Coating composition

Abstract

Disclosed is a composition comprising: a first component comprising a compound comprising an epoxy resin; a second component comprising an aliphatic amine, an amido amine, and a toughening amine; an accelerant; and elastomeric particles. Also disclosed is a substrate comprising a surface coated with any of the compositions disclosed herein. Methods of forming the coating and uses of the coating are also disclosed.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. Provisional Application No. 63 / 371,934, filed on August 9, 2022, “Coating Compositions,” the entire contents of which are incorporated herein by reference. Technical Field

[0003] The present disclosure relates to compositions and coatings formed therefrom. Background Art

[0004] Coating compositions (including binders) are used in a variety of applications to treat a variety of substrates or to bond two or more substrate materials together. Summary of the invention

[0005] The present disclosure relates to a composition comprising: a first component comprising an epoxy-containing compound; a second component comprising an aliphatic amine, an amidoamine, and a toughening amine; an accelerator; and elastomeric particles.

[0006] The present disclosure also relates to a substrate comprising a coating formed from any of the compositions disclosed herein on a portion of a surface of the substrate.

[0007] Also disclosed is an article comprising: one of the substrates disclosed herein; and a second substrate; wherein any of the coatings disclosed herein is located between the substrate and the second substrate.

[0008] Also disclosed is a method of coating a substrate comprising contacting a portion of a surface of the substrate with any of the compositions disclosed herein.

[0009] Also disclosed are methods of forming an article comprising extruding any of the compositions disclosed herein.

[0010] Also disclosed is the use of any of the coating compositions disclosed herein for coating a surface of a substrate, wherein the coating comprises (a) a lap shear strength of at least 12 MPa measured according to ASTM D1002-10 using a 0.8 mm thick HDG substrate dip-coated with a 10 wt % solution of Multidraw KTL N16 oil in heptane using an INSTRON 5567 machine in tensile mode at a pull rate of 10 mm per minute, and (b) a wedge impact peel resistance of at least 2.0 N / mm tested according to ISO 11343 dynamic splitting resistance test using a 0.8 mm thick HDG substrate dip-coated with a 10 wt % solution of Multidraw KTL N 16 oil in heptane using an INSTRON CEAST 9350 drop tower model at an impact velocity of 2 m / sec at -40°C, wherein the sample is conditioned at -40°C for at least 30 minutes prior to testing. DETAILED DESCRIPTION

[0011] For the purpose of this detailed description, it should be understood that the present disclosure may take alternative variations and step sequences except for the cases explicitly stated to the contrary. In addition, except in any operating examples, or in the case of other indications, all figures expressing the amount of ingredients such as used in this specification and claims should be understood to be modified by the term "about" in all cases. Therefore, unless otherwise indicated, the numerical parameters set forth in the following specification and the attached claims are approximate values ​​that can be changed according to the desired properties to be obtained by the present disclosure. At least, and not attempting to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be interpreted according to the number of reported significant figures and by applying common rounding techniques.

[0012]

[0013] While the numerical ranges and parameters setting forth the broad scope of the present disclosure are approximations, the numerical values ​​set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

[0013] Moreover, all numerical ranges recited herein are intended to include all subranges recited herein. For example, a range of "1 to 10" is intended to include all subranges between (and ratios of) the recited minimum value of 1 and the recited maximum value of 10, i.e., having a minimum value equal to or greater than 1 and a maximum value equal to or less than 10.

[0014] As used herein, "including," "containing," and similar terms are understood to be synonymous with "comprising" in the context of this application, and are thus open ended and do not exclude the presence of additional undescribed or unrecited elements, materials, components, or method steps. As used herein, open ended terms encompass closed terms, such as consisting essentially of and consisting of.

[0015] As used herein, "consisting of is to be understood in the context of this application as excluding the presence of any unspecified elements, ingredients or method steps.

[0016] As used herein, “consisting substantially of” is understood in the context of this application to include the specified elements, materials, ingredients, or method steps “as well as those elements, materials, ingredients, or method steps that do not materially affect the basic and novel characteristics of what is described.”

[0017] In this application, unless specifically stated otherwise, the use of the singular includes the plural, and the plural encompasses the singular. For example, although "an" epoxy resin-containing compound and "an" accelerator are mentioned herein, combinations of these components (i.e., a plurality of these components) may be used.

[0018] Additionally, in this application, the use of "or" means "and / or" unless specifically stated otherwise, even though "and / or" may be explicitly used in certain circumstances.

[0019] As used herein, the terms "on", "onto", "applied on", "applied onto", "formed on", "deposited on", "deposited onto", "injected on", "injected onto", and the like mean formed, covered, deposited, or disposed on a substrate surface, but not necessarily in contact with the substrate surface. For example, a composition "applied onto" a substrate surface does not exclude the presence of one or more other intermediate coatings or films of the same or different composition located between the composition and the substrate surface.

[0020] As used herein, "coating composition" refers to a composition, such as a solution, mixture or dispersion, that is capable of producing a coating on a portion of a substrate surface. As used herein, "coating" includes films, layers, and the like.

[0021] As used herein, the term "adhesive" means a coating that creates a load-bearing joint.

[0022] As used herein, the term "structural adhesive composition" means a composition that, when cured, forms a structural adhesive.

[0023] As used herein, the term "structural adhesive" means an adhesive that produces a load-bearing joint having a lap shear strength of at least 10.0 MPa as measured in accordance with ASTM D1002-10 using a hot dip galvanized (HDG) steel substrate having a thickness of 0.8 mm as measured using an INSTRON 5567 machine in tension mode at a pull rate of 10 mm per minute.

[0024] As used herein, the term "potentiator" refers to a sealant.

[0025] As used herein, the term "gap filler" refers to a coating that fills a gap.

[0026] As used herein, the term "prepreg" refers to a composition in which reinforcing fibers are pre-impregnated prior to curing.

[0027] As used herein, the term "liquid gasket" refers to a coating that eliminates gaps between substrate surfaces.

[0028] As further defined herein, ambient conditions generally refer to room temperature (e.g., 23°C) and humidity conditions or the temperature and humidity conditions typically found in the area where the composition is applied to the substrate, such as at 10°C to 40°C and 5% to 80% relative humidity.

[0029] As used herein, the term "two-component" or "2K" refers to a composition in which a portion of the reactive components readily associate to form an interaction or react to form a bond (physically or chemically) when mixed, i.e., cure without activation from an external energy source, such as under ambient conditions or slight heat conditions. It will be understood by those skilled in the art that the two components of the composition are stored separately from each other and mixed only prior to applying the composition. As described below, the two-component composition can be optionally heated or baked.

[0030] As used herein, the term "cure" or "curing" means that the components forming the composition crosslink (i.e., interact and / or react) to form a coating or bond. In the case of a 2K composition, the composition begins to cure when the components of the composition are mixed so that the reactive functional groups of the components of the composition react.

[0031] As used herein, "monoamine" refers to an organic compound having one amino functional group.

[0032] As used herein, "diamine" refers to an organic compound having two amino functional groups.

[0033] As used herein, "polyamine" refers to an organic compound having more than two amino functional groups.

[0034] As used herein, "amino functional group" refers to a functional group including a nitrogen atom connected to a hydrogen atom, an alkyl group and / or an aryl group via a single bond.

[0035] As used herein, "epoxide functional group" refers to a functional group including a cyclic ether having a three-atom ring.

[0036] As used herein, "amine hydrogens" refers to the number of active hydrogens directly bonded to the nitrogen atom of an amine or another nitrogen-containing functional group. "Active hydrogens" refers to hydrogens that can be displaced when an amine-containing or nitrogen-containing functional group reacts as a nucleophile with a suitable electrophile, and can be determined, for example, by the Zerevitenov test. Active hydrogens on all accelerators and curing agents (e.g., diamines and / or polyamines) are included in the amine hydrogens of the compositions of the present disclosure.

[0037] As used herein, "epoxide equivalent weight" refers to the weight (in grams) of a material containing one stoichiometric equivalent of epoxy functional groups. Epoxide equivalent weight can be determined, for example, by titrating a sample using a Metrohm 808 or 888 Titrando, using 0.06 g / 100 g / equivalent to predict the epoxy equivalent weight of the sample and dissolving the sample in 20 mL of dichloromethane or tetrahydrofuran, and then adding 40 mL of glacial acetic acid and one gram of tetraethylammonium bromide, and then titrating with 0.1 N perchloric acid in glacial acetic acid.

[0038] As used herein, "Mw" refers to the weight average molecular weight, such as the theoretical value determined by gel permeation chromatography using a Waters 2695 separation module with a Waters 410 differential refractometer (RI detector) and polystyrene standards, where tetrahydrofuran (THF) is used as the flow rate of 1 ml min -1 The eluate was mixed with two PL gel C columns for separation.

[0039] As used herein, "polymer" refers to a molecule comprising chemically bonded repeating units or monomeric units and may include oligomers, homopolymers, and copolymers.

[0040] As used herein, "small molecule" refers to a molecule comprising a discrete chemical structure, having a molecular weight less than 1200 g / mol and not a polymer (i.e., not consisting of repeating monomer units). The molecular weight of a small molecule can be determined by mass spectrometry. Suitable mass spectrometry for various types of small molecules is available in many references, such as Mass Spectrometry: A Textbook (3rd edition, 2018, edited by Jürgen Gross).

[0041] As used herein, the term "reactive diluent" refers to a molecule or compound used to reduce the viscosity of a formulation and having at least one functional group capable of reacting with a functional group on a molecule or compound in the composition.

[0042] As used herein, the term "plasticizer" refers to a molecule or compound that has no functional groups capable of reacting with functional groups on molecules or compounds in the composition and is added to the composition to reduce viscosity, lower the glass transition temperature (Tg) and impart flexibility.

[0043] As used herein, the term "promoter" means a substance that increases the rate of a chemical reaction or decreases the activation energy of a chemical reaction compared to the same reaction in the absence of the promoter. A promoter can be a "catalyst," i.e., does not undergo any permanent chemical change itself, or can be reactive, i.e., capable of chemical reaction and comprising any level of reaction from partial reaction of the reactants to complete reaction.

[0044] As used herein, unless otherwise indicated, the term "substantially free" means that the particular material has not been purposefully added to the mixture or composition and that the particular material is present only as a trace impurity of less than 5 wt %, based on the total weight of the mixture or composition.

[0045] As used herein, unless otherwise indicated, the term "substantially free" means that the particular material has not been purposefully added to the mixture or composition and that the particular material is present only as a trace impurity of less than 2 weight percent based on the total weight of the mixture or composition.

[0046] As used herein, unless otherwise indicated, the term "entirely free of" means that a mixture or composition does not include a particular material, ie, the mixture or composition includes 0% by weight of such material.

[0047] Disclosed herein is a composition comprising, or consisting essentially of, or consisting of: a first component comprising, or consisting essentially of, or consisting of, an epoxy-containing compound; a second component comprising, or consisting essentially of, or consisting of, aliphatic amines, amidoamines, and toughening amines; an accelerator; and elastomeric particles.

[0048] Component 1

[0049] As discussed above, the first component of the composition may include an epoxy-containing compound.

[0050] In some cases, the epoxy-containing compound may include an aromatic epoxy resin. As used herein, the term "aromatic epoxy resin" refers to an epoxy-containing compound that includes at least one aromatic group.

