Epoxy resin composition and coating system

Abstract

Embodiments of the present disclosure generally relate to epoxy resin compositions and coating systems for forming epoxy resin compositions. In one embodiment, an epoxy resin composition is provided. The resin composition comprises epoxy resin; a curing agent; and an acetoacetoxy functionalized polymer comprising an acetoacetoxy functionalized monomer unit and a comonomer unit.

Description

Technical Field

[0001] Embodiments of the present disclosure generally relate to epoxy resin compositions and coating systems formed from the epoxy resin compositions. Background Art

[0002] Epoxy resins are widely used as coatings and sealants due to their excellent thermal and mechanical properties. Bisphenol epoxy resins, such as bisphenol A and bisphenol F, account for the majority of epoxy resins used. Cycloaliphatic epoxy resins are currently used as replacements for bisphenol epoxy resins due to certain performance properties. However, due to lower reactivity, cycloaliphatic epoxy resins have much slower drying times.

[0003] To date, conventional techniques for accelerating the drying time of cycloaliphatic epoxy resins using amines have caused other problems. For example, low molecular weight polyacetoacetates and polyesters have shown the ability to accelerate the drying time of resins, but the resulting resins have poor chemical resistance, poor gloss retention and poor mechanical properties.

[0004] Therefore, there is a need for new and improved epoxy resin compositions and coating systems for forming epoxy resin compositions. Summary of the invention

[0005] Embodiments of the present disclosure generally relate to epoxy resin compositions and coating systems for forming epoxy resin compositions. Unlike previous technologies, embodiments of the present disclosure can be fast-drying, high molecular weight resin compositions. In addition, the embodiments described herein can be used for exterior and interior applications.

[0006] In one embodiment, a resin composition is provided. The resin composition includes: an epoxy resin; a curing agent; and an acetoacetoxy-functionalized polymer having a weight average molecular weight of about 1000 g / mol to about 100,000 g / mol, wherein the acetoacetoxy-functionalized polymer includes: an acetoacetoxy-functionalized monomer unit; and a comonomer unit, wherein the comonomer unit includes an acrylate monomer, a methacrylate monomer, an α-olefin monomer, a vinyl halide monomer, a carboxylic acid diester monomer, an unsaturated nitrile monomer, an α,β-unsaturated carboxylic acid monomer, an α,β-unsaturated amide monomer, or a combination thereof.

[0007] In another embodiment, a composition is provided, comprising an epoxy polymerization product of a reaction mixture. The reaction mixture comprises: an epoxy resin; a curing agent; and an acetoacetoxy-functionalized polymer having a weight average molecular weight of about 1000 g / mol to about 100,000 g / mol, the acetoacetoxy-functionalized polymer comprising: an acetoacetoxy-functionalized monomer unit; and a comonomer unit, the comonomer unit comprising an acrylate monomer, a methacrylate monomer, an α-olefin monomer, a vinyl halide monomer, a carboxylic acid diester monomer, an unsaturated nitrile monomer, an α,β-unsaturated carboxylic acid monomer, an α,β-unsaturated amide monomer, or a combination thereof.

[0008] In another embodiment, a coating system is provided. The coating system includes a first component and a second component. The first component includes: an epoxy resin; and an acetoacetoxy-functionalized polymer having a molecular weight of about 1000 g / mol to about 100,000 g / mol, the acetoacetoxy-functionalized polymer including: an acetoacetoxy-functionalized monomer unit; a comonomer unit, the comonomer unit comprising an acrylate monomer, a methacrylate, an α-olefin, a vinyl halide monomer, a carboxylic acid diester monomer, an unsaturated nitrile monomer, an α,β-unsaturated carboxylic acid monomer, an α,β-unsaturated amide monomer, or a combination thereof. The second component of the coating system includes a curing agent. DETAILED DESCRIPTION

[0009] Embodiments of the present disclosure generally relate to epoxy resin compositions and coating systems for forming epoxy resin compositions. Compared with conventional resin compositions, resin compositions described herein are fast-drying, high molecular weight resin compositions. Epoxy resin compositions described herein can also tolerate degradation of chemicals and can be used for external and internal applications. Although acetoacetoxy functionalized materials (such as polyacetoacetate) have been used with conventional epoxy resins, the molecular weight of the acetoacetoxy functionalized materials of such conventional resins is relatively low, such as less than 1,000 g / mol. Typically, polyacetoacetate is the acetoacetate of an alcohol (such as trimethylolpropane). In contrast, acetoacetoxy functionalized polymers described herein have a higher molecular weight and can increase drying speed when formulated with epoxy resins and polyamines.

[0010] In addition, embodiments described herein relate to coating systems and coating formulations made from two or more components, often referred to as "2K systems" or "2K coating formulations". The first and second components are mixed together prior to application to the resin. The terms "coating system", "2K system" and "2K coating formulation" are used interchangeably such that reference to one includes reference to the other. For example, reference to a "coating system" includes reference to a "coating system", "2K coating formulation" and "2K system". In a 2K system, the first component is a resin and the second component is a curing agent. In some embodiments, and as further described below, the coating systems described herein may include a first component and a second component. The first component includes an acetoacetoxy-functional polymer and an epoxy resin, and the second component includes a curing agent.

[0011] Embodiments described herein generally relate to epoxy resin compositions. Epoxy resin compositions described herein can be used as coatings, sealants, adhesives and other applications. The inventors have found that, relative to conventional techniques, the resin compositions described herein have properties such as fast drying. As used herein, "composition" may include one or more components of the composition, one or more reaction products of two or more components of the composition, one or more remaining starting components, or a combination thereof. The compositions disclosed herein can be prepared by any suitable mixing process.

[0012] In some embodiments, the resin composition of the present disclosure includes an acetoacetoxy-functional polymer, an epoxy resin component, and a curing agent. The resin composition may include the reaction product of an acetoacetoxy-functional polymer, an epoxy resin component, a curing agent, or a combination thereof.

[0013] The acetoacetoxy-functional polymer is formed from one or more polymerizable monomers. The one or more polymerizable monomers include a first monomer, which includes one or more acetoacetoxy-functional acrylate monomers or acetoacetoxy-functional methacrylate monomers. The one or more polymerizable monomers may also include a second monomer different from the first monomer. Such second monomers include, but are not limited to, acrylate monomers, methacrylate monomers, vinyl monomers, combinations thereof, and other polymerizable monomers as further described below. The term "(meth)acrylate" refers to both acrylate and methacrylate.

[0014] The acetoacetoxy-functional polymer can be a polymer or a copolymer, and can have a weight average molecular weight (Mw) of about 1,000 g / mol or greater, about 100,000 g / mol or less, or both. In at least one embodiment, the Mw of the acetoacetoxy-functional polymer can be from about 1,000 g / mol to about 60,000 g / mol, such as from about 1,000 g / mol to about 50,000 g / mol, such as from about 2,000 g / mol to about 20,000 g / mol, such as from about 3,000 to about 15,000 g / mol, such as from about 4,000 g / mol to about 14,000 g / mol, such as from about 5,000 g / mol to about 13,000 g / mol, such as from about 6,000 g / mol to about 12,000 g / mol, such as from about 7,000 g / mol to about 11,000 g / mol, such as from about 8,000 g / mol to about 10,000 g / mol.In some embodiments, the Mw (in g / mol) of the acetoacetoxy-functional polymer may be 1,000, 2,000, 3,000, 4,000, 5,000, 6,000, 7,000, 8,000, 9,000, 10,000, 11,000, 12,000, 13,000, 14,000, 15,000, 16,000, 17,000, 18,000, 19,000, 20,000, 21,000, 22,000, 23,000, 24,000, 25,000, , 26,000, 27,000, 28,000, 29,000, 30,000, 31,000, 32,000, 33,000, 34,000, 35,000, 36,000, 37,000, 38,000, 39,000, 41,000, 42,000, 43,000, 44,000, 45,000, 46,000, 47,000, 48,000, 49,000, 50,000, 51,000, 52, 000、53,000、54,000、55,000、56,000、57,000、58,000、59,000、60,000、61,000、62,000、63,000、64,000、65,000、66,000、67,000、68,000、69,000、70,000、71,000、72,000、73,000、74,000、75,000、76,000、77,000 , 78,000, 79,000, 80,000, 81,000, 82,000, 83,000, 84,000, 85,000, 86,000, 87,000, 88,000, 89,000, 90,000, 91,000, 92,000, 93,000, 94,000, 95,000, 96,000, 97,000, 98,000, 99,000 or 100,000 or its scope, but also consider higher or lower value.Each of the aforementioned numerals can be preceded by the word "about", "at least about", "less than about" or "greater than about", and any of the aforementioned numerals can be used to describe open-ended ranges individually or in combination to describe closed-ended ranges.The weight average molecular weight (Mw) is measured as described in the examples.

[0015] The glass transition temperature (Tg) of the acetoacetoxy functional polymer may be from about -50°C to about 110°C, such as from about -10°C to about 100°C, such as from about 0°C to about 80°C, such as from about 20°C to about 70°C, such as from about 30°C to about 60°C, such as from about 40°C to about 50°C. In some embodiments, the Tg (in °C) of the acetoacetoxy functional polymer may be -50, -49, -48, -47, -46, -45, -44, -43, -42, -44, -45, -46, -47, -48, -49, -50, -51, -52, -53, -54, -56, -57, -58, -59, -60, -61, -62, -63, -64, -65, -66, -67, -68, -69, -70, -71, -72, -73, -74, -75, -76, -77, -78, -79, -80, -81, -82, -83, -84, -85, -86, -87, -88, -89, -90, -91, -92, -93, -94, -95, -96, -97, -98 41, -40, -39, -38, -37, -36, -35, -34, -33, -32, -31, -30, -29, -28, -27, -26, -25, -24, -23, -22, -21, -20, -19, -18, -17, -16, -15, -14, -13, -12, -11, -10 , -9, -8, -7, -6, -5, -4, -3, -2, -1, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 3 6, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78 , 79, 80, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109 or 110 or ranges thereof, but higher or lower values ​​are also contemplated. Each of the aforementioned numerals may be preceded by the words "about," "at least about," "less than about," or "greater than about," and any of the aforementioned numerals may be used individually to describe an open-ended range or in combination to describe a closed-ended range. The Tg of the acetoacetoxy-functionalized polymer is measured as described in the Examples.

