WO2016176568A1

WO2016176568A1 - Hardener composition

Info

Publication number: WO2016176568A1
Application number: PCT/US2016/030084
Authority: WO
Inventors: Markus Schroetz; Marcus PFARHERR; Eva-Maria Michalski; Susanne Maier; Christina Fritsche
Original assignee: Blue Cube Ip Llc
Priority date: 2015-04-30
Filing date: 2016-04-29
Publication date: 2016-11-03
Also published as: TW201641531A

Abstract

Cold curing hardener compositions comprise: component A, at least one adduct of a first amine compound and at least one polyfunctional epoxy compound; component B, at least one adduct of a second amine compound and at least one monofunctional epoxy compound; component C, at least one adduct of a third amine compound based on a polyalkylene oxide; on a cycloaliphatic, aliphatic or araliphatic amine; and a modifier wherein the hardener compositions has a low VOC, a low free amine content, and a low viscosity. Curable compositions include (a) at least one epoxy resin and (b) at least one of the above cold curing hardener composition. Processes for preparing the hardener compositions and the curable compositions will be presented.

Description

HARDENER COM POSITION

FIELD OF THE INVENTION

[0001] The present disclosure generally relates to hardener compositions;

processes for preparing these hardener compositions; curable formulations including these hardener compositions; and cured products produced from the curable

formulations containing these hardener compositions.

BACKG ROUND OF THE INVENTION

[0002] Epoxy resins are widely used for a variety of applications including coating formulations. Such coating formulations are used in various end uses such as for the protection of metal and concrete substrates; for flooring, potting, encapsulation applications; and similar end uses.

[0003] Many known aminic adduct hardener formulations are used in epoxy resin based curable compositions to provide a curable coating compositions. In these compositions, the aminic adduct hardener formulations contain up to 50 percent (%) monomeric amine. In addition to being a hardener, the monomeric amine also lowers the viscosity of the hardener formulation.

[0004] One or more volatile organic compounds (VOCs) are known to be employed in hardener formulations. Benzyl alcohol is added to hardener formulations to reduce the viscosity of the formulation and improve the surface appearance of a cured system produced from a curable composition. A non-reactive material or a modifier is also used in hardener formulation in amounts up to 75 %. These non-reactive materials such as nonylphenol reduce the viscosity of the hardener formulation and enhance the flexibility property of a cured system. However, these non-reactive materials adversely impact the mechanical properties of the cured system.

[0005] VOC-free formulations are known and are used primarily in waterborne hardener formulations. Examples of these VOC-free formulations are described in EP0995767 and EP1 136509. The compositions of EP0995767 and EP1 136509 require polyalkylene oxide moieties in order to achieve homogeneity in the compositions in water. However, after water evaporation from the compositions, the polyalkylene oxide moieties will be present in an order of magnitude that will weaken the polymeric matrix. Furthermore, these weakened polymeric matrices reduce the chemical resistance of the coating made from the compositions. WO201 1059500 also discloses curable coating compositions containing no VOCs. Such compositions include an epoxy resin component, a Mannich base; and adducts of (1) epoxy compounds and (2) amines as hardeners. In addition, WO2011059500 discloses coated articles made from the above curable coating compositions. Generally, Mannich bases are conversion products of (alkyl) phenols with amines and formaldehyde. These conversion products can achieve a degree of chemical resistance. Yet, these Mannich bases are labeled with exposure risk designated "risk phrase R 62" which corresponds to a "risk of impaired fertility" due to the presence of (alkyl) phenols in the coating compositions. Accordingly, it would be advantageous to provide a curable coating composition without the use of a Mannich base as disclosed in WO201 1059500 and provide lowered exposure risk and improved chemical resistance.

[0006] Adducts, distilled adducts, and the above-mentioned modifiers are also known in the art. m-Xylylenediamine (MXDA)-adducts are disclosed in Vandezande et al., Epoxy Hardeners for 2K Systems, FATIPEC Congress (2010), 30th (Vol. 2), 620- 629; in Marks et al., ACS Applied Materials & Interfaces (2009), 1 (4), 921-926; and in Mirchandani, Girish, "Assessment of Relative Reactivities and Kinetics of Various Polyamines, and Polyamide Hardeners with Epoxy Resins for Designing High

Performance Epoxy Coatings Using Differential Scanning Calorimetry, Paintindia (2007), 57(6), 69-70, 72, 74, 76, 78, 80, 82, 84, 86, 88, 90, 92. The above references do not disclose a curable coating composition with desirable properties such as a monomeric amine content of less than [<] 20 %, a low VOC content, flexibility, surface appearance, and chemical resistance.

[0007] EP1213312B1 discloses isolated (e.g., distilled) adducts of

phenylglycidylether (Ph-GE) with triethylenetetramine (TETA), wherein the resulting adducts have a viscosity of > 10,000 mPa s. EP1213312B1 does not teach the use of cresylglycidylether (CGE) or 2-methylpentamethylenediamine (MPMD) in such adducts. The processes disclosed in EP1213312B1 cannot achieve an adduct having a low viscosity less than < 10,000 mPa s, more preferably in the range of 6,000-7,000 mPa s or less.

[0008] In spite of advancements in the art of manufacturing hardener

formulations for use in coating compositions and coating end uses, there is still a need in the industry for a hardener formulation wherein the hardener formulation exhibits a combination of desired beneficial properties including, but not limited to, (1) a low VOC content (e.g., about 0-5 g/L; according to the boiling point [b.p.] definition, a substance with a b.p. of less than [<] 250 °C is considered to be a VOC); (2) a low free amine content (e.g., < 20 weight percent [wt %]); (3) a low viscosity (e.g., < 1,500 mPa s at 25 °C); and (4) improved chemical resistance. Furthermore, hardener compositions with such attributes that can be used in preparing a curable epoxy resin formulation or composition.

SUMMARY OF THE INVENTION

[0009] Disclosed herein are low VOC, cold curing hardener compositions and methods for preparing these hardener compositions. Further, a curable composition using these cold curing hardener composition, and method for preparing and curing these compositions on an article.

[0010] In one aspect, a low VOC, cold curing hardener compositions comprise four components: an adduct of a first amine compound and a polyfunctional epoxy compound (component A), an adduct of a second amine compound and a

monofunctional epoxy compound (component B), a third amine adduct based on a polyalkylene oxide; on a cycloaliphatic, aliphatic or araliphatic amine (component C), and a modifier are presented wherein the composition has low viscosity and a monomeric amine content is less than 20 wt%.

[001 1] In another aspect, disclosed herein are curable compositions comprising at least one epoxy compound and at least one cold curing hardener wherein the curable composition has a low VOC content.

[0012] In a further aspect, methods for preparing the cold curing hardener compositions comprise admixing the four components, component A, component B, and component C, and a modifier. Other additives known to the skilled artisan may also be added.