[0051] Useful aromatic epoxy resins that may be used include polyepoxides (having an epoxy functionality greater than 1), epoxy adducts, or combinations thereof. Suitable polyepoxides include polyglycidyl ethers of bisphenol A, such as 828 and 1001 epoxy resins, and bisphenol F polyepoxides such as 862, which is commercially available from Hexion Specialty Chemicals, Inc. Other non-limiting aromatic epoxy resins include bisphenol S diglycidyl ether, epoxidized bisphenol A novolac, epoxidized phenolic resin novolac, epoxidized cresol novolac, triglycidyl p-aminophenol, triglycidyl p-aminophenol bismaleimide, tetraglycidyl 4,4'-diaminodiphenylmethane, tetraglycidyl m-xylene diamine, and tetraglycidyl 4,4'-diaminodiphenyl sulfone.

[0052] The aromatic epoxy resin may include a monoepoxide. Suitable aromatic monoepoxides include glycidyl ethers of phenols, such as phenyl glycidyl ether or cresyl glycidyl ether. The epoxy-containing compound may include a combination of any of the above aromatic polyepoxides and any of the above aromatic monoepoxides.

[0053] In some cases, the compound containing epoxy resin can include aliphatic epoxy resin. As used herein, the term "aliphatic epoxy resin" refers to a compound containing epoxy resin without any aromatic group. Useful aliphatic epoxy resins include polyglycidyl ethers of polyols, polyglycidyl esters of polycarboxylic acids, polyepoxides derived from the epoxidation of olefinically unsaturated alicyclic compounds, or polyepoxides containing oxyalkylene groups in epoxy molecules. The compound containing epoxy resin can also include acrylic acid containing epoxy resin, such as a copolymer comprising glycidyl methacrylate. The non-limiting examples of aliphatic epoxy resins include ethylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, hexanediol diglycidyl ether, isosorbide diglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolethane diglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether and triglycidyl isocyanurate.

[0054] Aliphatic epoxy resins may include monoepoxides. Suitable aliphatic monoepoxides that may be used include glycidol, monoglycidyl ethers of aliphatic alcohols (such as n-butyl glycidyl ether, isopropyl glycidyl ether, tert-carbonic acid glycidyl esters (e.g., CARDURA E commercially available from Shell Chemical Co., UK), glycidyl ethers of aliphatic alcohols (e.g., Epodil 748 commercially available from Evonik Industries (Evonik)) and glycidyl esters of monocarboxylic acids (such as glycidyl ester neodecanoate), and mixtures of any of the foregoing. Further non-limiting examples include epoxidized vegetable oils and epoxidized polyether glycols, such as polypropylene glycol diglycidyl ether or poly (butylene glycol) diglycidyl ether.

[0055] The epoxy-containing compound may include a combination of any of the above-described aromatic epoxides and any of the above-described aliphatic epoxides.

[0056] The epoxy-containing compound may include an epoxy adduct. The composition may include one or more epoxy adducts. As used herein, the term "epoxy adduct" refers to a reaction product comprising a residue of an epoxy resin and at least one other compound that does not contain an epoxide functional group. The epoxy adduct may include an aromatic epoxy resin or an aliphatic epoxy resin. The epoxy-containing compound may include a carboxyl-terminated butadiene-acrylonitrile copolymer added to the epoxy-containing compound. In addition, the epoxy adduct may include a reaction product of reactants that include an epoxy resin, a polyol, and an anhydride. The term "epoxy adduct" used with respect to the epoxy-containing compound is different from the epoxide functional adduct described below.

[0057] The epoxy resin used to form the epoxy adduct may include any of the epoxy-containing compounds listed above as being included in the composition.

[0058] The polyol for forming epoxy resin adduct can comprise diol, triol, tetraol and higher functional polyol.Can also use the combination of such polyol.Polyol can be based on the polyether chain produced by ethylene glycol, propylene glycol, butylene glycol, hexylene glycol etc. and its mixture.Polyol can also be based on the polyester chain (hereinafter referred to as polyol based on polycaprolactone) produced by the ring-opening polymerization of caprolactone.Suitable polyol can also comprise polyether polyol, polyurethane polyol, polyurea polyol, acrylic polyol, polyester polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, polycarbonate polyol, polysiloxane polyol and its combination.Can also use the polyamine corresponding to polyol, and in this case, will form amide instead of carboxylate with acid anhydride.

[0059] The polyol may include a polycaprolactone-based polyol. The polycaprolactone-based polyol may include a diol, a triol, or a tetraol terminated with a primary hydroxyl group. Commercially available polycaprolactone-based polyols include those from the Perstorp Group under the trade name Capa TM Those sold, for example, Capa 2054, Capa 2077A, Capa 2085, Capa 2205, Capa 3031, Capa 3050, Capa 3091 and Capa 4101.

[0060] The polyol may include a polytetrahydrofuran-based polyol. The polytetrahydrofuran-based polyol may include a diol, a triol, or a tetrols terminated with primary hydroxyl groups. Commercially available polytetrahydrofuran-based polyols include those available from Invista under the trade name Polyols based on polytetrahydrofuran are sold as PTMEG 250 and PTMEG 650, these are blends of linear diols in which the hydroxyl groups are separated by repeating tetramethylene ether groups. Alternatively, polyols available from Corning under the trade name Solvermol TM and Polyols based on dimer diols are sold as such or bio-based polyols such as the tetrafunctional polyol Agrol 4.0 available from BioBased Technologies.

[0061] The anhydride that can be used to form the epoxy adduct can include any suitable anhydride known in the art. For example, the anhydride can include hexahydrophthalic anhydride and its derivatives (e.g., methylhexahydrophthalic anhydride); phthalic anhydride and its derivatives (e.g., methylphthalic anhydride); maleic anhydride; succinic anhydride; trimellitic anhydride; pyromellitic dianhydride (PMDA); 3,3',4,4'-oxydiphthalic dianhydride (ODPA); 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA); and 4,4'-diphthalic acid (hexafluoroisopropyl) anhydride (6FDA).

[0062] The epoxy adduct may include a diol, a monoanhydride, and a diepoxide, wherein a molar ratio of the diol, the monoanhydride, and the diepoxide in the epoxy adduct may be in a range of 0.5:0.8:1.0 to 0.5:1.0:6.0.

[0063] The epoxy adduct may include a triol, a monoanhydride, and a diepoxide, wherein a molar ratio of the triol, the monoanhydride, and the diepoxide in the epoxy adduct may be in a range of 0.5:0.8:1.0 to 0.5:1.0:6.0.

[0064] The epoxy adduct may include a tetraol, a monoanhydride, and a diepoxide, wherein a molar ratio of the tetraol, the monoanhydride, and the diepoxide in the epoxy adduct may be in a range of 0.5:0.8:1.0 to 0.5:1.0:6.0.

[0065] Other suitable epoxy-containing compounds include epoxy adducts such as epoxy polyesters formed as the reaction product of reactants including an epoxy-containing compound, a polyol, and an anhydride, as described in U.S. Pat. No. 8,796,361 at column 3, line 42 to column 4, line 65, the cited portion of which is incorporated herein by reference.

[0066] The first component optionally may include an epoxy-containing reactive diluent, such as those commonly used in coating compositions such as adhesive compositions, and such reactive diluents may be included as epoxy-containing compounds.

[0067] Based on the total weight of the first component, the first component may include at least 30% by weight, such as at least 35% by weight, such as at least 40% by weight of the epoxy resin-containing compound. Based on the total weight of the first component, the first component may include no more than 100% by weight, such as no more than 60% by weight, such as no more than 55% by weight, such as no more than 50% by weight of the epoxy resin-containing compound. Based on the total weight of the first component, the first component may include up to 100% by weight, such as 30% to 100% by weight, such as 30% to 60% by weight, such as 35% to 55% by weight, such as 40% to 50% by weight of the epoxy resin-containing compound.

[0068] As described above, the first component may include aromatic monoepoxides, aliphatic monoepoxides and / or aliphatic polyepoxides. If present, based on the total weight of the first component, the first component may include at least 0.1 wt %, such as at least 0.2 wt %, such as at least 0.5 wt % of such epoxides. Based on the total weight of the first component, the first component may include no more than 30 wt %, such as no more than 25 wt %, such as no more than 20 wt % of such epoxides. If present, based on the total weight of the first component, the first component may include 0.1 wt % to 30 wt %, such as 0.2 wt % to 25 wt %, such as 0.5 wt % to 20 wt % of such epoxides.

[0069] Second component

[0070] The second component of the composition disclosed herein may include an aliphatic amine. As used herein, when used with respect to an ingredient of the second component, the term "aliphatic amine" refers to an aliphatic amine that is substantially free of oxygen, sulfur, and / or selenium and comprises a molecular weight of no more than 295 g / mol as measured using mass spectrometry as described herein above.

[0071] Aliphatic amines may include alicyclic amines, linear or branched aliphatic amines without cyclic groups, aromatic aliphatic amines, or amines containing ethyleneimine subunits. Useful aliphatic diamines include, but are not limited to, ethylenediamine, tetramethylenediamine, hexamethylenediamine, octamethylenediamine, 2-methylpentamethylenediamine (commercially available from INVISTA with Dytek A). Useful alicyclic amines include, but are not limited to, isophoronediamine, 4,4-diaminodicyclohexylmethane, 4,4'-methylenebis(2-methylcyclohexyl-amine), diaminocyclohexane, bis(aminomethyl)norbornane, bis(aminomethyl)cyclohexane, piperazine, and aminoethylpiperazine. Useful aromatic aliphatic amines include ortho-isomers, meta-isomers, and para-isomers of benzyl diamine and mixtures thereof. Useful amines containing ethyleneimine subunits include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, higher oligomers, and tris(aminoethyl)amine.

[0072] The aliphatic amine may comprise a molecular weight of at least 60 g / mol, such as at least 80 g / mol, such as at least 110 g / mol. The aliphatic amine may comprise a molecular weight of no more than 295 g / mol, such as no more than 260 g / mol, such as no more than 250 g / mol. The aliphatic amine may comprise a molecular weight of 60 g / mol to 295 g / mol, such as 80 g / mol to 260 g / mol, such as 110 g / mol to 250 g / mol. The molecular weight of the aliphatic amine may be measured using mass spectrometry as described above.

[0073] The second component may comprise an amidoamine. Amidoamine refers to any compound comprising an amide bond and an amine functional group. Fatty acid amidoamine refers to an amidoamine comprising a fatty acid residue.

[0074] The suitable example of amidoamine comprises the reaction product of any acid-functional compound and any polyamine or the combination of polyamine.The suitable example of the acid-functional compound that is suitable for producing amidoamine comprises fatty acid, dimer fatty acid, trimer fatty acid, acid-functional polymer such as polyester or acrylic copolymer and / or acid-functional small molecule.Suitable acid includes but is not limited to succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, cyclohexanedicarboxylic acid, azelaic acid, sebacic acid, undecane dioic acid, dodecanedioic acid, tridecanedioic acid, malic acid, tartaric acid, phthalic acid, isophthalic acid and terephthalic acid.Additional suitable acid comprises acrylic copolymer, and it comprises acid-functional monomer such as acrylic acid, methacrylic acid, maleic acid or itaconic acid.

[0075] In some cases, the amidoamine may include a fatty acid amidoamine comprising the reaction product of a fatty acid, a dimerized fatty acid, and / or a trimerized fatty acid with any polyamine or combination of polyamines. Suitable fatty acid amidoamines include Versamid 100, Versamid 125, Versamid 140, and Versamid 150, commercially available from Huntsman Corporation. Additional suitable fatty acid amidoamines include Versamid 100, Versamid 125, Versamid 140, and Versamid 150, commercially available from Evonik Industries AG. Amidoamine products, commercially available from Epochemie International, Jointmide products, commercially available from Cargill, Inc. Amidoamine and Epikure commercially available from Westlake Corporation TM Amidoamine curing agent. In some cases, the amidoamine can be the reaction product of a fatty acid and an amine containing an ethyleneimine subunit, such as diethylenetriamine, triethylenetetramine, or tetraethylenepentamine. In some cases, the amidoamine can be the reaction product of a fatty acid and an aliphatic amine or an alicyclic amine.

