Dual-curing epoxy coating and preparation method thereof

Abstract

A method of coating an article, the method comprising: preparing a coating composition, the coating composition having: an epoxy component; an amine component; and a catalyst; the epoxy component and the amine component are present in the coating composition in a ratio of 0.8: 1 to 1.5: 1; applying the coating composition to an article; and curing the coating composition at a temperature of 135 DEG C to 250 DEG C within 60 minutes of application to form a cured coating having a glossiness rating of 60 glossiness units (GU) or higher. A coating composition and a coated article are also provided.

Description

Cross-references to related applications

[0001] This application claims the benefit of U.S. Provisional Application No. 63 / 532,215, filed August 11, 2023, the disclosure of which is incorporated herein by reference in its entirety. Technical Field

[0002] This disclosure relates to epoxy coatings. This disclosure also relates to epoxy coatings prepared using a dual-curing method. Background Technology

[0003] Protective coatings are widely used to protect surfaces from abrasion, corrosion, and chemical, mechanical, and physical damage. Coatings play an indispensable role in various industries, including petroleum, fuel oil, natural gas, and chemical transportation. Due to their excellent corrosion resistance and, consequently, acid and alkali resistance, enhanced by their superior mechanical properties, epoxy coatings are finding increasingly wider applications.

[0004] Traditionally, two-component epoxy-amine cured coatings utilize higher molecular weight epoxy resins with hardeners / catalysts and are cured under specific conditions to achieve desired properties. Higher molecular weight epoxides perform better than lower molecular weight epoxides, but using higher molecular weight epoxides requires the use of more high volatile organic compounds (VOCs) in the formulation. The curing process releases VOCs into the atmosphere during curing or baking cycles or air drying. Reducing the VOC content in epoxy coatings is challenging and can lead to uneven coating on substrates and blistering. It is desirable to provide coatings with excellent performance. Furthermore, it would be beneficial to provide coatings with excellent performance while reducing the release of high VOC content. It is desirable to provide coatings with low VOC content without blistering or uneven coatings or substrates.

[0005] Further improvements are needed in the preparation of coating compositions comprising epoxy and amine components, and in the methods for applying these coating compositions as coatings to the surface of substrates, to avoid side reactions that could affect product quality. Furthermore, there is a strong need for methods to provide epoxy-amine coatings with high molecular weight epoxides in epoxy-amine coating systems while simultaneously preventing the release of VOCs into the atmosphere. Summary of the Invention

[0006] This disclosure broadly relates to the preparation of coating compositions comprising an epoxy component, an amine component, and optionally a catalyst and other additives, and to methods of applying these coating compositions as coatings to the surface of a substrate. This disclosure also relates to coatings applied with coating compositions and coated articles.

[0007] In some embodiments, the method of coating an article includes preparing a coating system. In some embodiments, the coating system comprises an epoxy component, an amine component, and a catalyst. The epoxy component and the amine component may be present in the coating composition at a ratio of 0.8:1 to 1.5:1. In some embodiments, the stoichiometric ratio of the epoxy component to the amine component may be 1:1 to 5:1.

[0008] In some embodiments, the epoxy component may have a molecular weight range of 175 to 1200. In some preferred embodiments, the epoxy component may have a molecular weight range of 200 to 350. In some embodiments, the epoxy component may have 1 to 5 epoxy groups. In some embodiments, the epoxy component may comprise at least two different epoxy resins. In some embodiments, the amine component may comprise at least two different amine components. In some embodiments, the catalyst may comprise at least two different catalysts. In some embodiments, the coating composition may be free of or substantially free of additional solvents. In some embodiments, the coating composition may comprise less than 1% by weight of organic solvents based on the weight of the coating composition. In some embodiments, the coating composition may comprise 100% by weight of solids based on the weight of the coating composition.

[0009] In some embodiments, the coating method includes applying a coating composition to an article and curing the coating composition to form a cured coating. In a preferred embodiment, the coating composition can cure within 60 minutes of being applied to the substrate. In some preferred embodiments, the coating composition applied to the substrate can be cured at a temperature of 135°C to 250°C to form a cured coating.

[0010] The prepared cured coating may comprise epoxy homopolymer segments. In some embodiments, the cured coating may comprise epoxy homopolymer segments having repeating units separated by ether bonds. In some preferred embodiments, the cured coating may comprise epoxy homopolymer segments comprising two or more repeating units separated by ether bonds.

[0011] The coating composition can be applied to any article that can benefit from being coated with a cured coating. The cured coating of this disclosure can exhibit excellent properties and characteristics, such as higher gloss and stronger solvent resistance. In some embodiments, the cured coating can exhibit a friction test result of 50 cycles or higher. In a preferred embodiment, the cured coating can have a gloss level of 60 gloss units (GU) or higher. In some embodiments, the coating composition of this disclosure can be used to coat pipes, chemical tanks (container and processing tanks), pipelines, connectors, etc., as a substrate. In a preferred embodiment, the substrate is made of steel.

[0012] definition

[0013] Unless otherwise stated, all scientific and technical terms used herein have their common meaning in the art. The definitions provided herein are for ease of understanding of certain terms used frequently herein and are not intended to limit the scope of this disclosure.

[0014] Unless otherwise specified, the terms "polymer" and "polymeric material" include, but are not limited to, organic homopolymers, copolymers such as, for example, block, graft, random and syndiotactic copolymers, terpolymers, and their blends and modifications. Furthermore, unless otherwise specifically limited, the term "polymer" shall include all possible geometries of the material. These geometries include, but are not limited to, isotactic, syndiotactic, and random symmetry.

[0015] The term "aliphatic group" refers to a saturated or unsaturated straight-chain or branched hydrocarbon group. For example, the term is used to cover alkyl groups, alkenyl groups, and alkynyl groups.

[0016] The term "alkyl" is used in this disclosure to describe a monovalent group of an alkane group and includes straight-chain, branched, cyclic, and bicyclic alkyl groups and combinations thereof, including unsubstituted and substituted alkyl groups. Unless otherwise specified, alkyl groups typically contain 1 to 30 carbon atoms. In some embodiments, the alkyl group contains 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, 1 to 4 carbon atoms, or 1 to 3 carbon atoms. Examples of alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, isobutyl, tert-butyl, isopropyl, n-octyl, n-heptyl, ethylhexyl, cyclopentyl, cyclohexyl, cycloheptyl, etc.

[0017] The term "alkylation" is used in this disclosure to describe a compound that reacts to replace a hydrogen atom or a negatively charged part of the compound with an alkyl group, such that the alkyl group is covalently bonded to the compound.

[0018] As used in this disclosure, the term "aromatic ring" refers to a conjugated ring system of an organic compound. An aromatic ring may consist of only carbon atoms, or it may include one or more heteroatoms, such as oxygen, nitrogen, or sulfur.

[0019] Organic groups that can be substituted for compounds disclosed herein. When the term "group" is used herein to describe a chemical substituent, the described chemical substance may include unsubstituted groups and / or groups that, for example, have O, N, Si, or S atoms in the chain (such as in an alkoxy group) and carbonyl groups or other conventionally substituted groups. For example, the phrase "alkyl group" is intended to include not only pure open-chain saturated hydrocarbon alkyl substituents, such as methyl, ethyl, propyl, tert-butyl, etc., but also alkyl substituents carrying other substituents known in the art, such as hydroxyl, alkoxy, alkylsulfonyl, halogen atom, cyano, nitro, amino, carboxyl, etc. Thus, "alkyl group" includes ether groups, haloalkyl, nitroalkyl, carboxylalkyl, hydroxyalkyl, sulfonalkyl, etc.

[0020] The term "crosslinking agent" refers to a molecule capable of forming covalent bonds between polymers or between two different regions of the same polymer. As used herein, the term "crosslinking agent" is interchangeable with "curing agent." The term "curing agent" refers to a component that contains (or can be used as) both a "crosslinking agent" or "curing agent" and a "catalyst" or "catalyst package."

[0021] Unless otherwise specified, references to "(meth)acrylate" compounds (where "methyl" is enclosed in parentheses) mean that they include both acrylate compounds and methacrylate compounds.

[0022] Unless otherwise specified, all parts, ratios, and percentages are by weight, and all molecular weights are number average molecular weights (Mn). Molecular weights can be determined by various techniques well known in the art. For the components and / or compositions described herein, molecular weights are preferably determined by gel permeation chromatography (GPC).

[0023] As used herein, the term "substantially" has the same meaning as "significantly" and can be understood to modify the following term by at least about 90%, at least about 95%, or at least about 98%. The term "substantially free of" for a specific compound means that the composition of the present invention contains less than 1,000 parts per million (ppm) of the compound. The term "substantially free of" for a specific compound means that the composition of the present invention contains less than 100 parts per million (ppm) of the compound. The term "completely free of" for a specific compound means that the composition of the present invention contains less than 20 parts per billion (ppb) of the compound. In the context of the above phrases, the composition of the present invention contains less than the amounts of the compound described above, whether the compound is present in an unreacted form or has reacted with one or more other materials.