[0013] In still another aspect, methods for preparing a curable composition comprising at least one cold curing hardener and at least one epoxy compound are presented.

[0014] In yet another aspect, disclosed herein are cured products prepared by curing the low viscosity, low VOC, curable composition.

[0015] Other features and iterations of the invention are described in more detail below.

BRIEF DESCRIPTION OF THE FIGURES

[0016] The following figures illustrate non-limiting embodiments of the present invention wherein:

[0017] Figure 1 is a graphical illustration showing the chemical resistance testing of a cured system comprising a combination of a hardener (Formulation #1 1) of the present invention and D. E. R.TM 3531 as the epoxy resin.

[0018] Figure 2 is a graphical illustration showing the chemical resistance testing of a cured system comprising a combination of another hardener (Formulation #12) of the present invention and D.E. R. 3531 as the epoxy resin.

[0019] Figure 3 is a graphical illustration showing the chemical resistance testing of a cured system comprising a combination of a hardener (Formulation #1) not of the present invention and D. E. R. 3531 as the epoxy resin.

[0020] Figure 4 is a graphical illustration showing the results of flexibility testing (E-modulus {E(b) [GPa]}) of one of the Examples (Formulation #1 1) of the present invention: Formulation 1 1.

DETAILED DESCRIPTION OF THE INVENTION

[0021] As previously mentioned, disclosed herein are cold curing hardener compositions comprise four components; component A, component B, component C, and a modifier. Component A comprises an adduct comprising at least one of a first amine and at least one polyfunctional epoxy compound having a monomeric amine content less than 20 wt%. Component B comprises an adduct comprising at least one of a second amine and a monofunctional epoxy compound having a monomeric amine content less than 20 wt%. Component C comprises an adduct of third amine based on a polyalkylene oxide. The cold curing hardener composition and at least one epoxy resin compound provide a curable composition. After the curable compositions are applied and cured, the resulting coatings or thermosets have many beneficial aspects such as low volatile organic compound (VOC), enhanced flexibility, a shiny, undistorted, smooth appearance, improved chemical resistance, and an E modulus below 2.5 MPa.

(I) Cold Curing Hardener Compositions

[0022] In one aspect, the cold curing hardener composition comprises four components. In general, the cold curing composition has a monomeric amine content less than 20 wt%.

(a), component A: first amine adduct

[0023] In one aspect, component A in the cold curing hardener composition comprises (a) at least one of a first amine compound; and (b) at least one polyfunctional epoxy compound, wherein the adduct has a monomeric amine content of less than about 20 weight %.

(i). first amine compound

[0024] The first amine compound used in component A may include for example, m-xylylenediamine (MXDA), isophoronediamine (IPDA), diethylenetriamine (DETA), triethylenetetramine (TETA) trimethylpentamethylenediamine (TMD), and mixtures thereof. In a preferred embodiment, the first amine compound may be MXDA. MXDA may be sensitive to blushing, and may yield good chemical resistant coatings.

[0025] In general, the concentration of the first amine compound may range generally from 10 wt % to about 90 wt %. In various embodiments, the concentration of the first amine compound may range from 10 wt% to about 90 wt%, from 20 wt % to about 80 wt %, from 25 wt % to about 75 wt %, or from 30 wt% to about 70 wt %. If a concentration is less than about 10 wt % of the amine compound, then the viscosity of the hardener formulation may be too high. If a concentration is greater than about 90 wt % of the amine compound, then the blushing may increase due to reaction of the monomeric amine with CCVwater from the air during the hardening reaction.

(II) polyfunctional epoxy compound

[0026] The polyfunctional epoxy compound in component A may include, for example, adducts of liquid epoxy resins (LER). The LERs may include for example bisphenol A diglycidyl ether (BADG E); bisphenol F diglycidyl ether (BFDGE); low (e.g., < 500-800 g/mole) molecular weight (MW) novolacs; and mixtures thereof. In one preferred embodiment, the adduct hardener composition may include BADG E such as D.E. R. 331 and D. E. R. 330, epoxy resins commercially available from The Dow

Chemical Company. In another preferred embodiment the adduct hardener

composition may be based on D.E. R. 331 because this polyfunctional epoxy compound exhibits a higher viscosity and a higher EEW (e.g., in comparison to D.E. R. 330), but produces a slightly lower viscous adduct (e.g., at a fixed rate epoxy/amine) due to less epoxy groups by weight.

[0027] In general, the concentration of the polyfunctional epoxy compound may range generally from 10 wt % to about 90 wt %. In various embodiments, the concentration of the polyfunctional epoxy compound used in component A may range from 10 wt% to 90 wt%, from 20 wt% to 80 wt%, from 25 wt% to 75 wt%, or from 30 wt% to 70 wt%. If a concentration of less than about 10 wt % of the polyfunctional epoxy compound is used, this leads to a greater amount of amine used, which in turn increases the blushing of the resultant coating; and if a concentration of greater than about 90 wt % of the polyfunctional epoxy compound is used, the resultant composition will exhibit a high viscosity (e.g., 50,000 mPa s at 25 °C).

(b). component B: second amine adduct

[0028] Component B in the cold curing hardener composition comprises a second amine compound and a monofunctional epoxy compound wherein the adduct has a monomeric amine content of less than about 20 weight %. (i) . second amine compound

[0029] The second amine compound used in component B may include any of the same amines described above with reference to the first amine. In addition, all distillable amines known in the art, (e.g., amines which are distillable at moderate conditions such as 200 °C and 5 mbar). In one preferred embodiment, the second amine compound may be methylpentamethylenediamine (MPMD). MPMD produces adducts (e.g., at a given ratio of epoxy to amine) with the lowest viscosity.

[0030] In general, the concentration of the second amine compound may range generally from 10 wt % to about 90 wt %. In various embodiments, the concentration of the first amine compound may range from 10 wt% to about 90 wt%, from 20 wt % to about 80 wt %, from 25 wt % to about 75 wt %, or from 30 wt% to about 70 wt %. based on the total weight of the components in the hardener composition.

(ii) . monofunctional epoxy compound

[0031] The monofunctional epoxy compound may include any glycidyl ether (GE). Non-limiting examples of glycidyl ethers may be o-cresylglycidyl ether (CGE), para-tert- butylphenylglycidylether, a mixture of glycidyl ethers such as a mixture of (i) a 1- dodecanol (C12 alkyi) glycidylether and (ii) a 1-tetradecanol (C14 alkyi) glycidylether (C12/C14 alkyi GE mixture), 1,4 butandiolglycidylether (BDDG E), 1,6- hexandiolglycidylether (HDDGE), a C12 to C14-alky glycidylether, 2-ethylhexyl glycidylether; and mixtures thereof. In a preferred embodiment, the monofunctional epoxy compound can be for example CGE. CGE is monofunctional; and therefore, CGE produces per se lower viscous adducts (e.g., compared to D.E. R. 331 or other epoxy resin compounds). In addition, CGE has an aromatic backbone, (e.g., similar to D.E. R. 331 ); and therefore, the chemical resistance of a coating cured with an adduct containing CGE can be increased.

