056] The compositions of the present invention are defined herein as " Basically contains " Certain compounds, elements, ions, or other similar components. (Term)" Basically contains"Intended to mean that compounds, elements, ions, or other similar components are not intentionally added to the composition and are present at most only in trace amounts that will have no (adverse) effect on the desired properties of the coating. An exemplary trace amount is less than 1000 ppm by weight of the composition. The term " Basically contains "Including embodiments in which the specified compound, element, ion, or other similar component is not present in the composition at all, or is not present in any amount measurable by techniques commonly used in the art."

[0057] the term" waterless "It is intended to be equivalent to being substantially water-free, and thus also includes embodiments in which water is not present in the composition at all, or not in any amount measurable by techniques commonly used in the art." Detailed Implementation

[0058] a) Elastomer-modified epoxy resin The compositions of the present invention necessarily comprise at least one epoxy resin modified with a hydrophobic elastomer, wherein the epoxy equivalent weight of the modified epoxy resin is 200 to 1000 g / eq. The epoxy equivalent weight of the elastomer-modified resin, or each elastomer-modified resin, should preferably be 200 to 800 g / eq, for example, 250 to 750 g / eq.

[0059] Without limiting the invention, it is preferred that a) the at least one elastomer-modified epoxy resin accounts for 50 to 90% by weight of the composition, preferably 60 to 90% by weight or 65 to 85% by weight.

[0060] Elastomer modification of epoxy resin (hereinafter referred to as E1) can be carried out by any suitable method known to those skilled in the art, but it should generally be carried out by a catalytic addition reaction between the functional groups of the modifier (hereinafter referred to as M1) and the ethylene oxide groups of the epoxy resin (E1). This addition reaction can be carried out in a suitable solvent and under at least one of the following conditions: i) a temperature of 40°C to 200°C; ii) a reaction duration of 0.5 to 5 hours; and iii) catalysis. Exemplary catalysts include: tertiary amine catalysts, such as tributylamine; quaternary ammonium salts, such as tetrabutylammonium chloride; tertiary phosphate esters, such as triphenyl phosphate; quaternary phosphonium salts, such as ethyltriphenylphosphonium iodide (ETPPI); metal salts, such as AMC-2 (chromium octoate); and combinations of these catalysts (in which case a stepwise addition reaction is achieved).

[0061] The epoxy resin to be modified (E1) has a 1,2-epoxy equivalent greater than 1, and preferably at least 2. The epoxy resin (E1) can be linear or branched, saturated or unsaturated, aliphatic, alicyclic, aromatic, or heterocyclic. Examples of epoxy resins (E1) include: polyglycidyl ethers of polyhydroxy compounds; brominated epoxy resins; epoxy linear phenolic or similar polyhydroxyphenolic resins; polyglycidyl ethers of ethylene glycol or polyethylene glycol; and polyglycidyl esters of polycarboxylic acids.

[0062] It can be confirmed that polyglycidyl ethers of polyphenols are preferably used as the epoxy resin (E1). For example, the epoxy resin (E1) can be selected from bisphenol A diglycidyl ether and bisphenol F diglycidyl ether.

[0063] The functionalized modifier (M1) is functionalized at the terminal or non-terminal sites of the epoxy group of the epoxy resin (E1) by a group reactive to the ethylene oxide group. Suitable functional groups include, but are not limited to: carboxyl; amino; hydroxyl; epoxy; thiol; acid anhydride; and isocyanate. In addition, the modifier (M1) can be a functionalized homopolymer or a functionalized random, block, or star copolymer.

[0064] In the implementation scheme, the hydrophobic modifier (M1) used for functionalizing the epoxy resin (E1) is a diene-containing polymer with functionally-terminated groups having the following general formula: YBY in: B is a polymer backbone formed by polymerization of monomers selected from the following: C4-C 10 Diene; C4-C 10 Diene and at least one vinyl aromatic monomer, such as styrene, C1-C6 alkyl-substituted styrene, or halogen-substituted styrene; C4-C 10 Diene and at least one vinyl nitrile monomer, such as acrylonitrile or methacrylonitrile; C4-C 10 Diene, at least one vinyl nitrile monomer and at least one vinyl aromatic monomer; or C4-C 10 Diene, at least one vinyl nitrile monomer, and the formula CH2=CR-COOR 1 acrylates, wherein R and R 1 They are independently selected from hydrogen or C1-C. 10 Alkyl; and Y can be any functional group capable of reacting with an ethylene oxide group, suitable examples of which include carboxyl, amino, hydroxyl, epoxy, thiol, anhydride, and isocyanate groups.

[0065] As a reactant modifier (M1), the diene-containing polymer with functional groups capped should generally be characterized by a functionality of 1.1 to 2.5, for example 1.5 to 2.5 or 1.6 to 2.4. In addition, it is not excluded that the polymer backbone (B) is partially hydrogenated.

[0066] As a non-limiting example, the functional group-terminated diene-containing polymer (M1) may be selected from: carboxyl-terminated polybutadiene; carboxyl-terminated poly(butadiene-acrylonitrile); and carboxyl-terminated poly(butadiene-acrylonitrile-acrylic acid).

[0067] It can be noted that, as a modifier (M1), carboxyl-terminated poly(butadiene-acrylonitrile) (CTBN) is preferred, particularly carboxyl-terminated poly(butadiene-acrylonitrile) (CTBN) composed of 5 to 30 wt% acrylonitrile and 70 to 95 wt% butadiene. Independent of or in conjunction with this composition, the number average molecular weight (Mn) of the carboxyl-terminated poly(butadiene-acrylonitrile) (CTBN) should be 1000 to 50000 g / mol, for example 2000 to 10000 g / mol. Furthermore, it is not excluded that the carboxyl-terminated poly(butadiene-acrylonitrile) may contain other functional groups attached to the chain besides the terminal carboxyl group, such as amino, phenolic, hydroxyl, epoxy, thiol, or anhydride groups.

[0068] In addition to diene-containing polymers with functional groups at the ends, the use of diene-containing polymers functionalized along the chain backbone at non-terminal sites can be useful in some embodiments. For example, such functionalized polymers (M1) may include: carboxylated polybutadiene; carboxylated poly(butadiene-styrene); mesoblock carboxylated poly(styrene-ethylene / butadiene-styrene); amidated poly(butadiene-styrene); mercapto-polybutadiene; epoxidized polybutadiene; and epoxidized poly(butadiene-styrene).

[0069] In another embodiment of the invention, the composition is characterized in that the at least one elastomer-functionalized epoxy resin comprises at least one urethane-modified epoxy resin, or is composed of at least one urethane-modified epoxy resin. In this embodiment, the functionalized hydrophobic modifier (M1) that modifies the epoxy resin (E1) is an isocyanate-terminated urethane prepolymer, which can be obtained by reacting a polyisocyanate compound (I) with a polyhydroxy (P) compound. Without limiting this embodiment, the urethane prepolymer (M1) should be characterized by: i) an NCO content of 5 to 30% by weight, preferably 10 to 25% by weight, based on the prepolymer; and ii) a functionality of 1.1 to 2.5. These characterizing properties can be found in known commercially available prepolymers. Alternatively, components (I) and (P) can be reacted in proportions and under conditions that result in these properties of the obtained prepolymer.

[0070] The polyisocyanate (I) used in the preparation of the prepolymer (M1) includes any aliphatic, alicyclic, arylaliphatic, heterocyclic, or aromatic polyisocyanate, or mixtures thereof, having an average isocyanate functionality of at least 2.0 and an equivalent weight of at least 80. The isocyanate functionality of the polyisocyanate (I) will more typically be from 2.2 to 4.0, for example, from 2.3 to 3.5. While functionality greater than 4.0 can be used, its use will result in excessive crosslinking. The equivalent weight of the polyisocyanate is typically from 100 to 300, preferably from 110 to 250, and more preferably from 120 to 200.

[0071] Where necessary, polyisocyanates may have been biureted and / or isocyanurized by commonly known methods (as described in British Patent No. 889,050).