[0076] The second component may include a toughening amine. As used herein, the term "toughening amine" refers to an ether amine having a molecular weight greater than 140 g / mol or a fatty acid dimer or trimer amine having a molecular weight greater than 295 g / mol.

[0077] Suitable toughening amines include oligomeric or polymeric diamines or polyamines having a glass transition temperature greater than -150°C and less than 30°C, such as calculated using the Fox equation.

[0078] Suitable examples of toughening amines include amine terminated polyethers such as amine terminated poly(propylene glycol) or amine terminated poly(ethylene glycol)-poly(propylene glycol) copolymers. Suitable examples include Jeffamine D-400, Jeffamine ED-600 and Jeffamine ED-900, commercially available from Huntsman Corporation.

[0079] In some preferred cases, the toughening amine may include an amine-terminated polymer or oligomer comprising poly(tetramethylene ether glycol) subunits. A suitable example is an amine-terminated poly(tetramethylene ether glycol)-poly(propylene glycol) copolymer, commercially available as Jeffamine THF-100 from Huntsman.

[0080] Additional useful aliphatic etheramines include ethylene glycol bis(2-aminoethyl) ether (commercially available as Jeffamine EDR-148 from Huntsman), diethylene glycol bis(2-aminoethyl) ether, diethylene glycol bis(3-aminopropyl) ether (commercially available as Ancamine 1922A from Evonik Industries or Baxxodur EC 130 from BASF SE), bis(aminopropyl) 1,4-butanediol (commercially available from BASF SE), or combinations thereof. In some cases, these etheramines can be modified by reaction / adduction with other molecules such as epoxy resins, carboxylic acids, or phenolic resins.

[0081] The toughening amine including etheramine may include a molecular weight greater than 140g / mol, such as at least 170g / mol, such as at least 210g / mol. The toughening amine including etheramine may include a molecular weight of no more than 2,000g / mol, such as no more than 1,700g / mol, such as no more than 1,300g / mol, such as no more than 1,200g / mol. The toughening amine may include a molecular weight greater than 140g / mol to 2,000g / mol, such as 170g / mol to 1,700g / mol, such as 210g / mol to 1,300g / mol, such as 210g / mol to 1,200g / mol. The molecular weight of the toughening amine can be measured using mass spectrometry as described above.

[0082] Additional suitable examples of toughening amines include fatty acid dimer or trimer diamines commercially available from Croda Smart Materials. Suitable examples include Priamine 1071, Priamine 1074 and Priamine 1075.

[0083] The toughening amine comprising a fatty acid dimer or trimer amine may comprise a molecular weight greater than 295 g / mol, such as at least 400 g / mol, such as at least 500 g / mol. The toughening amine may comprise a molecular weight of no more than 2,000 g / mol, such as no more than 1,700 g / mol, such as no more than 1,300 g / mol, such as no more than 1200 g / mol. The toughening amine may comprise a molecular weight of greater than 295 g / mol to 2,000 g / mol, such as 400 g / mol to 1,700 g / mol, such as 500 g / mol to 1,300 g / mol, such as 500 g / mol to 1,200 g / mol. The molecular weight of the toughening amine may be measured using mass spectrometry as described above.

[0084] Based on the total weight of the toughening amine, the aliphatic amine and the amidoamine, the second component may include at least 15 wt %, such as at least 25 wt % of the toughening amine. Based on the total weight of the toughening amine, the aliphatic amine and the amidoamine, the second component may include no more than 75 wt %, such as no more than 65 wt %, such as no more than 60 wt % of the toughening amine. Based on the total weight of the toughening amine, the aliphatic amine and the amidoamine, the second component may include 15 wt % to 75 wt %, such as 25 wt % to 65 wt %, such as 25 wt % to 60 wt % of the toughening amine.

[0085] Based on the total weight of the toughening amine, the aliphatic amine and the amidoamine, the second component may include at least 5 wt%, such as at least 10 wt%, such as at least 15 wt% of the aliphatic amine. Based on the total weight of the toughening amine, the aliphatic amine and the amidoamine, the second component may include no more than 50 wt%, such as no more than 45 wt%, such as no more than 40 wt% of the toughening amine. Based on the total weight of the toughening amine, the aliphatic amine and the amidoamine, the second component may include 5 wt% to 50 wt%, such as 10 wt% to 45 wt%, such as 15 wt% to 40 wt% of the toughening amine.

[0086] Based on the total weight of the toughening amine, the aliphatic amine and the amidoamine, the second component may include at least 5 wt %, such as at least 10 wt %, such as at least 15 wt % of the toughening amine. Based on the total weight of the toughening amine, the aliphatic amine and the amidoamine, the second component may include no more than 75 wt %, such as no more than 50 wt %, such as no more than 40 wt % of the toughening amine. Based on the total weight of the toughening amine, the aliphatic amine and the amidoamine, the second component may include 5 wt % to 75 wt %, such as 10 wt % to 50 wt %, such as 15 wt % to 40 wt % of the toughening amine.

[0087] Accelerator

[0088] In addition to the above-mentioned aliphatic amines, toughening amines and curing agents based on amidoamines, additional accelerators may also be included to further improve adhesive properties. These include but are not limited to additional amines, amine adducts, thiols or other nucleophilic compounds. These curing agents may be monofunctional, difunctional or multifunctional with respect to their epoxy reactive functional groups. Useful monoamines include but are not limited to aniline, ethanolamine, N-methylethanolamine, butylamine, benzylamine, allylamine, ethylhexylamine, polypropylene glycol monoamines (such as Jeffamine-M600 commercially available from Huntsman). Adducts of any of the above-mentioned amines and epoxy resins may be included. Additional curing agents based on amine groups may be included, such as phenalkamines.

[0089] In other examples, the accelerator may include or consist essentially of or consist of guanidine. It should be understood that, as used herein, "guanidine" refers to guanidine and its derivatives. For example, curing agents that may be used include guanidine, substituted guanidine, substituted urea, melamine resins, guanamine derivatives, and / or mixtures thereof. Examples of substituted guanidines are methylguanidine, dimethylguanidine, trimethylguanidine, tetramethylguanidine, methylisobiguanide, dimethylisobiguanide, tetramethylisobiguanide, hexamethylisobiguanide, heptamethylisobiguanide, and specifically cyanoguanidine (dicyandiamide, such as available from AlzChem) Representatives of suitable guanamine derivatives which may be mentioned are alkylated benzoguanamine resins, benzoguanamine resins or methoxymethylethoxymethylbenzoguanamine.

[0090] For example, guanidine may include compounds, moieties and / or residues having the following general structure:

[0091]

[0092] Wherein R1, R2, R3, R4 and R5 (that is, the substituent of structure (IV)) each comprises hydrogen, (cyclo) alkyl, aryl, aromatic, organometallic, polymer structure, or can form cycloalkyl, aryl or aromatic structure together, and wherein R1, R2, R3, R4 and R5 can be identical or different.As used herein, " (cyclo) alkyl " refers to both alkyl and cycloalkyl.When any R group in R group " can form (cyclo) alkyl, aryl and / or aromatic group together ", it means that any two adjacent R groups connect to form cyclic part, such as the ring in structure (V)-(VIII) below.

[0093] It should be understood that the double bond between the carbon atom and the nitrogen atom depicted in structure (IV) can be positioned between the carbon atom of structure (IV) and another nitrogen atom. Thus, various substituents of structure (IV) can be attached to different nitrogen atoms depending on where the double bond is positioned within the structure.

[0094] The guanidine may include cyclic guanidines, such as guanidines of structure (IV), wherein two or more R groups of structure (IV) together form one or more rings. In other words, cyclic guanidines may include > 1 ring. For example, the cyclic guanidine can be a monocyclic guanidine (1 ring), such as depicted in structures (V) and (VI) below, or the cyclic guanidine can be a bicyclic or polycyclic guanidine ( > 2 rings), such as depicted below in structures (VII) and (VIII).

[0095]

[0096]

[0097] Each substituent, R1-R7, of structures (V) and / or (VI) may include hydrogen, (cyclo)alkyl, aryl, aromatic, organometallic, polymeric structures, or together may form cycloalkyl, aryl or aromatic structures, and wherein R1-R7 may be the same or different. Similarly, each substituent, R1-R9, of structures (VII) and (VIII) may be hydrogen, alkyl, aryl, aromatic, organometallic, polymeric structures, or together may form cycloalkyl, aryl or aromatic structures, and wherein R1-R9 may be the same or different. Furthermore, in some examples of structures (V) and / or (VI), certain combinations of R1-R7 may be part of the same ring structure. For example, R1 and R7 of structure (V) may form part of a monocyclic structure. Furthermore, it should be understood that any combination of substituents (R1-R7 of structures (V) and / or (VI) and R1-R9 of structures (VII) and / or (VIII)) may be selected so long as the substituents do not substantially interfere with the catalytic activity of the cyclic guanidine.

[0098] Each ring in a cyclic guanidine may contain > 5 members. For example, a cyclic guanidine can include a 5-membered ring, a 6-membered ring, and / or a 7-membered ring. As used herein, the term "member" designates an atom located in a ring structure. Thus, a 5-membered ring will have 5 atoms in the ring structure ("n" and / or "m" = 1 in Structures (V)-(VIII)), a 6-membered ring will have 6 atoms in the ring structure ("n" and / or "m" = 2 in Structures (V)-(VIII)), and a 7-membered ring will have 7 atoms in the ring structure ("n" and / or "m" = 3 in Structures (V)-(VIII)). It should be understood that if a cyclic guanidine consists of > If the cyclic guanidine comprises two rings (e.g., structures (VII) and (VIII)), the number of members in each ring of the cyclic guanidine can be the same or different. For example, one ring can be a 5-membered ring and the other ring can be a 6-membered ring. >3 rings, then, except for the combinations recited in the preceding sentence, the number of members in the first ring of the cyclic guanidine may be different from the number of members in any other ring of the cyclic guanidine.

[0099] It should also be understood that the nitrogen atom of structures (V)-(VIII) may further have additional atoms attached thereto. In addition, the cyclic guanidine may be substituted or unsubstituted. For example, as used herein in conjunction with cyclic guanidines, the term "substituted" refers to a cyclic guanidine in which R5, R6 and / or R7 of structures (V) and / or (VI) and / or R9 of structures (VII) and / or (VIII) are not hydrogen. As used herein in conjunction with cyclic guanidines, the term "unsubstituted" refers to a cyclic guanidine in which R1-R7 of structures (V) and / or (VI) and / or R1-R9 of structures (VII) and / or (VIII) are hydrogen.

[0100] The cyclic guanidine may include a bicyclic guanidine, and the bicyclic guanidine may include 1,5,7-triazabicyclo[4.4.0]dec-5-ene ("TBD" or "BCG") or 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD).

[0101] Other useful accelerators may include amines, amino-containing phenols, dihydrazides, imidazoles or dicyandiamide adducts and complexes, such as those commercially available from Ajinomoto Fine Techno Company, product, 3,4-dichlorophenyl-N,N-dimethylurea (also known as Diuron), which is commercially available from AlzChem, or a combination thereof.