[0032] In general, the concentration of the monofunctional epoxy compound may range generally from 10 wt % to about 90 wt %. In various embodiments, the

concentration of the first amine compound may range from 10 wt% to about 90 wt%, from 20 wt % to about 80 wt %, from 25 wt % to about 75 wt %, or from 30 wt% to about 70 wt %. based on the total weight of the components in the hardener composition. [0033] In a preferred embodiment, the objective of the reaction mixture is to obtain a 1 : 1 mole:mole adduct between the second amine compound and the monofunctional epoxy compound. Therefore, 2 moles of amine are reacted with 1 mole of the monofunctional epoxy compound. Then, the excess of 0.2 to 1 mole of the second amine is removed by distillation, and the residual monomelic amine content of the composition is below about 2 wt %. If the reaction mixture contains a mole ratio below 1 : 1, then more higher adducts of type (CGE)x-(MPMD)1 , for x > 1 are formed which are undesirable. If the reaction mixture contains a mole ratio above 1 : 1 , then an undesirable increased amount of amine is required to be distilled from the reaction mixture.

(c) . component C: third amine adduct

[0034] The third amine adduct, Component C, may be based on a polyalkylene oxide, a cycloaliphatic, aliphatic, araliphatic amine, or a combination thereof. Non- limiting examples of component C may be a polyoxyalkylene amine such as Jeffamine D-230 and Jeffamine D-400 which are commercially available from Huntsman. These polyoxyalkylene amines assist in improving the flexibility and the surface appearance of the cured product.

[0035] In general, the concentration of Component C, the third amine adduct, used in the cold curing hardener composition may range generally from 1 wt % to about 20 wt %. In various embodiments, the concentration of Component C may range from 1 wt% to about 20 wt%, from 1 wt % to about 15 wt % from 1 wt % to about 10 wt % and from 2 wt % to about 5 wt % based on the total weight of the components in the hardener composition. When Component C is used beyond 20 wt %, the chemical resistance of the coating made using the hardener is lowered. Conversely, if

Component C is used at a concentration of less than 1 wt %, the composition exhibits a high viscosity.

(d) . modifier compound

[0036] In another aspect, the cold curing hardener composition may use a high boiling point modifier (b.p. > 250 °C, no VOC) which is compatible with the epoxy and amine mixture. Non-limiting examples of high boiling modifiers may include styrenated phenol, diisopropylnaphthaline (Dl), and mixtures thereof. In a preferred embodiment, the high boiling modifier compound may be Dl since Dl works well in terms of compatibility with the amines, adducts of amines, the epoxy resin, and the cured system.

[0037] In general, the concentration of the high boiling modifier compound used in the cold curing hardener composition may range from 1 wt % to about 50 wt %. In various embodiments, the concentration of the high boiling point modifier may range from 1 wt% to 50 wt%, from 5 wt % to about 40 wt %, from 10 wt % to about 30 wt %, and from 15 wt % to about 25 wt % based on the total weight of the components in the hardener composition. When the high boiling modifier compound is used beyond 50 wt %, the mechanical properties of the coating produced using the modifier are lowered. Conversely, if the modifier is used at a concentration of less than 1 wt %, the

composition exhibits a high viscosity.

(e) . optional additives

[0038] In another aspect, an optional additive may be added to the cold curing hardener composition. Non-limiting examples of optional additives may be an accelerator such as salicylic acid, 2,4,6-tris(N,N,-dimethylamino)phenol (e.g., DMP-30), or mixtures thereof.

[0039] Generally, the concentration of the optional additives may range from 0 wt % to about 5 wt %. In various embodiments, the concentration of the optional additives may range from 0 wt% to 5 wt%, from 0.1 wt % to about 2.5 wt %, and from 0.1 wt % to about 1 wt %.

(f) . properties of the cold curing hardener composition

[0040] In general, the cold curing hardener composition, before curing may be a liquid. The viscosity of the cold curing hardener composition may range from 100 mPa s to about 1500 m Pa s at 25°C. In various embodiments, the viscosity of the cold curing hardener composition may range from 100 m Pa s to about 1500 mPa s at 25°C, from 200 mPa s to about 1 ,400 m Pa s at 25°C; from 300 mPa s to about 1 ,300 m Pa s at 25° C; and from 400 mPa s to about 1 ,200 mPa s at 25° C.

[0041] The cold curing hardener composition advantageously has no VOC content or a low VOC content (according to the > 250 °C boiling point definition).

Additionally, the content of non-reactive material in the cold curing composition may range from 1 wt % to about 50 wt %. In various embodiments, the content of non- reactive material may range from 1 wt % to about 50 wt %, from about 5 wt % to about 40 wt %; and from about 10 wt % to about 30 wt %.

[0042] The content of the free amine in the cold curing hardener composition may range from 1 wt % to about 20 wt %. In various embodiments, the content of the free amine may range from 1 wt% to 20 wt%, from 5 wt % to about 20 wt %, and from 10 wt % to about 20 wt %.

(II) Curable Compositions

[0043] Another aspect of the disclosure provides curable composition comprising (I) at least one epoxy resin and (II) the cold curing hardener described above. Other optional additives (III) may be added to the curable compositions.

(a), epoxy resin compound (I)

[0044] The curable composition using the cold curing hardener composition includes at least one epoxy resin compound. The epoxy resin compound, component (I), may be any conventional epoxy resin compound. The epoxy resin may be a single epoxy resin compound or a mixture of two or more epoxy compounds used in combination, i.e., component A of the curable epoxy resin coating composition which is cured to form the coating material of the present invention includes at least one epoxy resin. Non-limiting examples of the at least one epoxy resin may include aliphatic epoxy resins, cycloaliphatic epoxy resins, bisphenol A epoxy resins, bisphenol F epoxy resins, phenol novolac epoxy resins, cresol-novolac epoxy resins, biphenyl epoxy resins, polyfunctional epoxy resins, naphthalene epoxy resins, divinylbenzene dioxide, 2- glycidylphenylglycidyl ether, dicyclopentadiene-type epoxy resins, phosphorous containing epoxy resin, multi aromatic resin type epoxy resins, and mixture therefore. Other non-limiting examples of the at least one epoxy resin may include

trim ethyl propane epoxide; cycl oh exanedi methanol diglycidyl ether; diglycidyl-1 ,2- cyclohexane dicarboxylate; diglycidyl ether of bisphenol A; diglycidyl ether of bisphenol F; resorcinol diglycidyl ether; triglycidyl ethers of para aminophenols; halogen (for example, chlorine or bromine)-containing epoxy resins such as diglycidyl ether of tetrabromobisphenol A; epoxidized phenol novolac; epoxidized bisphenol A novolac; an oxazolidone-modified epoxy resin; an epoxy-terminated polyoxazolidone; and mixtures thereof.