[0016] The total solid content (in % non-volatile solids) of acetoacetoxy functionalized polymer can be at least about 30% of the total percentage based on acetoacetoxy functionalized polymer, such as about 30% to about 90%, such as about 40% to about 70%, such as about 50% to about 60%. In some embodiments, the total solid content (in % non-volatile solids) of acetoacetoxy functionalized polymer can be about 5,10,15,20,25,30,35,40,45,60,65,70,75,80,85,90 or 95 or its scope, but also consider higher or lower value. Each aforementioned numeral can be preceded by the word "about", "at least about", "less than about" or "greater than about", and any aforementioned numeral can be used to describe open-ended ranges individually or in combination to describe closed-ended ranges. The total solid content of acetoacetoxy functionalized polymer is measured according to ASTM D2369-92.

[0017] As described above, the acetoacetoxy-functional polymer includes a first monomer that includes at least one acetoacetoxy-functional acrylate monomer or acetoacetoxy-functional methacrylate monomer. Suitable acetoacetoxy-functional acrylate monomers or acetoacetoxy-functional methacrylate monomers include vinyl acetoacetate or allyl esters or diesters of formula (I):

[0018] (I)

[0019] in:

[0020] R 1 is methyl (CH3) or hydrogen; and

[0021] n is a number from 1 to 6, such as 1 to 4.

[0022] Suitable acetoacetoxy-functional acrylate monomers or acetoacetoxy-functional methacrylate monomers of formula (II) include, for example, vinyl acetoacetate, allyl acetoacetate, or acetoacetate esters of β-hydroxyethyl acrylate or methacrylate or hydroxypropyl acrylate or methacrylate. In some examples, the acetoacetoxy-functional acrylate monomers or acetoacetoxy-functional methacrylate monomers of formula (II) include acetoacetoxyethyl methacrylate (AAEM). One or more acetoacetoxy-functional acrylate monomers or acetoacetoxy-functional methacrylate monomers can be used in the compositions described herein.

[0023] The acetoacetoxy-functional polymer includes a second monomer that is different from the first monomer. One or more second monomers may be used in the compositions described herein. Such second monomers include acrylate monomers or methacrylate monomers, such as alkyl acrylate monomers or alkyl methacrylate monomers. Suitable alkyl acrylate monomers or alkyl methacrylate monomers as the one or more second monomers that can be used with the compositions described herein include monomers having the general formula (II):

[0024] (II).

[0025] R of formula (II) 2 is methyl (CH3) or hydrogen. R of formula (II) 3 has any suitable number of carbon atoms, such as 1 to 100 carbon atoms, such as 2 to 50 carbon atoms, such as 3 to 30 carbon atoms, such as 6 to 24 carbon atoms, such as 9 to 20 carbon atoms, such as 12 to 14 carbon atoms or 18 to 22 carbon atoms. In some embodiments, R of formula (II) 3 The number of carbon atoms in can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30. Each of the foregoing numbers may be preceded by the words "about," "at least about," "less than about," or "greater than about," and any of the foregoing numbers may be used alone to describe an open-ended range or in combination to describe a closed range. R of formula (II) 3 can be unsubstituted or substituted, linear or branched, saturated or unsaturated, cyclic or acyclic. With respect to the degree of saturation, R of formula (II) 3 It may be fully saturated, partially unsaturated, or fully unsaturated. With respect to the degree of saturation, R of formula (II) 3 It may be fully saturated, partially unsaturated, or fully unsaturated.

[0026] An unsubstituted R group refers to an R group consisting only of hydrogen and carbon atoms. A substituted R group refers to an R group in which at least one hydrogen of the R group has been replaced by at least one heteroatom or heteroatom-containing group, such as one or more elements of Groups 13-17 of the Periodic Table of Elements, such as halogen (F, Cl, Br or I), O, N, Se, Te, P, As, Sb, S, B, Si, Ge, Sn, Pb, etc., such as C(O)R*, C(C)NR*2, C(O)OR*, NR*2, OR*, SeR*, TeR*, PR*2, AsR*2, SbR*2, SR*, SO x(where x = 2 or 3), BR*2, SiR*3, GeR*3, SnR*3, PbR*3, etc., where R* is independently hydrogen or a hydrocarbon group, or where at least one heteroatom has been inserted into the R group. "Hydrocarbon group" refers to a group consisting only of hydrogen and carbon atoms.

[0027] Illustrative but non-limiting examples of the alkyl acrylate monomer or alkyl methacrylate monomer of formula (II) include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, pentyl acrylate, pentyl methacrylate, n-hexyl acrylate, hexyl methacrylate, heptyl acrylate, heptyl methacrylate, n-octyl acrylate, n-octyl methacrylate, ethyl-2-hexyl acrylate, ethyl-2-hexyl methacrylate, isooctyl acrylate, isooctyl methacrylate, nonyl acrylate, nonyl methacrylate, n-decyl acrylate, n-decyl methacrylate, decyl acrylate, isodecyl acrylate, isodecyl methacrylate, undecyl acrylate, undecyl methacrylate, n-dodecyl acrylate, n-dodecyl methacrylate, tridecyl acrylate, tridecyl methacrylate, tetradecyl acrylate, tetradecyl methacrylate, pentadecyl acrylate, pentadecyl methacrylate, hexadecyl acrylate, hexadecyl methacrylate, heptadecyl acrylate, heptadecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, nonadecyl acrylate, nonadecyl methacrylate, eicosyl acrylate, eicosyl methacrylate, hexonedecyl acrylate, hexonedecyl methacrylate, tricosyl acrylate, tricosyl methacrylate, or a combination thereof.

[0028] In some embodiments, R of formula (II) 3 Having 1 to 12 carbons, such as 1 to 6 carbons, such as 1 to 4 carbons. In at least one embodiment, the one or more second monomers of formula (II) may include methyl methacrylate, butyl acrylate, methyl acrylate, butyl methacrylate, or a combination thereof.

[0029] In some embodiments, the one or more second monomers optionally include one or more monomers formed from vinyl esters of organic carboxylic acids, and the acid portion of the organic carboxylic acid contains 1 to 30 carbon atoms, such as 1 to 20 carbon atoms, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl isononanoate, and vinyl esters of branched monocarboxylic acids with up to 20 carbon atoms, such as vinyl pivalate and vinyl versatate, such as vinyl neodecanoate (CAS No. 51000-52-3); esters of acrylic acid or methacrylic acid with 1 to 30 carbon atoms (such as 1 to 20 carbon atoms) in the alcohol portion, such as ethyl acrylate, isopropyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, butyl methacrylate. Other second monomers that can be used to form acetoacetoxy-functionalized polymers include aromatic, aliphatic, 6-unsaturated hydrocarbons or combinations thereof, such as α-olefins, such as C2 to C 40 α-olefins, such as ethylene, propylene, styrene, vinyl toluene. The α-olefin monomer can be selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methylpent-1-ene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-hexadecene, etc. and any combination thereof, such as 1-butene, 1-hexene, 1-octene and combinations thereof. In some embodiments, the second monomer may include a polyene such as isoprene, chloroprene, butadiene, 1,3-hexadiene, 1,4-hexadiene, cyclopentadiene, dicyclopentadiene, 4-vinylcyclohex-1-ene, methyloctadiene, 1-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 1,5-cyclooctadiene, norbornadiene, ethylidene norbornene, 5-vinylidene-2-norbornene, 5-vinyl-2-norbornene, or a combination thereof.

[0030] Other second monomers include vinyl halide monomers, such as vinyl chloride; unsaturated nitrile monomers, such as acrylonitrile; carboxylic acid diester monomers, such as maleic acid diesters or fumaric acid diesters, for example dibutyl maleate or dibutyl fumarate; α, β-unsaturated carboxylic acid monomers, such as acrylic acid, methacrylic acid, crotonic acid, maleic acid or fumaric acid and derivatives thereof, for example α, β-unsaturated amide monomers, such as acrylamide or methacrylamide. More than one second monomer may be utilized to form the acetoacetoxy-functionalized polymer of the composition described herein.

[0031] The acetoacetoxy-functional polymer includes acetoacetoxy-functional monomer units (corresponding to the first monomer after polymerization) and comonomer units (corresponding to the second monomer after polymerization). In these and other embodiments, the acetoacetoxy-functional polymer may have the following characteristics:

[0032] (a) The amount of acetoacetoxy-functional monomer units in the acetoacetoxy-functional polymer may be from about 0.1 wt % to about 50 wt %, such as from about 1 wt % to about 50 wt %, such as from about 5 wt % to about 40 wt %, such as from about 10 wt % to about 30 wt %, such as from about 15 wt % to about 25 wt %, based on the total weight percentage of the acetoacetoxy-functional polymer. In some embodiments, the total amount of one or more acetoacetoxy-functional acrylate monomers or acetoacetoxy-functional methacrylate monomers (first monomers) in the acetoacetoxy-functional polymer (in weight percent (wt %)) based on the total weight percent of the acetoacetoxy-functional polymer may be 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49 or 50 or ranges thereof, although higher or lower amounts are also contemplated. Each of the aforementioned numbers may be preceded by the word "about," "at least about," "less than about," or "greater than about," and any of the aforementioned numbers may be used alone to describe an open range or in combination to describe a closed range.

[0033] The amount of comonomer units in the acetoacetoxy-functional polymer may be from about 50 wt % to about 99.9 wt %, such as from about 50 wt % to about 99 wt %, such as from about 60 wt % to about 95 wt %, such as from about 70 wt % to about 90 wt %, such as from about 75 wt % to about 85 wt %, based on the total weight percentage of the acetoacetoxy-functional polymer. In some embodiments, the total amount (wt %) of the one or more second monomers in the acetoacetoxy-functional polymer, based on the total weight percent of the acetoacetoxy-functional polymer, can be 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5, 99.9, or ranges thereof, although higher or lower amounts are also contemplated. Each of the foregoing numbers may be preceded by the words "about," "at least about," "less than about," or "greater than about," and any of the foregoing numbers may be used alone to describe an open-ended range or in combination to describe a closed range.

[0034] The acetoacetoxy functionalized polymer can be prepared by mixing one or more first monomers, one or more second monomers, or a combination thereof, with an initiator. Suitable initiators include, but are not limited to, free radical initiators, such as peroxides. Suitable peroxides include 1,1-bis(tert-amylperoxy)cyclohexane (CAS # 15667-10-4), 1,1-bis(tert-butylperoxy)cyclohexane (CAS # 3006-86-8), or a combination thereof. Other suitable peroxides include benzoyl peroxide, tert-butyl hydroperoxide, di-tert-butyl hydroperoxide, hydrogen peroxide, potassium persulfate, methylcyclohexyl peroxide, cumene hydroperoxide, acetylbenzoyl peroxide, tetralin hydroperoxide, phenylcyclohexane hydroperoxide, tert-butyl peracetate, diisopropylbenzene peroxide, tert-butyl perbenzoate, di-tert-amyl perphthalate, di-tert-butyl peradipate, tert-amyl percarbonate, and the like and mixtures thereof; azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-dimethyl azobisisobutyrate, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyramide, and the like. Other initiators are contemplated. One or more initiators may be used with the compositions described herein. The initiator may be used as a solution or suspension in a suitable solvent (such as a mineral solvent) at a desired concentration.