[0102] Useful promoters that can be included in the second component of the composition can include secondary amines, tertiary amines, cyclic tertiary amines, amidines, or combinations thereof. Cyclic tertiary amines can include 1,4-diazabicyclo[2.2.2]octane ("DABCO"), 1,8-diazabicyclo[5.4.0]undec-7-ene ("DBU"), 1,5-diazabicyclo[4.3.0]non-5-ene ("DBN"), and combinations thereof. Additional examples of suitable promoters include pyridine, imidazole, dimethylaminopyridine, 1-methylimidazole, N,N'-carbonyldiimidazole, [2,2]bipyridine, 2,4,6-tris(dimethylaminomethyl)phenol, 3,5-dimethylpyrazole, and combinations thereof. Additional examples of useful promoters include Mannich bases, tetraalkyl quaternary ammonium salts, metal salts, and metal salts.

[0103] The accelerator may contain both a tertiary amine and a group that reacts with an epoxy group. The accelerator may contain a tertiary amine and a primary amine. Examples of such accelerators include tris(2-aminoethyl)amine, tris(3-aminopropyl)amine, tris[2-(methylamino)ethyl]amine, 2-(dimethylamino)ethylamine, 3-(dimethylamino)-1-propylamine, 1,4-bis(3-aminopropyl)piperazine, N,N,N',N,-tetra(3-aminopropyl)-1,4-butanediamine.

[0104] Based on the total weight of the composition, the composition may include at least 0.1 wt %, such as at least 0.2 wt %, such as at least 0.5 wt % of the accelerator. Based on the total weight of the composition, the composition may include no more than 10 wt %, such as no more than 5 wt %, such as no more than 2.5 wt % of the accelerator. Based on the total weight of the composition, the composition may include 0.1 wt % to 10 wt %, such as 0.2 wt % to 5 wt %, such as 0.5 wt % to 2.5 wt % of the accelerator.

[0105] Elastomer particles

[0106] The composition may further include elastomeric particles. The elastomeric particles may be in the first component, the second component, the third or higher component, or a combination thereof. As used herein, "elastomeric particles" refer to particles consisting of one or more materials having at least one glass transition temperature (Tg) greater than -150°C and less than 30°C, the glass transition temperature being calculated, for example, using the Fox equation or, for example, measured using differential scanning calorimetry. As used herein, the term "glass transition temperature" ("Tg") refers to the temperature at which an amorphous material such as a glass or polymer changes from a brittle glass state to a plastic state or from a plastic state to a brittle glass state.

[0107] The elastomeric particles may be phase separated from the epoxy-containing component. As used herein, the term "phase separated" means the formation of discrete domains within the matrix of the epoxy-containing component.

[0108] Elastomer particles can have a core / shell structure. Suitable core-shell elastomer particles can be made up of acrylic shell and elastomer core. The core can include natural or synthetic rubber, polybutadiene, styrene-butadiene, polyisoprene, chloroprene, acrylonitrile-butadiene, butyl rubber, polysiloxane, polysulfide, ethylene-vinyl acetate, fluoroelastomer, polyolefin or its combination. Elastomer particles, for example, can include polybutadiene core, styrene-butadiene core and / or polysiloxane core. As used herein, " elastomer particles " is not a part for following auxiliary toughening agent.

[0109] According to the present disclosure, as measured by transmission electron microscope (TEM), the average particle size of elastomer particles can be at least 20nm, such as at least 30nm, such as at least 40nm, such as at least 50nm. As measured by transmission electron microscope (TEM), the average particle size of elastomer particles can be no more than 400nm, such as no more than 300nm, such as no more than 200nm, such as no more than 150nm. According to the present disclosure, as measured by TEM, the average particle size of elastomer particles can be 20nm to 400nm, such as 30nm to 300nm, such as 40nm to 200nm, such as 50nm to 150nm. The suitable method of measuring particle size by TEM includes suspending elastomer particles in a solvent selected to make particles not swellable and then drop casting the suspension onto a TEM grid, making the TEM grid dry under ambient conditions. For example, the core-shell rubber elastomer particles containing epoxy resin from Kaneka Texas Corporation can be diluted in butyl acetate to be drop cast. Particle size measurements can be obtained from images acquired using a Tecnai T20 TEM operated at 200 kV and analyzed using ImageJ software or equivalent instrumentation and software.

[0110] According to the present disclosure, the elastomer particles can be optionally included in the epoxy carrier resin to be introduced into the coating composition. Suitable finely dispersed core-shell elastomer particles comprising an average particle size as described above can be made into a masterbatch in an epoxy resin with a concentration of 1 wt % to 80 wt %, such as 5 wt % to 50 wt %, such as 15 wt % to 35 wt % of core-shell elastomer particles based on the total weight of the elastomer dispersion, such as aromatic epoxides, phenol novolac epoxy resins, bisphenol A and / or bisphenol F diepoxides, and / or aliphatic epoxides, which contain cycloaliphatic epoxides. Suitable epoxy resins can also include a mixture of epoxy resins. When used, the epoxy carrier resin can be a component containing epoxy resins of the present disclosure, so that the weight of the component containing epoxy resins present in the coating composition includes the weight of the epoxy carrier resin.

[0111] Exemplary non-limiting commercial core-shell elastomeric particle products using poly(butadiene) rubber particles that can be used in the coating compositions of the present disclosure can include core-shell poly(butadiene) rubber powder (which can be PARALOID TM EXL 2650A is commercially available from Dow Chemical), a dispersion of core-shell poly(butadiene) rubber in bisphenol F diglycidyl ether (25 wt. % core-shell rubber) (commercially available as Kane Ace MX 136), a core-shell poly(butadiene) rubber in 828 (33 wt % core-shell rubber) (commercially available as Kane Ace MX 153), core-shell poly(butadiene) rubber A dispersion of core-shell rubber in EXA-835LV (33 wt % core-shell rubber) (commercially available as Kane Ace MX 139), a dispersion of core-shell poly(butadiene) rubber in bisphenol A diglycidyl ether (37 wt % core-shell rubber) (commercially available as Kane Ace MX 257), and a dispersion of core-shell poly(butadiene) rubber in A dispersion in Kane Ace 863 (37 wt. % core-shell rubber) (commercially available as Kane Ace MX 267), each of these dispersions being commercially available from Kane Corporation.

[0112] Exemplary non-limiting commercial core-shell elastomeric particle products using styrene-butadiene rubber particles that can be used in coating compositions include core-shell styrene-butadiene rubber powder (which can be XT100 is commercially available from Arkema), MMA-styrene-butadiene core-shell rubber (commercially available as Clearstrength XT 100 from Arkema), core-shell styrene-butadiene rubber powder (commercially available as PARALOID TM EXL 2650J is commercially available), a dispersion of core-shell styrene-butadiene rubber in bisphenol A diglycidyl ether (33 wt. % core-shell rubber) (available from Fortegra TM 352 from Olin TM commercially available), core-shell styrene-butadiene rubber dispersion in low viscosity bisphenol A diglycidyl ether (33 wt % rubber) (commercially available as Kane Ace MX 113), core-shell styrene-butadiene rubber dispersion in bisphenol A diglycidyl ether (25 wt % core-shell rubber) (commercially available as Kane Ace MX 125), core-shell styrene-butadiene rubber dispersion in bisphenol F diglycidyl ether (25 wt % core-shell rubber) (commercially available as Kane Ace MX 135), core-shell styrene-butadiene rubber dispersion in DEN TM -438 phenol novolac epoxy resin dispersion (25 wt% core-shell rubber) (commercially available as KaneAce MX 215), core-shell styrene-butadiene rubber dispersed in bisphenol A epoxy resin (such as KDAD-7101 35 wt% core-shell rubber) (commercially available from Kukdo Chemical), core-shell styrene-butadiene rubber in A dispersion of core-shell styrene-butadiene rubber in MY-721 multifunctional epoxy resin (25 wt% core-shell rubber) (commercially available as Kane Ace MX 416), a dispersion of core-shell styrene-butadiene rubber in MY-0510 multifunctional epoxy resin (25 wt% core-shell rubber) (commercially available as Kane Ace MX 451), a dispersion of core-shell styrene-butadiene rubber in Syna Epoxy 21 cycloaliphatic epoxy resin from Synasia (25 wt% core-shell rubber) (commercially available as Kane Ace MX 551), and a dispersion of core-shell styrene-butadiene rubber in polypropylene glycol (MW 400) (25 wt% core-shell rubber) (commercially available as Kane Ace MX 715), each of which is commercially available from Kane Ace Texas Co., Ltd.

[0113] Exemplary non-limiting commercial core-shell elastomeric particle products using polysiloxane rubber particles that can be used in the coating compositions of the present disclosure include core-shell polysiloxane rubber powders (which can be P52 is commercially available from Wacker), a dispersion of core-shell polysiloxane rubber in bisphenol A diglycidyl ether (40 wt. % core-shell rubber) (can be EP2240A commercially available from Evonick), dispersion of core-shell polysiloxane rubber in Epon 828 (25 wt% core-shell rubber) (commercially available as Kane Ace MX 960), core-shell polysiloxane rubber in A dispersion in 863 (25 wt. % core-shell rubber) (commercially available as Kane Ace MX 965), each of these dispersions being commercially available from Kane Ace Texas Instruments.

[0114] The composition may include at least 2.5 wt %, such as at least 5 wt %, such as at least 7.5 wt %, of the elastomer particles, based on the total weight of the composition. The composition may include no more than 25 wt %, such as no more than 22.5 wt %, such as no more than 20 wt %, of the elastomer particles, based on the total composition weight. The composition may include 2.5 to 25 wt %, such as 5 to 22.5 wt %, such as 7.5 to 20 wt %, of the elastomer particles, based on the total composition weight.

[0115] Reinforcement filler

[0116] Optionally, the composition may further include a reinforcing filler. The reinforcing filler may be present in the first component, the second component, the third or higher component or a combination thereof. The composition may include particles of a single type of reinforcing filler or may include particles of two or more types of reinforcing fillers. That is, the reinforcing filler may include particles of a first reinforcing filler and may further include particles of a second (i.e., second, third, fourth, etc.) reinforcing filler that is different from the first reinforcing filler. As used herein with respect to the types of reinforcing fillers used in the compositions disclosed herein, references to "first", "second", etc. are only for convenience and do not refer to the order of addition to the composition or the components that make up the composition.

[0117] Can be incorporated into the binder composition to provide useful reinforcing fillers for improved mechanical properties including fiber materials, such as glass fiber, fibrous titanium dioxide, whisker-type calcium carbonate (aragonite), carbon fiber (it includes graphite and carbon nanotubes), basalt fiber and ceramic fiber. Additional reinforcing fillers include those with plate-like or needle-like morphology, including but not limited to wollastonite (calcium inosilicate), talc (hydrated magnesium silicate), mica, mica iron oxide, glass flakes, aluminum flakes and boron nitride. Additional reinforcing fillers include those with spherical or irregular morphology, such as titanium dioxide, spherical aluminum or calcium carbonate.

[0118] The reinforcing filler of maximum size can comprise at least 5 microns, such as at least 8 microns, such as an average particle size of at least 10 microns. The reinforcing filler of maximum size can comprise an average particle size of no more than 1000 microns, such as no more than 500 microns, such as no more than 100 microns. The reinforcing filler of maximum size can comprise an average particle size of 5 microns to 1000 microns, such as 8 microns to 500 microns, such as 10 microns to 100 microns. Particle size can be measured, for example, using dynamic light scattering (DLS), such as using MalvernAutosizer Lo-C or equivalent instruments, or scanning electron microscope (SEM), such as Quanta 250FEG SEM or equivalent instruments.

