Claims:We Claim:

1. Ambient temperature curing/ coating formulations thereof comprising
(i) at least one ß-hydroxy carbamate-functional materials ambient curing resin/ binder involving hydroxyl non-isocyanate polyurethane (HNIPU)binder ofselective amine hydrogen equivalent weight (AHEW) in the range of 600–1200and having the following structure (I) below

(I)

wherein:n=2; x=0-4
R1,R2,R3, and R5 comprises hydrogen or alkyl or aryl or aliphatic, cyclo aliphatic radicals that may include one or more hetero atom containing functionality; said alkyl, aryl, aliphatic or cyclo aliphatic radical may contain 1-30 or higher carbon atoms as linear and/or branched moieties;
R4 comprises residues of di and/or polyamine or amide-amine or imido-amine compound that may be aliphatic, aromatic, cyclo aliphatic, linear or branched moietiescontaining 1-30 or higher carbon atoms including one or more hetero atom containing functionality; and

at least one (ii) hardener comprising at least one acid rich acrylic resin having acid value in the range of 18 to 50 mg/KOH per gm reactive with said hydroxyl non-isocyanate polyurethane (HNIPU) binder.

2. Ambient temperature curing/ coating formulations thereof as claimed in claim 1 which is either a coating comprising ambient cured reaction product of said (i) and (ii), or, is a formulation comprising ambient curing ready to apply said (i) and (ii) as components of a formulation favoring generation of said coating.

3. Ambient temperature curing/ coating formulations thereof as claimed in anyone of claims 1 or 2 wherein curing and subsequent drying is due to curing between the acid part of acrylic resin and the hydroxyl part of HNIPU wherein said acrylic resin is devoid of any acrylic double bondfor polymerization during curing.

4.Ambient temperature curing/ coating formulations thereof as claimed in anyone of claims 1-3 wherein said ß-hydroxy carbamate-functional materialas ambient curing resin/binder involvessaid hydroxyl non-isocyanate polyurethane (HNIPU) binder end capped with phthalic anhydride having residual amine AHEW above 800 and upto 1200.

5. Ambient temperature curing/ coating formulations thereof as claimed in anyone of claims 1-4 wherein said hardener (ii) comprises said acid rich acrylic resin selectively obtained of at least one acid-functional acrylic monomer and/or anhydride molecule as a source of acid.

6. Ambient temperature curing/ coating formulations thereof as claimed in anyone of claims 1-5 wherein said (i) comprising ambient curing resin/ binder involving hydroxyl non-isocyanate polyurethane (HNIPU) binder hasamine AHEW between 600 and 1200 and wherein said hardener (ii) comprises an acid rich acrylic resin having glycidyl functionality of 4-10 wt% on resin solid.

7. Ambient temperature curing/ coating formulations thereof as claimed in anyone of claims 1-6wherein said (i) comprising ambient curing resin/ binder involving hydroxyl non-isocyanate polyurethane (HNIPU) binder has amine AHEW between 600-1200; and said hardener (ii) comprises a blend of said acid rich acrylic resin and glycidyl functional resin, said glycidyl functional resin being present in amounts of 10-30 wt.% with respect to said acid rich acrylic resin.

8. Ambient temperature curing/ coating formulations thereof as claimed in anyone of claims 1-7 wherein said (i) HNIPU binder and said (ii) hardener of acid rich acrylic resin is mixed from 50/50 (wt%) to about 70/30 (wt%).

9. Ambient temperature curing/ coating formulations thereof as claimed in anyone of claims 1-8 having 30% to about 40% by weight solid.

10. Ambient temperature curing/ coating formulations thereof as claimed in anyone of claims 1-9 having viscosity from J to about Pin gardener scale; wherein the touch dried film was formed only after 20min; and wherein the dried film has gloss of 45 to 85 gloss unit measured at 60°.

11. Ambient temperature curing/ coating formulations thereof as claimed in anyone of claims 1-10 wherein said component (i) involving (HNIPU) binder have aromatic content chemically connected with said HNIPU binder and is sourced from the groups selected from the group consisting of one or more aromatic polyamines, one or more aromatic epoxy resins, one or more epoxy functional polymers, one or more benzene ring containing polymers, one or more polyanhydrides, one or more anhydride functional polymers and combinations thereof.

12. Ambient temperature curing/ coating formulations thereof as claimed in anyone of claims 1-11 wherein said component (i) involving (HNIPU) binder comprises amines and/or imine reacted polycyclic carbonate and/or cyclic carbonate based (HNIPU) binder, said polycyclic carbonate and/or cyclic carbonate includes reaction products of at least one aryl or alkyl carbonate and diol/glycol; cyclic ether and carbon dioxide; carbon dioxide and ring closed diol/ glycols as precursors to cyclic ethers also including epoxy, oxirane, glycidyl, oxetanes, oxanes based precursors to cyclic ethers.