[0035] The acetoacetoxy functional polymer can be prepared by feeding one or more first monomers, one or more second monomers and an initiator to a reactor equipped with a solvent and reacting to form the acetoacetoxy functional polymer under effective conditions. The conditions may include a reactor temperature of about 50°C to about 200°C, and may include a reaction time of about 5 minutes to about 24 hours. Other temperatures and times are contemplated, and the temperatures and times may differ, for example, according to the monomers, solvents or initiators used for polymerization. The conditions for effectively forming the acetoacetoxy functional polymer may include stirring, mixing, agitation or a combination thereof. The conditions may optionally include the use of a non-reactive gas, such as N2, Ar or a combination thereof. For example, the reaction mixture comprises a monomer, a solvent and an initiator, and these or other non-reactive gases are used to remove the gas of the various components or otherwise remove oxygen from the reaction mixture.

[0036] Suitable solvents for forming the acetoacetoxy-functionalized polymer include organic solvents. Organic solvents may include, but are not limited to, alcohols; aliphatic, cycloalkane, and aromatic hydrocarbons; ethers; esters; and ketones. Illustrative but non-limiting examples of organic solvents include hexane, heptane, octane, methylcyclohexane, xylene, toluene, ethanol, isopropanol, butanol, monomethyl ether of diethylene glycol, monobutyl ether of ethylene glycol, tetrahydrofuran alcohol, ethylene glycol monomethyl ether, ethyl acetate, isopropyl acetate, butyl acetate, amyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and combinations thereof. Other solvents are contemplated. In some embodiments, the resin composition is free of or substantially free of water.

[0037] Resin combination as herein described also comprises one or more epoxy resin components.Each of the one or more epoxy resin components includes epoxy resin.Epoxy resin can also be monomeric or polymeric.Epoxy resin is a compound containing at least one ortho-epoxy group.Epoxy resin can be saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or heterocyclic, and can be substituted.In some instances, the selection of epoxy resin is based on, for example, the desired UV resistance.

[0038] The epoxy resin used may be, for example, an epoxy resin or epoxy resin combination prepared from epihalohydrin and phenol or a phenol-type compound, from epihalohydrin and an amine, from epihalohydrin and a carboxylic acid, or prepared by oxidation of an unsaturated compound.

[0039] Suitable epoxy resins that can be used for the embodiments described herein may include non-aromatic epoxy resins. Each molecule of the epoxy resin may contain more than one 1,2-epoxy group, and in some embodiments, each molecule may contain two 1,2-epoxy groups. In some embodiments, the epoxy resin may be liquid rather than solid. In at least one embodiment, the epoxide equivalent of the epoxy resin is from about 100 to about 5,000, such as from about 100 to about 2,000, such as from about 100 to 500, as determined by the titration method described in ASTM D1652.

[0040] In some embodiments, the epoxy resin may be a non-aromatic hydrogenated cyclohexanedimethanol and diglycidyl ether of hydrogenated bisphenol A type epoxy resins, such as hydrogenated bisphenol A-epichlorohydrin epoxy resins, cyclohexanedimethanol diglycidyl ether, and cycloaliphatic epoxy resins.

[0041] In at least one embodiment, the epoxy resin utilized in the resin combination of the present disclosure includes those resins produced by epihalohydrin and phenol or phenol-type compounds.Phenol-type compounds include compounds that each molecule contains more than one aromatic hydroxyl group on average.The example of phenol-type compounds includes dihydric phenol, biphenol, bisphenol, halogenated biphenol, halogenated bisphenol, hydrogenated bisphenol, alkylated biphenol, alkylated bisphenol, trisphenol, phenolic resin, novolac resin (reaction product of phenol and simple aldehyde (such as formaldehyde)), halogenated novolac resin, substituted novolac resin, phenol-hydrocarbon resin, substituted phenol-hydrocarbon resin, phenol-hydroxybenzaldehyde resin, alkylated phenol-hydroxybenzaldehyde resin, hydrocarbon-phenol resin, hydrocarbon-halogenated phenol resin, hydrocarbon-alkylated phenol resin or its combination.

[0042] In some embodiments, epoxy resins utilized in the compositions described herein include those derived from epihalohydrins and bisphenols, halogenated bisphenols, hydrogenated bisphenols, novolac resins, and polyalkylene glycols, or combinations thereof.

[0043] In at least one embodiment, the epoxy resin compounds utilized in the compositions of the present disclosure preferably include those resins derived from epihalohydrins and resorcinol, catechol, hydroquinone, biphenol, bisphenol A, bisphenol AP (1,1-bis(4-hydroxyphenyl)-1-phenylethane), bisphenol F, bisphenol K, tetrabromobisphenol A, phenol-formaldehyde novolac resins, alkyl-substituted phenol-formaldehyde resins, phenol-hydroxybenzaldehyde resins, cresol-hydroxybenzaldehyde resins, dicyclopentadiene-phenol resins, dicyclopentadiene-substituted phenol resins, tetramethylbiphenol, tetramethyl-tetrabromobiphenol, tetramethyltribromobiphenol, tetrachlorobisphenol A, or combinations thereof.

[0044] In some embodiments, epoxy resins utilized in the compositions of the present disclosure include those produced from epihalohydrins and amines. Suitable amines include diaminodiphenylmethane, aminophenol, xylene diamine, aniline, and the like, or combinations thereof.

[0045] In at least one embodiment, the epoxy resin utilized in the composition of the present disclosure may include those resins produced by epihalohydrin and carboxylic acid. Suitable carboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid, isophthalic acid, methylhexahydrophthalic acid, etc. or a combination thereof.

[0046] In some embodiments, the epoxy resin compound utilized in the composition of the present disclosure includes those resins produced by epihalohydrin and a compound with at least one aliphatic hydroxyl group. In such embodiments, it should be understood that the resin composition produced contains more than one aliphatic hydroxyl group on average. The example of the compound having at least one aliphatic hydroxyl group per molecule includes aliphatic alcohol, aliphatic diol, polyether diol, polyether triol, polyether tetraol, any combination thereof, etc. The alkylene oxide adduct of the compound containing at least one aromatic hydroxyl group is also suitable. In this embodiment, it should be understood that the resin composition produced contains more than one aromatic hydroxyl group on average. The example of the oxide adduct of the compound containing at least one aromatic hydroxyl group per molecule includes dihydroxyphenol, biphenyl, bisphenol, halogenated bisphenol, alkylated bisphenol, trisphenol, phenol aldehyde phenolic resin, halogenated phenol aldehyde phenolic resin, alkylated phenol aldehyde phenolic resin, hydrocarbon-phenol resin, hydrocarbon-halogenated phenol resin or hydrocarbon-alkylated phenol resin ethylene oxide, propylene oxide or epoxybutylene adduct, or a combination thereof.

[0047] In some embodiments, epoxy resins may refer to advanced epoxy resins, which are the reaction products of one or more epoxy resin components as described above with one or more phenolic compounds as described above and / or one or more compounds having more than one aliphatic hydroxyl group per molecule. Alternatively, epoxy resins may react with carboxyl substituted hydrocarbons. Carboxyl substituted hydrocarbons are described herein as having a hydrocarbon backbone (such as C1-C 40 A compound having a hydrocarbon backbone) and one or more carboxyl moieties (such as more than one, such as two). 40 The hydrocarbon backbone can be a straight or branched alkane or alkene, which optionally contains oxygen. Fatty acids and fatty acid dimers are useful carboxylic acid-substituted hydrocarbons. Fatty acids include caproic acid, caprylic acid, capric acid, caprylic acid, neopentanoic acid, neodecanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, erucic acid, pentadecanoic acid, heptadecanoic acid, arachidic acid and dimers thereof.

[0048] In at least one embodiment, the epoxy resin is the reaction product of a polyepoxide and a compound containing more than one isocyanate moiety or a polyisocyanate. The epoxy resin produced in such a reaction may be an epoxy-terminated polyoxazolidinone.

[0049] In some embodiments, the epoxy resin includes a polymer of 4,4'-(1-methylethylidene)bis-cyclohexanol and 2-(chloromethyl)oxirane (CAS No. 30583-72-3).

[0050] The resin composition described herein also includes a curing agent. The curing agent that can be used with the composition described herein includes but is not limited to aliphatic polyamines, cycloaliphatic amines, aromatic amines, Mannich bases, ketimines, oxazolines, amidoamines, and modified polyamine resins prepared by reacting aliphatic or cycloaliphatic polyamines with compounds containing functional groups that react with amine groups (such as compounds containing glycidyl ether or containing carboxyl groups). The reaction product of polyamines with compounds containing glycidyl ether groups is referred to as "polyamine-epoxy adducts". The reaction product of dicarboxylic acids and polyamines is referred to as "polyamide resins". The latter is usually prepared by condensation of dicarboxylic acids with excess polyalkylene polyamines. Polyamides based on dicarboxylic acids having more than 10 carbon atoms, especially based on C 36 Those polyamides of dicarboxylic acids are preferred due to the water resistance and flexibility of the resulting coatings. Examples of suitable polyamines that can be used with the methods of the present application include, but are not limited to, 1,3-bis(aminomethyl)cyclohexane, diethylenetriamine, triethylenetetramine, hexamethylenediamine, trimethylhexamethylenediamine, tetraethylenepentamine, N,N',-dimethylpropylenediamine, 1,3-bis(4-amino-3-methylcyclohexyl)methane, bis(p-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, 3,5,5-trimethyl-3-(aminomethyl)-cyclohexylamine, N-aminoethylpiperazine, m-phenylenediamine, p-phenylenediamine, bis(p-aminophenyl)methane, bis(p-aminophenyl)sulfone, m-phenylenediamine, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, 1,4-bis(aminomethyl)cyclohexane, and combinations thereof.

[0051] In some embodiments, the curing agent includes a polyamine of formula (IVa):

[0052] (IVa)

[0053] in:

[0054] n in formula (IVa) is 1, 2, 3, 4, 5 or 6.

[0055] Illustrative but non-limiting examples of polyamines of formula (IVa) include diethylenetriamine, ethylenediamine, triethylenediamine, hydrazine, or combinations thereof.

[0056] In some embodiments, the curing agent may include a polyetheramine compound. Polyetheramine compounds have several general formulas. One such formula is:

[0057] (IVb)

[0058] in:

[0059] x of formula (IVb) is from about 2.5 to about 68, such as from about 2.5 to about 6.1.