[0119] If used, the composition may include such reinforcing fillers in an amount of at least 2.5 wt %, such as at least 5 wt %, based on the total weight of the composition. If used, the composition may include such reinforcing fillers in an amount of no more than 30 wt %, such as no more than 25 wt %, such as no more than 20 wt %, based on the total weight of the composition. If used, the composition may include such reinforcing fillers in an amount of up to 30 wt %, such as 2.5 wt % to 25 wt %, such as 5 wt % to 20 wt %, based on the total weight of the composition.

[0120] additive

[0121] The composition may optionally include at least one additive. As used herein, "additive" refers to a rheology modifier, a tackifier, a surfactant, a wetting agent, a flame retardant, a corrosion inhibitor, a UV stabilizer, a colorant, a stain, a solvent, a plasticizer, an adhesion promoter, an antioxidant, a defoamer, an oil, a rust inhibitor, a silane, a silane-terminated polymer, a silane-terminated polymer, and / or a moisture scavenger.

[0122] The rheology modifier may optionally include a thixotrope. The thixotrope may be a sag control agent. Useful thixotropes and / or sag control agents that may be used include waxes, fumed silica, castor wax, clays, organoclays, fibers such as Fiber and Fiber, ceramic fiber and / or engineered cellulose fiber. The wax that can be used for the composition disclosed herein is not particularly limited, as long as the wax has a characteristic suitable for thixotropy and / or sag control. In general, the wax can have a weight average molecular weight of less than 10,000. Examples of suitable waxes that can be used for the composition disclosed herein include microcrystalline wax, polyethylene wax, Fischer-Tropsch wax, paraffin wax, castor wax, polypropylene wax, amide derivatives of the former, or a combination thereof. Further examples of suitable thixotropes and / or sag control agents include organic resins or solids containing chemical bonds with hydrogen bonding ability, such as polyurethanes, polyureas, polyesters, polyamides, polyimides, carbodiimides, and combinations thereof. Such polyureas may be included in those disclosed in U.S. Patent No. 4,965,317, Column 5, Line 10 to Column 6, Line 24, which are incorporated herein by reference. The organic resin or solid may optionally include reactive functional groups, such as epoxides, isocyanates, or ethylenically unsaturated. Combinations of thixotropes may be used to achieve sag control.

[0123] Examples of suitable wetting agents include those commercially available under the name DOWSIL TM , Wet and TERGITOL TM Those wetting agents.

[0124] Examples of suitable corrosion inhibitors include, for example, zinc phosphate based corrosion inhibitors such as micronized ZnPhosphate commercially available from Halox SZP-391, 430 Calcium phosphate, ZP zinc phosphate, SW-111 Strontium phosphosilicate, 720 Mixed Metal Phosphor-Carbonate and 550 and 650 proprietary organic corrosion inhibitors. Other suitable corrosion inhibitors include those commercially available from Heucotech Ltd. ZPA zinc aluminum phosphate ZMP zinc molybdenum phosphate.

[0125] The corrosion inhibitor may include lithium silicate, such as lithium orthosilicate (Li4SiO4) and lithium metasilicate (Li2SiO3), MgO, azoles, or any combination of the foregoing. The corrosion inhibiting component may further include at least one of magnesium oxide (MgO) and azoles.

[0126] Useful colorants or tints may include phthalocyanine blue and ultramarine blue.

[0127] The composition provided by the present disclosure can include a flame retardant or a combination of flame retardants. For example, some thermally conductive materials (such as aluminum hydroxide and magnesium hydroxide) can also be flame retardants. As used herein, "flame retardant" refers to a material that slows down or prevents the spread of fire or reduces its intensity. The flame retardant can be obtained in the form of a powder, which can be mixed with a composition, foam or gel. In an example, when the composition disclosed herein includes a flame retardant, such a composition can form a coating on the substrate surface, and such a coating can act as a flame retardant.

[0128] As described in more detail below, the flame retardant may comprise a mineral, an organic compound, an organohalogen compound, an organophosphorus compound, or a combination thereof.

[0129] Suitable examples of minerals include magnesite, hydromagnesite, various hydrates, red phosphorus, boron compounds such as borates, carbonates such as calcium carbonate and magnesium carbonate, and combinations thereof.

[0130] Suitable examples of organic halogen compounds include organic chlorine, such as chlorobridgeic acid derivatives and chlorinated paraffins; organic bromine, such as decabromodiphenyl ether (decaBDE), decabromodiphenyl ethane (a substitute for decaBDE), polymeric brominated compounds such as brominated polystyrene, brominated carbonate oligomers (BCO), brominated epoxy resin oligomers (BEO), tetrabromophthalic anhydride, tetrabromobisphenol A (TBBPA) and hexabromocyclododecane (HBCD). Such halogenated flame retardants can be used in combination with synergists to enhance their efficiency. Other suitable examples include antimony trioxide, antimony pentoxide and sodium antimonate.

[0131] Suitable examples of organophosphorus compounds include triphenyl phosphate (TPP), resorcinol bis(diphenyl phosphate) (RDP), bisphenol A diphenyl phosphate (BADP), and tricresyl phosphate (TCP); phosphonates such as dimethyl methylphosphonate (DMMP); and phosphites such as aluminum diethylphosphite. In an important class of flame retardants, compounds contain both phosphorus and halogens. The compounds include tris(2,3-dibromopropyl) phosphate (brominated tris) and chlorinated organophosphates such as tris(1,3-dichloro-2-propyl) phosphate (chlorinated tris or TDCPP) and tetrakis(2-chloroethyl)dichloroisopentyl diphosphate (V6).

[0132] Suitable examples of organic compounds include carboxylic acids, dicarboxylic acids, melamine and organic nitrogen compounds.

[0133] Other suitable flame retardants include ammonium polyphosphate and barium sulfate.

[0134] Suitable solvents include toluene, methyl ethyl ketone, benzene, n-hexane, xylene, and combinations thereof.

[0135] Useful plasticizers that may be used include polymers, trimellitates, sebacates, esters, phthalates, citrates, adipates, benzoates, and the like. Non-limiting examples of such plasticizers include diisononyl phthalate (commercially available from Exxon Mobil as Jayflex TM DINP), dioctyl phthalate (Cereplas DOA available from Valtris TM ), diisodecyl phthalate (commercially available from ExxonMobil as Jayflex TM DIDP) and alkyl benzyl phthalates (Santicizer 278 available from Valtris); benzoate-based plasticizers such as dipropylene glycol dibenzoate (available from Emerald Performance Materials ); and other plasticizers, including terephthalate-based dioctyl terephthalate (DEHT commercially available from Eastman Chemical Company), phenol alkyl sulfonates (Mesamoll commercially available from Borchers), epoxidized soybean oil (Plaschek 775 commercially available from Valtris), citrate esters (Citroflex commercially available from Morflex), phenyl phosphate (Santicizer 148 from Solutia), and diisononyl 1,2-cyclohexanedicarboxylate (Hexamoll DINCH commercially available from BASF AG).

[0136] Adhesion promoters may be included in any component of the composition. Suitable adhesion promoters may include silanes such as epoxysilanes ((3-glycidyloxypropyl)trimethoxysilane, (3-glycidyloxypropyl)triethoxysilane, 3-glycidyloxypropyldimethoxymethylsilane), aminosilanes ((3-aminopropyl)trimethoxysilane, (3-aminopropyl)triethoxysilane), methyl mercaptosilanes ((3-mercaptopropyl)methyldimethoxysilane, (3-mercaptopropyl)trimethoxysilane), or acrylate silanes (3-(trimethoxysilyl)propyl acrylate, 3-(trimethoxysilyl)propyl methacrylate), titanates (such as monoalkoxy, neoalkoxy, oxyacetate, and cyclic heteroatoms), or zirconates (such as coordination, cyclic heteroatoms, and neoalkoxy).

[0137] Stabilizers can be blended to prevent molecular weight reduction due to heating, gelation, coloring, odor generation, etc., thereby improving the stability of the adhesive. The stabilizer that can be used in the composition disclosed herein is not particularly limited. Examples of stabilizers that can be used for the composition disclosed herein include antioxidants, ultraviolet light absorbers, or combinations thereof. Stabilizers can optionally be lactone-based. Antioxidants can be used to prevent oxidative degradation of the disclosed composition. Examples of antioxidants include phenol-based antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants. Ultraviolet light absorbers can be used to improve the light resistance of the disclosed composition. Examples of ultraviolet light absorbers include benzotriazole-based ultraviolet light absorbers and benzophenone-based ultraviolet light absorbers. Specific examples of suitable stabilizers include SUMILIZER GM (trade name), SUMILIZER TPD (trade name) and SUMILIZER TPS (trade name) manufactured by Sumitomo Chemical Co., Ltd.; IRGANOX 1010 (trade name), IRGANOX HP2225FF (trade name), IRGAFOS168 (trade name), IRGANOX 1520 (trade name) and TINUVIN P manufactured by Ciba Specialty Chemicals; JF77 (trade name) manufactured by Johoku Chemical Co., Ltd.; TOMINOX TT (trade name) manufactured by API Corporation and AO-4125 (trade name) manufactured by ADEKA CORPORATION.

[0138] Oils useful for the compositions disclosed herein can include unsaturated renewable oils, such as sunflower oil, safflower oil, soybean oil, linseed oil, castor oil, orange oil, rapeseed oil, tall oil, vegetable processed oils, sulfurized vegetable oils, high oleic sunflower oil, cottonseed oil, nut oils, and combinations thereof. Useful oils can include mineral oils, such as Novadex B111 or Catenex T129 (available from Shell).

[0139] The composition may also include at least one silane terminated polymer. The silane terminated polymer may be capable of crosslinking in the presence of moisture. The polymer may be an alkoxysilane terminated polyether, an alkoxysilane terminated polyurethane or a combination thereof. The alkoxysilane may be a methoxysilane or an ethoxysilane, each silane having one, two or three alkoxy groups. Commercial examples of alkoxysilane terminated polymers include Kaneka MS polymers such as SAX 350, SAX 400 and SAX750 or Wacker STP-E series such as STP-E30.

[0140] Suitable water scavengers include vinyl trimethoxy silane (Silquest A-171 from Momentive), vinyl triethoxy silane (Silquest A-151NT from Momentive), gamma-methacryloyloxypropoxy trimethoxy silane (Silquest A-174NT from Evonik Industries), molecular sieves, calcium oxide (POLYCAL OS325 available from Mississippi Lime), or combinations thereof.

[0141] The composition optionally may further include a dispersant. As used herein, the term "dispersant" refers to a substance that can be added to the composition to promote separation of the particles by wetting the thermally conductive filler particles and breaking down agglomerates. Dispersants suitable for use in the composition include fatty acids, phosphates, polyurethanes, polyamines, polyacrylates, polyalkoxylates, sulfonates, polyethers and polyesters or any combination thereof. Non-limiting examples of commercially available dispersants include ANTI-TERRA-U100, DISPERBYK-102, DISPERBYK-103, DISPERBYK-111, DISPERBYK-171, DISPERBYK-2151, DISPERBYK-2059, DISPERBYK-2000, DISPERBYK-2117, and DISPERBYK-2118, commercially available from BYK Company; and SOLSPERSE 24000SC, SOLSPERSE 16000, and SOLSPERSE 8000 hyperdispersants, commercially available from The Lubrizol Corporation.