[0072] Examples of suitable polyisocyanates (I) include, but are not limited to: ethylene diisocyanate; 1,4-tetramethylene diisocyanate; hexamethylene diisocyanate (HDI); biuret or trimer of HDI; 1,12-dodecane diisocyanate; cyclobutane-1,3-diisocyanate; cyclohexane-1,3-diisocyanate and cyclohexane-1,4-diisocyanate and mixtures of these isomers; 1-isocyano-3,3,5-trimethyl-5-isocyanomethylcyclohexane; 2,4-hexahydrotoluene diisocyanate and 2,6-hexahydrotoluene diisocyanate and mixtures of these isomers; hexahydro-1,3-phenylene diisocyanate and / or hexahydro-1,4-phenylene diisocyanate; perhydro-2 ,5'-diphenylmethane diisocyanate and / or perhydro-4,4'-diphenylmethane diisocyanate; 1,3-phenylene diisocyanate and 1,4-phenylene diisocyanate; 2,4-tolyl diisocyanate and 2,6-tolyl diisocyanate and mixtures of these isomers; diphenylmethane-2,4'-diisocyanate and / or diphenylmethane-4,4'-diisocyanate (MDI); naphthylene-1,5-diisocyanate; triphenylmethane-4,4',4'-triisocyanate; and polyphenylmethylene polyisocyanates of this type, which are obtained by condensing aniline with formaldehyde and then subjecting it to phosgenation (as described in British Patent Nos. 874,430 and 848,671). It should be noted that diisocyanates and / or polyisocyanates comprising ester groups, urea groups, ureocarbamate groups, carbodiimide groups, uretdione groups, and / or carbamate groups may also be used in the method according to the invention.

[0073] The number-average molecular weight (Mn) of the polyhydroxy compound (P) used to obtain the urethane prepolymer (M1) should conventionally be from 400 to 10,000 g / mol. The hydroxyl value of the polyhydroxy compound (P) should conventionally be from 20 to 850 mg KOH / g, preferably from 25 to 500 mg KOH / g. Furthermore, it is desirable that the polyhydroxy compound (P) is selected from divalent or polyvalent: polyether polyols; polyester polyols; poly(ether-ester) polyols; poly(alkylene carbonate) polyols; hydroxyl-containing polysulfides; polymeric polyols; and mixtures thereof.

[0074] While low molecular weight (e.g., 60 to 400 g / mol., or 60 to 300 g / mol.) diols and triols can be reactive to isocyanates (I), these polyols are generally used only as starting molecules, chain extenders, and / or crosslinking agents in reaction mixtures containing one or more active hydrogen compounds (P). In this regard, aliphatic, alicyclic, and / or araliphatic diols having 2 to 14 (preferably 4 to 10) carbon atoms, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, o-dihydroxycyclohexane, m-dihydroxycyclohexane, and p-dihydroxycyclohexane; diethylene glycol; dipropylene glycol; bis(2-hydroxyethyl)hydroquinone; and triols, such as 1,2,4-trihydroxycyclohexane and 1,3,5-trihydroxycyclohexane, glycerol, and trimethylolpropane.

[0075] Polyether polyols are well known in the art and include polyoxyethylene, polyoxypropylene, polyoxybutene, and polytetramethylene ether glycols and triols. Polyether polyols can typically have a weight-average molecular weight (Mw) of 400 to 10,000 g / mol, for example 1,000 to 7,000 g / mol, and can be prepared by polymerizing alkylene oxides (e.g., as described in U.S. Patent Nos. 4,269,9945, 4,218,543, and 4,374,210) in the presence of an initiator compound containing active hydrogen. alkylene oxide monomers are typically selected from: ethylene oxide; propylene oxide; butane oxide; styrene oxide; epichlorohydrin; epibromopropane; and mixtures thereof. Active hydrogen initiators are typically selected from: water; ethylene glycol; propylene glycol; butanediol; hexanediol; glycerol; trimethylolpropane; pentaerythritol; hexanetriol; sorbitol; sucrose; hydroquinone; resorcinol; catechol; bisphenol; linear phenolic resins; phosphoric acid; amines; and mixtures thereof.

[0076] As is known in the art, polyester polyols can be prepared by reacting a polycarboxylic acid or its anhydride with a polyol. Examples of suitable polycarboxylic acids include succinic acid, adipic acid, octanoic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, maleic acid, trimellitic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, bridged methylenetetrahydrophthalic anhydride, maleic anhydride, glutaric anhydride, fumaric acid, and mixtures thereof. Examples of polyols that can be used to prepare polyester polyols include ethylene glycol, propylene glycol, butanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, glycerol, trimethylolpropane, pentaerythritol, p-cyclohexanediol, mannitol, sorbitol, methyl glycosides, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol, and mixtures thereof. In relation to the present invention, the weight-average molecular weight (Mw) of the polyester polyols available will typically be between 1,000 and 10,000 g / mol.

[0077] In embodiments of the present invention, the average functionality of one or more reactant polyhydroxy compounds (P) is at least 1.5, preferably at least 1.8, more preferably at least 2.0, but not greater than 4.0, preferably not greater than about 3.5, and more preferably not greater than 3.0. Independently or additionally, the equivalent weight of one or more reactant polyhydroxy compounds (P) is at least 200 g / eq., preferably at least 500 g / eq., more preferably at least 1000 g / eq., but not greater than 3500 g / eq., preferably not greater than 3000 g / eq., and more preferably not greater than 2500 g / eq.

[0078] Starting with components (P) and (I) as defined above, a polyurethane prepolymer (M1) can be prepared under anhydrous conditions by any suitable method, such as bulk polymerization and solution polymerization. The amount of one or more polyhydroxy compounds (P) present is sufficient to react with most of the isocyanate groups, but leaves enough isocyanate groups to meet the desired free isocyanate content of the urethane prepolymer (M1). Additionally, in this embodiment where one or more polyhydroxy compounds (P) comprise a mixture of diols and triols, the ratio of diol to triol must be selected to achieve the desired isocyanate functionality of the urethane prepolymer (M1).

[0079] In another and preferred embodiment of the invention, the composition is characterized in that a) the at least one elastomer-functionalized epoxy resin comprises or is composed of at least one dimer acid-modified epoxy resin. The hydrophobic dimer acid modifier (M1) may be cyclic or acyclic, but will conventionally be a C36 to C44 aliphatic diacid, which can be prepared by oxidative coupling of a C18 to C22 unsaturated monocarboxylic acid. Dimer acids obtained by oxidative coupling of oleic acid, linoleic acid, or tall oil fatty acids may be mentioned as exemplary dimer acid modifiers (M1).

[0080] According to an interesting embodiment of this disclosure, based on the weight of the composition, component a) of the composition comprises: 60 to 80% by weight of at least one dimer acid-modified epoxy resin; and 0 to 10% by weight of at least one elastomer-modified resin, wherein the elastomer-modified resin is selected from carboxyl-terminated poly(butadiene-acrylonitrile) (CTBN) modified epoxy resin and urethane modified epoxy resin. Each modified resin of component a) is characterized by having an epoxy equivalent weight of 200 to 1000 g / eq, preferably 250 to 750 g / eq. Regarding this embodiment, the dimer acid-modified epoxy resin or each dimer acid-modified epoxy resin of component ai) is preferably characterized by having an epoxy equivalent weight of 500 to 750 g / eq; alternatively or additionally, the elastomeric modified resin or each elastomeric modified resin of component aii) is preferably characterized by having an epoxy equivalent weight of 250 to 500 g / eq.

[0081] Considering the preferred embodiments discussed above, commercial examples of suitable elastomer-modified epoxy resins include: Struktol, available from Schill and Seilacher. (R) Polydis 3614, Polycavit 3632, and Polycavit 3530; available from CVC Thermosets' Hypox. (R) Resins, including Hypox DA 323; EPON 58005 and EPON 58034 available from Miller-Stephenson; JER871 and JER872 available from Mitsubishi Chemical Corporation; B-Tough A1, A2 and A3 available from Croda Coatings and Polymers; YD-171 and YD-172 available from Nippon Steel Chemical Co., Ltd.; and EPU-6, EPU-7N, EPU-11F, EPU-15F, EPU-1395, EPU-738, EPU-17, EPU-17T-6 and EPU-80 available from Adeka Corporation.