[0060] Another general formula of polyetheramine is formula (IVc):

[0061] (IVc),

[0062] in:

[0063] x+y+z of formula (IVc) is an integer in the range of about 5 to about 85, such as about 15 to about 60, such as about 20 to about 40.

[0064] Other general formulas of polyetheramines include formula (IVd):

[0065] (IVd)

[0066] in:

[0067] R of formula (IVd) 4 For ethylene oxide (EO), it is a hydrogen atom (H), and R 4 For propylene oxide (PO), it is CH3;

[0068] x of formula (IVd) is from about 1 to about 40; and

[0069] The y of formula (IVd) is from about 1 to about 40.

[0070] In some embodiments of formula (IVd), when y=9, x=1, when y=3, x=19, or when y=29-35, x=6. Other combinations are contemplated. The PO / EO ratio of formula (IVd) may be from about 9:1 to about 10:31, such as about 9:1, about 3:19, about 29:6, or about 10:31.

[0071] Other general formulas of polyetheramines include formula (IVe):

[0072] (IVe)

[0073] in:

[0074] x+z of formula (IVe) is from about 1.2 to about 6; and

[0075] The y of formula (IVe) is from about 2 to about 39.

[0076] Examples of suitable polyamines that can be used with the compositions described herein include, but are not limited to, 1,3-bis(aminomethyl)cyclohexane, diethylenetriamine, triethylenetetramine, hexamethylenediamine, trimethylhexamethylenediamine, tetraethylenepentamine, N,N',-dimethylpropylenediamine, 1,3-bis(4-amino-3-methylcyclohexyl)methane, bis(p-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, 3,5,5-trimethyl-3-(aminomethyl)-cyclohexylamine, N-aminoethylpiperazine, m-phenylenediamine, p-phenylenediamine, bis(p-aminophenyl)methane, bis(p-aminophenyl)sulfone, m-phenylenediamine, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, 1,4-bis(aminomethyl)cyclohexane, and combinations thereof.

[0077] Other suitable polyamines include any suitable amine functionalized polymers including, but not limited to, aminosilanes, amine-diacid adducts (known in the industry as polyamidoamines), and amine-epoxy adducts.

[0078] Examples of suitable polyamines include the following polyetheramines: polyoxypropylene diamine having a molecular weight of about 230 (for formula (IVb), x is 2.5), polyoxypropylene diamine having a molecular weight of about 430 (for formula (IVb), x is 6.1), and combinations thereof.

[0079] The curing agent may include one or more of any of the above compounds, such as one or more polyamines. The weight average molecular weight (Mw) of one or more polyamines suitable as curing agent may be from about 15 g / mol to about 2000 g / mol, such as from about 25 g / mol to about 1000 g / mol, such as from about 35 g / mol to about 500 g / mol. In at least one embodiment, the Mw (g / mol) of one or more polyamines is 15, 25, 50, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950 or 1000 or its scope, but also consider higher or lower values. Each of the aforementioned numbers can be preceded by the word "about", "at least about", "less than about" or "greater than about", and any of the aforementioned numbers can be used to describe the open range individually or in combination to describe the closed range. Mw is measured as described in the examples.

[0080] In addition to the acetoacetoxy functional polymer, epoxy resin and curing agent, the resin composition described herein may also include other components. Such components include one or more solvents, one or more additives or combinations thereof. Suitable solvents include organic solvents. Organic solvents may include, but are not limited to, alcohols; aliphatic, cycloalkane and aromatic hydrocarbons; ethers; esters; and ketones. Exemplary but non-limiting examples of organic solvents include hexane, heptane, octane, methylcyclohexane, xylene, toluene, ethanol, isopropanol, butanol, monomethyl ether of diethylene glycol, monobutyl ether of ethylene glycol, tetrahydrofuran alcohol, ethylene glycol monomethyl ether, ethyl acetate, isopropyl acetate, butyl acetate, amyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone and combinations thereof. Other solvents are contemplated. In some embodiments, the resin composition is free of or substantially free of water. In some embodiments, the organic solvent includes n-butanol, toluene, xylene or a mixture thereof.

[0081] Suitable additives known in the art can be used with the resin compositions described herein. Such additives include, but are not limited to, accelerators; fillers and extenders such as silica, mica, quartz, cryolite, Portland cement, limestone, atomized alumina, barite, talc, zinc powder, pyrophyllite, clay, diatomaceous earth; pigments such as titanium dioxide, red lead, basic lead silica chromate, basic zinc chromate, zinc, zinc oxide, lead, barium chromate, strontium chromate, calcium plumbate, barium metaborate, calcium molybdate, strontium molybdate, and zinc molybdate; and resin modifiers such as phenolic resins, urea resins, melamine resins, acrylic resins, polyester resins, vinyl resins, asphalt resins, and polystyrene; surfactants; UV absorbers; and combinations thereof. Other additives are contemplated.

[0082] The amounts of acetoacetoxy-functional polymer or monomers used to form the polymer, epoxy resin component or monomers used to form the epoxy resin component, curing agent, and other components such as solvents and initiators can be used to define the molecular structure, chemical properties, and physical properties of the resin composition.

[0083] The total amount of one or more acetoacetoxy-functional acrylate monomers or acetoacetoxy-functional methacrylate monomers (first monomers) in the acetoacetoxy-functional polymer may be from about 0.1 wt % to about 50 wt %, such as from about 1 wt % to about 50 wt %, such as from about 5 wt % to about 40 wt %, such as from about 10 wt % to about 30 wt %, such as from about 15 wt % to about 25 wt %, based on the total weight percentage of the acetoacetoxy-functional polymer. In some embodiments, the total amount of one or more acetoacetoxy-functional acrylate monomers or acetoacetoxy-functional methacrylate monomers (first monomers) in the acetoacetoxy-functional polymer (in weight percent (wt %)) based on the total weight percent of the acetoacetoxy-functional polymer may be 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49 or 50 or ranges thereof, although higher or lower amounts are also contemplated. Each of the aforementioned numbers may be preceded by the word "about," "at least about," "less than about," or "greater than about," and any of the aforementioned numbers may be used alone to describe an open range or in combination to describe a closed range.

[0084] The total amount of the one or more second monomers in the acetoacetoxy-functional polymer can be from about 50 wt % to about 99.9 wt %, such as from about 50 wt % to about 99 wt %, such as from about 60 wt % to about 95 wt %, such as from about 70 wt % to about 90 wt %, such as from about 75 wt % to about 85 wt %, based on the total weight percentage of the acetoacetoxy-functional polymer. 98, 99, 99.5, 99.9, or ranges thereof, although higher or lower amounts of the one or more second monomers are also contemplated. Each of the aforementioned numbers may be preceded by the word "about," "at least about," "less than about," or "greater than about," and any of the aforementioned numbers may be used alone to describe an open range or in combination to describe a closed range.

[0085] The weight % of each component in the acetoacetoxy-functional polymer is based on the solid weight basis percentage (% solid weight basis). The total weight % of the acetoacetoxy-functional polymer described herein does not exceed 100 weight %.

[0086] The amount of one or more initiators used to form the acetoacetoxy-functional polymer or for use in the compositions described herein may be about 0.1% to about 2% by weight, such as about 0.5% to about 1.5% by weight, based on the total weight percentage of the one or more first monomers, the one or more second monomers, and the one or more initiators. In some embodiments, the total amount (weight %) of the one or more initiators based on the total weight percentage of the one or more first monomers, the one or more second monomers, and the one or more initiators may be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9 or 2 or a range thereof, but higher or lower amounts of one or more initiators are also contemplated. Each of the aforementioned numbers may be preceded by the words "about", "at least about", "less than about", or "greater than about", and any of the aforementioned numbers may be used alone to describe an open-ended range or in combination to describe a closed range.

[0087] In some examples, the acetoacetoxy-functional polymer may be formed from the following non-limiting mixtures:

[0088] (a) from about 1 wt % to about 50 wt %, such as from about 10 wt % to about 30 wt % of a first monomer comprising acetoacetoxy ethyl methacrylate (AAEM);

[0089] (b) from about 50 wt % to about 99 wt %, such as from about 70 wt % to about 90 wt % of a second monomer comprising methyl methacrylate (MMA), butyl acrylate (BA), isobornyl methacrylate (IBOMA), styrene, vinyl neodecanoate, or a combination thereof; and

[0090] (c) about 0.1 wt % to 2 wt % of a peroxide initiator, wherein the wt % of each component is based on the total weight of the first monomer, the second monomer, and the initiator, and the total wt % does not exceed 100 wt %. The wt % of each of the first monomer, the second monomer, and the initiator can be those weight percentages described above.

[0091] In some embodiments, the resin composition includes an acetoacetoxy-functional polymer, an epoxy resin component, and a curing agent. Such resin compositions can be formulated using the following components, wherein the weight % of each component is based on a % solid weight basis, and the total weight % of the resin composition does not exceed 100 weight %:

[0092] (a) the amount of the acetoacetoxy functionalized polymer in the resin combination is based on about 1 % by weight to about 50 % by weight of resin combination, such as about 5 % by weight to about 30 % by weight, such as about 10 % by weight to about 20 % by weight, and the gross weight of the resin combination is no more than 100 % by weight (solid basis). In at least one embodiment, the amount (weight %, solid basis) of the acetoacetoxy functionalized polymer in the resin combination is 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29,30,31,32,33,34,35,36,37,38,39,40,41,42,43,44,45,46,47,48,49 or 50 or its scope, but also consider higher or lower amount. Each of the aforementioned numbers may be preceded by the word "about," "at least about," "less than about," or "greater than about," and any of the aforementioned numbers may be used alone to describe an open range or in combination to describe a closed range.

[0093] (b) The amount of epoxy resin in the resin composition may be from about 25 wt % to about 99 wt %, such as from about 30 wt % to about 80 wt %, such as from about 40 wt % to about 70 wt %, based on the total weight of the resin composition. In at least one embodiment, the amount of epoxy resin in the resin composition (wt %, solid basis) is 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75 9, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98 or 99 or ranges thereof, but higher or lower amounts are also contemplated. Each of the foregoing numbers may be preceded by the word "about," "at least about," "less than about," or "greater than about," and any of the foregoing numbers may be used alone to describe an open range or in combination to describe a closed range.

[0094] (c) The amount of the curing agent in the resin composition may be about 1 wt % to about 67 wt %, such as about 5 wt % to about 60 wt %, such as about 10 wt % to about 50 wt %, based on the total weight of the resin composition. In at least one embodiment, the amount of epoxy resin in the resin composition (wt % solids basis) is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66 or 67 or ranges thereof, but higher or lower amounts are also contemplated. Each of the aforementioned numbers may be preceded by the word "about," "at least about," "less than about," or "greater than about," and any of the aforementioned numbers may be used alone to describe an open range or in combination to describe a closed range.