[0024] The term “substantially not” as used in this article has the same meaning as “not significant” and can be understood to have the opposite meaning of “substantially”, i.e., modifying the term following it with no more than 25%, no more than 10%, no more than 5%, or no more than 2%.

[0025] The term “about” is used herein in conjunction with numerical values ​​to include normal variation in measurements as would be expected by those skilled in the art, and is understood to have the same meaning as “approximately” and to cover typical error limits, such as ±5% of the value.

[0026] Terms such as “a”, “an” and “the” are not intended to refer only to singular entities, but rather to include general categories whose specific examples can be used to illustrate them.

[0027] The terms “an,” “a,” and “the” are used interchangeably with the term “at least one.” The phrases “at least one” and “including at least one” following the list refer to any item in the list and any combination of two or more items in the list.

[0028] As used herein, unless otherwise expressly stated in the text, the term "or" is generally used in its conventional meaning, including "and / or". The term "and / or" means one or all of the listed elements or a combination of any two or more of the listed elements.

[0029] A range of values ​​listed by endpoints includes all values ​​contained within that range (for example, 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc., or 10 or less includes 10, 9.4, 7.6, 5, 4.3, 2.9, 1.62, 0.3, etc.). When the range of values ​​is "at most" or "at least" a specific value, that value is included in the range.

[0030] As used herein, terms such as “have / having,” “include / including,” and “comprise / comprising” are used in their open-ended sense and generally mean “including but not limited to.” It should be understood that phrases such as “consistently composed of,” “comprises from,” etc., fall under the category of “comprising.” As used herein, “consistently composed of” when referring to compositions, products, methods, etc., means that the components of the composition, product, method, etc., are limited to the listed components and any other components that do not materially affect the essential and novel characteristics of the composition, product, method, etc.

[0031] The terms "preferred" and "ideally" refer to embodiments that provide certain beneficial effects under certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, the description of one or more preferred embodiments does not imply that other embodiments are unavailable, and is not intended to exclude other embodiments from the scope of this disclosure (including the claims).

[0032] Any orientations mentioned herein, such as “top,” “bottom,” “left,” “right,” “upper,” “lower,” and other directions and orientations, are described herein with reference to the accompanying drawings for clarity and do not limit the actual device or system or the use of such a device or system. Devices or systems as described herein can be used in multiple orientations and directions.

[0033] When used in the context of coatings applied to a surface or substrate, the term "on" includes coatings applied directly or indirectly to a surface or substrate. Thus, for example, coatings applied to a primer layer covering a substrate constitute coatings applied to a substrate. Detailed Implementation

[0034] This disclosure broadly relates to the preparation of coating compositions comprising an epoxy component, an amine component, and optionally a catalyst and other additives, and to methods of applying these coating compositions as coatings to the surface of a substrate. This disclosure also relates to coatings applied with coating compositions and coated articles.

[0035] The coating compositions disclosed herein can be used for a wide range of purposes. The coating compositions disclosed herein can be used to coat various surfaces. The coating compositions disclosed herein can be used to coat the surface of articles. Such articles can be made of a variety of materials. This disclosure provides methods for preparing coating compositions, methods for coating articles with coating compositions, methods for preparing coatings, and articles coated with coating compositions. In some embodiments, the coating compositions can be used to coat articles that come into contact with chemicals during chemical processing or manufacturing, such as pipes, chemical containers (container and processing tanks), pipelines, connectors, etc.

[0036] Epoxy coatings are typically formulated as two-component systems with epoxy and amine components as the two main components. The amine component reacts with the epoxy component to open the ethylene oxide ring (epoxy-amine curing), followed by chain extension polymerization (polymerization curing).

[0037] According to one embodiment, the coating composition of this disclosure is based on three or more reactive compounds: an epoxy component, an amine component, and a catalyst. The coating is applied to an article and cured at an elevated temperature within 60 minutes of application. In other words, the coating cures at an elevated temperature without a long delay, which is commonly used in industry to allow solvent evaporation and / or to allow epoxy-amine curing. According to one embodiment, the coating composition is cured at a temperature from 70°C to 250°C. The cured coating may exhibit a gloss level of 60 gloss units (GU) or higher. The cured coating may contain epoxy homopolymer segments that are longer than the corresponding epoxy segments in prior art coatings. The cured coating may contain epoxy homopolymer segments comprising two or more repeating units separated by ether bonds.

[0038] In typical epoxy-amine coatings, an epoxy resin component is mixed with an amine component, and the mixture is applied to a product having the surface to be coated. The reaction (also known as epoxy-amine curing) allows the epoxy and amine components to react at a specific temperature. N The reaction proceeds in two ways to provide the ring-opening product of the epoxy. Typically, epoxy-amine curing is carried out at room temperature and requires several hours before the reaction proceeds to the polymerization step (also known as polymerization curing). After epoxy-amine curing, the article with the coated surface can be baked at elevated temperatures to polymerize the epoxy-amine coating composition. This epoxy-condensation reaction (polymerization or chain growth) provides the polymer product. High molecular weight epoxy components are typically used as starting materials to obtain superior properties from the product. However, it is generally understood in industry that the use of high molecular weight epoxy components requires the use of solvents, and therefore necessitates the use of additional VOCs. Furthermore, solvent-based epoxy-amine coatings currently used as internal pipe coatings in the petrochemical industry are typically prepared by first coating the article, storing the coated article at ambient temperature for several hours (e.g., overnight or 6 to 24 hours), and then at 110°C (230°F). The coating cures during a 2.5-hour baking process. The long storage time allows most of the solvent to evaporate before oven curing.

[0039] According to embodiments of this disclosure, an epoxy component is mixed with an amine component and a catalyst, and the mixture is applied to an article having a surface to be coated. The coated article is then cured at an elevated temperature within a predetermined time period (e.g., within 60 minutes of coating application). This allows epoxy-amine curing and polymerization curing to occur simultaneously, thus providing a “dual cure” for the coating. Compared to conventional coatings, the coating compositions of this disclosure reduce reaction time. The coating compositions of this disclosure help streamline the coating process due to the absence of a long waiting time between application and curing. Additionally, the coating compositions of this disclosure reduce or minimize amine whitening. Furthermore, the coating compositions of this disclosure provide high-quality coatings from low molecular weight epoxy component starting materials. In exemplary embodiments, the coating compositions of this disclosure provide coatings with excellent performance properties while reducing VOC usage.

[0040] Coating composition

[0041] According to one embodiment, the coating composition disclosed herein comprises an epoxy component, an amine component, and a catalyst. The coating composition is curable to form a cured coating. The coating composition may also contain optional additives. Each component will be discussed in further detail below.

[0042] According to one embodiment, at least some of the components (epoxy component, amine component, catalyst, and optional additives) are liquids. Preferably, when mixed together, the components have a viscosity such that the coating composition does not require the use of any solvent. The coating composition can be prepared without any additional solvent to the extent that some of the epoxy component, amine component, catalyst, and optional additives will be considered solvents. The term "additional solvent" is used herein to refer to any solvent added to the composition for solvation or dilution purposes and not present in the composition due to its role as an epoxy component, amine component, catalyst, or additive providing the functions of the additives described below. In some embodiments, the coating composition contains 10% or less, 7% or less, 5% or less, 4% or less, 3% or less, 2% or less, or 1% or less of additional solvent. In some embodiments, the coating composition contains no or substantially no additional solvent.

[0043] In some embodiments, the coating composition comprises a single type of epoxy component.

[0044] The epoxy component and amine component may be present in the coating composition at a ratio of at least 0.8 parts epoxy component per part amine component. In some embodiments, the coating composition contains an epoxide in at least an equal or excess amount relative to the amine. The excess epoxy component may also promote homopolymerization of the epoxy component during curing. The epoxy component and amine component may be present in the coating composition at a ratio of 1 part or more epoxy component per part amine component, 1.2 parts or more epoxy component per part amine component, 1.5 parts or more epoxy component per part amine component, 1.8 parts or more epoxy component per part amine component, or 2 parts or more epoxy component per part amine component.

[0045] The epoxy components, amine components, catalysts, and optional additives are discussed in further detail below.

[0046] Epoxy components

[0047] As used in this disclosure, "epoxy component" includes resins or compounds containing epoxy groups (also known as ethylene oxide groups or ethoxy groups). These epoxy components include a variety of curable epoxy compounds and combinations thereof. Useful epoxy components include liquids, solids, and mixtures thereof. In some embodiments, the coating composition comprises a single type of epoxy component. In some embodiments, the coating composition comprises more than one type of epoxy component. In some embodiments, the coating composition comprises more than one type of epoxy component, wherein one of the epoxy components is the dominant epoxy component, comprising 80% or more, 85% or more, 90% or more, 95% or more, or 98% or more of the total epoxy component.