[0082] b) Optional additional epoxy resin The composition also comprises an epoxy resin different from the modified resin of component a). Based on the weight of the composition, the composition may, for example, contain up to 15% by weight, such as 1 to 10% by weight or 1 to 5% by weight of the additional epoxy resin described in b).

[0083] The epoxy resins used in component b) herein may include monofunctional epoxy resins, multifunctional epoxy resins, and combinations thereof. Epoxy resins may be pure compounds, but may also be mixtures of epoxy-functional compounds, including mixtures of compounds having a different number of epoxy groups per molecule. Epoxy resins may be saturated or unsaturated, aliphatic, alicyclic, aromatic, or heterocyclic, and may be substituted. Furthermore, epoxy resins may be monomeric or polymeric.

[0084] Without limiting the invention, exemplary monoepoxide compounds include: epoxide alkanes; epoxy-substituted alicyclic hydrocarbons, such as cyclohexene oxide, vinylcyclohexene monoxide, (+)-cis-limonene oxide, (+)-cis, trans-limonene oxide, (-)-cis, trans-limonene oxide, cyclooctene oxide, cyclododecene oxide, and α-pinene oxide; epoxy-substituted aromatic hydrocarbons; monoepoxide-substituted alkyl ethers of monohydric alcohols or phenols, such as glycidyl ethers of aliphatic, alicyclic, and aromatic alcohols. Ethers; monoepoxy-substituted alkyl esters of monocarboxylic acids, such as glycidyl esters of aliphatic, alicyclic, and aromatic monocarboxylic acids; monoepoxy-substituted alkyl esters of polycarboxylic acids, wherein one or more other carboxyl groups are esterified with an alkanol; alkyl and alkenyl esters of epoxy-substituted monocarboxylic acids; epoxy alkyl ethers of polyols, wherein one or more other OH groups are esterified or etherified with a carboxylic acid or an alcohol; and monoesters of polyols and epoxy monocarboxylic acids, wherein one or more other OH groups are esterified or etherified with a carboxylic acid or an alcohol.

[0085] For example, the following glycidyl ethers may be mentioned as monoepoxide compounds particularly applicable to this document: 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-tolyl glycidyl ether; m-tolyl glycidyl ether; and p-tolyl glycidyl ether.

[0086] In the implementation scheme, the monoepoxide compound conforms to the following formula (EI): (EI) Where: R w R x R y and R zThey can be the same or different, and are independently selected from hydrogen, halogen atoms, C1-C8 alkyl groups, and C3-C4 atoms. 10 cycloalkyl, C2-C 12 alkenyl, C6-C 18 Aryl, or C7-C 18 Aryl alkyl group, under the condition that R y and R z At least one of them is not hydrogen.

[0087] Preferably, R w R x and R y It is hydrogen, and R z It is phenyl or C1-C8 alkyl, more preferably C1-C4 alkyl.

[0088] Considering this implementation, exemplary monoepoxide compounds include: ethylene oxide; 1,2-epoxide ( Epoxy Propylene alkyl ), 1,2-epoxybutane; cis-2,3-epoxybutane; trans-2,3-epoxybutane; 1,2-epoxypentane; 1,2-epoxyhexane; 1,2-epoxyheptane; epoxydecane; butadiene oxide; isoprene oxide; and styrene oxide.

[0089] In this invention, reference is made to the use of at least one monoepoxide compound selected from the following: ethylene oxide; propylene oxide; cyclohexene oxide; (+)-cis-limonene oxide; (+)-cis, trans-limonene oxide; (-)-cis, trans-limonene oxide; cyclooctene oxide; and cyclododecene oxide.

[0090] Similarly, without limiting the invention, suitable polyepoxides can be liquids, solids, or solutions in solvents. Furthermore, such polyepoxides should have an epoxy equivalent weight of 100 to 700 g / eq, for example 120 to 320 g / eq. Additionally, generally, diepoxides with an epoxy equivalent weight of less than 500 g / eq or even less than 400 g / eq are preferred: this is primarily from a cost perspective, as lower molecular weight epoxy resins require more limited processing during purification in their production.

[0091] Examples of types or groups of polyepoxide compounds that can be polymerized in this invention include: glycidyl ethers of polyols and polyphenols; glycidyl esters of polycarboxylic acids; and epoxidized polyethylenically unsaturated hydrocarbons.

[0092] Suitable diglycidyl ether compounds can be aromatic, aliphatic, or alicyclic in nature, and therefore can be derived from diphenols and diols. Additionally, useful classes of such diglycidyl ethers include: diglycidyl ethers of aliphatic and alicyclic diols (such as 1,2-ethylene glycol, 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 phthalate, diglycidyl isophthalate, and diglycidyl terephthalate; diglycidyl ethers based on polyalkylene glycols, particularly polypropylene glycol diglycidyl ethers; and diglycidyl ethers based on polycarbonate diols. Other suitable diepoxide compounds that may also be mentioned include: diunsaturated fatty acid C1-C... 18 Diepoxides of alkyl esters; butadiene diepoxides; polybutadiene diglycidyl ether; vinylcyclohexene diepoxides; and limonene diepoxides.

[0093] Other illustrative polycyclic epoxy 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.

[0094] Additionally, examples of highly preferred polyepoxy compounds include: bisphenol A epoxy resins, such as DER™ 331, DER™ 330, DER™ 337, and DER™ 383; bisphenol F epoxy resins, such as DER™ 354; bisphenol A / F epoxy resin blends, such as DER™ 353; aliphatic glycidyl ethers, such as DER™ 736; polypropylene glycol diglycidyl ether, such as DER™ 732; solid bisphenol A epoxy resins, such as DER™ 661 and DER™ 664 UE; solutions of solid bisphenol A epoxy resins, such as DER™ 671-X75; linear epoxy phenolic resins, such as DEN™ 438; brominated epoxy resins, such as DER™ 542; castor oil triglycidyl ether, such as ERISYS™ GE-35H; and polyglycerol-3-polyglycidyl ether, such as ERISYS™ GE-38; and sorbitol glycidyl ether, such as ERISYS™ GE-60.

[0095] In addition to the above, in some embodiments, component b) of the composition may comprise a glycidoxyalkylalkoxysilane having the following formula: Wherein: each R is independently selected from methyl or ethyl; and n is between 1 and 10.

[0096] Exemplary silanes include, but are not limited to: γ-glycidoxypropyltrimethoxysilane, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxymethyltrimethoxysilane, γ-glycidoxymethyltriethoxysilane, γ-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, and 8-glycidoxyoctyltrimethoxysilane. When present, the epoxy-functionalized silane should comprise less than 10% by weight, preferably less than 5% by weight, based on the total weight of the epoxy compound.

[0097] This disclosure also does not exclude the curable composition from comprising one or more cyclic monomers selected from: oxetanes; cyclic carbonates; cyclic anhydrides; and lactones. The following cited disclosures may be instructive in disclosing suitable cyclic carbonate functional compounds: U.S. Patent Nos. 3,535,342; 4,835,289; 4,892,954; British Patent No. GB-A-1,485,925; and EP-A-0 119 840. However, based on the total weight of the epoxy compound, such cyclic comonomers should comprise less than 20% by weight, preferably less than 10% by weight, or less than 5% by weight.

[0098] c) Curing agents for epoxy compounds As described above, the composition comprises at least one compound that provides at least two amine hydrogens reactive to epoxy groups. In an important embodiment, the composition may comprise at least one polyamine having at least two amine hydrogens reactive to epoxy groups. However, it is not excluded that component c) of the composition comprises or is composed of a latent amine that generates the reactive amine hydrogens upon exposure to triggering conditions.

[0099] When formulating a curable composition, the composition is characterized in that the molar ratio of epoxy groups to epoxy reactive groups is from 0.9:1 to 1.4:1, for example, from 1:1 to 1.3:1 or from 1:1 to 1.2:1. It is contemplated that the composition provides a molar excess of epoxy groups relative to the epoxy reactive groups, with a molar ratio of up to and including 1.4:1, 1.3:1, or 1.2:1. For completeness, the term epoxy reactive group includes latent reactive groups.