[0095] In some embodiments, the resin composition may further include a solvent, such as those described herein. The amount of the solvent in the resin composition may be from about 0% by weight to about 50% by weight, such as from about 10% by weight to about 40% by weight, such as from about 20% by weight to about 30% by weight, based on the total weight of the resin composition.

[0096] In some embodiments, the epoxy resin polymerization product is formed from the resin composition described herein.The resin composition described herein can be applied by a suitable method such as brushing, dipping, spraying, air coating, combinations thereof, and the like.

[0097] Curing can generally be carried out by exposing the applied composition to ambient conditions for a suitable period of time, such as 30 minutes to one week, although other periods of time are also contemplated. Typically, curing can be carried out in accordance with ASTM D5895. With respect to the dry-through stage (or Stage IV) of ASTM D5895, the curing conditions are 25° C. and 50% relative humidity.

[0098] In some embodiments, the resin compositions described herein may have one or more of the following non-limiting properties:

[0099] (a) The pencil hardness (1 day) of the composition may be from about 6B to about H, such as from about 2B to about HB, although other values ​​are contemplated. The pencil hardness is determined as described in the Examples.

[0100] (b) The methyl ethyl ketone (MEK) resistance (7 days) of the composition can be about 150 rubs or more, such as about 200 rubs or more, although other values ​​are contemplated. MEK resistance is determined as described in the Examples.

[0101] (c) The composition may have an impact resistance (normal direction) of about 4 to about 160, such as about 40 to about 120, although other values ​​are contemplated. Impact resistance (normal direction) is determined as described in the Examples.

[0102] (d) The impact resistance (reverse) of the composition may be from about 4 inch pounds to about 160 inch pounds, such as from about 20 inch pounds to about 80 inch pounds, although other values ​​are contemplated. Impact resistance (reverse) is determined as described in the Examples.

[0103] (e) The adhesion of the composition to CRS (x-cut method) can be any value between 0A and 5A. The adhesion of the x-cut method is determined as described in the Examples. CRS refers to cold rolled steel (QD-46 plate, smooth steel plate).

[0104] (g) The adhesion of the composition to CRS (cross-cut method) can be any value between 0A and 5B. The adhesion of the cross-cut method is determined as described in the Examples.

[0105] The resin compositions described herein can be used as, for example, coatings, adhesives, paints, tackifiers, sealants, and the like. Therefore, in some embodiments, the present disclosure also relates to such systems, such as coating systems, such as coating systems and coating formulations made of two or more components, which are generally referred to as "2K systems" or "2K coating formulations". The first and second components are mixed together before being applied to the resin. The terms "coating system", "2K system" and "2K coating formulation" are used interchangeably, so that reference to one includes reference to the other. For example, reference to a "coating system" includes reference to a "coating system", "2K coating formulation" and "2K system".

[0106] The coating system of the present disclosure may include two or more components. The first component of the coating system may include an epoxy resin and an acetoacetoxy-functional polymer, such as those epoxy resins and acetoacetoxy-functional polymers described above. The second component may include a curing agent, such as those curing agents described above. The coating system may be provided as a dual container system, for example, a first container contains the first component, and a second container contains the second component.

[0107] In some embodiments, the first component of the coating system can include an acetoacetoxy-functional polymer in an amount of about 1 wt % to about 50 wt %, such as 10 wt % to about 25 wt %, such as 15 wt % to about 20 wt %, based on the total weight percentage of the first component of the coating system, and the total weight percentage of the first component does not exceed 100 wt %. In at least one embodiment, the amount of acetoacetoxy-functional polymer in the first component of the coating system (wt %, solid basis) is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49 or 50 or ranges thereof, but higher or lower amounts are also contemplated. Each of the aforementioned numbers may be preceded by the word "about," "at least about," "less than about," or "greater than about," and any of the aforementioned numbers may be used alone to describe an open range or in combination to describe a closed range.

[0108] In some embodiments, the amount of epoxy resin in the first component of the coating system (solid basis) may be from about 50% to about 90% by weight, such as from 60% to about 80% by weight, such as from 65% to about 75% by weight, such as from wt% to about wt%, based on the total weight percentage of the first component of the coating system. In at least one embodiment, the amount of epoxy resin in the first component of the coating system (wt%, solid basis) is 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98 or 99 or ranges thereof, but higher or lower amounts are also contemplated. Each of the aforementioned numbers may be preceded by the word "about," "at least about," "less than about," or "greater than about," and any of the aforementioned numbers may be used alone to describe an open range or in combination to describe a closed range.

[0109] The weight % of the acetoacetoxy functional polymer and epoxy resin in the first component is based on the weight % of the solid basis of the first component. Solvents and other components can be used with the first component. In such cases, the amount of acetoacetoxy functional polymer and epoxy resin can be varied as desired.

[0110] In some embodiments of the coating system, the amount of the first component comprising the acetoacetoxy functional polymer and the epoxy resin and the amount of the second component comprising the curing agent can vary. For such embodiments, the molar ratio of the first component to the second component is from about 80:20 to about 20:80, such as from about 70:30 to about 30:70, such as from about 60:40 to about 40:60, such as from about 55:45 to about 45:55, such as about 50:50. In some embodiments of the coating system, the molar ratio of the first component to the second component is about 80:20, 70:30, 69:31, 68:32, 67:33, 66:34, 65:35, 64:36, 63:37, 62:38, 61:39, 60:40, 59:41, 58:42, 57:43, 56:44, 55:45, 54:46, 53:47, 52:48, 51:49, 50:50, 49:51, 48:52, 47:53, 46:54, 45:55, 44:56, 43:57, 42:58, 41:59 or 40:60 or ranges thereof, although higher or lower molar ratios are also contemplated. Each of the aforementioned numbers may be preceded by the word "about," "at least about," "less than about," or "greater than about," and any of the aforementioned numbers may be used alone to describe an open range or in combination to describe a closed range.

[0111] The molar ratio of the first component to the second component is based on functional equivalence (reactive groups present in each component). That is, the molar ratio refers to the molar amount of (epoxy groups + acetoacetoxy groups): (active hydrogen on the amine group of the curing agent).

[0112] As discussed above, the coating system may include two or more components, wherein the first component includes an acetoacetoxy-functional polymer and an epoxy resin, and the second component includes a curing agent. In some embodiments, the coating system (total amount of the first and second components) may have the following formulation, wherein the weight % of each component is based on a % solid weight basis, and the total weight % of the resin composition does not exceed 100 weight %:

[0113] (a) The amount of acetoacetoxy-functional polymer in the coating system is from about 1 wt % to about 50 wt %, such as from about 5 wt % to about 30 wt %, such as from about 10 wt % to about 20 wt %, based on the total weight of the coating system, and the total weight of the coating system does not exceed 100 wt %. In at least one embodiment, the amount of acetoacetoxy-functional polymer in the coating system (wt %, solid basis) is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49 or 50 or ranges thereof, but higher or lower amounts are also contemplated. Each of the aforementioned numbers may be preceded by the word "about," "at least about," "less than about," or "greater than about," and any of the aforementioned numbers may be used alone to describe an open range or in combination to describe a closed range.

[0114] (b) The amount of epoxy resin in the coating system may be from about 25 wt % to about 99 wt %, such as from about 30 wt % to about 80 wt %, such as from about 40 wt % to about 70 wt %, based on the total weight of the coating system. In at least one embodiment, the amount of epoxy resin in the coating system (wt %, solid basis) is 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75 9, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98 or 99 or ranges thereof, but higher or lower amounts are also contemplated. Each of the foregoing numbers may be preceded by the word "about," "at least about," "less than about," or "greater than about," and any of the foregoing numbers may be used alone to describe an open range or in combination to describe a closed range.

[0115] (c) The amount of the curing agent in the coating system may be from about 1 wt % to about 67 wt %, such as from about 5 wt % to about 60 wt %, such as from about 10 wt % to about 50 wt %, based on the total weight of the coating system. In at least one embodiment, the amount of epoxy resin in the coating system (wt % solids basis) is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66 or 67, or ranges thereof, although higher or lower amounts are also contemplated. Each of the aforementioned numbers may be preceded by the word "about," "at least about," "less than about," or "greater than about," and any of the aforementioned numbers may be used alone to describe an open range or in combination to describe a closed range.

[0116] The other components may be used with the first component, the second component, or as a third component of the coating system. In such cases, the amounts of the acetoacetoxy-functional polymer, epoxy resin, and curing agent may vary as desired.

[0117] Any suitable solvent, additive or additional component (such as those described above) can be included in the first component, the second component or both. Additionally or alternatively, any suitable solvent, additive or additional component (such as those described above) can be included as a separate component.

[0118] When the components of the coating system are mixed, a coating composition is formed. Similar to the resin composition described herein, an epoxy resin polymer product is formed after mixing the components of the coating system. The coating composition can be applied by a suitable method, such as brushing, dipping, spraying, air coating, combinations thereof, and the like.

[0119] Curing can generally be carried out by exposing the applied composition to ambient conditions for a suitable period of time (such as 30 minutes to one week), but other time periods are also contemplated. Generally, curing can be carried out in accordance with ASTM D5895. With respect to the complete drying stage (or Stage IV) of ASTM D5895, the curing conditions are 25° C. and 50% relative humidity.

[0120] The coating composition may have the same or similar physical properties as those described above for the resin composition, such as pencil hardness, MEK resistance, impact resistance (forward), impact resistance (reverse), mandrel bend, adhesion (hatch method), or adhesion (cross-hatch method).

[0121] Embodiments of the present disclosure also relate to uses of the resin compositions and coating compositions described herein. The compositions described herein can be used as coatings, adhesives, paints, adhesives, sealants and other applications. For example, the compositions can be used in construction, installing concrete and cement, such as high gloss concrete installation. Another use includes coating metals. Other end-use applications of the compositions described herein include, but are not limited to: cellulose, lignocellulose and wood products; plastics; fabrics (woven and non-woven); and glass. The compositions can generally be used to produce composite materials, adhesives, insulation materials, molded products, adhesives, laminates and other articles and products.

[0122] The following examples are presented to provide those of ordinary skill in the art with a complete disclosure and description of how to make and use the embodiments of the present disclosure, and are not intended to limit the scope of the embodiments of the present disclosure. Efforts have been made to ensure accuracy with respect to the numbers used, but some experimental errors and deviations should be accounted for.

[0123] Example

[0124] Test Method

[0125] Various tests were performed on the compositions described herein. The dry film formation rate (cycle drying time) of the sample compositions was measured according to ASTM D5895 using a cyclic mechanical drying time recording apparatus.

[0126] Evaluation of the solvent resistance of the sample compositions was determined by methyl ethyl ketone (MEK) resistance using ASTM D5402. The MEK resistance of the compositions was determined after curing for 7 days at 25°C.