[0045] Suitable commercially available epoxy resin compounds may include D.E. R.™ 300 series, the D.E.N.™ 400 series, the D. E. R.™ 500 series, the D.E. R.™ 600 series and the D. E.R.™ 700 series of epoxy resins commercially available from The Dow Chemical Company. Other non-limiting examples of epoxy resins may include liquid epoxy resins (LERs), such as D.E. R. 331 (a bisphenol A diglycidyl ether,

BADGE), D.E. R. 354 (a bisphenol F diglycidyl ether), D. E. R. 324 (a diluent modified epoxy resin), other low viscosity epoxy resin blends, and other well-known epoxy resins and blends or mixtures of the above known epoxy resins. D.E. R. 324, D. E. R. 330, D.E. R. 331 , D. E. R. 332, and D. E. R. 354 are commercially available epoxy resins from The Dow Chemical Company. Other commercially available epoxy resin compounds may include for example BADG E with a MW < 700. As an illustration, the at least one epoxy resin compound useful in the present invention may include a liquid epoxy resin, such as D. E. R. 331 a diglycidylether of bisphenol A (DGEBPA) having an epoxide equivalent weight of from about 170 to about 190 a viscosity of about 10 Pa-s and a density of about 1.2 g/cc.

[0046] An extensive enumeration of epoxy resins useful in the present invention can be found in Lee, H. and Neville, K., "Handbook of Epoxy Resins," McGraw-Hill Book Company, New York, 1967, Chapter 2, pages 257-307; incorporated herein by reference. The preparation of epoxy compounds useful in the present invention is described for example in Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd Ed., Vol. 9, pp 267-289, incorporated herein by reference. Other suitable epoxy resins useful as component (I) are disclosed in, for example, U.S. Patent Nos. 3,018,262; 7, 163, 973; 6,887,574; 6,632,893; 6,242,083; 7,037,958; 6,572,971;

6, 153,719; 5, 137,990; 6,451 ,898, 5,405,688, 7,655, 174, 7,871 ,556, 7,923,073, and 8,048,819, all of which are incorporated herein by reference.

(b) . cold curing hardener composition (II)

[0047] The cold curing hardener compound, component (II), (also referred to as a curing agent or crosslinking agent) can be selected from one or more of the cold curing hardener compositions described above.

[0048] In general, an equivalent ratio of the epoxy resin compound (I) to the hardener composition (II) is sufficient to form a coating or a thermoset. The equivalent ratio of the epoxy resin (I) to the hardener composition (II) such that the epoxy/hardener is in a ratio of 1 epoxy -equivalent to 1 amine-equivalent. In various embodiments, the epoxy-equivalent to amine-equivalent ratio may be generally from about 1: 1 to about 1 :0.9, or from about 1 : 1 to about 1 : 1.1. The use of any concentration outside the above ranges may weaken the network formed.

(c) . optional additives (III)

[0049] Other optional additives may be added to the coating composition. Non- limiting examples of the other optional compounds or additives may include dispersant additives; deformer additives; flowing additives; catalysts; solvents; fillers; pigments; toughening agents; flexibilizing agents, processing aides; flow modifiers; adhesion promoters; diluents; stabilizers; plasticizers; catalyst de-activators; flame retardants; aromatic hydrocarbon resins, coal tar pitch; petroleum pitch; carbon nanotubes;

graphene; carbon black; carbon fibers, or mixtures thereof.

[0050] Generally, the amount of the optional compounds or additives may be from 0 wt % to about 5 wt %. In various embodiments, the amount of the optional compounds or additives may be from 0 wt % to about 5 wt %, from 0.1 wt % to about 2.5 wt %, and from 0.1 wt % to about 1 wt %. (d). properties of the curable composition

[0051] The curable composition exhibits a low viscosity sufficient to allow the curable composition to be easily processed and handled in conventional formulation equipment. Generally, the curable composition prepared by the above process advantageously exhibits a low viscosity of less than or equal to about 5,000 mPa s at 25°C. In various embodiments, the viscosity of curable composition may be from 500 mPa s to about 5,000 mPa s, from 1,000 mPa s to about 4,000 mPa s in, and from 2,000 mPa s to about 2,500 mPa s at 25°C. The curable composition with a viscosity of greater than about 5,000 mPa s leads to bad de-aeration which in turn leads to the formation of bubbles in the composition.

[0052] Other beneficial properties which the curable composition include a curable composition capable of being cold cured at a temperature of less than room temperature, i.e., from about 10°C to 25°C to form a thermoset; and a curable composition capable of being cured at efficient curing speeds (for example a curable composition that cures within hours at room temperature and at 13°C).

[0053] Generally, the curing temperature of the curable composition may range from 0°C to about 50°C. In various embodiments, curing temperature of may range from 0°C to about 50°C, from 5°C to about 40°C, and from 10°C to about 30°C. If the temperature of cure is below about 0 °C, the curing speed may be too low; and if the temperature of cure is above 50 °C, the curing speed may be too fast for reaction control.

[0054] One embodiment includes curing the curable composition discussed above to form a cured product such as a coating or a thermoset. For example, the curing of the curable composition may be carried out at a predetermined temperature and for a predetermined period of time sufficient to cure the composition to form a cured coating material.

(Ill) Processes for Producing Cold Curing Hardener Composition

[0055] In general, the processes for preparing the above described cold curing hardener composition generally includes the steps of preparation of each component; preparation of component A then removing the excess monomeric amine by distillation, preparation of component B then removing the excess monomeric amine by distillation, and component C. These components, A, B, and C, are admixed (mixed) together with the modifier and optional additives.

[0056] Component A is prepared by admixing the first amine compound (a)(i) and polyfunctional epoxy compound (a)(ii) at a temperature from 70°C to about 90°C. The excess monomeric amine is removed from the reaction mixture by vacuum distillation (for example at 200 °C and 5 mbar).

[0057] Component B is prepared by admixing the second amine compound (b)(i) and the monofunctional epoxy compound (b)(ii). The excess monomeric amine is removed from the reaction mixture by vacuum distillation (for example at 200 °C and 5 mbar).

[0058] The curable composition comprising the components, A, B, and C, may be mixed with the modifier and any other desired optional additive at a temperature of from about 20° C to about 100°C.

[0059] For example, the preparation of the curable composition of the present invention may be achieved by blending, in known mixing equipment, the first amine adduct, component A, the second amine adduct, component B, and the third amine adduct, component C, and the modifier. These components may be admixed in a sequential order, in a random order, or sequentially. Any of the above-mentioned optional additives may be added to the composition during the mixing or prior to the mixing to form the curable composition.