[0100] In alternative formulations not intended to contradict the statements given above, it is preferred that, based on the weight of the composition, the composition comprises 1 to 15% by weight of at least one compound of c) that provides at least two amine hydrogens reactive to epoxy groups, and the composition preferably comprises 1 to 10% by weight, for example, 1 to 5% by weight of at least one compound of c)

[0101] In the case where component c) comprises a polyamine providing at least two amine hydrogens reactive to epoxy groups, or is composed of a polyamine providing at least two amine hydrogens reactive to epoxy groups, it is preferred that the polyamine or each polyamine should contain primary amine groups and / or secondary amine groups, and the equivalent weight of each primary amine group or secondary amine group does not exceed 150 g / eq., more preferably not more than 125 g / eq.

[0102] Suitable polyamines that can be used alone or in combination include, but are not limited to, the following: i) Aliphatic, alicyclic, or aryl aliphatic primary diamines, including the following examples: 2,2-dimethyl-1,3-propanediamine; 1,3-pentanediamine (DAMP); 1,5-pentanediamine; 1,5-diamino-2-methylpentane (MPMD); 2-butyl-2-ethyl-1,5-pentanediamine (C11-neodiamine); 1,6-hexanediamine (hexamethylenediamine, HMDA); 2,5-dimethyl-1,6-hexanediamine; 2,2,4-trimethylhexamethylenediamine and / or 2,4,4-trimethylhexamethylenediamine; 1,7-heptanediamine; 1,8-octanediamine; 1,9-nonanediamine; 1,10-decanediamine; 1,11-undecanediamine; 1,12-dodecanediamine; 1,2-diaminocyclohexane, 1 ,3-Diaminocyclohexane and 1,4-Diaminocyclohexane; bis(4-aminocyclohexyl)methane; bis(4-amino-3-methylcyclohexyl)methane; bis(4-amino-3-ethylcyclohexyl)methane; bis(4-amino-3,5-dimethylcyclohexyl)methane; bis(4-amino-3-ethyl-5-methylcyclohexyl)methane; 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isophorone diamine, IPDA); 2-methyl-1,3-diaminocyclohexane and / or 4-methyl-1,3-diaminocyclohexane; 1,3-bis(aminomethyl)-cyclohexane; 1,4-bis(aminomethyl)cyclohexane; 2,5(2,6)-bis(aminomethyl)-bicyclo[2.2.1]heptane (norborane diamine) diamine), NBDA); 3(4),8(9)-bis(aminomethyl)tricyclic [5.2.1.0] 2,6 ]-decane (TCD-diamine); 1,4-diamino-2,2,6-trimethylcyclohexane (TMCDA); 1,8-menthanediamine; 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]undecane; and 1,3-bis(aminomethyl)benzene (MXDA).

[0103] ii) Polyamines containing tertiary amine groups having two or three aliphatic primary amine groups, such as the following specific examples: N,N'-bis(aminopropyl)-piperazine; N,N-bis(3-aminopropyl)methylamine; N,N-bis(3-aminopropyl)ethylamine; N,N-bis(3-aminopropyl)propylamine; N,N-bis(3-aminopropyl)cyclohexylamine; N,N-bis(3-aminopropyl)-2-ethylhexylamine; tris(2-aminoethyl)amine; tris(2-aminopropyl)amine; tris(3-aminopropyl)amine; and products of the double cyanoethylation and subsequent reduction of aliphatic amines derived from natural fatty acids, such as N,N-bis(3-aminopropyl)dodecylamine and N,N-bis(3-aminopropyl)tartrate alkylamine, which are commercially available as Triameen® Y12D and Triameen® YT (from Akzo Nobel).

[0104] iii) Aliphatic primary polyamines containing ether groups, including the following specific examples: bis(2-aminoethyl) ethers; 3,6-dioxane-1,8-diamine; 4,7-dioxane-1,10-diamine; 4,7-dioxane-2,9-diamine; 4,9-dioxadodecane-1,12-diamine; 5,8-dioxadodecane-3,10-diamine; 4,7,10-trioxatridecane-1,13-diamine and higher oligomers of these diamines; bis(3-aminopropyl)polytetrahydrofuran and other polytetrahydrofuran diamines. Amines; alicyclic ether-containing diamines obtained by propoxylation and subsequent amination of 1,4-dihydroxymethylcyclohexane, such as those commercially available as Jeffamine® RFD-270 (from Huntsman); polyalkylene diamines or polyalkylene triamines, which are obtained as products of amination of polyalkylene diols and polyalkylene triols and are commercially available under the names Jeffamine® (from Huntsman), polyetheramines (from BASF), or PC Amines® (from Nitroil). It is noteworthy that Jeffamine® D-230, Jeffamine® D-400, Jeffamine® D-600, Jeffamine® D-2000, Jeffamine® D-4000, Jeffamine® T-403, Jeffamine® T-3000, Jeffamine® T-5000, Jeffamine® EDR-104, Jeffamine® EDR-148 and Jeffamine® EDR-176, as well as the corresponding amines from BASF or Nitroil, are particularly preferred.

[0105] iv) Primary diamines having secondary amine groups, examples of which may be mentioned include: 3-(2-aminoethyl)aminopropylamine, bis(hexamethylene)triamine (BHMT); diethylenetriamine (DETA); triethylenetetramine (TETA); tetraethylenepentamine (TEPA); pentaethylenehexamine (PEHA); higher homologues of linear polyethyleneamines, such as polyethylene polyamines having 5-7 ethyleneamine units (so-called "higher ethylene polyamines", HEPA); products from the polycyanoethylation or cyanobutylation of primary diamines and primary polyamines having at least two primary amine groups and subsequent hydrogenation, wherein the primary diamine... Amines and primary amines include dipropylenetriamine (DPTA), N-(2-aminoethyl)-1,3-propanediamine (N3-amine), N,N'-bis(3-aminopropyl)ethylenediamine (N4-amine), N,N'-bis(3-aminopropyl)-1,4-diaminobutane, N5-(3-aminopropyl)-2-methyl-1,5-pentanediamine, N3-(3-aminopentyl)-1,3-pentanediamine, N5-(3-amino-1-ethylpropyl)-2-methyl-1,5-pentanediamine, or N,N'-bis(3-amino-1-ethylpropyl)-2-methyl-1,5-pentanediamine.

[0106] v) Polyamines having one primary amino group and at least one secondary amino group, examples of which may be mentioned include: N-butyl-1,2-ethylenediamine; N-hexyl-1,2-ethylenediamine; N-(2-ethylhexyl)-1,2-ethylenediamine; N-cyclohexyl-1,2-ethylenediamine; 4-aminomethylpiperidine; N-(2-aminoethyl)piperazine; N-methyl-1,3-propanediamine; N-butyl-1,3-propanediamine; N-(2-ethylhexyl)-1,3-propanediamine; N-cyclohexyl-1,3-propanediamine; 3-methylamino-1-pentanylamine; 3-ethylamino-1-pentanylamine; 3-cyclohexylamino-1-pentanylamine; aliphatic diamines such as N-cocoyl-1,3-propanediamine; and aliphatic primary diamines with acrylonitrile, maleate diester or fumarate diester, citrate diester, acrylate and Products of Michael addition reactions of methacrylates, acrylamides, and itaconic acid diesters in a 1:1 molar ratio; products of partial reductive alkylation of primary polyamines with aldehydes or ketones, especially N-monoalkylated products of polyamines having two primary amine groups as previously mentioned, particularly N-monoalkylated products of 1,6-hexanediamine, 1,5-diamino-2-methylpentane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)benzene, BHMT, DETA, TETA, TEPA, DPTA, N3-amines, and N4-amines, wherein preferred alkyl groups are benzyl, isobutyl, hexyl, and 2-ethylhexyl; and partially stylated polyamines, such as those commercially available from Gaskamine® 240 (from Mitsubishi Gas Chemical).

[0107] vi) Secondary diamines, particularly the N,N'-dialkylated products of polyamines having two primary amine groups as previously mentioned, especially the N,N'-dialkylated products of 1,6-hexanediamine, 1,5-diamino-2-methylpentane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)benzene, BHMT, DETA, TETA, TEPA, DPTA, N3-amine or N4-amine, wherein the preferred alkyl groups are 2-phenylethyl, benzyl, isobutyl, hexyl and 2-ethylhexyl.