[0048] The epoxy component in the coating composition disclosed herein may include, for example, bisphenol A diglycidyl ether (DGBA), bisphenol F diglycidyl ether (DGBF), tetrabromobisphenol A diglycidyl ether (DGBTA), epoxy resins based on phenolic varnishes, triepoxy resins, higher molecular weight resins (including, for example, bisphenol A diglycidyl ether promoted by bisphenol A), or polymerized unsaturated monoepoxides (including, for example, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, etc.).

[0049] In some embodiments, the epoxy component of this disclosure may contain one to five epoxy groups per molecule. The epoxy component of this disclosure includes bisphenol A-based epoxy resins. For example, a preferred epoxy resin in the coating compositions of this disclosure is a bisphenol A diglycidyl ether (DGBA) resin having the following structure:

[0050]

[0051] Typically, n = 0.15 or greater.

[0052] DGBA resin can be used, for example, as EPON. ™ 828RS (available from Westlake Epoxy, Columbus, OH) or EPON ™ 828LS (available from Westlake Epoxy) or DER ™ 331 (available from Midland, MI, Dow Inc.). Suitable epoxy components of coating compositions include epoxy resins and modified epoxy resins selected from bisphenol A, bisphenol F, phenolic epoxy resins, non-aromatic epoxy resins, alicyclic epoxy resins, glycidyl esters, epoxy-functionalized acrylics, and any combination thereof. In some embodiments, the epoxy component of this disclosure may comprise two different epoxy resins. Some suitable commercially available epoxy resins (in addition to the epoxy resins described above) include, for example, EPIKOTE. ™ 828 (available from Westlake Epoxy, Houston, TX), ARALDITE ® GY 250 (available from Huntsman Corp., The Woodlands, TX), EPIKOTE ™ 1004 (available from Westlake Epoxy), DER ™ 664-20 (available from Dow Chemicals Corp.), EPIKOTE ™ 1001-X-75 (available from Westlake Epoxy), ARALDITE ® GZ 7071-X-75BD (available from Huntsman Corp.), DER ™ 352 (available from Dow Chemicals Corp.), EPIKOTE ™ 232 (available from Westlake Epoxy), EPIKOTE ™ 862 (available from Westlake Epoxy), DEN ™ 438-X-80 (available from Palmer Holland, Westlake, OH) and EPIKOTE ™ 154 (available from Westlake Epoxy) and mixtures and combinations thereof. In some embodiments, the epoxy component includes or is DGBA, such as that available as EPON. ™ 828RS (available from Westlake Epoxy), EPON ™828LS (available from Westlake Epoxy) and DER ™ Those available from 331 (available from Dow Chemicals Corp.).

[0053] Epoxy components can be described in part by their epoxide equivalent (“EEW”). Knowing the EEW of a particular epoxy component is often helpful when determining the amount of other components to be added to the composition to prepare the coating compositions disclosed herein. Some resins (e.g., DER) ™ 331) can have an epoxy equivalent in the range of about 180 g / mol to 195 g / mol. Other resins (such as DER) ™ 332) can have an epoxy equivalent in the range of approximately 170 g / mol to 175 g / mol. It can be marketed under trade names such as EPON. ™ 828, EPON ™ 1001, EPON ™ 1007 and EPON ™ Some commercially available epoxy component materials, such as 1009 (available from Westlake Epoxy), may have varying EEWs that can be adjusted prior to use. The desired EEW can be achieved by adding a dihydroxy compound (e.g., bisphenol A). The amount of bisphenol A used to adjust the EEW in the epoxy component of this disclosure depends on the desired EEW. Commercially available epoxy component materials may contain a mixture of diepoxides, monoepoxides, and aromatic polyethers. In some embodiments, the epoxy component has a molecular weight range of 175 Daltons to 1200 Daltons. In some embodiments, the epoxy component has a molecular weight range of 200 Daltons to 350 Daltons.

[0054] amine components

[0055] The coating compositions disclosed herein comprise an amine component. The amine component may be a polyamine. As used herein, the term "polyamine" may also refer to a multifunctional amine and describes a compound having an amine functional group and containing at least two active amine hydrogens. These amine components have, on average, more than one active hydrogen atom, wherein the active hydrogen atoms may be bonded to the same nitrogen atom or different nitrogen atoms. Such amine components may include those compounds containing a primary amine moiety, as well as compounds containing two or more primary, secondary, or amide moieties connected to a common central organic moiety.

[0056] Polyamines or polyfunctional amines within the scope of this disclosure include, for example, aliphatic polyamines, polyether amines, alicyclic amines, aromatic amines, heterocyclic amines, aryl aliphatic amines, amides, and polyamides. Polyamines also include Mannich base derivatives of aliphatic amines, alicyclic amines, aromatic amines, polyamides, or amides, as well as monoglycidyl ethers of aliphatic amines, alicyclic amines, aromatic amines, polyamides, or amides with glycols or phenols, bisphenol A or bisphenol F glycidyl ethers, or amine-epoxy adduct derivatives of epoxy phenolic varnish resins, and mixtures and combinations thereof.

[0057] Examples of aliphatic polyamines as amine components in coating compositions include: polyethyleneamine (including, for example, ethylenediamine, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), etc.), polyacrylamine (including, for example, dipropylenetriamine, tripropylenetetramine, etc.), and aminopropylated ethylenediamine (including, for example, N-3-aminopropylethylenediamine, N,N'-bis(3-aminopropyl)ethylenediamine, etc.). Diamines, N,N,N'-tris(3-aminopropyl)ethylenediamine, aminopropylated propylenediamine, 1,6-hexanediamine (HMDA), 2,4,4-trimethyl-1,6-hexanediamine, N-3-aminopropyl-1,3-diaminopropane, N,N'-bis(3-aminopropyl)-1,3-diaminopropane, N,N,N'-tris(3-aminopropyl)-1,3-diaminopropane, 2-methyl-1,5-pentanediamine, and mixtures and combinations thereof.

[0058] Examples of polyether amines used as amine components in coating compositions include poly(epoxide) monoamines, diamines, and triamines. In some embodiments, the polyether amines include, for example, poly(ethylene oxide), poly(propylene oxide), and poly(tetrahydrofuran) monoamines, diamines, and triamines. In some embodiments, the poly(propylene oxide) monoamines, diamines, and triamines used in this disclosure may be branded JEFFAMINE. ® Commercially available. Exemplary examples include: poly(ethylene glycol-block-propylene glycol)(2-amino-2-methyl) methyl ether (available as JEFFAMINE). ® M-600, JEFFAMINE ® M-1000, JEFFAMINE ® M-2005 and JEFFAMINE ® M-2070 is available from Huntsman Corp., and poly(ethylene glycol-block-propylene glycol) bis(2-amino-2-methyl) ether (available as a JEFFAMINE). ® ED600, JEFFAMINE ® ED900 and JEFFAMINE ®ED2001 is obtained from Huntsman Corp., and tris(2-amino-2-methylethyl)trimethylolpropane ether (available as JEFFAMINE) ® T-403 is available from Huntsman Corp., tris(2-aminopoly(propylene oxide)) glycerol ether (available as JEFFAMINE) ® T-5000 is obtained from Huntsman Corp.), bis(3-aminopropyl)polypropylene glycol ether (available as JEFFAMINE) ® D230, JEFFAMINE ® D400, JEFFAMINE ® D2000 and JEFFAMINE ® D4000 is available from Huntsman Corp., as well as mixtures and combinations thereof. Polyethylene oxide monoamines, diamines, and triamines include, for example, triethylene glycol diamine (available as JEFFAMINE). ® XTJ 504 is obtained from Huntsman Corp., and bis(3-aminopropyl)diethylene glycol ether (which can be used as an ANCAMINE) ® 1922A was obtained from Evonik Industries AG in Essen, Germany, and di(2-aminopropylated)diethylene glycol (which can be used as JEFFAMINE). ® XTJ-511 is obtained from Huntsman Corp.), polyoxyethylene methyl (3-aminopropyl) ether, and polyethylene glycol diamine (which can be used as JEFFAMINE). ® XTJ-512 is obtained from Huntsman Corp., polyoxyethylene bis(3-aminopropyl) ether, and any mixtures and combinations thereof. Polytetrahydrofuran monoamines, diamines, and triamines include, for example, bis(3-aminopropyl)polytetrahydrofuran (M... n 350), bis(3-aminopropyl)polytetrahydrofuran (M n 750), poly(propylene oxide-block-tetrahydrofuran) bis(2-amino-2-methylethyl) ether (can be used as JEFFAMINE) ® XTJ-533 and JEFFAMINE ® XTJ-536 (obtained from Huntsman Corp.) at least one of them, as well as mixtures and combinations thereof.