[0060] All the compounds used in preparing the curable composition are typically mixed and dispersed at a temperature enabling an effective curable composition having the desired balance of properties for a particular application. For example, the temperature during the mixing of all components may be generally from about 20°C to about 100°C. In various embodiments, the temperature during the mixing may range from 20°C to about 100°C, from 30°C to about 90°C, from 40°C to about 80°C, or from 50°C to about 70° C. [0061] The preparation of cold curing hardener composition and/or any of the steps thereof may be a batch or a continuous process. The mixing equipment used in the process may be any vessel and ancillary equipment well known to those skilled in the art.

(IV) Process for Preparing a Curable Composition

[0062] Generally, the curable composition is produced by first admixing, blending or mixing: (I) the epoxy resin described above, and (II) at least one of the cold curing hardener compounds described above; and then heating the mixture at a temperature sufficient to mix the components and produce a curable coating composition, which can subsequently be cured by heating. Optionally, the curable composition may include any one or more of the optional additives (III) as desired and as described above.

[0063] For example, the preparation of the composition may be achieved by blending, in known mixing equipment, (I) at least one epoxy resin; and (II) at least one of the cold curing hardener compounds described above; and optionally (III) any other desirable additives. Any of the above-mentioned optional additives may be added to the composition during the mixing or prior to the mixing to form the curable composition.

[0064] All the compounds of the composition are typically mixed and dispersed at a temperature enabling the preparation of an effective curable composition having the desired balance of properties for a particular application. For example, the temperature during the mixing of all components may be generally from about 0 °C to about 50 °C in one embodiment, and from about 0 °C to about 30 °C in another embodiment.

[0065] The preparation of curable composition and/or any of the steps thereof, may be a batch or a continuous process. The mixing equipment used in the process may be any vessel and ancillary equipment well known to those skilled in the art.

(V) Process for Curing the Curable Composition

[0066] Another aspect of the present disclosure provides processes for preparing a cured composition. The processes comprise providing a curable composition, which is detailed above, and exposing the curable composition to heat to form the cured coating. Generally, the curable is applied to at least a portion of a surface of an article to be coated, prior to subjecting it to heat for curing.

(a) curable composition

[0067] Suitable curable compositions are described above.

(b) articles

[0068] In a further aspect of the present disclosure encompasses an article comprising a cured or uncured curable composition adhering to at least one portion of the substrate. The article, in broad terms, may be defined as a material wherein the curable composition is initially applied and adheres to at least a portion of at least one surface of the substrate. The curable epoxy resin composition may be cured at a exposing the composition to heat to form a therm oset or cured composition such that the coating bonds to the substrate. The article may be any material that can withstand the curing temperature to form a cured coating.

[0069] In various embodiments, the article may be a metal. The article, as defined herein, may be a single metal or an alloy of various metals. Non-limiting examples of these metals include cast iron, aluminum, tin, brass, steel, copper, zinc aluminum alloy, nickel, or combinations thereof.

[0070] In other embodiments, the substrate may be a cellulose product. Non- limiting examples of cellulose products may be paper, paperboard, paper cardstock, cardboard, and wood.

[0071] In still another embodiment, the substrate may be a plastic. Non-limiting examples of plastics may be bakelite, polyester, polyethylene terephthalate, polyethylene, high density polyethylene, polyvinyl chloride, polyvinylidene chloride, polypropylene, polystyrene, polyamides (Nylon), acrylonitrile butadiene styrene, polycarbonates, polyurethanes, and combinations thereof.

[0072] In a further embodiment, the article may be a stone. Non-limiting examples of stones may be granite, brick, limestone, concrete, and combinations thereof. [0073] In yet another embodiment, the article may be flooring. Non-limiting examples of flooring may be cement, acrylic flooring, vinyl flooring, laminate flooring, wood flooring, ceramic tile, and linoleum.

[0074] In various embodiments, the article may be in various configurations. Non-limiting configuration examples of the article may be a roll, a coil, a plate, a sheet, a tube, a brick, a slab, a boulder, or a pipe. The configuration of the article may be of various dimensions, shapes, thicknesses, and weights.

(c) applying the curable composition

[0075] The process further comprises applying the curable composition to a portion of at least one surface of an article. Suitable articles are detailed above.

Application of the curable coating composition may be applied through various means. For example, the coating composition may be applied using a drawdown bar, a roller, a knife, a paint brush, a sprayer, dipping, or other methods known to the skilled artisan. As detailed above, the curable coating composition may be applied to one or more surfaces of the article to be coated.

(d) curing the curable composition

[0076] The process further comprises curing the curable epoxy resin composition to a portion of at least one surface of an article. The curable composition, as detailed herein, may be cured by exposing the composition to heat to form a cured composition or therm oset.

[0077] In general, the process for producing the cured coating material includes carrying out the curing reaction at process conditions to enable the preparation of an effective cured material having the desired balance of properties for a particular application, particularly for forming the coating product. The temperature for curing the curable composition may range from -10°C to about 50°C. In various embodiments, the temperature for curing may range from -10°C to about 50°C, from -5°C to about 50°C, from 0°C to about 45°C, and from 5°C to about 40°C. [0078] Generally, the curing time can and will vary. In various embodiments, the curing time to may range from 0.1 hour to about 7 days, from 0.5 hours to about 1 day, and from 1 hour to about 6 hours.

[0079] The preparation of the cured coating material and/or any of the steps thereof, may be a batch or a continuous process. The equipment employed to carry out the reaction includes equipment known to those skilled in the art.

(VI) Properties of the Cured Products

[0080] In another aspect encompasses end use applications of the cured product. Non-limiting examples of end use products of the cured composition may include coatings, lacquer paints, potting, encapsulation applications, flooring, thermosets, and primers.

[0081] Still another aspect encompasses the properties of the cured products or thermoset. A cured thermoset product prepared by curing the above curable

composition containing the hardener composition exhibits unexpected and unique properties. For example, the cured thermoset product such as a coating exhibits enhanced flexibility; a shiny, undistorted, smooth surface when cured at room

temperature, and a "fair slightly matted, slightly distorted, not smooth" at 13°C upon visual inspection; and a cured thermoset produced from a curable composition containing the hardener composition exhibits at least "medium" chemical resistance (3 days in the cotton pad test); and E modulus below 2.5 MPa.

[0082] The cured coating (i.e. the cross-linked coating product made from the curable composition) shows several improved and beneficial performance properties over conventional cured coating products made from conventional curable compositions containing conventional curing agents. Generally, the cured composition may exhibit increased flexibility. Generally, the cured coating may exhibit a flexibility property generally between 1 and 2.5. In various embodiments, flexibility property may be range from 1 to about 2.5, from 1.2 to about 2.2, and from 1.5 to about 2. The flexibility properties of the cured coating material can be determined using a 3-point bending test according ATSM D 790. [0083] The cured coating may also advantageously exhibit good surface appearance. In general, the cured coating may exhibit a surface appearance property generally from fair to good, from good to medium, and from medium to about fair. The surface properties of the cured coating material can be determined by visual inspection.