[0108] vii) Aromatic polyamines, including the following: m-phenylenediamine and p-phenylenediamine; 4,4'-diaminodiphenylmethane, 2,4'-diaminodiphenylmethane and 2,2'-diaminodiphenylmethane; 3,3'-dichloro-4,4'-diaminodiphenylmethane (MOCA); 2,4-toluenediamine and 2,6-toluenediamine; mixtures of 3,5-dimethylthio-2,4-toluenediamine and 3,5-dimethylthio-2,6-toluenediamine (which can be Ethacure® 300 obtained from Albermarle); a mixture of 3,5-diethyl-2,4-toluenediamine and 3,5-diethyl-2,6-toluenediamine (DETDA); 3,3',5,5'-tetraethyl-4,4'-diaminodiphenylmethane (M-DEA); 3,3',5,5'-tetraethyl-2,2'-dichloro-4,4'-diaminodiphenylmethane (M-CDEA); 3,3'-diisopropyl-5,5'-dimethyl-4,4'-diaminodiphenylmethane (M-MIPA); 3,3',5 ,5'-Tetraisopropyl-4,4'-diaminodiphenylmethane (M-DIPA); 4,4'-diaminodiphenyl sulfone (DDS); 4-amino-N-(4-aminophenyl)benzenesulfonamide; 5,5'-methylenedi-o-aminobenzoic acid; dimethyl-(5,5'-methylenedi-o-aminobenzoate); 1,3-propylidene-bis(4-aminobenzoate); 1,4-butylidene-bis(4-aminobenzoate); polytetramethylene oxide-bis(4-aminobenzoate) (which may be obtained from Air Products via Versalink®); 1,2-bis(2-aminophenylthio)ethane, 2-methylpropyl-(4-chloro-3,5-diaminobenzoate); and tert-butyl-(4-chloro-3,5-diaminobenzoate).

[0109] viii) Polyamide amines, the indicative members of which include reaction products of monocarboxylic or polycarboxylic acids or their esters or anhydrides (especially dimer fatty acids) with aliphatic, alicyclic, or aromatic polyamines (e.g., polyalkyleneamines such as DETA or TETA). Commercially available polyamide amines include: Versamid® 100, 125, 140, and 150 (from Cognis); Aradur® 223, 250, and 848 (from Huntsman); Euretek® 3607 and 530 (from Huntsman); and Beckopox® EH 651, EH 654, EH 655, EH 661, and EH 663 (from Cytec).

[0110] In addition to the above, it is also envisioned that component c) of the composition may contain or consist of dicyandiamide. When used, the dicyandiamide is preferably in a finely ground form: an average particle size (d50) of 0.5 to 100 µm, for example 1 to 50 µm or 2 to 20 µm is desirable. The particle size refers to the diameter or maximum size of the particles in the particle distribution and can be measured by dynamic light scattering.

[0111] Other exemplary latent curing agents used in or as component c) of the composition include, but are not limited to: ketimines obtained by reacting aliphatic polyamines with ketones; polyethyleneimines, particularly those with a weight-average molecular weight (Mw) of 700 to 1,000,000. g / mol polyethyleneimine; imidazole derivatives, such as 2-heptadeoylimidazole, 2-phenyl-4,5-dihydroxymethylimidazolium, 2-phenyl-4-methyl-5-hydroxymethylimidazolium, 2-phenyl-4-benzyl-5-hydroxymethylimidazolium; 2,4-diamino-8-2-methylimidazolyl-(1)-ethyl-5-triazine; addition products of triazine with isocyanuric acid; acyl hydrazides, such as succinohydrazide, adipohydrazide, isophtholohydrazide, o-oxybenzohydrazide and salicylohydrazide.

[0112] d) Accelerator The composition of the present invention comprises at least one accelerator, said accelerator being a promoter that promotes the reaction of epoxy groups with a curing agent ( Element c The composition is a substance that reacts with the reactive epoxy groups, particularly with amines. Based on the weight of the composition, the composition contains 0.01 to 5% by weight of at least one accelerator described in d). In some embodiments, the composition may contain 0.01 to 2% by weight, for example, 0.01 to 1% by weight of at least one accelerator described in d).

[0113] Without intending to limit the accelerators used in this invention, suitable accelerators may be mentioned as follows: i) acids or compounds that can be hydrolyzed into acids, particularly a) organic carboxylic acids, such as acetic acid, benzoic acid, salicylic acid, 2-nitrobenzoic acid, and lactic acid; b) organic sulfonic acids, such as methanesulfonic acid, p-toluenesulfonic acid, and 4-dodecylbenzenesulfonic acid; c) sulfonate esters; d) inorganic acids, such as phosphoric acid; e) Lewis acid compounds, such as BF3 amine complexes, SbF6 sulfonium compounds, and diaromatic iron complexes; f) Brønsted acid compounds, such as pentafluoroantimony acid complexes; and e) mixtures of the above acids and esters; ii) phenols, particularly bisphenols; ii) tertiary amines, such as 2-piperazine-1-ylethylamine, 1,4-diazabicyclo[ 2.2.2] Octane, benzyl dimethylamine, α-methylbenzyl dimethylamine, triethanolamine, dimethylaminopropylamine, and salts of such tertiary amines; iv) imidazoles, including imidazole, 1-methylimidazolium, 2-methylimidazolium, 2-ethylimidazolium, 2-ethyl-4-methylimidazolium, 1-vinylimidazolium, and N-(3-aminopropyl)imidazolium; v) quaternary ammonium salts, such as benzyltrimethylammonium chloride; vi) amidines, such as 1,8-diazabicyclo[5.4.0]undec-7-ene; vii) urea derivatives; viiii) thiourea derivatives; ix) guanidines, such as 1,1,3,3-tetramethylguanidine; x) phenolic resins; and xi) phosphites, such as diphenyl phosphite and triphenyl phosphite.

[0114] Those skilled in the art will recognize that the selection of an accelerator is not simply a matter of which accelerator is added fastest. Other decisive factors in accelerator selection include: cost; toxicity; solubility; processing effects such as working time, premature gelation, exothermic degradation, expansion, and venting; and final properties such as glass transition temperature (T). g ), modulus, strength, elongation at break and chemical resistance; regulatory issues; and ease of use.

[0115] Preferably, in this disclosure, component d) comprises or consists of at least one accelerator selected from the group consisting of: tertiary amines; urea derivatives; thiourea derivatives; and amidines. More specifically, the at least one accelerator shall comprise or consist of at least one compound according to formula (I) or formula (II):

[0116] in: X is O or S; R a R b and R c Independently selected from C1-C 12 Alkyl, C1-C 12 Hydroxyalkyl, C3-C 18cycloalkyl, or C6-C 18 Aryl; and R d It is C6-C 18 aryl or C7-C 18 Alkyl aryl group.

[0117] Regarding equations (I) and (II), the preferred orientation is: X is O; R a R b and R c Independently selected from C1-C8 alkyl, C1-C8 hydroxyalkyl, C3-C 12 cycloalkyl or C6 aryl; and R d It is C6-C 18 aryl or C7-C 18 Alkyl aryl group.

[0118] For completeness, exemplary urea promoters include, but are not limited to: phenyl dimethylurea; N,N'-dimethyl-N,N'-diphenyl-urea; N,N-dimethyl-N'-tolylurea; N,N-dibutyl-N'-phenylurea; N,N-dihydroxyethyl-N'-phenylurea; N,N-dicyclohexyl-N'-isopropylurea; 1,1'-(4-methyl-1,3-phenylene)bis(3,3-dimethylurea); 3,4-dichlorophenyl dimethylurea (diuron); 4-chlorophenyl dimethylurea (meturon); and 4,4'-methylenebis(phenyl dimethylurea).

[0119] In addition, exemplary commercially available urea derivatives that can be used in this disclosure include: Omicure U-24, Omicure U-35, Omicure U-410, Omicure U-52, Omicure U-415, and Omicure U-405, available from CVCCorporation; Amicure UR, Amicure UR7 / 10, Amicure UR200, Amicure UR300, Amicure UR500, Amicure UR2T, Amicure UR41, and Amicure UR-D, available from The Air Products Corporation; and Dyhard UR200, Dyhard UR300, Dyhard UR500, Dyhard UR700, and Ecure 30, available from Alzchem Corporation.