[0142] Based on the gross weight of the composition, the additive (if present) can be present in the composition with at least 0.01 % by weight, such as a combined amount of 0.05 % by weight. Based on the gross weight of the composition, the additive (if present) can be present in the composition with a combined amount of no more than 15 % by weight, such as no more than 12 % by weight, such as no more than 10 % by weight, such as no more than 3 % by weight. Based on the gross weight of the composition, such additive (if present) can be present in the composition with an amount of 0.01 % by weight to 15 % by weight, such as 0.01 % by weight to 12 % by weight, such as 0.05 % by weight to 12 % by weight, such as such as 0.05 % by weight to 10 % by weight.

[0143] Compositions, systems and methods

[0144] The 2K compositions disclosed herein may comprise, or may consist essentially of, or may consist of: a first component comprising, or consisting essentially of, an epoxy-containing compound; a second component comprising, or consisting essentially of, an aliphatic amine, an amidoamine, a toughening amine, and an accelerator; and elastomeric particles; and optional reinforcing fillers, additives, or combinations thereof; wherein the elastomeric particles, reinforcing fillers, and additives may each be in the first component and / or the second component.

[0145] The 3K compositions disclosed herein may comprise, or may consist essentially of, or may consist of: a first component comprising, or consisting essentially of, an epoxy-containing compound; a second component comprising, or consisting essentially of, an aliphatic amine, an amidoamine, a toughening amine; an accelerator; and elastomeric particles; and optional reinforcing fillers, additives, or combinations thereof; wherein the accelerator, elastomeric particles, reinforcing fillers, and additives may each be in the first component, the second component, and / or the third component or higher-order components (i.e., the fourth component, the fifth component, etc.).

[0146] The composition may comprise an amine hydrogen:epoxy equivalent of at least 0.75:1, such as at least 0.9:1, such as no more than 1.25:1, such as no more than 1.1:1, such as from 0.75:1 to 1.25:1, such as from 0.9:1 to 1.1:1.

[0147] The composition may be substantially free, essentially free, or completely free of polyurethane resin. As used herein, the term "polyurethane resin" refers to a resin containing more than one urethane or urea linkage.

[0148] Based on the total weight of the composition, the composition may include at least 50% by weight, such as at least 60% by weight, such as 70% by weight of the first component. Based on the total weight of the composition, the composition may include no more than 90% by weight, such as no more than 85% by weight, such as no more than 80% by weight of the second component. Based on the total weight of the composition, the composition may include 50% to 90% by weight, such as 60% to 85% by weight, such as 70% to 80% by weight of the first component.

[0149] Based on the total weight of the composition, the composition may include at least 10% by weight, such as at least 15% by weight, such as at least 20% by weight of the second component. Based on the total weight of the composition, the composition may include no more than 50% by weight, such as no more than 40% by weight, such as no more than 30% by weight of the second component. Based on the total weight of the composition, the composition may include 10% to 50% by weight, such as 15% to 40% by weight, such as 20% to 30% by weight of the second component.

[0150] It has been surprisingly discovered that coating compositions comprising (i) a curing agent comprising a combination of an aliphatic amine, an amidoamine, and a toughening amine, (ii) an accelerator, and (iii) the elastomeric particles disclosed herein form coatings that exhibit a combination of improved structural adhesive performance and improved wedge impact peel resistance at -40°C compared to adhesives formed from compositions not comprising this combination of materials that exhibit no improvement in either parameter. The adhesives formed from the compositions disclosed herein surprisingly exhibit: (a) a lap shear strength of at least 12 MPa measured according to ASTM D1002-10 using a 0.8 mm thick HDG substrate dip coated with a 10 wt % heptane and Multidraw KTL N 16 oil solution using an INSTRON 5567 machine in tensile mode at a pull rate of 10 mm per minute, and (b) a wedge impact peel resistance of at least 2.0 N / mm tested according to the ISO 11343 dynamic splitting resistance test using a 0.8 mm thick HDG substrate dip coated with a 10 wt % heptane and Multidraw KTL N 16 oil solution using an INSTRON CEAST 9350 drop tower model at an impact velocity of 2 m / sec at -40°C, wherein the samples were conditioned at -40°C for at least 30 minutes prior to testing.

[0151] Also disclosed herein is a method for preparing one of the above compositions. The method may optionally include mixing the first component and the second component at a temperature below 50°C, such as 0°C to 50°C, such as 15°C to 35°C, such as at ambient temperature, and optionally mixing a third or higher component.

[0152] The above-mentioned compositions can be applied individually or as part of a system that can be deposited on a plurality of different substrates in a variety of different ways. Therefore, disclosed herein is a method for applying a composition to a substrate, the method comprising, or substantially consisting of, or consisting of: applying one of the above-mentioned compositions to a portion of the surface of the substrate. That is, the composition can be applied to the surface of the substrate in any number of different ways, non-limiting examples of which include brushes, rollers, films, pellets, trowels, scrapers, dippers, spray guns, and applicator guns for forming a coating on a portion of the substrate surface.

[0153] After being applied on substrate, composition can be cured to form coating, layer or film on substrate surface.Coating, layer or film can be for example adhesive.For example, composition can be allowed to solidify any required time (for example, from 5 minutes to 30 minutes to several weeks, such as at least 1 week, such as at least 2 weeks, such as at least 3 weeks) under room temperature or slightly heated condition, be enough to solidify composition on substrate.Optionally, then can solidify said composition by baking and / or curing at elevated temperature, such as at least 120 ℃, such as at least 130 ℃, such as at least 135 ℃, such as no more than 180 ℃ temperature and continue any required time period (for example, at least 1 minute, such as at least 2 minutes, such as at least 3 minutes, such as at least 4 minutes, such as at least 5 minutes to 1 hour). The composition can optionally be cured under mild thermal conditions, such as 110°C or less, such as 100°C or less, such as 90°C or less, such as 80°C or less, such as 70°C or less, but above ambient temperature, such as greater than 40°C, such as greater than 50°C and for any desired period of time (e.g., at least 1 minute, such as at least 2 minutes, such as at least 3 minutes, such as at least 4 minutes, such as at least 5 minutes to 1 hour). The elevated temperature can be achieved by laser spot heating, induction heating, other electromagnetic heating methods, or a combination thereof.

[0154] Also disclosed is a method for forming a bond between two substrates for various potential applications, wherein the bond between the substrates provides mechanical properties related to lap shear strength. The method may include, or be substantially composed of, or be composed of: applying the above composition to a first substrate; contacting the surface of a second substrate with the composition so that the composition is located between the first substrate and the second substrate; and curing the composition under ambient conditions or slight thermal conditions. For example, the composition can be applied to one or both of the substrate materials bonded to form an adhesive bond therebetween, and the substrates can be aligned, and pressure and / or spacers can be added to control the bond thickness. The composition can be applied to a clean or uncleaned (i.e., including an oily or oiled) substrate surface.

[0155] The composition can be injected or otherwise placed in a die casting machine or mold and dried or cured under ambient conditions or by exposure to an external energy source, such as by heating to a temperature below 180°C, such as below 130°C, such as below 90°C to form a part or component and optionally can be machined into a specific configuration.

[0156] 3-D Printing

[0157] The compositions of the present disclosure can be applied or deposited using any suitable method, including the methods described above. Alternatively, the composition can be cast, extruded, molded or machined to form a part or component.

[0158] The compositions disclosed herein can be used in any suitable additive manufacturing technology, such as three-dimensional (3D) printing, extrusion, spraying, and binder jetting.Additive manufacturing refers to the process of producing parts or components by layered building, such as building one layer at a time.

[0159] The present disclosure also relates to the use of additive manufacturing processes (such as 3D printing) to produce structural articles, such as acoustic damping pads as a non-limiting example. 3D printing refers to a computerized process, optionally including artificial intelligence modulation, by which materials are printed or deposited in successive layers to produce a 3D part or component, such as, as a non-limiting example, an acoustic damping pad in a battery assembly. The 3D part or component can be produced by depositing successive parts or layers on a substrate in any spatial configuration, and then depositing additional parts or layers on the underlying deposited parts or layers and / or adjacent to previously deposited parts or layers to produce a 3D printed part or component.

[0160] It will be appreciated that the configuration of the 3D printing process, including the selection of suitable deposition equipment, depends on a variety of factors, such as the deposition volume, the viscosity of the composition, and the complexity of the component being manufactured. Any suitable mixing, conveying, and 3D printing equipment known to those skilled in the art may be used. The composition may be printed or deposited in any size and / or shape of droplets or extrudates and in any pattern to produce a 3D structure.

[0161] The compositions disclosed herein can be applied or deposited by any suitable 3D printing method known to those skilled in the art. The first component and the second component of the 2K composition can be mixed and then deposited, or the first component and the second component can be deposited separately, such as simultaneously and / or sequentially.

[0162] The first component and the second component may be premixed, i.e., mixed together, prior to application and then deposited. The mixture may react or thermally cure as the material is deposited; the deposited reaction mixture may partially react after deposition and may also react with previously deposited portions of the article and / or subsequently deposited portions, such as underlying layers or overlying layers of the article.

[0163] In one non-limiting example, the first component and the two components can be released from their respective storage containers and pushed (such as pumped through a conduit (such as a hose)) to a mixer (such as a static or dynamic mixer), where the composition can be mixed for a time sufficient to homogenize the composition, where the composition can then be released through an outlet. The outlet can be a deposition device (such as a print head), and / or the material can leave the mixing unit and be pushed, such as by a pump, through a conduit (such as a hose) to the print head. The print head can optionally be mounted on a 3D rotating robot to allow the 3D printing composition to be delivered to any substrate in any spatial configuration and / or the substrate can be manipulated in any spatial configuration during the 3D printing process.

[0164] Alternatively, the first component and the second component can be deposited independently from different print heads. The first component can be deposited from one print head and the second component can be deposited from a second print head. The first component and the second component can be deposited in any pattern so that the first component and the second component including any deposited layer can react together and with the layer below and / or the layer above to produce a 3D printed part or component.

[0165] The method provided by the present disclosure comprises printing a composition on a manufactured part. The method provided by the present disclosure comprises directly printing a part.

[0166] Using the methods provided by the present disclosure, parts can be manufactured. The entire part can be formed from one of the compositions disclosed herein, one or more parts of a part can be formed from one of the compositions disclosed herein, one or more different parts of a part can be formed using the compositions disclosed herein, and / or one or more surfaces of a part can be formed from the compositions provided by the present disclosure. In addition, the internal area of ​​a part can be formed from the compositions provided by the present disclosure.

[0167] Coatings and molded parts and their uses

[0168] The compositions disclosed herein may be adhesive compositions, potting compositions, gap filler compositions, prepreg compositions, liquid gasket compositions, or combinations thereof. That is, the compositions disclosed herein may form a coating. Such coatings may be adhesives, potting agents, gap fillers, liquid gaskets, composite materials formed from prepregs, or combinations thereof.

[0169] The compositions disclosed herein can be used to form coatings, such as structural adhesives, having (a) a lap shear strength of at least 12 MPa measured according to ASTM D1002-10 using a 10 wt % heptane and Multidraw KTL N 16 oil solution on a 0.8 mm thick HDG substrate oiled using an INSTRON 5567 machine in tensile mode at a pull rate of 10 mm per minute, and (b) a wedge impact peel resistance of at least 2.0 N / mm tested according to ISO 11343 dynamic cleavage resistance test using a 10 wt % heptane and Multidraw KTL N 16 oil solution on a 0.8 mm thick HDG substrate oiled using an INSTRON CEAST 9350 drop tower model at an impact velocity of 2 m / sec, wherein the samples are conditioned at -40°C for at least 30 minutes prior to testing.