[0059] Examples of cycloaliphatic amines as amine components in coating compositions include: 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, hydrogenated o-toluenediamine, hydrogenated m-toluenediamine, hydrogenated m-xylenediamine, or 1,3-bis(aminomethyl)cyclohexane (1,3-BAC), isophorone diamine (IPDA), norbornene diamine, 3,3'-dimethyl-4,4"-diaminodicyclohexylmethane, di(aminocyclohexyl)methane (including various isomers, such as up to about 5% by weight of 2,4-(diaminocyclohexyl)methane and at least about 95% by weight of 4,4'-(diaminocyclohexyl)methane (which can be used as AMICURE). ® PACM obtained from Evonik Industries AG), 1,3-di(aminocyclohexyl)propane, 1-cyclohexylamino-3-aminopropane, di(aminocyclohexyl)sulfone, 4,4'-di(aminocyclohexyl)methane, 1-cyclohexylamino-3-aminopropane, mixtures of methylene-bridged poly(cyclohexyl-aromatic)amines, and mixtures and combinations thereof.

[0060] Some examples of aromatic polyamines as amine components in coating compositions include: m-phenylenediamine (MPD), p-phenylenediamine (PPD), diaminophenylmethane (DDM), tris(aminoethyl)benzene, tris(aminobutyl)naphthalene, toluenediamine (2-methyl-p-phenylenediamine), diethyltoluenediamine (DETDA), diaminodiphenyl sulfone (DDS), mixtures of methylene-bridged poly(cyclohexyl-aromatic)amines, and mixtures and combinations thereof.

[0061] Some examples of heterocyclic polyamines as amine components in coating compositions include: N-aminoethylpiperazine (NAEP), 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, piperazine, 4,4'-trimethylenedipiperidine, 1,4-bis(3-aminopropyl)piperazine, 2,5-dimethylpiperazine, 2,6-dimethylpiperazine, 2-methylpiperazine, homopiperazine, and mixtures and combinations thereof.

[0062] Some examples of aryl aliphatic polyamine components in coating compositions include m-phenylenediamine (MXDA), p-phenylenediamine, di(aminoethyl)benzene, tri(aminoethyl)benzene, tri(aminobutyl)naphthalene, and mixtures and combinations thereof.

[0063] Some examples of the Mannich base amine component in coating compositions include polyamines derived from the reaction of the aforementioned aliphatic amines, alicyclic amines, polyether amines, or aromatic amines with phenol or substituted phenols and formaldehyde. An exemplary substituted phenol used to prepare the Mannich base, which is practically applicable in this disclosure, is cashew nut shell phenol, obtained from cashew nut shell liquid. Alternatively, the Mannich base can be prepared by an exchange reaction of a polyfunctional amine with at least one tertiary amine containing the Mannich base, such as 2,4,6-tris(N,N-dimethylaminomethyl)phenol (which can be used as an ANCAMINE). ® K54 was obtained from Evonik Industries AG.

[0064] In some embodiments, the amine is or includes a phenol containing a tertiary amine that does not include a reactive hydrogen group. An example of such an amine is ANCAMINE. ® K54.

[0065] Some examples of amide components in coating compositions include iodoamines derived from monocarboxylic acids and polyamines (such as aliphatic amines, alicyclic amines, heterocyclic amines, or aromatic amines). Monocarboxylic acids are typically derived from fats and oils, particularly from at least one of C16, C18, and C19 fatty acids derived from soybean, tall oil, and ricinoleic acid, as well as mixtures and combinations thereof. Polyamines may include, for example, DETA, TETA, TEPA, piperazine, alkylated amines, and benzylated amines. If desired, amides can be modified by reacting a portion of the amine hydrogen with bifunctional and monofunctional epoxy resins (such as those described above). As amine components in coating compositions, amides offer advantages over linear polyamines, namely reduced volatility and potential for skin irritation, easier mixing ratios, and increased flexibility and impact strength.

[0066] The higher temperatures during the synthesis of amides typically lead to the formation of a closed-ring imidazoline structure derived from the amine and amide groups. The ratio of amide to imidazoline depends on the reaction conditions. The imidazoline moiety improves surface wetting, thereby enhancing adhesion, and also increases the chemical and heat resistance of the cured product. Exemplary examples of amide amines include those based on the reaction products of C16, C18, and C19 fatty acids, particularly tall oil fatty acids (TOFA) and TEPA, which can serve as ANCAMIDEs. ® 500, ANCAMIDE ® 501, ANCAMIDE ® 506, ANCAMIDE ® 502, ANCAMIDE ® 503, ANCAMIDE ® 2447 or ANCAMIDE ®507 is obtained from Evonik Industries AG, as well as epoxy-modified amides, such as ANCAMIDE. ® 2426 (available from Evonik Industries AG).

[0067] Additionally, some examples of the diamine and polyamine components in this disclosure include: tris(aminophenyl)methane, bis(aminomethyl)norbornene, bis(aminopropyl) ether, bis(aminopropyl) sulfide, 4,4'-diaminodiphenyl ether, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenyl, 4,4'-diamino-α-methylstilbene, 4,4'-diaminobenzoylaniline, 4,4'-diaminostilbene, 1,4-bis(4-aminophenyl)-transcyclohexane, 1,1-bis(4-aminophenyl)cyclohexane, 1,4-bis(aminocyclohexyl)methane, 1,4-bis(aminomethyl)cyclohexane, 1,4-cyclohexanediamine, 2,2'-bis(4-aminocyclohexyl)propane, and any mixtures and combinations thereof.

[0068] Examples of suitable commercially available amine components include: CARDOLITE ® NC-541 (available from Cardolite Corp., Bristol, PA), CARDOLITE ® LITE 2001 (available from Cardolite Corp.), SUNMIDE ® CX-105X (available from Evonik Industries AG), EPIKURE ™ 3140 (available from Westlake Epoxy), SIQ AMIN 2030 (available from SIQ Kunstharze GmbH in Marl, Germany), EPIKURE ™ 3115X-70 (available from Westlake Epoxy), SIQ AMIN 2015 (available from SIQ Kunstharze GmbH), POLYPOX ® VH 40309 / 12 (available from Polymer-Chemie GmbH in Bad Sobernheim, Germany), CETEPOX ® 1490 H (available from Aditya Birla Advanced Materials, Mumbai, India), m-xylenediamine (MXDA, commercially available from Aalchem, Grand Rapids, MI), diethylaminopropylamine, GASKAMINE ®240 (available from Mitsubishi Gas Company Advanced Polymers, Inc., Colonial Heights, VA), CARDOLITE ® LITE 2002 (available from Cardolite Corp.), ARADUR ® 42 BD (available from Huntsman Corp.), Isophorone diamine (IPDA, available from ThreeBond Co. Ltd. in Tokyo, Japan), EPIKURE ™ 3090 (available from Westlake Epoxy), CRAYAMID ® E260 E90 (available from Arkema Coating Resins, Torrance, CA), ARADUR ® 943 CH (available from Huntsman Corp.), ARADUR ® 863 XW 80 CA (available from Huntsman Corp.), Diethylenetriamine (DETA), Triethylenetetramine (TETA), Tetraethylenepentamine (TEPA), Dipropylenediamine (DPDA), Diethylaminopropylamine (DEAPA), AMINE 248 (available from ThreeBond Co. Ltd.), N-Aminoethylpiperazine (N-AEP), LAMIRON C-260 (available from ThreeBond Co. Ltd.), ARALDITE ® HY-964 (available from Huntsman Corp.), menthol diamine (available from ThreeBond Co. Ltd.), 4,4'-methylene dicyclohexylamine (WANDAMIN HM, commercially available from ThreeBond Co. Ltd.), 1,3-bis(aminomethyl)cyclohexane (1,3-BAC, commercially available from Mitsubishi Gas Company Advanced Polymers, Inc.), 1,3-diaminobenzene, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone (DDS), and mixtures and combinations thereof.

[0069] catalyst

[0070] The coating composition may contain one or more catalysts. Adjustment of the epoxy component material may suitably include increasing its molecular weight. This increase in molecular weight can be enhanced by using a catalyst. Typical catalysts that can be used to increase the molecular weight of the epoxy component material in the coating composition include amines, hydroxides (e.g., potassium hydroxide, etc.), phosphonium salts, and combinations thereof. In some embodiments, the catalyst is an amine catalyst. The catalyst may be present in an amount sufficient to promote the desired condensation reaction. For example, the catalyst may be sufficient to promote the reaction of bisphenol A with a low epoxide equivalent epoxide (e.g., EPON). ™ The amount of condensation reaction between 828RS is present.