[0120] Additives and auxiliary ingredients The compositions obtained in this invention will generally also contain adjuvants and additives that can impart improved properties to these compositions. For example, adjuvants and additives may impart one or more of the following: improved elasticity; improved elastic recovery; longer permissible processing time; faster curing time; and lower residual tack. Such adjuvants and additives include plasticizers, stabilizers (including UV stabilizers), antioxidants, toughening agents, fillers, reactive diluents, driers, adhesion promoters, fungicides, flame retardants, rheology modifiers, color pigments or color pastes, and / or optionally, to a lesser extent, non-reactive diluents.

[0121] For the purposes of this invention, " plasticizer "Plasticizers are substances that reduce the viscosity of a composition and thus promote its processability. In this document, based on the total weight of the composition, plasticizers may comprise up to 10% by weight or up to 5% by weight, and are preferably selected from: polydimethylsiloxane (PDMS); diurethane; ethers of monofunctional, linear, or branched C4-C16 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; dicarboxylic acid esters; esters of fatty acids with OH groups or epoxidized fatty acids; glycolates; benzoates; phosphate esters; sulfonates; trimellitates; epoxidized plasticizers; polyether plasticizers, such as terminally capped polyethylene glycol or polypropylene glycol; polystyrene; hydrocarbon plasticizers; chlorinated paraffins; and mixtures thereof. It should be noted that phthalates can be used as plasticizers in principle, but they are not preferred due to their toxicological potential. Preferably, the plasticizer comprises or consists of one or more polydimethylsiloxanes (PDMS).

[0122] For the purposes of this invention, " stabilizer "Should be understood as antioxidant, UV stabilizer, or hydrolysis stabilizer. In this document, stabilizers may comprise up to 10% by weight or up to 5% by weight of the total composition. Standard commercial examples of stabilizers applicable to this document include: sterically hindered phenols; thioethers; benzotriazoles; benzophenones; benzoates; cyanoacrylates; acrylates; hindered amine light stabilizers (HALS) type amines; phosphorus; sulfur; and mixtures thereof."

[0123] The compositions of the present invention may optionally comprise toughening rubber in the form of core-shell particles dispersed in an epoxy resin matrix. The term "..." Core-shell rubber"or CSR, according to its standard meaning in the art, is used to refer to a rubber particle core formed of a polymer comprising an elastomer or rubbery polymer as a main component and a shell formed of a polymer grafted onto the core. The shell partially or completely covers the surface of the rubber particle core during the grafting polymerization process. The core shall account for at least 50% by weight of the core-shell rubber particle."

[0124] The polymer material of the core should have a glass transition temperature (T0) not higher than 0°C, preferably -20°C or lower, more preferably -40°C or lower, and even more preferably -60°C or lower. g The polymer of the shell is the glass transition temperature (T). g Non-elastic, thermoplastic, or thermosetting polymers with temperatures above room temperature, preferably above 30°C, and more preferably above 50°C.

[0125] Without limiting the invention, the core may consist of: diene homopolymers, such as butadiene or isoprene homopolymers; diene copolymers, such as butadiene or isoprene copolymers with one or more olefinically unsaturated monomers (such as vinyl aromatic monomers, (meth)acrylonitrile, or (meth)acrylate); polymers based on (meth)acrylate monomers, such as polybutyl acrylate; and polysiloxane elastomers, such as polydimethylsiloxane and crosslinked polydimethylsiloxane.

[0126] Similarly, without limiting the 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 in the shell may have acid groups that are ionicly crosslinked by forming metal carboxylates, particularly by forming salts of divalent metal cations. The shell polymer or copolymer may also be covalently crosslinked by monomers having two or more double bonds per molecule.

[0127] Preferably, any included core-shell rubber particles have an average particle size (d50) of 10 nm to 300 nm, for example 50 nm to 200 nm: the particle size refers to the diameter or maximum size of the particles in the particle distribution and is measured by dynamic light scattering.

[0128] This 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 smaller particles (first CSR type) may have an average particle size of 10 to 100 nm, and the larger particles (second CSR type) may have an average particle size of 120 nm to 300 nm, for example, 150 to 300 nm. Based on weight, the amount of smaller core-shell rubber particles should generally exceed that of larger particles: for example, a weight ratio of smaller CSR particles to larger CSR particles of 3:1 to 5:1 may be used.

[0129] The core-shell rubber can be selected from commercially available products, examples of which include: Paraaloid EXL 2650A, EXL 2655 and EXL2691 A available from The Dow Chemical Company; the Kane Ace® MX series available from Kaneka Corporation, particularly MX 120, MX 125, MX 130, MX 136, MX154, MX160, MX 551 and MX553; and METABLEN SX-006 available from Mitsubishi Rayon.

[0130] Based on the total weight of the composition, the core-shell rubber particles should be included in the composition in an amount of 0 to 10% by weight, for example, up to 5% by weight.

[0131] As described above, the compositions according to the invention may additionally contain fillers. Suitable fillers include, for example, chalk, lime powder, precipitated silica and / or pyrolytic silica, zeolite, bentonite, magnesium carbonate, diatomaceous earth, alumina, clay, talc, titanium dioxide, iron oxide, zinc oxide, sand, quartz, flint, mica, glass powder, and other ground minerals. Organic fillers may also be used, particularly carbon black, graphite, wood fiber, wood flour, sawdust, cellulose, cotton, pulp, cotton, wood chips, chopped straw, rice husks, ground walnut shells, and other chopped fibers. Short fibers such as glass fiber, glass filament, polyacrylonitrile, carbon fiber, Kevlar fiber, or polyethylene fiber may also be added. Aluminum powder is also suitable as a filler.

[0132] Pyrolytic silicic acid and / or precipitated silicic acid advantageously have 10 to 90 m 2 / g BET surface area. When used, they do not cause any additional increase in viscosity of the compositions according to the invention, but do help to enhance the cured compositions.

[0133] Similarly, it is conceivable to use areas with a high BET surface area, advantageously 100 to 250 m².2 / g, especially 110 to 170m 2 / g of pyrolytic silica and / or precipitated silica as fillers: Due to the larger BET surface area, a smaller weight proportion of silica is used to enhance the cured composition.

[0134] Hollow spheres with mineral or plastic shells are also suitable as fillers. For example, these can be hollow glass spheres, which are commercially available under the trade name Glass Bubbles®. Plastic-based hollow spheres (such as Expancel® or Dualite®) can also be used, and are described in EP 0 520 426 B1: they are composed of inorganic or organic materials and each has a diameter of 1 mm or less, preferably 500 µm or less.

[0135] Fillers that impart thixotropic properties to the composition may be preferred for many applications: such fillers are also described as rheology modifiers, such as hydrogenated castor oil, fatty acid amides, or expandable plastics (such as PVC). In this case, the use of mixed mineral thixotropic modifiers (such as Garamite 7305 available from BYK Chemie) may be mentioned.

[0136] Based on the total weight of the composition, the total amount of filler present in the composition of the present invention will preferably be 0 to 30% by weight, more preferably 0 to 20% by weight. The desired viscosity of the curable composition will generally be determined by the total amount of filler added, and it is considered that in order to be easily extruded from a suitable dispensing device (such as a tube), the curable composition should have a viscosity of 100 to 500 Pa·s, preferably 200 to 500 Pa·s, measured at 20°C.

[0137] It should be noted that compounds with metal chelating properties can be used in the compositions of this invention to help enhance the adhesion of the cured adhesive to the substrate surface. Additionally, acetoacetate-functionalized modified resins, marketed by King Industries under the trade name K-FLEX XM-B301, are also suitable as adhesion promoters.

[0138] Examples of suitable pigments are titanium dioxide, iron oxide, or carbon black.