[0127] The hardness of the sample composition was determined by measuring the pencil hardness according to ASTM D 1186. The pencil hardness was rated according to the scale provided in the ASTM standard. The pencil hardness of the composition was measured after curing for 1 day (or 24 hours) at 25°C.

[0128] The impact resistance (forward and reverse) of the sample compositions was determined using ASTM D2794. Impact resistance is a measure of the resistance of a composition to the effects of rapid deformation. The test involves applying an organic coating to a suitable 24 gauge metal panel and dropping a standard weight from a distance to cause the indenter to deform the composition.

[0129] The adhesion of the sample composition to the substrate was measured by tape testing according to ASTM D3359: Method A (cross-hatch method) and Method B (cross-hatch method). Adhesion was rated according to the grades provided in the ASTM standard. The substrate used for the adhesion test was cold-rolled steel (QD-46 plate, smooth steel plate).

[0130] The resistance of the sample compositions to cracking (flexibility) was determined by mandrel bend testing according to ASTM D522.

[0131] The weight average molecular weight (Mw) of acetoacetoxy functional polymer and curing agent is measured by size exclusion chromatography using Agilent 1100 high performance liquid chromatograph, which is commercially available from Agilent Technologies Inc. in Germany and is equipped with multiple columns (PLgel Mixed-E from Polymer Laboratories) to ensure sufficient molecular weight resolution. The mobile phase for transporting the analyte through the column is tetrahydrofuran at a rate of 1.0 ml / min. The particle concentration of elution over time is continuously monitored by a refractive index detector. The instrument is calibrated using the narrow weight distribution polystyrene standard of Polymer Laboratories.

[0132] The glass transition temperature (T) of the acetoacetoxy-functional polymer was calculated according to the Fox equation as shown in Equation 1. g ). The Fox equation states that the calculated glass transition temperature (T g ) is equal to the weight fraction of each component (W i ) divided by the glass transition temperature (T g,i ) is the sum of:

[0133] (Equation 1)

[0134] Exemplary acetoacetoxy-functionalized polymers

[0135] Exemplary acetoacetoxy functionalized polymers are prepared according to the following non-limiting examples. The amount in grams (g) is based on 1 liter (1 L), and the reactor is placed under a nitrogen atmosphere throughout the reaction. Xylene (30% by weight, 120 g) is loaded into the reactor and the reactor is heated to about 130°C. When the temperature in the reactor reaches about 130°C, a mixture of acetoacetoxyethyl methacrylate monomer (AAEM, 20% by weight, 80 g), methyl methacrylate monomer (MMA, 50% by weight, 200 g), n-butyl acrylate monomer (BA), neodecanoic acid vinyl ester monomer (20% by weight, 80 g) and 1,1-bis (tert-amyl peroxy) cyclohexane initiator (0.8% by weight, 3.2 g) is gradually pumped into the reactor in a continuous manner over a period of about 3 hours. During the addition of these monomers and initiators, the reactor temperature is controlled at about 130 ± 5°C. Three hours later, another portion of a solution of 1,1-bis(tert-amylperoxy)cyclohexane initiator (0.8 wt %, 3.2 g) in xylene (15 wt %, 60 g) was added over a period of about 1 hour while maintaining the temperature at about 130°C, and the resulting mixture was allowed to react for an additional 30 minutes after all the initiators were added. Next, the mixture was allowed to cool so that the temperature inside the reactor was about 110°C, at which time another portion of xylene (33 wt %, 132 g) was added. After the acetoacetoxy-functionalized polymer was fully reacted, the mixture was allowed to cool to about 60°C. The acetoacetoxy-functionalized polymer formed was a medium Tg liquid resin. The Tg of the acetoacetoxy-functionalized polymer was measured to be about 40°C, calculated according to the Fox equation. The solids content of the acetoacetoxy-functionalized polymer was determined to be about 55.6%. The solids content was measured according to ASTM D2369-92. Table 1 shows an exemplary process recipe for the above-mentioned procedure for forming an acetoacetoxy-functionalized polymer.

[0136] Table 1

[0137]

[0138] Exemplary compositions

[0139] Various amounts of acetoacetoxy functional polymers were blended with an exemplary epoxy resin (polymer of 4,4'-(1-methylethylidene)bis-cyclohexanol and 2-(chloromethyl)oxirane (CAS No. 30583-72-3). Other suitable epoxy resins may be utilized. Table 2A shows exemplary properties of various blends of acetoacetoxy functional polymers and epoxy resins. Blends were prepared at epoxy resin (ER) to acetoacetoxy functional polymer (AFP) ratios of about 50:50, about 60:40, about 70:30, about 80:20, and about 90:10. After blending the ER and AFP, each sample was mixed with 1,3-bis(aminomethyl)cyclohexane in a stoichiometric ratio of 1:1. Induction time was measured in minutes (min). Touch-dry time, tack-free time and dry-through time are all measured in hours (h).

[0140] Table 2A

[0141]

[0142] The exemplary, non-limiting data shown in Table 2A illustrate that the induction time of the blends is significantly reduced compared to the epoxy resin alone. Induction time refers to the waiting time after the two components of the coating are mixed. For conventional epoxy polyamides, the induction time before application to the surface after mixing is generally 30-60 minutes or even longer. In the absence of acetoacetoxy-functional polymers (Example 1), the induction time was measured to be about 30 minutes, which is consistent with conventional resins. In contrast, all exemplary blends of epoxy resins and acetoacetoxy-functional polymers show an induction time of about 0 minutes (Examples 3-7), which indicates that the materials dry fast enough and react fast enough so that no induction time is required.

[0143] The contact dry time, tack dry time, and through dry time mentioned in Table 2A are known alternative names for the stages listed in ASTM D5895 (Cycle Drying Time). The contact dry time of the blends is also significantly reduced, which is proportional to the amount of acetoacetoxy functional polymer used in the blend. For example, the contact dry time of the epoxy resin alone (Example 1) is about 5.5 hours, while the amount of acetoacetoxy functional polymer shown in Example 3 (50:50 blend; contact dry time is about 0.5 hours) is greater than that of Example 7 (90:10 blend; contact dry time is about 4.5 hours). The excellent contact dry time indicates that this drying stage is significantly shortened.

[0144] The surface drying time of all blends containing acetoacetoxy functional polymers is improved over the epoxy resin alone, from about 10 hours (Example 1) to less than about 8 hours. Here, for example, the surface drying time of the 50:50 blend (Example 3) is determined to be about 1 hour. Examples 4 and 7 show the highest surface drying time of blends containing acetoacetoxy functional polymers, but each surface drying time is significantly lower than the epoxy resin alone (Example 1). The complete drying time of all blends containing acetoacetoxy functional polymers is also significantly improved over the epoxy resin alone, and the complete drying time is reduced from more than about 24 hours (Example 1) to less than about 14 hours. Here, for example, the complete drying time of the 70:30 blend (Example 5) and the 50:50 blend (Example 3) is determined to have the lowest complete drying time, which is about 6.5 hours and about 8.5 hours, respectively. Overall, the results presented in Table 2A show that the exemplary compositions described herein dry quickly.

[0145] The exemplary resin compositions shown in Table 2B were prepared. All resin compositions were prepared using epoxy resin (polymer of 4,4'-(1-methylethylidene)bis-cyclohexanol and 2-(chloromethyl)oxirane (CAS No. 30583-72-3)). Comparative Example 1 (C.Ex.1) is an epoxy resin. Comparative Example 2 (C.Ex.2) is a blend of an epoxy resin and a commercially available acetoacetate functional reactive diluent (K-FLEX XM-B301). Comparative Example 3 (C.Ex.3) is a blend of a copolymer of glycidyl methacrylate (20%), methyl methacrylate (50%), butyl acrylate (5%), isobornyl methacrylate (9%) and vinyl neodecanoate (16%) with an epoxy resin. Example 7 is a blend of an epoxy resin and an acetoacetoxy functional polymer (10% AAEM in the polymer). Example 8 is a blend of epoxy resin and acetoacetoxy functionalized polymer (10% AAEM in polymer).

[0146] Each resin composition shown in Table 2B was then mixed with the curing agent 1,3-bis(aminomethyl)cyclohexane (1,3-BAC) at a stoichiometric ratio of 1: 1. After mixing the resin composition with the curing agent, the dry to touch time and through dry time were determined as measured by ASTM D5895.

[0147] Table 2B

[0148]

[0149] In Table 2B, "Weight % of Acetoacetoxy in Resin" refers to the weight percent of acetoacetoxy functional groups in the resin composition prior to mixing with the curing agent. "Weight % of Epoxy-Functionalized Acrylic Polymer" refers to the weight percent of epoxy-functionalized acrylic polymer in the resin composition prior to mixing with 1,3-BAC, while "Weight % of Acetoacetoxy-Functionalized Acrylic Polymer" refers to the weight percent of acetoacetoxy-functionalized acrylic polymer in the resin composition prior to mixing with 1,3-BAC. Epoxy-functionalized acrylic polymers have similar molecular weights to acetoacetoxy-functionalized acrylic polymers, but do not have acetoacetoxy functional groups.

[0150] The exemplary, non-limiting data shown in Table 2B illustrate that the compositions described herein dry quickly. The data in Table 2B also show that the fast drying compositions have sufficient acetoacetoxy functional groups to achieve reduced drying times compared to the comparative compositions. However, as observed when comparing the drying times of Comparative Example 2 with Example 8, this amount of acetoacetoxy functional groups is best delivered by an acetoacetoxy functional acrylic polymer. The data for Comparative Example 3 also show the superior drying properties of the acetoacetoxy functional groups relative to the epoxy functional groups, with the epoxy functional polymer of Comparative Example 3 having a higher loading than Example 8 (with an acetoacetoxy functional acrylic polymer), but with significantly longer drying times.

[0151] Another exemplary composition is prepared by mixing a first component (epoxy resin and acetoacetoxy functional polymer) and a second component (curing agent). The exemplary composition is a non-limiting example of a resin composition or a coating composition as described herein. In this example, 1,3-bis (aminomethyl) cyclohexane (1,3-BAC) is selected as a curing agent. Cyclohexanol, 4,4'-(1-methylethylidene) bis- and 2-(chloromethyl) oxirane polymers are selected as epoxy resins (ER). However, other suitable curing agents and epoxy resins are also considered. The weight percentages of each component of the exemplary composition are shown in Table 3, and are based on the gross weight of the resin composition. The comparative composition includes a first component (single epoxy resin) and a second component (1,3-BAC). The properties of the exemplary composition and the comparative composition are also shown in Table 3.