[0071] Some examples of catalysts suitable for coating compositions include any conventional and modified tertiary amines, amine adducts, imidazoles, imidazole adducts, urea derivatives (all anionic), as well as Lewis acids and onium salts (all cationic). Examples of suitable catalysts include, for instance, tertiary amines such as dimethylaminopyridine (DMAP); and amine adducts such as EPIKURE. ™ P-100 particles (available from Westlake Epoxy); imidazoles, such as 2-methylimidazolium; imidazole adducts, such as CUREDUCT ™ P0505 (available from Shikoku Chemicals Corp. of Kagawa, Japan); and mixtures and combinations thereof.

[0072] In some embodiments, the coating composition includes one or more catalysts. In some embodiments, the coating composition comprises an acid catalyst. Examples of acid catalysts include Lewis acids (e.g., boron trifluoride ethers, etc.) and protic acids (such as Brønsted acids, etc.). In some embodiments, the acid catalyst is an inorganic protic acid, such as phosphoric acid or sulfuric acid, or an organic protic acid, such as a carboxylic acid, phosphonic acid, or sulfonic acid. Exemplary carboxylic acids suitable for use as acid catalysts include, for example, acetic acid, trifluoroacetic acid, and propionic acid. An exemplary phosphonic acid is methylphosphonic acid. Exemplary sulfonic acids include, for example, methanesulfonic acid, benzenesulfonic acid, camphorsulfonic acid; p-toluenesulfonic acid (PTSA) and dodecylbenzenesulfonic acid (DBSA).

[0073] In some embodiments, the catalyst in the coating composition comprises a Lewis acid. Examples of suitable Lewis acid catalysts are aluminum trichloride (AlCl3); benzyltriethylammonium chloride (TEBAC); Cu(O3SCF3)2; (CH3)2BrSBr; FeCl3 (e.g., FeCl3∙6H2O); HBF4; BF3∙O(CH2CH3)2; TiCl4; SnCl4; CrCl2; NiCl2 and Pd(OC(O)CH3)2. The acid catalyst can be unsupported (excluding solid supports) or supported, for example, covalently bonded to a solid support.

[0074] In some embodiments, the catalyst in the coating composition may include a nitrogen base. The nitrogen base used as a catalyst may be a primary amine, secondary amine, or tertiary amine, or a basic nitrogen-containing heterocycle, such as imidazole. Thus, suitable bases include, for example, tertiary monoamines, secondary monoamines, primary, secondary, and tertiary diamines, tertiary triamines, mixed polyamines, and nitrogen heterocycles.

[0075] In some embodiments, the catalyst in the coating composition includes, for example, tertiary monoamines (such as 2-(N,N-dimethylamino)ethanol), secondary monoamines (such as diisobutylamine), primary diamines (such as 1,3-diaminopropane and 1,3-diaminobutane), secondary diamines (such as piperazine), mixed polyamines (such as 3-(dimethylamino)propylamine), and nitrogen heterocycles (such as 3-methylpyridine or 4-methylpyridine). Examples of other bases include tertiary monoamines such as tri-n-butylamine, triisobutylamine, octyl dimethylamine, benzyl dimethylamine, tri-n-propylamine, trihexylamine, N,N-diethylcyclohexylamine, 2-(diethylamino)ethanol, 3-(dimethylamino)-1-propanol, and 2-(dimethylaminomethyl)phenol; monosecondary amines such as 2-(methylamino)ethanol, di-n-pentylamine, and diisopentylamine; primary diamines such as isophorone diamine (5-aminoethyl-3,5,5-trimethylcyclohexylamine), 1,4-diaminobutane, 1,5-diaminopentane, and hexamethylene diamine; and secondary diamines such as N, N'-Diethylenediamine; tertiary diamines, such as N,N',N',N'-tetramethylbutanediamine, 1,7-bis(dimethylamino)heptane and bis(4-dimethylaminophenyl)methane; tertiary triamines, such as 2,4,6-tris(dimethylaminomethyl)phenol; mixed polyamines, such as triethylenetetramine, tetraethylenepentamine, diethylenetriamine, 3-(diethylamino)propylamine and N-(2-aminoethyl)piperazine; and nitrogen heterocycles, such as 1-methylimidazole, 2-methylimidazole, benzimidazole, 2-phenylimidazole, quinoline, benzyldimethylamine and mixtures and combinations thereof.

[0076] In some embodiments, the catalyst in the coating composition comprises a tertiary amine. In some embodiments, the tertiary amine is 2,4,6-tris(dimethylaminomethyl)phenol, which can be used as an ANCAMINE. ® K54 was purchased from Evonik Industries AG.

[0077] The catalyst may be present in any amount suitable for accelerating the curing of the epoxy-amine coating. In some embodiments, the catalyst may be present in amounts of 0.5% by weight or more, 1% by weight or more, 2% by weight or more, 3% by weight or more, 4% by weight or more, 5% by weight or more, 8% by weight or more, 10% by weight or more, 12% by weight or more, 15% by weight or more, or 18% by weight or more, based on the weight of the hardener composition. In some embodiments, the catalyst may be present in amounts of 20% by weight or less, 15% by weight or less, 15% by weight or less, 12% by weight or less, 10% by weight or less, 8% by weight or less, 5% by weight or less, 4% by weight or less, 3% by weight or less, or 2% by weight or less.

[0078] additive

[0079] The coating compositions disclosed herein may optionally include one or more additives. When used, the additives preferably enhance and preferably do not adversely affect the coating composition or the cured coating formed therefrom. For example, additives may be included in the coating composition to enhance the aesthetics of the coating, facilitate the manufacture, processing, treatment, or application of the composition, and further improve specific functional properties of the coating composition or the cured coating produced therefrom. Such optional additives include, for example, dyes, pigments, toners, extenders, fillers, lubricants, preservatives, flow control agents, thixotropic agents, dispersants, antioxidants, adhesion promoters, light stabilizers, co-resins, and mixtures thereof. Each optional additive is preferably included in an amount sufficient for its intended purpose, but not in an amount that adversely affects the coating composition or the resulting cured coating.

[0080] When used, fillers may be present in any available amount and can be determined by a person skilled in the art using this document as guidance. Typically, fillers may be present in the coating composition at concentrations of 0% or more, 0.5% or more, 1% or more, 2% or more, 3% or more, 4% or more, 5% or more, 8% or more, 10% or more, 12% or more, 15% or more, 20% or more, 25% or more, or 30% or more. Fillers may be present in the coating composition at concentrations of 35% or less, 30% or less, 25% or less, 20% or less, 15% or less, 12% or less, 10% or less, 8% or less, 5% or less, 4% or less, 3% or less, 2% or less, 1% or less, or 0.5% or less.

[0081] In some implementations, fillers may be optionally used. Some examples of optional fillers include mineral fillers such as calcium carbonate, calcium oxide, and talc. Calcium carbonate (e.g., under the trade name OMYA) ® (Available for sale from Proctor, VT's Omya, Inc.) Talc can be used for example to reduce shrinkage and increase corrosion resistance. ® (Available from Evonik Industries AG), and magnesium aluminum silicate (wollastonite), for example, can be traded under the name NYAD. ® Available for purchase at 200 (available from Imerys SA in Paris, France).

[0082] When used, the pigment may be present in any available amount, and this document can be used as guidance for those skilled in the art to determine its suitability. Typically, the pigment may be present in the coating composition at concentrations of 0% or more, 0.5% or more, 1% or more, 2% or more, 3% or more, 4% or more, 5% or more, 8% or more, 10% or more, 12% or more, or 15% or more. The pigment may also be present in the coating composition at concentrations of 20% or less, 15% or less, 12% or less, 10% or less, 8% or less, 5% or less, 4% or less, 3% or less, 2% or less, 1% or less, or 0.5% or less.

[0083] In some implementations, thixotropic agents and other viscosity modifiers may also be optionally used. One such example includes fumed silica (e.g., marketed under the trade name AEROSIL). ® (Available for sale, commercially available from Evonik Industries AG). Examples of thixotropic agents that further improve washability include blends of polyester and liquid epoxy resins (LER), such as DYNACOLL. ® (Available from Evonik Industries AG).

[0084] Another optional additive is a lubricant, which facilitates the manufacture of the coated article by imparting lubricity to the coated substrate. Examples of lubricants include, for instance, carnauba wax and polyethylene-based lubricants. In some embodiments, if a lubricant is used, it is present in the coating composition in an amount of at least about 0.1% by weight and no more than about 2% by weight or no more than about 1% by weight, based on the total solid weight of the coating composition. Castor oil wax with polyamides can also be used, and it is commercially available under the trade name RHEOTIX (e.g., RHEOTIX 240, available from BYK-Chemie, GmbH, Wesel, Germany). Other suitable gelling agents include, for example, LUVOTIX. ® Grades, such as LUVOTIX ® HT (available from LEHVOSS North America, LLC, Pawcatuck, CT) is a wax-free polyamide, or DISPARLON grade (available from King Industries, Norwalk, CT).

[0085] Another optional additive is an organosilicon material, such as a siloxane-based or polycrystalline silicon-based material.