[0084] The cured coating may also advantageously exhibit at least "medium" (3 days cotton pad testing, "good" is 7 days) chemical resistance. In general, the cured coating of the present invention exhibits a chemical resistance property from "medium to good". The chem ical resistance properties of the cured coating material can be measured using a cotton pad testing method.

[0085] The cured product may also exhibit improved chem ical resistance compared to other cured products not util izing the cold curing hardener composition. After homogenization of both components (the inventive or comparative hardener with D. E. R. 3531 epoxy resin) for 2 minutes, the liquid mixture was poured into molds, so that the film thickness was 3 mm and was cured for 7 days at room temperature.

[0086] These films were tested by exposing them to different solutions for 7 days

(168 hours) by placing a cotton pad that is saturated with the solution on the sample and covering the pad and sample. After 1 day (24 hours) of exposure, 2 days (48 hours) of exposure, and 7 days of exposure the Shore D hardness of the samples was measured. The Shore D hardness measurements are shown in Figures 1 and 2.

The percent change in Shore D hardness, as shown as percent %A, was determined with the initial hardness and the final hardness after 168 hours of exposure to the solutions. The percent change in Shore D hardness was calculated as (1 - (final hardness/initial hardness))*100, where a negative percent change in hardness indicated a greater value for initial hardness than final hardness.

DEFINITIONS

[0087] When introducing elements of the embodiments described herein, the articles "a", "an", "the" and "said" are intended to mean that there are one or more of the elements. The terms "comprising", "including" and "having" are intended to be inclusive and mean that there may be additional elements other than the listed elements.

[0088] The terms "elongation" or "tensile elongation," as used herein, refer to a mechanical property of a polymer to deform or change shape when under tensile stress. When a polymer sample deforms by stretching, it becomes longer. Elongation is typically expressed as percent (%) elongation, which is the length of the polymer sample after it is stretched (L), divided by the original length of the sample (Lo), and then multiplied by 100. Elongation at yield refers to the point at which an increase in stress does not result in an increase in length. "Elongation at break" corresponds to the point of rupture.

[0089] The "glass transition temperature" is the temperature at which a polymer transitions from a hard, glassy material to a soft, rubbery material.

[0090] The "cold crystallization temperature" is the temperature at a polymer crystallizes.

[0091] The terms "tensile modulus" or "Young's modulus" refer to the stiffness of a material, and are used to describe the elastic properties of the material. Tensile modulus is defined as the ratio of stress (force per unit area) along an axis to strain (ratio of deformation over initial length) along that axis.

[0092] The term "tensile strength at break" refers to the tensile stress at the moment at which a test sample breaks. Tensile strength is the force placed on the test sample divided by the cross-sectional area of the sample.

[0093] The term "low volatile organic compounds (VOC) content" refers to a composition with 0-5 g/L of VOC in the hardener composition.

[0094] The term "low free amine content" refers to a composition with less than 20 wt % of free amine in the hardener composition.

[0095] The term "low viscosity" refers to a composition with less than 1,500 mPa s at 25°C for the viscosity of the hardener composition. [0096] The term "cold curing" refers to a temperature of curing in the range of about 0°C to about 50°C.

[0097] The term "good surface appearance" refers to a composite with a shiny, glossy, undistorted, light yellowish, no whitening or blushing/blooming surface of a composite.

[0098] The term "fair surface appearance" refers to a composite with a slightly distorted with a bit of blushing, silk-mate surface of a composite.

[0099] The term "medium chemical resistance" refers to a cured material

(thermoset) or composite where a cured material can withstand at least for 3 days in a cotton pad chemical testing procedure without deterioration.

[0100] The term "flexibility" refers to a composite with an E-Modulus of < about 2.5 GPa of a composite.

[0101] The term "alkyl" as used herein describes saturated hydrocarbyl groups that contain from 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and most preferably 1 -10 carbon atoms. They may be linear, branched, or cyclic, may be substituted as defined below, and include methyl, ethyl, propyl, isopropyl, butyl, hexyl, heptyl, octyl, nonyl, and the like.

[0102] The term "alkenyl" as used herein describes hydrocarbyl groups which contain at least one carbon-carbon double bond and contain from 1 to 30 carbon atoms. They may be linear, branched, or cyclic, may be substituted as defined below, and include ethenyl, propenyl, isopropenyl, butenyl, isobutenyl, hexenyl, and the like.

[0103] The term "alkoxide" or "alkoxy" as used herein is the conjugate base of an alcohol. The alcohol may be straight chain, branched, cyclic, and includes aryloxy compounds.

[0104] The term "alkynyl" as used herein describes hydrocarbyl groups which contain at least one carbon-carbon triple bond and contain from 1 to 30 carbon atoms. They may be linear or branched, may be substituted as defined below, and include ethynyl, propynyl, butynyl, isobutynyl, hexynyl, and the like.

[0105] The term "aromatic" as used herein alone or as part of another group denotes optionally substituted homo- or heterocyclic conjugated planar ring or ring system comprising delocalized electrons. These aromatic groups are preferably monocyclic (e.g., furan or benzene), bicyclic, or tricyclic groups containing from 5 to 14 atoms in the ring portion. The term "aromatic" encompasses "aryl" groups defined below.

[0106] The term "aryl" as used herein alone or as part of another group denote optionally substituted homocyclic aromatic groups, preferably monocyclic or bicyclic groups containing from 6 to 10 carbons in the ring portion, such as phenyl, biphenyl, naphthyl, substituted phenyl, substituted biphenyl, or substituted naphthyl wherein "substituted" substituents include moieties in which a carbon chain atom or carbon atoms is (are) substituted with a heteroatom such as nitrogen, oxygen, silicon, phosphorous, boron, or a halogen atom, and moieties in which the carbon chain comprises additional substituents. These substituents include alkyl, alkoxy, acyl, acyloxy, alkenyl, alkenoxy, aryl, aryloxy, amino, amido, acetal, carbamyl, carbocyclo, cyano, ester, ether, halogen, heterocycio, hydroxyl, keto, ketal, phospho, nitro, and thio.

[0107] The terms "hydrocarbon" and "hydrocarbyl" as used herein describe organic compounds or radicals consisting exclusively of the elements carbon and hydrogen. These moieties include alkyl, alkenyl, alkynyl, and aryl moieties. These moieties also include alkyl, alkenyl, alkynyl, and aryl moieties substituted with other aliphatic or cyclic hydrocarbon groups, such as alkaryl, alkenaryl and alkynaryl. They may be straight, branched, or cyclic. Unless otherwise indicated, these moieties preferably comprise 1 to 20 carbon atoms.