[0152] Table 3

[0153]

[0154] The exemplary, non - limiting data shown in Table 3 illustrate the improved properties of the compositions described herein. For example, the exemplary composition was determined to have a pencil hardness of HB, which is harder than the comparative composition with a pencil hardness of 2B, indicating that the exemplary composition is a harder film relative to the comparative resin composition and is more resistant to certain types of deformation. The impact resistance (forward) of the exemplary composition was significantly improved compared to the comparative composition, as shown by a substantial increase to about 112 inch - pounds, which is almost 10 times that of the comparative composition. Similarly, the exemplary composition showed a significant increase in impact resistance (reverse) relative to the comparative composition, increasing from <4 to about 56. These impact resistance values indicate that the exemplary composition has enhanced deformability relative to the comparative composition without mechanical failure (such as cracking and delamination).

[0155] While the comparative composition failed in the mandrel bend test, the exemplary composition was determined to have a mandrel bend of <l / 8”, indicating that the exemplary composition has good flexibility. Additionally, the exemplary composition remains tolerant to chemicals and solvents, as measured by MEK tolerance, while showing significantly improved properties compared to the comparative composition.

[0156] Embodiments of the present disclosure generally relate to epoxy resin compositions and coating systems for forming epoxy resin compositions. Different from the prior art, embodiments of the present disclosure can be fast - drying, high - molecular - weight resin compositions. The resin compositions can also have good mechanical properties and can be used for external and internal applications. Embodiments described herein also relate to coating systems. The coating systems can be used to form coating compositions including epoxy resin compositions. The epoxy resin compositions described herein can be used as coatings, sealants, adhesives, etc. in applications.

[0157] List of Embodiments

[0158] Among other things, the present disclosure provides the following aspects, each of which can be considered to optionally include any alternative embodiments:

[0159] Clause 1. A resin composition, the resin composition comprising:

[0160] Epoxy resin;

[0161] A curing agent; and

[0162] An acetoacetoxy-functionalized polymer having a weight average molecular weight of about 1000 g / mol to about 100,000 g / mol, the acetoacetoxy-functionalized polymer comprising: an acetoacetoxy-functionalized monomer unit; and a comonomer unit, the comonomer unit comprising an acrylate monomer, a methacrylate monomer, an α-olefin monomer, a vinyl halide monomer, a carboxylic acid diester monomer, an unsaturated nitrile monomer, an α,β-unsaturated carboxylic acid monomer, an α,β-unsaturated amide monomer, or a combination thereof.

[0163] Clause 2. The resin composition of clause 1, wherein the acetoacetoxy-functional polymer comprises:

[0164] from about 10% to about 30% by weight of said acetoacetoxy-functional monomer units; and

[0165] From about 70 wt % to about 90 wt % of the comonomer units, the total wt % of the acetoacetoxy-functional polymer not exceeding 100 wt %.

[0166] Clause 3. The resin composition of Clause 1 or Clause 2, wherein the acetoacetoxy-functional polymer has:

[0167] a glass transition temperature of about -50°C to about 105°C;

[0168] A weight average molecular weight of about 1,000 g / mol to about 60,000 g / mol; or

[0169] Its combination.

[0170] Clause 4. The resin composition according to any one of clauses 1 to 3, wherein:

[0171] The amount of the acetoacetoxy-functional polymer is from about 1 wt % to about 74 wt % based on the total weight of the resin composition;

[0172] The amount of the epoxy resin is from about 25 wt % to about 99 wt % based on the total weight of the resin composition; and

[0173] The amount of the curing agent is from about 1 wt % to about 74 wt % based on the total weight of the resin composition, wherein the wt % of each component is based on a % solid weight basis, and the total weight of the resin composition does not exceed 100 wt %.

[0174] Clause 5. The resin composition of any one of Clauses 1 to 4, wherein the acetoacetoxy-functional monomer unit comprises, prior to polymerization, an acetoacetoxy-functional monomer having formula (I):

[0175] (I)

[0176] in:

[0177] R 1 is methyl (CH3) or hydrogen; and

[0178] n is a number from 1 to 6.

[0179] Clause 6. The resin composition of any one of clauses 1 to 5, wherein when the comonomer unit comprises an acrylate monomer, a methacrylate monomer, or a combination thereof, at least one of the acrylate monomer or the methacrylate monomer comprises a comonomer having formula (II) prior to polymerization:

[0180] (II)

[0181] in:

[0182] R 2 is methyl or hydrogen; and

[0183] R 3 Contains 1 to 30 carbon atoms.

[0184] Clause 7. The resin composition according to clause 6, wherein:

[0185] R 2 is methyl or hydrogen; and

[0186] R 3 Contains 1 to 10 carbon atoms.

[0187] Clause 8. The resin composition of any one of Clauses 1 to 7, wherein the epoxy resin is a non-aromatic epoxy resin.

[0188] Clause 9. The resin composition of any one of Clauses 1 to 8, wherein the non-aromatic epoxy resin is a cycloaliphatic epoxy resin comprising diglycidyl ether of hydrogenated cyclohexanedimethanol or hydrogenated bisphenol A type epoxy resin, or a combination thereof.

[0189] Clause 10. The resin composition of any one of Clauses 1 to 9, wherein the curing agent comprises an aliphatic polyamine, a polyetheramine, a cycloaliphatic amine, an aromatic amine, a Mannich base, a ketimine, an oxazoline, an amidoamine, or a combination thereof.

[0190] Clause 11. The resin composition according to Clause 10, wherein:

[0191] When the curing agent includes the aliphatic polyamine, the aliphatic polyamine includes a polyamine of formula (IVa):

[0192] (IVa), wherein n of formula (IVa) is 1, 2, 3, 4, 5 or 6;

[0193] When the curing agent includes the polyetheramine, the polyetheramine includes a polyetheramine of formula (IVb), a polyetheramine of formula (IVc), a polyetheramine of formula (IVd), a polyetheramine of formula (IVe), or a combination thereof:

[0194] (IVb), wherein x of formula (IVb) is 2.5 to 68;

[0195] (IVc), wherein x+y+z of formula (IVc) is 5 to 85;

[0196] (IVd), wherein R of formula (IVd) 4 is hydrogen or CH3, x of formula (IVd) is 1 to 40, and y of formula (IVd) is 1 to 40; or

[0197] (IVe), where

[0198] x+z of formula (IVe) is 1.2 to 6 and y in formula (IVe) is 2 to 39; or a combination thereof.

[0199] Clause 12. The resin composition of any one of Clauses 1 to 11, wherein the curing agent is selected from the group consisting of: including but not limited to 1,3-bis(aminomethyl)cyclohexane, diethylenetriamine, triethylenetetramine, hexamethylenediamine, trimethylhexamethylenediamine, tetraethylenepentamine, N,N',-dimethylpropylenediamine, 1,3-bis(4-amino-3-methylcyclohexyl)methane, bis(p-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, 3,5,5-trimethyl-3-(aminomethyl)-cyclohexylamine, N-aminoethylpiperazine, m-phenylenediamine, p-phenylenediamine, bis(p-aminophenyl)methane, bis(p-aminophenyl)sulfone, m-phenylenediamine, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, 1,4-bis(aminomethyl)cyclohexane, and combinations thereof.

[0200] Clause 13. The resin composition of any one of Clauses 1 to 12, further comprising from about 0.1 wt % to about 50 wt % of a solvent based on the total weight of the resin composition.

[0201] Clause 14. A composition comprising an epoxide polymerization product of a reaction mixture comprising:

[0202] Epoxy resin;

[0203] Curing agent; and

[0204] An acetoacetoxy-functional polymer having a weight average molecular weight of about 1000 g / mol to about 100,000 g / mol, the acetoacetoxy-functional polymer comprising:

[0205] Acetoacetoxy-functional monomer units; and

[0206] The comonomer unit comprises an acrylate monomer, a methacrylate monomer, an α-olefin monomer, a vinyl halide monomer, a carboxylic acid diester monomer, an unsaturated nitrile monomer, an α,β-unsaturated carboxylic acid monomer, an α,β-unsaturated amide monomer or a combination thereof.

[0207] Clause 15. The composition of Clause 14, wherein the acetoacetoxy-functional polymer comprises:

[0208] from about 10% to about 30% by weight of said acetoacetoxy-functional monomer units; and

[0209] From about 70 wt % to about 90 wt % of the comonomer units, the total wt % of the acetoacetoxy-functional polymer not exceeding 100 wt %.

[0210] Clause 16. The composition of Clause 14 or Clause 15, wherein the acetoacetoxy-functional polymer has:

[0211] a glass transition temperature of about -50°C to about 105°C;

[0212] A weight average molecular weight of about 1,000 g / mol to about 60,000 g / mol; or

[0213] Its combination.

[0214] Clause 17. The resin composition of any one of Clauses 14 to 16, wherein:

[0215] The amount of the acetoacetoxy-functional polymer is from about 1 wt % to about 74 wt % based on the total weight of the composition;

[0216] The epoxy resin is present in an amount of about 25% to about 99% by weight based on the total weight of the composition; and

[0217] The amount of the curing agent is from about 1 wt % to about 74 wt % based on the total weight of the composition, wherein the wt % of each component is based on a % solid weight basis, and the total weight of the composition does not exceed 100 wt %.

[0218] Clause 18. The resin composition according to any one of clauses 14 to 17, wherein:

[0219] The acetoacetoxy-functional monomer unit comprises, prior to polymerization, an acetoacetoxy-functional monomer having formula (I):

[0220] (I)

[0221] in:

[0222] R 1 is methyl (CH3) or hydrogen; and

[0223] n is a number from 1 to 6;

[0224] Wherein when the comonomer units comprise acrylate monomers, methacrylate monomers or a combination thereof, at least one of the acrylate monomers or the methacrylate monomers comprises a comonomer having formula (II) prior to polymerization:

[0225] (II)

[0226] in:

[0227] R 2 is methyl or hydrogen; and

[0228] R 3 contains 1 to 30 carbon atoms; or

[0229] Its combination.

[0230] Clause 19. A coating system, comprising:

[0231] A first component, the first component comprising:

[0232] Epoxy resin; and

[0233] An acetoacetoxy-functional polymer having a molecular weight of about 1000 g / mol to about 100,000 g / mol, the acetoacetoxy-functional polymer comprising:

[0234] Acetoacetoxy-functional monomer units; and

[0235] comonomer units, the comonomer units comprising acrylate monomers, methacrylate esters, α-olefins, vinyl halide monomers, carboxylic acid diester monomers, unsaturated nitrile monomers, α,β-unsaturated carboxylic acid monomers, α,β-unsaturated amide monomers or combinations thereof; and

[0236] The second component comprises a curing agent.