[0139] To further improve shelf life, it is generally recommended to use a desiccant to further stabilize the composition of the invention in terms of moisture permeability. Occasionally, it may also be necessary to reduce the viscosity of the adhesive or sealant composition according to the invention for a particular application by using one or more reactive diluents. Based on the total weight of the composition, the total amount of reactive diluent present will typically be at most 15% by weight, preferably 1 to 5% by weight.

[0140] The presence of solvents and non-reactive diluents in the compositions of the present invention is also not excluded, which can effectively adjust their viscosity. For example, but only for illustration, the composition may contain 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 Solvesso® products (available from Exxon); alkylphenols, such as tert-butylphenol, nonylphenol, dodecylphenol and 8,11,14-pentadecatrienylphenol; stylated phenols; bisphenols; aromatic hydrocarbon resins, especially those containing phenolic groups, such as ethoxylated or propoxylated phenols; adipates; sebacic acid esters; phthalates; benzoates; organophosphates or sulfonates; and sulfonamides.

[0141] In addition to the above, preferably, based on the total weight of the composition, the solvent and non-reactive diluent together account for less than 10% by weight, particularly less than 5% by weight or less than 2% by weight.

[0142] Illustrative embodiments of the composition According to an exemplary embodiment of the present invention, a one-component (1K) curable composition is provided, wherein, based on the weight of the composition, the one-component (1K) curable composition comprises: 60 to 90% by weight of a) at least one epoxy resin that has been modified with a hydrophobic elastomer, wherein said component a) comprises: 60 to 80% by weight of at least one dimer acid-modified epoxy resin; and 0 to 10% by weight of at least one elastomer-modified resin, wherein the elastomer-modified resin is selected from carboxyl-terminated poly(butadiene-acrylonitrile) (CTBN) modified epoxy resin and urethane modified epoxy resin, and Each modified resin of component a) is characterized in that the epoxy equivalent weight is 200 to 800 g / eq, preferably 250 to 750 g / eq. 1 to 10% by weight, preferably 1 to 5% by weight of b) at least one modified resin different from component a); 1 to 15% by weight, preferably 1 to 10% by weight, of at least one compound providing at least two amine hydrogens reactive to epoxy groups, wherein component c) comprises or is composed of dicyandiamide, and further wherein the dicyandiamide has an average particle size (d50) of 0.5 to 100 μm as determined by dynamic light scattering; and 0.01 to 2% by weight, preferably 0.01 to 1% by weight of d) at least one accelerator, wherein component d) comprises or consists of at least one compound according to formula (I) or formula (II):

[0143] in: X is O; R a R b and R c Independently selected from C1-C8 alkyl, C1-C8 hydroxyalkyl, C3-C 12 cycloalkyl or C6 aryl; and R d It is C6-C 18 aryl or C7-C 18 Alkyl arylene, Based on the total weight of the composition, the composition further comprises up to 10% by weight of core-shell rubber particles; and The composition is characterized in that the molar ratio of epoxy groups to epoxy reactive groups is 0.7:1 to 1.2:1, preferably 0.9:1 to 1.0:1.

[0144] Methods and Applications To form the composition, the above-mentioned components are brought together and mixed. As is known in the art, to form a one-component (1K) curable composition, the components of the composition are brought together and uniformly mixed under conditions that inhibit or prevent the reaction of reactive components: as will be readily understood by those skilled in the art, this may include mixing conditions that limit or prevent exposure to moisture, heat, or radiation, or that limit or prevent the activation of latent catalysts of the components. Therefore, it is generally preferred not to mix the curing agent components manually, but rather to mix them in predetermined amounts under anhydrous conditions without intentional heating or light irradiation using a machine (e.g., a static or dynamic mixer).

[0145] According to the broadest aspect of the invention, the above-described composition is applied to one or more material layers and then cured in situ. Pretreatment of the relevant surfaces to remove foreign matter is generally recommended before application of the composition; this step, if applicable, can promote subsequent adhesion of the composition to them. Such treatments are known in the art and can be carried out in a single-stage or multi-stage manner, consisting of, for example, one or more of the following: etching with an acid suitable for the substrate and optionally an oxidizing agent; ultrasonic treatment; plasma treatment, including chemical plasma treatment, corona treatment, atmospheric plasma treatment, and flame plasma treatment; immersion in an aqueous alkaline degreasing bath; treatment with an aqueous cleaning emulsion; treatment with a cleaning solvent (such as carbon tetrachloride or trichloroethylene); and rinsing with water, preferably with deionized water or demineralized water. In those cases where an aqueous alkaline degreasing bath is used, any degreasing agent remaining on the surface should be expected to be removed by rinsing the substrate surface with deionized water or demineralized water.

[0146] In some embodiments, adhesion of the coating composition of the present invention to a preferably pretreated substrate can be promoted by applying a primer thereto. In practice, a primer composition may be necessary to ensure effective fixation and / or curing time of the adhesive composition on an inactive substrate. While those skilled in the art will be able to select a suitable primer, guiding references for selecting a primer include, but are not limited to: U.S. Patent Nos. 3,855,040; 4,731,146; 4,990,281; 5,811,473; GB 2502554; and U.S. Patent No. 6,852,193.

[0147] The composition is then applied to a preferably pretreated, optionally primed, surface of a substrate by conventional application methods such as: brushing; roller coating using, for example, a 4-application roller apparatus in which the composition is solvent-free or a 2-application roller apparatus for solvent-containing compositions; doctor 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.

[0148] It is recommended to apply the composition to the surface with a wet film thickness of 10 to 500 μm. Applying thinner layers within this range is more cost-effective and offers a reduction in the possibility of harmful thick cured areas. However, strict control must be exercised when applying thinner coatings or layers to avoid the formation of discontinuous cured films.

[0149] The curing of the applied compositions of the present invention typically occurs at temperatures ranging from 40°C to 200°C, preferably from 50°C to 190°C, and particularly from 60°C to 180°C. A suitable temperature depends on the specific compound present and the desired curing rate, and can be determined in each case by those skilled in the art using simple preliminary tests (if necessary). Of course, curing at lower temperatures within the aforementioned range is advantageous because it eliminates the need for significant heating or cooling of the mixture from generally prevailing ambient temperatures. However, where applicable, conventional means, including microwave induction, can be used to raise the temperature of the mixture formed from the respective components of the single-component (1K) composition above the mixing temperature and / or the application temperature.

[0150] For the sake of completeness, it should be noted that this invention does not exclude the preparation of " membrane adhesive A prepolymer mixture of epoxy resin, hardener, and other desired components is applied as a coating to a plastic 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 metal or composite parts, the backing material is peeled off, assembly is completed, and it is cured in an oven or autoclave.

[0151] The curable compositions according to the invention are particularly suitable for: varnishes; inks; adhesives for fibers and / or particles; coatings for glass; coatings for mining materials (such as lime and / or cement-bonded plaster, 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 pavements containing asphalt and tar; coatings and sealants for various plastic surfaces; and coatings for leather and textiles.

[0152] Because the compositions of the present invention can produce high adhesive strength in a short time, they are best suited for forming composite structures by bonding the same or different materials surface to surface. Bonding wood and woody materials together, as well as bonding metal materials together, can be mentioned as exemplary adhesive applications of the compositions of the present invention. Bonding different metal materials together (e.g., bonding aluminum and steel) represents an important utility of the compositions of the present invention.

[0153] The compositions of the present invention are also considered suitable as castable sealant formulations for building electrical components such as cables, optical fibers, cover strips, or plugs. The sealant can be used to protect those components from water and other contaminants, from heat exposure, temperature fluctuations and thermal shock, and from mechanical damage.

[0154] In a particularly preferred embodiment, the compositions of the present invention are used as adhesives or sealants for shaped and joined metal parts, such as those found in vehicles, particularly automobile doors, trunks, hood covers, and panels. The sealants can be used during the manufacture or repair of such parts and will effectively seal those parts and prevent corrosion.

[0155] The following examples are illustrative of the present invention and are not intended to limit the scope of the invention in any way.

[0156] Example The following commercial products are used in the embodiments:

[0157] Example 1 The mixture forms formulation IA1 as described in Table 1 below.

[0158] Table 1

[0159] The following tests were performed on the composition of Example 1 and the reference composition provided by Teroson RB 5191 GB.