[0170] Substrate

[0171] The substrate that can be coated by the composition disclosed herein is not limited. Suitable substrates include but are not limited to materials such as metals or metal alloys, polymer materials such as duroplasts, and the polymer materials include filled or unfilled thermoplastic materials or thermosetting materials or composite materials. Other suitable substrates include but are not limited to glass or natural materials such as wood. For example, suitable substrates include rigid metal substrates, such as ferrous metals, aluminum, aluminum alloys, magnesium titanium, copper and other metal and alloy substrates. Ferrous metal substrates can include iron, steel and alloys thereof. Non-limiting examples of useful steel materials include cold-rolled steel, galvanized (zinc-coated) steel, electrogalvanized steel, stainless steel (including 3XX series, such as 301 series and 304 series), acid-dipped steel, zinc-iron alloys such as GALVANNEAL and combinations thereof. Combinations or composites of ferrous and nonferrous metals can also be used. Aluminum alloys of the 1XXX, 2XXX, 3XXX, 4XXX, 5XXX, 6XXX, 7XXX or 8XXX series and clad and cast aluminum alloys of the A356, 1XX.X, 2XX.X, 3XX.X, 4XX.X, 5XX.X, 6XX.X, 7XX.X or 8XX.X series may also be used as the substrate. Magnesium alloys of the AZ31B, AZ91C, AM60B or EV31A series may also be used as the substrate. The substrate may also include titanium and / or titanium alloys of grades 1-36, including H-grade variants. Other suitable non-ferrous metals include copper and magnesium and alloys of these materials. In an example, the substrate may be a multi-metal article. As used herein, the term "multi-metal article" refers to (1) an article having at least one surface comprising a first metal and at least one surface comprising a second metal different from the first metal, (2) a first article having at least one surface comprising a first metal and a second article having at least one surface comprising a second metal different from the first metal, or (3) both (1) and (2). Suitable metal substrates include metal substrates used in vehicle body assemblies (for example, but not limited to, doors, body panels, trunk lids, roof panels, hoods, roofs and / or stringers, rivets, landing gear components and / or skins used on aircraft), vehicle frames, vehicle parts, vehicle outer bodies, motorcycles, wheels, and industrial structures and components. As used herein, "vehicle" or variations thereof include, but are not limited to, civil, commercial and military aircraft and / or land vehicles, such as automobiles, motorcycles, bicycles (including electric bicycles) and / or trucks. The metal substrate can also be in the form of, for example, a metal sheet or a preform.It should also be understood that the substrate can be pretreated with a pretreatment solution comprising a zinc phosphate pretreatment solution, such as, for example, a zinc phosphate pretreatment solution described in U.S. Patent Nos. 4,793,867 and 5,588,989, or a zirconium-containing pretreatment solution, such as those described in U.S. Patent Nos. 7,749,368 and 8,673,091. The substrate can comprise a composite material, such as a plastic or a glass fiber composite. The substrate can be a glass fiber and / or carbon fiber composite. The compositions disclosed herein are particularly suitable for use in various industrial or transportation applications, including automotive, light and heavy commercial vehicles, marine or aerospace.

[0172] The following examples illustrate the disclosure, which, however, should not be considered to limit the disclosure to its details. Unless otherwise indicated, all parts and percentages in the following examples and throughout the specification are by weight.

[0173] Examples

[0174] Lap shear specimens were prepared with compositions I to XXIV according to ASTM D1002-10. The substrate used was a hot dip galvanized (HDG) steel sheet with dimensions of 25.4 mm × 101.6 mm × 0.8 mm. The galvanized coating weight was 60 grams per square meter with an exposed unpolished finish. The sheet was ultrasonically treated with methyl ethyl ketone (MEK) and wiped dry with a lint-free cloth. The sample was oiled using a 10% by weight solution of Multidraw KTL N 16 oil in heptane. The substrate was immersed to a depth of 25 mm, blotted to remove excess liquid, and placed on a lint-free cloth with the surface to be adhered facing up to allow the solvent to evaporate completely, which took about 30 minutes. The composition was applied to one end of the sheet covering the entire 25.4 mm width and ≥12.7 mm from one end. A second steel sheet prepared in the same manner was then placed on the composition layer in an end-to-end manner, resulting in a bonding area of ​​25.4 mm × 12.7 mm. The lap joints were secured with metal clamps and the excess composition was cleaned off, leaving a 45° radius. The lap joints were allowed to cure at ambient temperature for 7 days. The lap joint specimens were tested (according to ASTM D1002-10) using an INSTRON model 5567 in tensile mode at a pull rate of 10 mm per minute through a 25.4 mm steel substrate in each handle. Wedge impact peel specimens were prepared and tested according to ISO 11343; the substrate used was still HDG steel, with the same composition, thickness and oiling as the lap shear specimens. Wedge impact specimens were tested according to the ISO11343 dynamic splitting resistance test using an INSTRON CEAST 9350 drop tower model at an impact velocity of 2 m / sec. Samples tested at -40°C were conditioned at -40°C for at least 30 minutes before testing.

[0175] Synthesis of Epoxy Functional Polyester: To a round bottom flask were added 134.7 g of methyl hexahydrophthalic anhydride, 520.1 g of Epon 863, and 205.9 g of Capa 4101. The mixture was placed under a nitrogen blanket, heated to 90°C, and stirred for 30 minutes. A mixture of 0.3 g of triphenylphosphine in 50.8 g of Epon 863 was added and the mixture was slowly heated to 120°C for 4 hours. An additional 197.0 g of Epon 863 was added and the mixture was stirred at 120°C for an additional 15 minutes and then cooled to obtain a resin with a measured epoxy equivalent weight of 304 to 324 g / mol. The resulting material contained 43% of the auxiliary toughener and 57% of the unreacted (excess) Epon 863, and this unreacted amount was considered to be part of the epoxy resin-containing component.

[0176] Synthesis of Jeffamine EDR-148-Epon 863 Adduct: To a round bottom flask was added 1104.0 g of Jeffamine EDR-148. The material was placed under a nitrogen blanket and heated to 70°C. 967.3 g of Epon 863 was added dropwise via an addition funnel, ensuring that the temperature did not exceed 100°C during the addition. The mixture was maintained at 70°C until thin layer chromatography analysis confirmed that Epon 863 was consumed. The resulting material had a theoretical NH equivalent weight of 85 g / mol. The adduct was prepared at a 5.25:1.0 NH:E ratio. All amounts listed are in grams.

[0177] Five compositions were prepared from the ingredient mixtures shown in Table 1. All compositions were prepared at a 1:1 amine-hydrogen to epoxy equivalent, 10 to 20 wt% elastomer particle loading, 5% aliphatic epoxy loading, and 10 to 20 wt% wollastonite NYAD M200 loading, based on the total weight of the composition. The epoxy resin (including the masterbatch containing the elastomer particles) and filler were mixed in a dual asymmetric centrifugal mixer (DAC 600FVZ Speedmixer). TM ) was premixed in . The accelerator, curing agent (combination of aliphatic amine, amidoamine and toughening amine) and spacer beads were then added and the DAC was mixed at 2350 RPM for 2 minutes. Lap shear and wedge impact peel specimens were immediately prepared.

[0178]

[0179]

[0180] The results show that the proposed combination of aliphatic amine, amidoamine, toughening amine and accelerator can improve lap shear and low temperature wedge impact performance of oil-contaminated surfaces when combined with elastomeric particles and epoxy-containing compounds. These results show that by optimizing the ratio of aliphatic amine, amidoamine and toughening amine (Composition V), the material properties are further optimized.

[0181]

[0182] The results show that removal of the filler (Composition VI) slightly reduces wedge impact performance and increases variability, but still maintains adequate lap shear strength and low temperature wedge impact peel resistance. The results also show that changing the accelerator type (Composition VII) can slightly reduce lap shear and wedge impact performance, while completely removing the accelerator (Composition VIII) greatly reduces both properties. Further varying the ratio of aliphatic amines, amidoamines, and toughening amines in Composition IX to Composition IV further demonstrates the ability to achieve lap shear and low temperature wedge impact performance characteristics.

[0183]

[0184]

[0185] The results show that various toughening amines provide adequate lap shear strength and low temperature wedge impact peel resistance, but the use of a toughening amine containing poly(tetramethylene glycol)-units (Composition X) provides higher wedge impact performance than other polyetheramines of similar molecular weight.

[0186]

[0187] The results show that a variety of aliphatic and cycloaliphatic amines provide a combination of lap shear strength and low temperature wedge impact resistance when used in appropriate compositions.

[0188]

[0189]

[0190] The results show the effect of aliphatic epoxy resin on lap shear performance and low temperature wedge impact resistance. When the composition includes only aromatic epoxy resin (Composition XXII), the composition provides sufficient lap shear strength and low temperature wedge impact resistance. The inclusion of various aliphatic epoxy resins (Compositions XXIII-XXV) provides improved low temperature wedge impact resistance.

[0191] While features of the disclosure have been described above for purposes of illustration, it will be apparent to those skilled in the art that numerous changes may be made to the details of the coating compositions, coatings, and methods disclosed herein without departing from the scope of the appended claims.

Claims

1. A composition comprising: a first component comprising an epoxy-containing compound; a second component comprising an aliphatic amine, an amidoamine, and a toughening amine; Accelerators; and Elastomer particles.

2. The composition according to claim 1, wherein the second component comprises: (a) the toughening amine in an amount of at least 15 wt %, such as at least 25 wt %, such as no more than 75 wt %, such as no more than 65 wt %, such as no more than 60 wt %, such as 15 wt % to 75 wt %, such as 25 wt % to 65 wt %, such as 25 wt % to 60 wt %, based on the total weight of the toughening amine, the aliphatic amine and the amidoamine; (b) the aliphatic amine in an amount of at least 5 wt %, such as at least 10 wt %, such as at least 15 wt %, such as not more than 50 wt %, such as not more than 45 wt %, such as not more than 40 wt %, such as 5 wt % to 50 wt %, such as 10 wt % to 45 wt %, such as 15 wt % to 40 wt %, based on the total weight of the toughening amine, the aliphatic amine and the amidoamine; and / or (c) the amidoamine in an amount of at least 5 wt%, such as at least 10 wt%, such as at least 15 wt%, such as not more than 75 wt%, such as not more than 50 wt%, such as not more than 40 wt%, such as 5 wt% to 75 wt%, such as 10 wt% to 50 wt%, such as 15 wt% to 40 wt%, based on the total weight of the toughening amine, the aliphatic amine and the amidoamine.

3. A composition according to claim 1 or claim 2, wherein the epoxy-containing compound comprises more than one epoxy functional group, such as at least two epoxy functional groups, and / or comprises an aromatic epoxide and / or an epoxy adduct.

4. The composition of any of the preceding claims, wherein the epoxy-containing compound comprises bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, novolac resin, tetraglycidyl methylene dianiline, triglycidyl-p-aminophenol, tetraglycidyl m-xylylenediamine, or a combination thereof.

5. The composition according to any one of the preceding claims, wherein the first component comprises an aromatic monoepoxide, an aliphatic monoepoxide and / or an aliphatic polyepoxide.

6. The composition according to claim 5, wherein the first component comprises at least 0.1 wt %, such as at least 0.2 wt %, such as at least 0.5 wt %, such as no more than 30 wt %, such as no more than 25 wt %, such as no more than 20 wt %, such as 0.1 wt % to 30 wt %, such as 0.2 wt % to 25 wt %, such as 0.5 wt % to 20 wt % of the aromatic monoepoxide, the aliphatic monoepoxide and / or the aliphatic polyepoxide, based on the total weight of the first component.

7. The composition of claim 5 or claim 6, wherein the aliphatic epoxide comprises 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether or fatty alcohol monoglycidyl ether.