[0237] Clause 20. The coating system of Clause 19, wherein:

[0238] The acetoacetoxy-functional polymer comprises from about 10% to about 30% by weight of the acetoacetoxy-functional monomer units;

[0239] The acetoacetoxy-functional polymer has a glass transition temperature of about -50°C to about 105°C;

[0240] The acetoacetoxy-functional polymer has a weight average molecular weight of about 1,000 g / mol to about 60,000 g / mol; or

[0241] Its combination.

[0242] As used herein, when referring to an R group, an alkyl group, a substituted alkyl group, a hydrocarbyl group, or a substituted hydrocarbyl group without specifying a specific isomer (such as butyl), all isomers (such as n-butyl, isobutyl, sec-butyl, and tert-butyl) are explicitly disclosed. For example, a reference to an R group having 4 carbon atoms explicitly discloses all isomers thereof. When a compound is described herein such that a specific isomer, enantiomer, or diastereomer of the compound is not specified (e.g., in a formula or chemical name), the description is intended to include each isomer and enantiomer of the compound described alone or in any combination.

[0243] As is apparent from the foregoing general description and specific aspects, although the form of aspects has been illustrated and described, various modifications may be made without departing from the spirit and scope of the present disclosure. Therefore, the present disclosure is not intended to be limited thereto. Likewise, the term "comprising" is considered to be synonymous with the term "including". Likewise, whenever a composition, an element, or an element group is preceded by the transition phrase "comprising", it should be understood that we also consider the same composition or element group with the transition phrase "consisting essentially of", "consisting of", "selected from a group consisting of" or "is" in front of the composition, one or more element groups, and vice versa, such as the term "comprising", "consisting essentially of", "consisting of" also includes the product of the element combination listed after the term.

[0244] For the purpose of this disclosure, and unless otherwise specified, all numerical values ​​in the specific embodiments and claims herein are modified with "about" specified values ​​or "approximately" specified values, and experimental errors and variations expected by those of ordinary skill in the art are considered. For the sake of brevity, only certain ranges are explicitly disclosed herein. However, the range from any lower limit can be combined with any upper limit to list the range that is not explicitly listed, and the range from any lower limit can be combined with any other lower limit to list the range that is not explicitly listed, in the same way, the range from any upper limit can be combined with any other upper limit to list the range that is not explicitly listed. Additionally, even if it is not explicitly listed, each point or single value between its endpoints is also included in the range. Therefore, each point or single value can be used as its own lower limit or upper limit to be combined with any other point or single value or any other lower limit or upper limit, so as to list the range that is not explicitly listed.

[0245] As used herein, the indefinite article "a" shall mean "at least one" unless specified otherwise or the context clearly indicates otherwise. For example, aspects comprising "a monomer" include aspects comprising one, two, or more monomers unless specified otherwise or the context clearly indicates that only one monomer is included.

[0246] While the foregoing is directed to aspects of the present disclosure, other and further embodiments of the present disclosure may be envisaged without departing from the basic scope thereof, and the scope of the present disclosure is to be determined by the following claims.

Claims

1. A resin composition, comprising: Epoxy resin; Curing agent; and An acetoacetoxy-functional polymer having a weight average molecular weight of about 1000 g / mol to about 100,000 g / mol, the acetoacetoxy-functional polymer comprising: Acetoacetoxy-functional monomer units; and The comonomer unit comprises an acrylate monomer, a methacrylate monomer, an α-olefin monomer, a vinyl halide monomer, a carboxylic acid diester monomer, an unsaturated nitrile monomer, an α,β-unsaturated carboxylic acid monomer, an α,β-unsaturated amide monomer or a combination thereof.

2. The resin composition of claim 1, wherein the acetoacetoxy-functional polymer comprises: from about 10% to about 30% by weight of said acetoacetoxy-functional monomer units; and From about 70 wt % to about 90 wt % of the comonomer units, the total wt % of the acetoacetoxy-functional polymer not exceeding 100 wt %.

3. The resin composition of claim 1, wherein the acetoacetoxy-functional polymer has: a glass transition temperature of about -50°C to about 105°C; A weight average molecular weight of about 1,000 g / mol to about 60,000 g / mol; or Its combination.

4. The resin composition according to claim 1, wherein: The amount of the acetoacetoxy-functional polymer is from about 1 wt % to about 74 wt % based on the total weight of the resin composition; The amount of the epoxy resin is from about 25 wt % to about 99 wt % based on the total weight of the resin composition; and The amount of the curing agent is from about 1 wt % to about 74 wt % based on the total weight of the resin composition, wherein the weight % of each component is based on a % solid weight basis, and the total weight of the resin composition does not exceed 100 wt %.

5. The resin composition of claim 1, wherein the acetoacetoxy-functional monomer unit comprises an acetoacetoxy-functional monomer having formula (I) prior to polymerization: (I)， in: R 1 is methyl (CH3) or hydrogen; and n is a number from 1 to 6.

6. The resin composition of claim 1, wherein when the comonomer unit comprises an acrylate monomer, a methacrylate monomer, or a combination thereof, at least one of the acrylate monomer or the methacrylate monomer comprises a comonomer having formula (II) prior to polymerization: (II), in: R 2 is methyl or hydrogen; and R 3 Contains 1 to 30 carbon atoms.

7. The resin composition according to claim 6, wherein: R 2 is methyl or hydrogen; and R 3 Contains 1 to 10 carbon atoms.

8. The resin composition of claim 1, wherein the epoxy resin is a non-aromatic epoxy resin.

9. The resin composition of claim 8, wherein the non-aromatic epoxy resin is a cycloaliphatic epoxy resin comprising diglycidyl ether of hydrogenated cyclohexanedimethanol or hydrogenated bisphenol A type epoxy resin or a combination thereof.

10. The resin composition of claim 1, wherein the curing agent comprises an aliphatic polyamine, a polyetheramine, a cycloaliphatic amine, an aromatic amine, a Mannich base, a ketimine, an oxazoline, an amidoamine, or a combination thereof.

11. The resin composition according to claim 10, wherein: When the curing agent includes the aliphatic polyamine, the aliphatic polyamine includes a polyamine of formula (IVa): (IVa), wherein n of formula (IVa) is 1, 2, 3, 4, 5 or 6; When the curing agent includes the polyetheramine, the polyetheramine includes a polyetheramine of formula (IVb), a polyetheramine of formula (IVc), a polyetheramine of formula (IVd), a polyetheramine of formula (IVe), or a combination thereof: (IVb), wherein x of formula (IVb) is 2.5 to 68; (IVc), wherein x+y+z of formula (IVc) is 5 to 85; (IVd), wherein R of formula (IVd) 4 is hydrogen or CH3, x of formula (IVd) is 1 to 40, and y of formula (IVd) is 1 to 40; or (IVe), wherein x+z of formula (IVe) is 1.2 to 6 and y of formula (IVe) is 2 to 39; or a combination thereof.

12. The resin composition of claim 1, wherein the curing agent is selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane, diethylenetriamine, triethylenetetramine, hexamethylenediamine, trimethylhexamethylenediamine, tetraethylenepentamine, N,N',-dimethylpropylenediamine, 1,3-bis(4-amino-3-methylcyclohexyl)methane, bis(p-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, 3,5,5-trimethyl-3-(aminomethyl)-cyclohexylamine, N-aminoethylpiperazine, m-phenylenediamine, p-phenylenediamine, bis(p-aminophenyl)methane, bis(p-aminophenyl)sulfone, m-phenylenediamine, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, 1,4-bis(aminomethyl)cyclohexane, and combinations thereof. 13 . The resin composition of claim 1 , further comprising about 0.1 wt % to about 50 wt % of a solvent based on the total weight of the resin composition.

14. A composition comprising the epoxide polymerization product of a reaction mixture comprising: Epoxy resin; Curing agent; and An acetoacetoxy-functional polymer having a weight average molecular weight of about 1000 g / mol to about 100,000 g / mol, the acetoacetoxy-functional polymer comprising: Acetoacetoxy-functional monomer units; and The comonomer unit comprises an acrylate monomer, a methacrylate monomer, an α-olefin monomer, a vinyl halide monomer, a carboxylic acid diester monomer, an unsaturated nitrile monomer, an α,β-unsaturated carboxylic acid monomer, an α,β-unsaturated amide monomer or a combination thereof.

15. The composition of claim 14, wherein the acetoacetoxy-functional polymer comprises: from about 10% to about 30% by weight of said acetoacetoxy-functional monomer units; and From about 70 wt % to about 90 wt % of the comonomer units, the total wt % of the acetoacetoxy-functional polymer not exceeding 100 wt %.

16. The composition of claim 14, wherein the acetoacetoxy-functional polymer has: a glass transition temperature of about -50°C to about 105°C; A weight average molecular weight of about 1,000 g / mol to about 60,000 g / mol; or Its combination.

17. The composition of claim 14, wherein: The amount of the acetoacetoxy-functional polymer is from about 1 wt % to about 74 wt % based on the total weight of the composition; The amount of the epoxy resin is from about 25 wt % to about 99 wt % based on the total weight of the composition; and The amount of the curing agent is from about 1 wt % to about 74 wt % based on the total weight of the composition, wherein the wt % of each component is based on a % solid weight basis, and the total weight of the composition does not exceed 100 wt %.

18. The composition of claim 14, wherein: The acetoacetoxy-functional monomer unit comprises, prior to polymerization, an acetoacetoxy-functional monomer having formula (I): (I)， in: R 1 is methyl (CH3) or hydrogen; and n is a number from 1 to 6; Wherein when the comonomer units comprise acrylate monomers, methacrylate monomers or a combination thereof, at least one of the acrylate monomers or the methacrylate monomers comprises a comonomer having formula (II) prior to polymerization: (II), in: R 2 is methyl or hydrogen; and R 3 contains 1 to 30 carbon atoms; or Its combination.

19. A coating system, comprising: A first component, the first component comprising: Epoxy resin; and An acetoacetoxy-functional polymer having a molecular weight of about 1000 g / mol to about 100,000 g / mol, the acetoacetoxy-functional polymer comprising: Acetoacetoxy-functional monomer units; and comonomer units, the comonomer units comprising acrylate monomers, methacrylate esters, α-olefins, vinyl halide monomers, carboxylic acid diester monomers, unsaturated nitrile monomers, α,β-unsaturated carboxylic acid monomers, α,β-unsaturated amide monomers or combinations thereof; and The second component comprises a curing agent.

20. The coating system of claim 19, wherein: The acetoacetoxy-functional polymer comprises from about 10% to about 30% by weight of the acetoacetoxy-functional monomer units; The acetoacetoxy-functional polymer has a glass transition temperature of about -50°C to about 105°C; The acetoacetoxy-functional polymer has a weight average molecular weight of about 1,000 g / mol to about 60,000 g / mol; or Its combination.

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