[0160] Overlap shear strength test The substrates used are aluminum (AA6016) and stainless steel (HDG), each 0.1 inches thick. The adhesive composition being tested is sandwiched between the aluminum and steel substrates to form a… Aluminum-steel (alu- steel) "Adhesive Structure. Each substrate was cut into samples measuring 2.5 cm × 10 cm (1″ × 4″) for tensile testing. Tensile lap shear (TLS) tests were performed at room temperature based on DIN EN 2243-1:2007. The adhesive overlap area of ​​each substrate sample was 2.5 cm × 2.5 cm (1″ × 1″), with an adhesive thickness of 0.1 cm (40 mils). The applied one-component (1K) adhesive composition was cured in the overlap area by applying a temperature of 180°C for 30 minutes. The bonded structure was then stored at room temperature for 24 hours before the initial tensile test was performed."

[0161] Corrosion resistance conditionsFurther lap shear strength tests were conducted on the aluminum-steel bonded structure, which had undergone: i) neutral salt spray (NSS), in which the structure was arranged at 15-30° from the vertical position in a spray chamber (ERICHSEN model 606 / 400 L) for 500 hours; ii) corrosion cycles according to VDA 233-102 (VDA new) for 6 cycles; and iii) corrosion cycles according to VDA 621-415 (VDA old) for 10 cycles.

[0162] Viscosity The viscosity of the composition was measured using an Anton Paar viscometer (model MCR 72) at 45°C and 50% relative humidity (RH). Parallel plates (PP20) were used at 100 s⁻¹. -1 The shear rate was measured.

[0163] Tensile properties The tensile strength, tensile modulus and elongation at break of a composition cured at 180°C for 30 minutes and prepared as a type 5A specimen were determined at room temperature using an Instron 6800 series testing machine according to ISO EN 527-2.

[0164] Glass transition temperature (Tg) This is according to ASTM E1640 Vitrification was determined by dynamic mechanical analysis (DMA). Standard test method for transition temperature Measured by dynamic mechanical analysis (DMA). Temperature scans from 20 to 150 °C were performed at a ramp rate of 2 K / min.

[0165] Thermogravimetric analysis (TGA) Static TGA testing was performed, in which a certain weight of each cured adhesive was placed on a Mettler Toledo 851. e The sample was placed in a pinhole aluminum crucible in a TGA / SDTA apparatus; under nitrogen purging, the sample was held at 180°C for 30 minutes and the weight loss was measured.

[0166] The results of the above tests are provided in Table 2 below: Table 2

[0167] The specimens according to this disclosure exhibit significant elongation under tensile stress before fracture. Surprisingly, this elongation is not accompanied by a significant decrease in corrosion resistance. Furthermore, embodiments of the invention exhibit high flexibility and low modulus, resulting in good results in CTE (coefficient of thermal expansion) testing. In CTE testing, after bending an embodiment of the invention, the test specimen almost fully recovers its original shape upon cooling, while the reference specimen remains significantly bent.

[0168] In view of the foregoing description and examples, it will be apparent to those skilled in the art that equivalent modifications may be made thereto without departing from the scope of the claims.

Claims

1. A one-component (1K) curable composition, wherein, based on the weight of the composition, the one-component (1K) curable composition comprises: 50 to 90% by weight of a) at least one epoxy resin that has been modified with a hydrophobic elastomer, wherein the epoxy equivalent weight of the modified epoxy resin is 200 to 1000 g / eq. up to 15% by weight of b) at least one epoxy resin different from component a); c) at least one compound providing at least two amine hydrogens reactive to epoxy groups; and 0.01 to 5% by weight of d) at least one accelerator, The composition is characterized in that the molar ratio of epoxy groups to epoxy reactive groups is from 0.5:1 to 1.4:

1.

2. The one-component (1K) curable composition according to claim 1, comprising, based on the weight of the composition: 60 to 90% by weight, preferably 65 to 85% by weight of a) at least one epoxy resin that has been modified with a hydrophobic elastomer, wherein the epoxy equivalent weight of the modified epoxy resin is 200 to 1000 g / eq; 1 to 10% by weight, preferably 1 to 5% by weight of b) at least one modified resin different from component a); 1 to 15% by weight, preferably 1 to 10% by weight, of c) at least one compound providing at least two amine hydrogens reactive to epoxy groups; and 0.01 to 2% by weight, preferably 0.01 to 1% by weight of at least one accelerator (d). The composition is characterized in that the molar ratio of epoxy groups to epoxy reactive groups is 0.7:1 to 1.2:1, preferably 0.9:1 to 1.0:

1.

3. The composition according to claim 1 or claim 2, wherein, Based on the weight of the composition, component a) of the composition comprises: 60 to 80% by weight of at least one dimer acid-modified epoxy resin; and The resin comprises 0 to 20% by weight of at least one elastomer-modified resin, wherein the elastomer-modified resin is selected from carboxyl-terminated poly(butadiene-acrylonitrile) (CTBN) modified epoxy resin and urethane modified epoxy resin. Each modified resin of component a) is characterized by having an epoxy equivalent weight of 200 to 800 g / eq, preferably 250 to 750 g / eq.

4. The composition according to claim 3, wherein the dimer acid-modified epoxy resin of component a1) or each dimer acid-modified epoxy resin is characterized in that the epoxy equivalent weight is 500 to 750 g / eq.

5. The composition according to any one of claims 1-4, wherein component c) comprises a polyamine providing at least two amine hydrogens reactive to epoxy groups or is composed of a polyamine providing at least two amine hydrogens reactive to epoxy groups.

6. The composition according to claim 5, wherein the polyamine or each polyamine contains a primary amine group and / or a secondary amine group, and the equivalent weight of each primary amine group or secondary amine group does not exceed 150 g / eq., more preferably not more than 125 g / eq.

7. The composition according to any one of claims 1-6, wherein component c) comprises or is composed of dicyandiamide, and further wherein the dicyandiamide has an average particle size (d50) of 0.5 to 100 μm as determined by dynamic light scattering.

8. The composition according to any one of claims 1-7, wherein component d) comprises or consists of at least one accelerator selected from the group consisting of: Tertiary amines; urea derivatives; thiourea derivatives; and amidines.

9. The composition according to claim 8, wherein component d) comprises or consists of at least one compound according to formula (I) or formula (II): in: X is O or S; R a R b and R c Independently selected from C1-C 12 Alkyl, C1-C 12 Hydroxyalkyl, C3-C 18 cycloalkyl, or C6-C 18 Aryl; and R d It is C6-C 18 aryl or C7-C 18 Alkyl aryl group.

10. The composition according to claim 9, wherein with respect to formula (I) and formula (II): X is O; R a R b and R c Independently selected from C1-C8 alkyl, C1-C8 hydroxyalkyl, C3-C 12 cycloalkyl or C6 aryl; and R d It is C6-C 18 aryl or C7-C 18 Alkyl aryl group.

11. The composition according to claim 9, wherein component d) comprises at least one compound selected from: Phenylacetic dimethylurea; N,N'-dimethyl-N,N'-diphenyl-urea; N,N-dimethyl-N'-tolylurea; N,N-dibutyl-N'-phenylurea; N,N-dihydroxyethyl-N'-phenylurea; N,N-dicyclohexyl-N'-isopropylurea; 1,1'-(4-methyl-1,3-phenylene)bis(3,3-dimethylurea); 3,4-dichlorophenyldimethylurea (diuron); 4-chlorophenyldimethylurea (meturon); and 4,4'-methylenebis(phenyldimethylurea).

12. The composition according to any one of claims 1-11 further comprises, in an amount of up to 10% by weight of core-shell rubber particles based on the total weight of the composition.

13. The composition according to any one of claims 1-12, characterized in that, At 20℃, it took 15.5 s -1 The viscosity measured by the shear rate is 100 to 500 Pa·s, preferably 200 to 500 Pa·s.

14. A cured product obtained from a single-component (1K) composition as defined in any one of claims 1-13, wherein the cured product is preferably characterized by an elongation at break greater than 100% as determined at room temperature using a type 5A specimen according to ISO EN 527-2.

15. Use of the cured product as an adhesive or sealant in vehicle assembly or repair as defined in claim 14.

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