[0086] In some embodiments, when used, pyrolytic silica may be present in amounts of 2% or more, 4% or more, 6% or more, 8% or more, 10% or more, 12% or more, or 14% or more of the epoxy component. Pyrolytic silica may be present in amounts of 15% or less, 12% or less, 10% or less, 8% or less, 6% or less, or 4% or less of the epoxy component.

[0087] The coating compositions of this disclosure may optionally include reactive and non-reactive diluents. In some embodiments, the reactive diluent is blended with the epoxy component material. Reactive diluents that can be used in the coating compositions of this disclosure are also capable of undergoing a reaction to form a polymer, which is described as an interpenetrating network with the epoxy component or with an optional unsaturated moiety. In some embodiments, the reactive diluents suitable for the coating compositions of this disclosure include radical reactive monomers and oligomers. Small amounts of reactive diluents that can react with the epoxy component may be used, including, for example, hydroxy monomers such as 2-hydroxyethyl methacrylate; amide monomers such as acrylamide; and N-hydroxymethyl monomers such as N-hydroxymethylacrylamide. Additional examples of reactive diluents include vinyl compounds, acrylate compounds, methacrylate compounds, acrylamide, acrylonitrile, etc.

[0088] In some embodiments, reactive diluents are used as solvents or otherwise reduce the viscosity of reactant blends. Using one or more reactive diluents as a “solvent” eliminates or reduces the need for incorporation of large amounts of other cosolvents (such as butanol) during processing. A variety of cosolvents are suitable for the coating compositions of this disclosure. However, the use of cosolvents can result in undesirable high levels of volatile organic compounds (VOCs), which must be removed or recycled. Careful selection of cosolvents that can be used in the coating compositions of this disclosure is desirable to provide coating compositions with low VOC content. Typical cosolvents that can be used in the coating compositions of this disclosure include, for example, organic materials such as xylene, toluene, butanol, 2-butoxyethanol, pentanol, and 2-hexyloxyethanol. Some examples of cosolvents include 2-hexyloxyethanol (hexyl CELLOSOLVE, commercially available from Dow Inc.). ™ (e.g., pentanol). Co-solvents can be used in the coating compositions of this disclosure, for example, to enhance the solubility of reactive diluents and / or improve the performance of reactive diluents as solvents for other components.

[0089] Examples of reactive diluents for neodecanoic acid, such as monoglycidyl ester, can also act as viscosity reducers. It is commercially available, for example, under the trade name ERISYS GS-110 (available from Huntsman Corp.).

[0090] In some implementations, an adhesion promoter may also be optionally used. Examples of adhesion promoters include epoxy silanes, such as SILQUEST. ™ A-187 (available from Momentive Performance Materials Inc., Niskayuna, NY). In some embodiments, a surfactant or wetting agent may optionally be used. The wetting agent may be, for example, a nonionic fluoropolymer. In some embodiments, such agents are also capable of absorbing residual oil (e.g., manufacturing and processing oils) on the metal surface, thereby promoting adhesion to the metal surface.

[0091] In some embodiments, at least one aliphatic substituted phenol may optionally be used. Examples of aliphatic substituted phenols include phenolic derivatives having an aliphatic group at the meta position, such as cashew phenol. Such compounds promote adhesion and corrosion resistance. Cashew phenol may be marketed, for example, under the trade name CARDOLITE. ® The NC 700 (available from Cardolite Corp.) is commercially available.

[0092] Some non-limiting examples of other additives include flexible epoxy resins (such as fatty acid epoxy adducts), gelling compounds (such as polyesters or PVB), and flame retardants (such as aluminum hydroxide). Pigments or colorants, such as IRGALITE, may also be used. ®green (available from IMCD US, LLC, Oakland, CA) or ARALDITE ® blue (available from Huntsman Corp.).

[0093] method

[0094] According to one embodiment, the coating method includes applying a coating composition to an article and curing the coating composition to form a cured coating. The coating composition can be applied to any article that can benefit from being coated with a cured coating. In some embodiments, the coating compositions disclosed herein can be used to coat pipes, chemical tanks (container and processing tanks), pipelines, connectors, etc., as a substrate. In a preferred embodiment, the substrate is made of steel.

[0095] The epoxy components, amine components, catalysts, and any additives can be mixed in any order and by any suitable means known in the art to form the epoxy-amine coating compositions disclosed herein. Mixing can be accomplished according to any known mixing method, including, for example, mixing by a magnetic stirrer, high-shear mixing, manual mixing, mechanical mixing, or other suitable mixing methods.

[0096] In one embodiment, this disclosure provides a coating composition comprising: providing an epoxy component, an amine component, and a catalyst; and mixing them together. The method includes reacting the epoxy component with the amine component.

[0097] The coating composition can be applied by any suitable process known in the art. Processes for applying the coating composition to an article include, for example, sheet coating, roll coating, roller coating, spraying, doctor blade coating, brush coating, etc. In some embodiments, the coating composition is applied by spraying.

[0098] In some embodiments, the coating is applied to the article by direct roller coating. The coated article can be cured by any suitable method known in the art. In some embodiments, the coated article can be cured by forced ventilation, gas, or any suitable oven feed. Alternatively (or additionally), the coated article can be fed through a vacuum chamber to remove any solvents present in the coating composition. Other coating processes are also available and may vary depending on the equipment and processing capabilities.

[0099] After the coating composition is applied to the article, it is cured at an elevated temperature within a limited time from the time of application. The coating composition may cure within 60 minutes, 45 minutes, 30 minutes, 20 minutes, 15 minutes, 10 minutes, or 5 minutes after application. The coating composition may cure without any significant delay after application.

[0100] The coating composition can be cured at elevated temperatures that effectively cure the coating composition. The coating composition can be cured at temperatures of 70°C or higher, 80°C or higher, 90°C or higher, 100°C or higher, 110°C or higher, 120°C or higher, 130°C or higher, 140°C or higher, 150°C or higher, 160°C or higher, 175°C or higher, 200°C or higher, or 225°C or higher. The coating composition can be cured at temperatures of 250°C or lower, 225°C or lower, 200°C or lower, 175°C or lower, 160°C or lower, 150°C or lower, 140°C or lower, 130°C or lower, 120°C or lower, 110°C or lower, 100°C or lower, 90°C or lower, or 80°C or lower. The coating composition can be cured at temperatures between 135°C and 250°C, between 150°C and 225°C, or between 175°C and 200°C. The curing time can be selected based on the rate of the curing reaction. For example, a curing time can be selected such that the coating composition is fully cured by the end of the curing time. In some embodiments, the curing time can be 60 min or longer, 90 min or longer, 120 min or longer, 150 min or longer, 180 min or longer, 240 min or longer, 300 min or longer, 360 min or longer, 420 min or longer, or 540 min or longer. The curing time can also be 600 min or less, 540 min or less, 420 min or less, 360 min or less, 300 min or less, 240 min or less, 180 min or less, 150 min or less, 120 min or less, or 90 min or less.

[0101] According to one implementation, the coating is cured in a manner that achieves homopolymer curing before any epoxy-amine curing.

[0102] Coatings and products

[0103] The cured coating prepared as described above may contain epoxy homopolymer segments. These epoxy homopolymer segments have repeating units separated by ether bonds.

[0104] According to one embodiment, the cured coating prepared as described above comprises epoxy homopolymer segments that are longer than the corresponding epoxy segments in prior art coatings. The number of repeating units of the epoxy homopolymer segments and epoxy-amine units in the cured coating can be given as a calculated average. That is, although the number of repeating units is an integer, the calculated average can be a decimal. The cured coating may comprise epoxy homopolymer segments containing 1.5 or more, 1.6 or more, 1.7 or more, 1.8 or more, 1.9 or more, 2 or more, 2.1 or more, or 2.2 or more repeating units separated by ether bonds. An exemplary schematic diagram of the curing reaction of the epoxy component and the diamine is shown below. The epoxy homopolymer segment has n repeating units, and the polymer has m epoxy-amine repeating units. The repeating units of the epoxy-amine within the polymer can vary.

[0105] ,

[0106] Where R 1 and R 2 Independently an organic group (e.g., an aliphatic group, an alicyclic group, or an aromatic group).

[0107] n is 1.5 or greater, 1.6 or greater, 1.7 or greater, 1.8 or greater, 1.9 or greater, 2 or greater, 2.1 or greater, or 2.2 or greater; and

[0108] m is 15 or greater, 1.6 or greater, 1.7 or greater, 1.8 or greater, 1.9 or greater, 2 or greater, 2.1 or greater, or 2.2 or greater.

[0109] The polymer used to cure the coating can have any suitable main chain chemistry and can be a linear or branched polymer.