8. The composition of any one of the preceding claims, wherein the first component comprises an epoxy resin-containing compound in an amount of at least 30 wt %, such as at least 35 wt %, such as at least 40 wt %, such as no more than 100 wt %, such as no more than 60 wt %, such as no more than 55 wt %, such as no more than 50 wt %, such as 30 wt % to 100 wt %, such as 30 wt % to 60 wt %, such as 35 wt % to 55 wt %, such as 40 wt % to 50 wt %, based on the total weight of the first component.

9. according to the composition of any one of the preceding claims, wherein the aliphatic amine comprises a molecular weight of at least 60g / mol, such as at least 80g / mol, such as at least 110g / mol, such as no more than 295g / mol, such as no more than 260g / mol, such as no more than 250g / mol, such as 60g / mol to 295g / mol, such as 80g / mol to 260g / mol, such as 110g / mol to 250g / mol, measured by mass spectrometry.

10. The composition according to any one of the preceding claims, wherein the aliphatic amine comprises a cycloaliphatic amine, a linear or branched aliphatic amine without a cyclic group, an aromatic aliphatic amine and / or an amine comprising ethyleneimine subunits.

11. The composition of any one of the preceding claims, wherein the aliphatic amine comprises 4,4'-methylenebis(cyclohexylamine), 4,4'-methylenebis(2-methylcyclohexylamine), 1,3-bis(aminomethyl)cyclohexane, or isophoronediamine.

12. The composition of any of the preceding claims, wherein the amidoamine comprises the reaction product of reactants comprising an acid functional compound such as a fatty acid, a dimerized fatty acid, a trimerized fatty acid, an acid functional polymer such as a polyester and / or an acid functional small molecule and a polyamine.

13. The composition of any one of the preceding claims, wherein the amidoamine comprises the reaction product of reactants comprising fatty acids, dimerized fatty acids and / or trimerized fatty acids and polyamines and / or amines comprising ethyleneimine subunits.

14. The composition of any of the preceding claims, wherein the toughening amine comprises an etheramine comprising a molecular weight as measured by mass spectrometry of greater than 140 g / mol, such as at least 170 g / mol, such as at least 210 g / mol, such as no more than 2,000 g / mol, such as no more than 1,700 g / mol, such as no more than 1,300 g / mol, such as no more than 1,200 g / mol, such as greater than 140 g / mol to 2,000 g / mol, such as 170 g / mol to 1,700 g / mol, such as 210 g / mol to 1,300 g / mol, such as 210 g / mol to 1,200 g / mol.

15. The composition of any one of the preceding claims, wherein the toughening amine comprises a fatty acid dimer or fatty acid trimer comprising a molecular weight as measured by mass spectrometry of greater than 295 g / mol, such as at least 400 g / mol, such as at least 500 g / mol, such as no more than 2,000 g / mol, such as no more than 1,700 g / mol, such as no more than 1,300 g / mol, such as no more than 1,200 g / mol, such as greater than 295 g / mol to 2,000 g / mol, such as 400 g / mol to 1,700 g / mol, such as 500 g / mol to 1,300 g / mol, such as 500 g / mol to 1,200 g / mol.

16. The composition of any of the preceding claims, wherein the toughening amine comprises an amine-terminated poly(butylene glycol)-poly(propylene glycol) copolymer, an amine-terminated poly(butylene glycol), an amine-terminated poly(ethylene glycol), an amine-terminated poly(propylene glycol), a dimer fatty acid diamine, and / or a trimer fatty acid diamine.

17. The composition of any one of the preceding claims, wherein the accelerator comprises a primary amine, a secondary amine, a tertiary amine, a phenol, a guanidine and / or a guanidine derivative.

18. according to the composition described in any one of the preceding claims, wherein based on the gross weight of the composition, the composition comprises at least 0.1 wt %, such as at least 0.2 wt %, such as at least 0.5 wt %, such as no more than 10 wt %, such as no more than 5 wt %, such as no more than 2.5 wt %, such as 0.1 wt % to 10 wt %, such as 0.2 wt % to 5 wt %, such as 0.5 wt % to 2.5 wt % of the accelerator.

19. A composition according to any one of the preceding claims, wherein the second component and / or the third component comprises the accelerator.

20. The composition of any preceding claim, wherein the elastomeric particles comprise a core-shell structure.

21. The composition of any one of the preceding claims, wherein the first component, the second component and / or the third component comprises the elastomeric particles.

22. The composition of any one of the preceding claims, wherein the elastomeric particles are phase separated from the epoxy-containing component, the aliphatic amine, the amidoamine, and / or the toughening amine.

23. A composition according to any one of the preceding claims, wherein the elastomeric particles comprise a particle size of at least 20 nm, such as at least 30 nm, such as at least 40 nm, such as at least 50 nm, such as no more than 400 nm, such as no more than 300 nm, such as no more than 200 nm, such as no more than 150 nm, such as 20 nm to 400 nm, such as 30 nm to 300 nm, such as 40 nm to 200 nm, such as 50 nm to 150 nm, as measured by transmission electron microscopy.

24. A composition according to any one of the preceding claims, wherein the composition comprises at least 2.5 wt. %, such as at least 5 wt. %, such as at least 7.5 wt. %, such as no more than 25 wt. %, such as no more than 22.5 wt. %, such as no more than 20 wt. %, such as 2.5 to 25 wt. %, such as 5 to 22.5 wt. %, such as 7.5 to 20 wt. % of the elastomer particles, based on the total weight of the composition.

25. A composition according to any one of the preceding claims, wherein the first component, the second component and / or the third component comprises reinforcing fillers and / or additives.

26. The composition of claim 25, wherein the reinforcing filler comprises wollastonite, ceramic fiber, carbon fiber, iron oxide, talc, mica, or a combination thereof.

27. A composition according to claim 25 or claim 26, wherein: (a) the composition comprises the reinforcing filler in an amount of at least 2.5 wt%, such as at least 5 wt%, such as not more than 30 wt%, such as not more than 25 wt%, such as not more than 20 wt%, such as 2.5 wt% to 30 wt%, such as 2.5 wt% to 25 wt%, such as 5 wt% to 20 wt%, based on the total weight of the composition; and / or (b) the composition comprises the additive in an amount of at least 0.01 wt%, such as at least 0.05 wt%, such as not more than 15 wt%, such as not more than 12 wt%, such as not more than 10 wt%, such as not more than 3 wt%, such as 0.01 wt% to 15 wt%, such as 0.01 wt% to 12 wt%, such as 0.05 wt% to 10 wt%, such as 0.05 wt% to 3 wt%, based on the total weight of the composition.

28. The composition of any one of the preceding claims, wherein the composition is substantially free, generally free, or completely free of polyurethane resin.

29. A composition according to any one of the preceding claims comprising an amine-hydrogen:epoxy equivalent weight of at least 0.75:1, such as at least 0.9:1, such as no more than 1.25:1, such as no more than 1.1:1, such as from 0.75:1 to 1.25:1, such as from 0.9:1 to 1.1:

1.

30. A composition according to any one of the preceding claims, comprising: (a) the first component in an amount of at least 50 wt %, such as at least 60 wt %, such as at least 70 wt %, such as not more than 90 wt %, such as not more than 85 wt %, such as not more than 80 wt %, such as 50 wt % to 90 wt %, such as 60 wt % to 85 wt %, such as 70 wt % to 80 wt %, based on the total weight of the composition; and / or (b) the second component in an amount of at least 10 wt %, such as at least 15 wt %, such as at least 20 wt %, such as not more than 50 wt %, such as not more than 40 wt %, such as not more than 30 wt %, such as 10 wt % to 50 wt %, such as 15 wt % to 40 wt %, such as 20 wt % to 30 wt %, based on the total weight of the composition.

31. The composition of any of the preceding claims, wherein the composition is formulated as an adhesive composition, such as a structural adhesive composition, a potting agent composition, a gap filler composition, a prepreg composition, a liquid gasket composition, or a combination thereof.

32. A substrate comprising a coating formed from the composition according to any one of claims 1 to 31 on a portion of a surface of the substrate.

33. The substrate of claim 32, wherein the substrate comprises stainless steel or an alloy thereof.

34. A substrate according to claim 32 or claim 33, wherein the surface is partially covered with oil.

35. The substrate of any one of claims 32 to 34, wherein the surface comprises an outer body of a vehicle.

36. The substrate of any one of claims 32 to 35, wherein the coating comprises an adhesive, a structural adhesive, a potting agent, a gap filler, a composite material formed from a prepreg, a liquid gasket, or a combination thereof.

37. An article comprising: The substrate according to any one of claims 32 to 36; and a second substrate; The coating is located between the first substrate and the second substrate.

38. The article of claim 36, wherein the coating comprises (a) a lap shear strength of at least 12 MPa measured according to ASTM D1002-10 using a 0.8 mm thick HDG substrate dip coated with a 10 wt % solution of Multidraw KTL N 16 oil in heptane using an INSTRON 5567 machine in tensile mode at a pull rate of 10 mm per minute, and (b) a wedge impact peel resistance of at least 2.0 N / mm tested according to ISO 11343 dynamic splitting resistance test using a 0.8 mm thick HDG substrate dip coated with a 10 wt % solution of Multidraw KTL N 16 oil in heptane using an INSTRON CEAST 9350 drop tower model at an impact velocity of 2 m / sec at -40°C, wherein the samples were conditioned at -40°C for at least 30 minutes prior to testing.

39. The article of claim 37 or claim 38, wherein the article comprises a vehicle, a component, or a combination thereof.

40. The article of manufacture of claim 39, wherein the vehicle comprises an aircraft or a land vehicle.

41. A method of coating a substrate, the method comprising contacting a portion of a surface of the substrate with a composition according to any one of claims 1 to 31.

42. The method of claim 41, further comprising mixing the first component and the second component according to any one of claims 1 to 31; and exposing the composition to ambient conditions for at least 30 minutes; and optionally, further comprising exposing the composition to a temperature of at least 120°C, such as at least 130°C, such as at least 135°C, such as at least 140°C, such as for at least 30 seconds, such as at least 1 minute, such as at least 2 minutes; wherein the exposure optionally comprises the use of an electromagnetic activation source.

43. The method of claim 41 or claim 42, further comprising contacting a surface of a second substrate with the composition such that the composition is located between the substrate and the second substrate.

44. A method of forming an article, the method comprising extruding the composition of any one of claims 1 to 31.

45. The method of claim 44, wherein the extruding comprises three-dimensional printing.

46. ​​The method of claim 44 or claim 45, further comprising mixing the first component and the second component prior to extrusion.

47. A method according to any one of claims 44 to 46, wherein the extruding comprises applying successive layers to build up the article.

48. An article formed by the method of any one of claims 44 to 47.

49. Use of a composition according to any one of claims 1 to 31 for coating a surface of a substrate, wherein the coating comprises (a) a lap shear strength of at least 12 MPa measured according to ASTM D1002-10 using a HDG substrate having a thickness of 0.8 mm dip-coated with a 10 wt. % solution of Multidraw KTL N 16 in heptane oil using an INSTRON 5567 machine in tensile mode at a pull rate of 10 mm per minute, and (b) a wedge impact peel resistance of at least 2.0 N / mm tested according to ISO 11343 dynamic splitting resistance test using a HDG substrate having a thickness of 0.8 mm dip-coated with a 10 wt. % solution of Multidraw KTL N 16 in heptane oil using an INSTRON CEAST 9350 drop tower model at an impact velocity of 2 m / sec at -40°C, wherein the samples are conditioned at -40°C for at least 30 minutes prior to testing.

Images