[0108] The "substituted hydrocarbyl" moieties described herein are hydrocarbyl moieties which are substituted with at least one atom other than carbon or hydrogen, including moieties in which a carbon chain atom is substituted with a heteroatom such as nitrogen, oxygen, silicon, phosphorous, boron, or a halogen atom, and moieties in which the carbon chain comprises additional substituents. These substituents include alkyl, alkoxy, acyl, acyloxy, alkenyl, alkenoxy, aryl, aryloxy, amino, amido, acetal, carbamyl, carbocyclo, cyano, ester, ether, halogen, heterocycio, hydroxyl, keto, ketal, phospho, nitro, and thio. [0109] Having described the invention in detail, it will be apparent that modifications and variations are possible without departing from the scope of the invention defined in the appended claims.

EXAMPLES

[01 10] The following examples and comparative examples further illustrate the present invention in detail but are not to be construed to limit the scope thereof.

[01 1 1] In the following examples, various materials, terms and designations are used such as for example the raw materials listed in Table I as follows:

Table 1 : Raw Materials

Example 1: Preparation of (BADGE/MXDA Adduct)

[01 12] In this Example 1 , a MXDA adduct is prepared which can be generally described as 4,4'-isopropylidenediphenol, oligom eric reaction products with 1-chloro- 2,3-epoxypropane, reaction products with m-phenylenebis(methylamine) in accordance with the following general procedures:

Part A: Small Scale

[01 13] On a small laboratory scale, 1 gram (g) of a mixture of MXDA with bisphenol A diglycidylether (D. E.R. 331) (4 moles: 1 mole) was prepared at room temperature (about 25°C). Then, a droplet of the mixture was transferred into a differential scanning calorimeter (DSC) crucible and heated to 80°C. The heat flux of the heated mixture was measured. After 25 minutes (min) the reaction was considered to be finished.

Part B: Larger Scale [01 14] On a larger laboratory scale, 600 g of the amine (MXDA) was placed in a flask with a heating jacket; the amine was stirred; and while being stirred the amine was heated to a temperature of 80°C. The epoxy compound 400 g (D. E. R. 331) was then added to the flask from above. The epoxy compound was added to the flask at a rate of addition sufficient to maintain the temperature at about 80-90°C. If necessary, the flask was cooled by removing the heating jacket. After addition of the epoxy compound, a post-reaction was performed for at least 25 min at the reaction temperature of 80°C.

Example 2: Preparation of CEG- MPMD Adduct

Part A: Small Scale

[01 15] 1 g of a mixture of MPMD with o-cresol glycidylether (D. E. R. 723) (2 moles: 1 mole) was prepared at room temperature and a droplet transferred into a DSC crucible, heated to 80°C and the heat flux was measured. After 25 min the reaction was considered to be finished.

Part B: Larger Scale

[01 16] On a larger scale, the amine was placed in a flask with heating jacket and stirrer and was heated. The epoxy compound was then added from above at a rate of addition to maintain the temperature. If necessary, the flask was cooled by removing the heating jacket. After addition, the post reaction was performed for at least 25 min at the reaction temperature. After reaction, the molar excess of MPMD was removed by a vacuum distillation.

Example 3: Preparation of Cured Samples

[01 17] The hardeners were mixed with a D.E. R. 3531, a diluted epoxy resin which is a blend of bisphenol A epoxy resin, bisphenol F epoxy resin with a mixture of dodecanol and tetradecanol mono glycidyl ether as a reactive diluent at 1 epoxy equivalent to 1 amine equivalent at room temperature to yield a curable composition. The above hardener/epoxy resin curable composition was then cured at a curing temperature of 13°C and 23° C.

[01 18] In the Examples, standard analytical equipment and methods are used to measure properties including for example, the following: Flexibility (E-Modulus)

[01 19] Flexibility was determined using a 3-point bending test according to the procedure described in ATSM D 790.

Early Water Spot Testing

[0120] The water drop test was performed as follows: a water drop is placed on the not fully cured surface of a thermoset substrate, and the water evaporates leaving white carbamates on the surface of the thermoset. If the water does not evaporate leaving white carbamates on the surface of the non-fully cured thermoset, the hardener is insensitive to the water drop, which is desired.

Chemical Resistance Comparison

[0121] After homogenizing a hardener of the present invention with D.E. R. 3531 epoxy resin or a comparative hardener with D.E. R. 3531 epoxy resin for 2 min, the liquid mixture was poured into molds to form a film, so that a film thickness, when the liquid mixture is cured, is about 3 millimeters (mm); and then the liquid mixture was cured for 7 days (168 hours [hr]) at room temperature.

[0122] The films were tested by exposing the films to different test liquid solutions for 7 days (168 hr) by placing a cotton pad that is saturated with the solution on the sample and covering the pad and sample with a plastic lid. After 1 day (24 hr) of exposure, 2 days (48 hr) of exposure, and 7 days (168 hr) of exposure, the Shore D hardness of each of the samples was measured according to the procedure described in ASTM D2240. The Shore D hardness measurements are shown in Figures 1 and 2, and the percent change in Shore D hardness, as shown as percent delta (% A), was determined by measuring the initial hardness and the final hardness after 168 hr of exposure to the solutions. The percent change in Shore D hardness was calculated using the following equation: (1 - [final hardness/initial hardness])*100; where a negative percent change in hardness indicated a greater value for initial hardness than a value for final hardness.

[0123] The test liquids used in the chemical resistance comparisons were acetic acid, sulfuric acid, sodium hydroxide, gasoline, Bau- und Prufgrundsatze Gruppe 5b (B. P.G. 5b), xylene, and methylisobutyl ketone (MIBK). The specific compounds used for testing included the follows:

[0124] The acetic acid, sulfuric acid, and sodium hydroxide, were of analytical grade and are commercially available from Merck KGaA.

[0125] Bau- und Prufgrundsatze Gruppe 5b of the DIBT (Policy for Construction and Testing Group 5b of the German Institute for Construction Technique) (hereinafter designated as "B.P.G. 5b") is a mixture of 48 volume percent methanol, 48 volume percent isopropanol, and 4 volume percent water. The methanol and isopropanol used were of analytical grade and commercially available from Merck KGaA.

[0126] The gasoline used for testing is commercially available from Esso (Exxon).

[0127] The xylene, ethanol, and methylisobutyl ketone (MIBK) used for testing were of analytical grade and are commercially available from Merck KGaA.

Examples 5-12 and Comparative Examples 1-4

[0128] Hardeners were produced by (physical) mixing/blending, at 23°C. The ingredients in the formulations used in Examples 5-12 (Formulation #5-#12) of the present invention and in Comparative Examples 1-4 (Formulations #1-#4) are described in Table II.