[0110] According to one implementation, the cured coating exhibits a high gloss level. A high gloss level indicates excellent reflective properties of the coating. The gloss level can be determined using the specular gloss test as described in ASTM D523-14, a standard of the American Society for Testing and Materials (ASTM). Cured coatings can exhibit gloss levels of 60 Gloss Units (GU) or higher at 60° incident light, 70 GU or higher, 80 GU or higher, 90 GU or higher, or 100 GU or higher at 60° incident light, where Gloss Unit is the ratio of specularly reflected light to total reflected light, and specularly reflected light is light in which the angle of incidence equals the angle of reflection. While there is no expected upper limit to the gloss level, in practice, gloss levels are typically below 100 GU.

[0111] The cured coating exhibits high solvent resistance. Solvent resistance can be determined using the reciprocating friction test as described in ASTM D5402-19 MEK, a standard of the American Society for Testing and Materials (ASTM).

[0112] The performance of a cured coating can be tested using a friction test. Cured coatings can exhibit friction test results of 40 or more cycles of reciprocating friction (i.e., one back-and-forth motion), 50 or more cycles of reciprocating friction, 60 or more cycles of reciprocating friction, 70 or more cycles of reciprocating friction, or 80 or more cycles of reciprocating friction. While there is no expected upper limit to friction test results, in practice, results are typically below 200 cycles of reciprocating friction.

[0113] The performance of a cured coating can also be tested by evaluating its corrosion resistance via a salt spray test (also known as a salt spray test). The standard salt spray test can be performed according to ASTM B117, as described by the American Society for Testing and Materials (ASTM), an international organization for standards. In this test, the coated test substrate is scratched with a knife to expose the bare metal of the substrate. The scratched substrate is placed in a test chamber maintained at a constant temperature, where a salt solution is continuously sprayed onto the substrate. The coated substrate is exposed to the salt spray environment for a specific period of time, such as 500 hours or 1000 hours. After exposure, the coated substrate is removed from the test chamber, and corrosion is evaluated along the scratches. Corrosion is measured by "scratch creep," which is defined as the total distance the corrosion has traveled across the scratch, measured in millimeters. Cured coatings can exhibit scratch creep of 0 mm or greater, 0.5 mm or greater, 1 mm or greater, 2 mm or greater, 3 mm or greater, 4 mm or greater, or 5 mm or greater. The cured coating can exhibit scribing creep of 6 mm or less, 5 mm or less, 4 mm or less, 3 mm or less, 2 mm or less, 1 mm or less, or 0.5 mm or less. The cured coating can exhibit scribing creep from 0 mm to 6 mm.

[0114] This disclosure also provides articles coated with a cured coating as described above.

[0115] Exemplary Implementation

[0116] Exemplary embodiments according to this disclosure are provided below. The numbering of the exemplary aspects should not be interpreted as specifying a level of importance.

[0117] Implementation Scheme 1 is a method for coating an article, the method comprising:

[0118] Prepare a coating composition, the coating composition comprising:

[0119] Epoxy components;

[0120] Amine components; and

[0121] catalyst;

[0122] The epoxy component and the amine component are present in the coating composition in a ratio of 0.8:1 to 1.5:1;

[0123] Applying the coating composition to the article; and

[0124] The coating composition is cured at a temperature of 135°C to 250°C within 60 minutes of application to form a cured coating with a gloss level of 60 gloss units (GU) or higher.

[0125] Implementation Scheme 2 is the method according to Implementation Scheme 1, wherein the cured coating comprises epoxy homopolymer segments, the epoxy homopolymer segments comprising two or more repeating units separated by ether bonds.

[0126] Implementation scheme 3 is the method according to implementation scheme 1 or 2, wherein the epoxy component has a molecular weight range of 175 Daltons to 1200 Daltons.

[0127] Implementation scheme 4 is the method according to any one of implementation schemes 1 to 3, wherein the epoxy component has a molecular weight range of 200 Daltons to 350 Daltons.

[0128] Implementation scheme 5 is a method according to any one of implementation schemes 1 to 4, wherein the stoichiometric ratio of the epoxy component to the amine component is 1:1 to 5:1.

[0129] Implementation Scheme 6 is the method according to any one of Implementation Schemes 1 to 5, wherein the epoxy component comprises 1 to 5 epoxy groups.

[0130] Implementation scheme 7 is a method according to any one of implementation schemes 1 to 6, wherein the epoxy component comprises at least two different epoxy resins.

[0131] Embodiment 8 is a method according to any one of Embodiments 1 to 7, wherein the amine component comprises at least two different amine components.

[0132] Implementation scheme 9 is a method according to any one of implementation schemes 1 to 8, wherein the catalyst comprises at least two catalysts.

[0133] Embodiment 10 is a method according to any one of Embodiments 1 to 9, wherein the coating composition comprises 100% by weight of solids based on the weight of the coating composition.

[0134] Embodiment 11 is the method according to any one of Embodiments 1 to 10, wherein curing the coating composition is accomplished by heating the coating from a temperature of about 150°C to a temperature of about 225°C.

[0135] Implementation scheme 12 is the method according to any one of implementation schemes 1 to 11, wherein the cured coating exhibits a friction test result of 50 reciprocating friction cycles or higher.

[0136] Embodiment 13 is the method according to any one of Embodiments 1 to 12, wherein the coating composition contains less than 1% by weight of an organic solvent based on the weight of the coating composition.

[0137] Embodiment 14 is an article coated with a cured coating according to any one of the preceding embodiments.

[0138] Embodiment 15 is a composition comprising:

[0139] The cured coating is prepared by the following steps:

[0140] Prepare a coating composition, the coating composition comprising:

[0141] Epoxy components;

[0142] Amine components; and

[0143] catalyst;

[0144] Applying the coating composition to the article; and

[0145] The coating composition is cured within 60 minutes of application to form the cured coating.

[0146] Embodiment 16 is the composition according to Embodiment 15, wherein curing is carried out at a temperature of 135°C to 250°C.

[0147] Embodiment 17 is the composition according to Embodiment 15 or 16, wherein the cured coating has a gloss level of 60 gloss units (GU) or higher.

[0148] Embodiment 18 is a composition according to any one of Embodiments 15 to 17, wherein the cured coating comprises an epoxy homopolymer segment comprising two or more repeating units separated by ether bonds.

[0149] Embodiment 19 is a composition according to any one of Embodiments 15 to 18, wherein the epoxy component has a molecular weight range of 175 Daltons to 1200 Daltons.

[0150] Embodiment 20 is a composition according to any one of Embodiments 15 to 19, wherein the epoxy component has a molecular weight range of 200 Daltons to 350 Daltons.

[0151] Embodiment 21 is a composition according to any one of embodiments 15 to 20, wherein the stoichiometric ratio of the epoxy component to the amine component is 1:1 to 5:1.

[0152] Embodiment 22 is a composition according to any one of embodiments 15 to 21, wherein the epoxy component comprises 1 to 5 epoxy groups.

[0153] Embodiment 23 is a composition according to any one of embodiments 15 to 22, wherein the epoxy component comprises at least two different epoxy resins.

[0154] Embodiment 24 is a composition according to any one of embodiments 15 to 23, wherein the amine component comprises at least two different amine components.

[0155] Embodiment 25 is a composition according to any one of embodiments 15 to 24, wherein the catalyst comprises at least two catalysts.

[0156] Embodiment 26 is a composition according to any one of embodiments 15 to 25, wherein the coating composition comprises 100% by weight of solids based on the weight of the coating composition.

[0157] Embodiment 27 is a composition according to any one of embodiments 15 to 26, wherein curing the coating composition is accomplished by heating the coating from a temperature of about 150°C to a temperature of about 225°C.

[0158] Embodiment 28 is a composition according to any one of Embodiments 15 to 26, wherein the cured coating exhibits a friction test result of 50 cycles of reciprocating friction or higher.

[0159] Embodiment 29 is a composition according to any one of embodiments 15 to 28, wherein the coating composition contains less than 1% by weight of an organic solvent based on the weight of the coating composition.

[0160] Implementation scheme 30 is an article of manufacture, said article of manufacture comprising:

[0161] Main body; and

[0162] A cured coating is applied to the body, the cured coating being prepared by the following:

[0163] Prepare a coating composition, the coating composition comprising:

[0164] Epoxy components;

[0165] Amine components; and

[0166] catalyst;

[0167] Applying the coating composition to the article; and

[0168] The coating composition is cured within 60 minutes of application to form the cured coating.

[0169] Implementation scheme 31 is the article according to implementation scheme 30, wherein curing is carried out at a temperature of 135°C to 250°C.

[0170] Embodiment 32 is an article of manufacture according to Embodiment 30 or 31, wherein the cured coating has a gloss level of 60 gloss units (GU) or higher.

[0171] Embodiment 33 is an article of any one of embodiments 30 to 32, wherein the cured coating comprises an epoxy homopolymer segment comprising two or more repeating units separated by ether bonds.