Table 2:

bubbles distorted

Formulation #

INGREDIENTS #7 #8 #9 #10 #11 #12

BADGE- MXDA Add uct (Example 1) 35 35 35 35 33 35

CEG-MPMD Adduct

35 35 35 35 33 35 (Example 2)

Styrenated Phenol

30

(Novares LS-500)

Diisopropylnaphthalene (Ruetasolv

20 27 27 18 22 18

Dl)

D.E. H. 36 30

Jeffamine D-400 10 9 10 9

Isophoronediamine (IPD) 5

Trimethylhexamethylenediamine 3 2 3 (TMD)

1 ,3-Bis(aminomethyl)cyclohexane

3 3

(1 ,3-BAC)

PROPERTIES

Mixing Ratio (with D.E. R. 3531) 100/55 100/55 100/55 100/51 100/55 100/51

Mass D.E. R. 3531 (g) 23 23 23 23 23 23

Mass hardener (g) 12 12 12 12 12 12

Dynamic viscosity at 25°C

1620 1360 1460 1610 1022 1370

(mPa s)

Shore D hardness of thermoset at 23°C after:

16 hours 62 64 62 71 64 68

18 hours 66 65 66 74 66 71

24 hours 71 70 70 75 70 73

48 hours 73 74 72 78 76 77

7 days 78 76 75 80 77 80

Shore D hardness of thermoset at 13°C after:

16 hours 15 19 24 21 15 19

18 hours 24 32 38 42 15 25

24 hours 51 59 56 60 49 52

48 hours 65 67 71 71 66 69

7 days 74 72 72 71 73 73

Early water spotting resistance of thermoset

16 hours at 23°C + + + + + +

16 hours at 13°C + + + + + +

Surface Appearance of thermoset

Surface Appearance at 23°C by Very little Slightly Slightly Clear,

visual observation Glossy hazy, hazy, hazy, small

bubbles bubble bubble bubbles

Surface Appearance at 13°C by

visual observation

[0129] Table II describes the compositions of the present invention (compositions #4 to #12) and the comparative compositions (compositions #0 to #3). As shown in Table II, composition #11 is the most efficient composition.

Claims

CLAIMS What is claimed is:

1. A cold curing hardener composition comprising component A, component B, and component C; wherein a. component A comprises:

i. at least one adduct of a first amine compound;

ii. at least one polyfunctions epoxy; and

iii. a modifier;

wherein component A has a volatile organic compound from 0 g/l to about 5 g/L, a free amine content of from about 1 to about less than about 20 wt% (weight percent) and a viscosity of from about 150 mPa s to about less than about 1 ,500 mPa s;

b. component B, comprising:

i. at least one adduct of a second amine compound;

ii. at least one monofunctional epoxy; and

iii. a modifier;

wherein component B has a volatile organic compound content of less than about 5 g/L; a free amine content of less than about 20 wt%; and a viscosity of less than about 1 ,500 m Pa s at 25 °C; and

c. component C, comprising at least one third amine adduct based on a

polyalkylene oxide; on a cycloaliphatic, aliphatic or araliphatic amine; or a combination thereof;

wherein component C has a volatile organic compound content of less than about 5 g/L; a free amine content of less than about 20 wt%; and a viscosity of less than about 1 ,500 m Pa s at 25 °C.

2. The hardener composition of claim 1, wherein the at least one adduct of a first amine compound is m-xylylenediamine.

3. The hardener composition of either of claims 1 or 2, wherein the concentration of the at least one adduct of a first amine compound is from about 20 wt% to about 50 wt%.

4. The hardener composition of any of the claims 1-3, wherein the at least one

polyfunctional epoxy is at least one difunctional epoxy resin.

5. The hardener composition of any of the claims 1-4, wherein the at least one

difunctional epoxy resin is bisphenol A diglycidyl ether.

6. The hardener composition of any of the claims 1-5, including further a modifier.

7. The hardener composition of any of the claims 1-6, wherein the concentration of the modifier is from about 5 wt% to about 50 wt%.

8. The hardener composition of any of the claims 1-7, wherein the at least one

adduct of a second amine compound is methylpentamethylenediamine.

9. The hardener composition of any of the claims 1-8, wherein the concentration of the at least one adduct of a second amine compound is from about 20 weight percent to about 50 weight percent.

10. The hardener composition of any of the claims 1-9, wherein the at least one

monofunctional epoxy is cresylglycidylether.

1 1 The hardener composition of any of the claims 1-10, further including a modifier.

12. The hardener composition of any of the claims 1-11 , wherein the concentration of the high boiling modifier is from about 5 wt% to about 50 wt%.

13. The hardener composition of any of the claims claim 1-12, wherein the at least one third amine adduct is an amine selected from group consisting of

polyoxyalkyleneamines, trimethylpentamethylenediamines, and mixtures thereof.

14. The hardener composition of any of the claims 1-13, wherein the concentration of the at least one third amine adduct is from about 0.1 wt% to about 10 wt%.

15. A process for preparing a cold curing hardener composition comprising admixing: a. component A;

b. component B; and

c. component C.

16. A process for preparing component A of a cold curing hardener composition

comprising admixing:

a. at least one adduct of a first amine compound; and

b. at least one polyfunctions epoxy;

wherein the hardener composition has a volatile organic compound content of less than about 5 g/L; a free amine content of less than about 20 wt%; and a viscosity of less than about 1 ,500 mPa s at 25 °C.

17. A process for preparing component B of a cold curing hardener composition

comprising admixing:

i. at least one adduct of a second amine compound; and

ii. at least one monofunctional epoxy;

18. A process for preparing component C of a cold curing hardener composition

comprising admixing at least one third amine adduct based on a polyalkylene oxide or a cycloaliphatic or aliphatic or araliphatic amine, or a combination thereof with one or more additives wherein the hardener composition has a volatile organic compound content of less than about 5 g/L; a free amine content of less than about 20 wt%; and a viscosity of less than about 1 ,500 m Pa s at 25 °C.

19. A curable coating composition comprising:

A. at least one epoxy resin; and B. at least one cold curing hardener composition of claim 1 , 8, and 14;

wherein the hardener composition has a volatile organic compound content of less than about 5 g/L; a free amine content of less than about 20 wt%; and a viscosity of less than about 1,500 mPa s at 25° C.

20. The curable coating composition of claim 19, wherein the at least one epoxy resin is a blend of bisphenol A epoxy resin, bisphenol F epoxy resin with a mixture of dodecanol and tetradecanol mono glycidyl ether as a reactive diluent.

21. The curable coating composition of either of the claims 19 or 20, wherein the concentration of the at least one epoxy resin is from about 1 amine equivalent to 1 epoxy equivalent.

22. The curable coating composition of any of the claims 1 -21 , wherein the

concentration of at least one hardener composition is about 1 amine equivalent to 1 epoxy equivalent.

23. The curable coating composition of any of the claims 1 -22, further including a filler, a modifier, a second therm osettable resin, or mixtures thereof.

24. A process for preparing a curable coating composition comprising admixing:

A. at least one epoxy resin compound; and

B. at least one cold curing hardener composition of claim 1 , 8, and 14;

wherein the hardener composition has a volatile organic compound content of less than 5 about 5 g/L; a free amine content of less than about 20 wt%; and a viscosity of less than about 1 ,500 mPa s at 25° C.

25. A cured coating product prepared by curing the curable composition of claim 19.