[0172] Embodiment 34 is an article according to any one of Embodiments 30 to 33, wherein the epoxy component has a molecular weight range of 175 Daltons to 1200 Daltons.

[0173] Embodiment 35 is an article according to any one of Embodiments 30 to 34, wherein the epoxy component has a molecular weight range of 200 Daltons to 350 Daltons.

[0174] Embodiment 36 is an article according to any one of Embodiments 30 to 35, wherein the stoichiometric ratio of the epoxy component to the amine component is 1:1 to 5:1.

[0175] Embodiment 37 is an article according to any one of Embodiments 30 to 36, wherein the epoxy component comprises 1 to 5 epoxy groups.

[0176] Embodiment 38 is an article according to any one of embodiments 30 to 37, wherein the epoxy component comprises at least two different epoxy resins.

[0177] Embodiment 39 is an article according to any one of embodiments 30 to 38, wherein the amine component comprises at least two different amine components.

[0178] Embodiment 40 is an article according to any one of embodiments 30 to 39, wherein the catalyst comprises at least two catalysts.

[0179] Embodiment 41 is an article of any one of embodiments 30 to 40, wherein the coating composition comprises 100% by weight of solids based on the weight of the coating composition.

[0180] Embodiment 42 is an article of any one of embodiments 30 to 41, wherein the curing of the coating composition is accomplished by heating the coating from a temperature of about 150°C to a temperature of about 225°C.

[0181] Embodiment 43 is an article according to any one of Embodiments 30 to 42, wherein the cured coating exhibits a friction test result of 50 cycles of reciprocating friction or higher.

[0182] Embodiment 44 is an article of any one of embodiments 30 to 43, wherein the coating composition comprises less than 1% by weight of an organic solvent based on the weight of the coating composition.

[0183] Example

[0184] Various coatings were prepared according to embodiments of this disclosure. The performance of the coatings was evaluated and compared with a control.

[0185] Example 1

[0186] Prepare coating compositions according to Table 1A below and apply them to sample substrates Sample 1, Sample 2, Comparative Sample 1C, Comparative Sample 2C and Comparative Sample 3C.

[0187] Preparation of epoxy-amine coating compositions :

[0188]

[0189] The calculated amount of bisphenol A diglycidyl ether (DGBA) resin EPON is loaded into a tank (tank-1, 1000 gallons) equipped with a stirrer. ™ 828LS was then added, followed by the leveling additive BYK 077 with defoaming properties and the rheology modifier SUSPENO 201 NBA wax. Next, the solvent xylene and the viscosity and leveling agent MODAFLOW were added. ® Subsequently, a portion of the n-butylurea crosslinking agent CYMEL was added to the reaction mixture in the tank. ® U-216 (commercially available as a mixture of n-butanol and xylene). To improve coating performance, microcrystalline talc MISTRON Monomix was combined with micronized functional filler MINEX. ® 7 and calcium carbonate additive OMYACARB ®3. Add together to the tank. Also add the anti-settling and thickening agent AEROSIL 200 pyrolytic silica to the reaction vessel. To provide color to the coating, synthetic iron oxide red is added with the additional color pigment additive RAVEN. ® 1035 powder was added to the mixture. Finally, a low-viscosity monofunctional epoxy reactive diluent was added to the reaction mixture along with n-butanol as a co-solvent. The contents of tank 1 were then thoroughly mixed using the provided stirrer.

[0190] The calculated amount of the modified aliphatic amine component ANCAMINE is loaded into another suitably sized tank (tank-2, 200 gallons) equipped with a stirrer. ® 2089M and polyamide imidazolineamine component ARADUR ® 140 BDB. Add benzyl alcohol as a solvent. Then add 2,4,6-tris(dimethylaminomethyl)phenol (which can be used as an ANCAMINE). ® K54 (commercially available) was used as the selected catalyst. The mixture in tank-2 was vigorously stirred with a stirrer to thoroughly mix the contents of the tank.

[0191] The contents of cans 1 and 2 are mixed. The mixture is then applied to a flat steel substrate, namely, sample 1, sample 2, comparative sample 1C, comparative sample 2C, and comparative sample 3C.

[0192] Within 1 hour of applying the mixture, sample 1 was placed at a temperature set to 90°C (194°F). In an oven, sample 1 was cured for 4 hours.

[0193] Sample 2 was placed at 110°C (230°F) for one hour after the mixture was applied. In an oven, sample 2 was cured for 2.5 hours.

[0194] Comparative sample 1C was dried at room temperature for 24 hours and then placed at a temperature set to 90°C (194°F). The comparative samples were cured in an oven at 1°C for 4 hours.

[0195] Comparative sample 2C was dried at room temperature for 24 hours and then placed at a temperature set to 110°C (230°F). The samples were placed in an oven and cured at 2C for 2.5 hours.

[0196] The comparison sample 3C was dried at room temperature for 24 hours and then placed at a temperature set to 110°C (230°F). The samples were placed in an oven and cured for 4 hours using the 3C curing method.

[0197] The quality of the cured coatings on Sample 1, Sample 2, Comparative Sample 1C, Comparative Sample 2C, and Comparative Sample 3C was evaluated according to the standards ASTM D5402-19 Solvent Friction Test and ASTM D523-14 Specular Gloss Test as described by the American Society for Testing and Materials (ASTM). The results are shown in Table 1B below.

[0198]

[0199] Surprisingly, Samples 1 and 2 exhibited superior properties in the gloss test, with values ​​of 100 GU and 82.1 GU, respectively. In comparison, Samples 1C, 2C, and 3C showed gloss values ​​of only 32.1 GU, 10.8 GU, and 7.2 GU, respectively. Similar superior properties were observed in the solvent rubbing test. Samples 1 and 2 outperformed Comparative Samples 1C, 2C, and 3C, with both Samples 1 and 2 showing exceptionally high solvent rubbing resistance values.

[0200] Example 2

[0201] An exemplary coating according to an embodiment of this application may be prepared from the components in Table 2 below.

[0202]

[0203] The composition can be prepared as described herein and applied as a coating. For example, the composition can be prepared as described in Example 1 and applied as a coating.

[0204] All references and publications cited herein are expressly incorporated in their entirety by reference unless they may directly contradict this disclosure. While specific embodiments have been illustrated and described herein, those skilled in the art will understand that various alternatives and / or equivalent embodiments may be substituted for the specific embodiments shown and described without departing from the scope of this disclosure. It should be understood that this disclosure is not intended to be unduly limited to the illustrative embodiments and examples set forth herein, and such embodiments and embodiments are presented by way of example only, and the scope of this disclosure is intended to be limited only by the claims set forth herein.

Claims

1. A method of coating an article, the method comprising: preparing a coating composition, the coating composition comprising: an epoxy component; an amine component; and a catalyst; the epoxy component and the amine component present in the coating composition in a ratio of 0.8: 1 to 1.5: 1; applying the coating composition to the article; and curing the coating composition at a temperature of 135 °C to 250 °C within 60 minutes of the applying to form a cured coating having a gloss level of 60 gloss units (GU) or greater.

2. The method of claim 1, wherein the cured coating comprises epoxy homopolymer segments comprising 2 or more repeating units separated by ether linkages.

3. The method of claim 1, wherein the epoxy component has a molecular weight range of 175 daltons to 1200 daltons.

4. The method of claim 1, wherein the epoxy component has a molecular weight range of 200 daltons to 350 daltons.

5. The method of claim 1, wherein the stoichiometric ratio of the epoxy component to the amine component is 1: 1 to 5:

1.

6. The method of claim 1, wherein the epoxy component comprises 1 to 5 epoxy groups.

7. The method of claim 1, wherein the epoxy component comprises at least two different epoxy resins.

8. The method of claim 1, wherein the amine component comprises at least two different amine components.

9. The method of claim 1, wherein the catalyst comprises at least two catalysts.

10. The method of claim 1, wherein the coating composition comprises 100 wt% solids by weight of the coating composition.

11. The method of claim 1, wherein the curing the coating composition is accomplished by heating the coating from a temperature of about 150 °C to a temperature of about 225 °C.

12. The method of claim 1, wherein the cured coating exhibits a rub test result of 50 reciprocal rubs or greater.

13. The method of claim 1, wherein the coating composition comprises less than 1 wt% organic solvent by weight of the coating composition.

14. An article coated with the cured coating of any of the preceding claims.

15. A composition comprising: a cured coating made by: preparing a coating composition, the coating composition comprising: an epoxy component; an amine component; and a catalyst; applying the coating composition to the article; and curing the coating composition within 60 minutes of the applying to form the cured coating.

16. An article comprising: a body; and a cured coating disposed on the body, the cured coating made by: preparing a coating composition, the coating composition comprising: an epoxy component; an amine component; and a catalyst; applying the coating composition to the article; and curing the coating composition within 60 minutes of the applying to form the cured coating.

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