13. Ambient temperature curing/ coating formulations thereof as claimed in anyone of claims 1-12 wherein said amine and/or imine is selected from IPDA (isophorone diamine); poly(ethylene imine); polyvinylamine; polyallylamine; dentriticpolypropyleneimine; chitosan and polylysine; 1,4-butane diamine; 1,6-hexamethylene diamine; 1,12-dodecane diamine; and isophorone diamine; alkylated phenolic polyamine (Phenalkamine); 2-methylpentamethylene, polyoxypropylene, diamine and polyoxypropylenetriamine diamine, metaxylenediamine, polyetheramineJeffamine EDR-148, diethylenetriamine, N,N-dimethyl-1,3-propanediamine, bis-(4,4'-aminocyclo hexyl)methane, tricyclodecanediamine (or 3(4), 8(9)-bis-(aminomethyl)tricyclo [5 .2 .l . l0]decane; 2-methylpentane-1,5-diamine; octylamine and hexylamine; polyalkylenamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine,pentaethylenehexamine,propylenediamine, dipropylenetriamine, N,N-bis (3-aminopropyl)-methylamine, 2,2,4- and/or 2,4,4 trimethylhexamethylenediamine, N,N'-bis-(3 -aminopropyl) ethylenediamine, neopentanediamine, 2-methyl-1,5 pentanediamine, 1,3-diaminopentane, andhexamethylenediamine; cycloaliphatic amines such as 1, 2- or 1,3 -diaminocyclohexane, 1, 4-diamino-3, 6-diethylcyclohexane; 1,2-diamino-4-ethylcyclohexane; 1,4-diamino-3,6-diethyl-cyclohexane,1-cyclohexyl-3,4-diaminocyclohexane; 4,4'-diaminodicyclohexylmethane, propane, 2,2-bis-(4-aminocyclohexyl)-methane and –pro pane, 3,3'-dimethyl-4,4'-diaminodicyclohexyl-methane, 3-amino-1-cyclohexylaminopropane, 1,3- and 1,4-bis (amininomethyl)-cyclohexane; polyoxyalkylenaminessuchas poly(oxyethylenediamine), poly(oxyethylenetriamine), poly(oxypropylenediamine), and poly (oxypropylenetriamine); heterocyclic amines such as N-aminoethylpiperazine and 1,4-bis-(3'-aminopropyl) piperazine; and meta- and para-xylylenediamines, 3-aminopropyltriethoxysilane;polyethyleneglycol monoamine, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, cyclohexylamine, ethanol amine, benzyl amine, isopropyl amine, and is preferably IPDA (isophorone diamine).

14. Ambient temperature curing/ coating formulations thereof as claimed in claim 12 wherein said cyclic ether precursors to polycyclic carbonate and/or cyclic carbonate includes precursors of epoxidized soybean oil; diglycidyl ether of bisphenols and cycloaliphatic diols, and poly-glycidyl terminated polyether oligomers/polymers thereof.

15. Ambient temperature curing/ coating formulations thereof as claimed in claim 12 wherein said polycyclic carbonate and/or cyclic carbonate are selected from jeffsol® glycerinecarbonate; ethylene carbonate, propylene carbonate, Glycerol Carbonate, cyclic (chloromethyl)-ethylene carbonate, 3,4-O-isopropylidene-D-mannitol-1,2:5,6-dicarbonate and D-mannitol-1,2:5,6-dicarbonate, isosorbide based bis-cyclic carbonate, 4-Phenyl-1,3-dioxolan-2-one, 4-Trifluoromethyl-1,3-dioxolan-2-one, bisphenol A polycarbonate,DivinylbenzeneDicarbonate, carbonated soybean, (CSBO) and carbonated linseed (CLSO) oils, cyclic limonene dicarbonate, terpene-based cyclic carbonates, carbonate-modified bis(4- glycidyloxy phenyl) phenyl phosphine oxide, cyclic carbonate polysiloxane compound, trimethylolpropanetricyclocarbonate, chlorine-contained aliphatic tricyclocarbonates, 2-oxo-1,3-dioxolan-4-yl)methyl N-allyl carbamate, 4-(2-oxo-1,3-dioxolan-4-yl)butyl N-allyl carbamate, 4-(allyloxymethyl)-1,3-dioxolan-2-one, (2-oxo-1,3-dioxolan-4-yl)methyl N-dodecylcarbamate, butanediolbiscycliccarbonates, 4-(2-oxo-1,3-dioxolan-4-yl)butyl N-dodecylcarbamate, diglyceroldicarbonate, trimethylol propane cylic carbonate derivative, vinyl carbonate, vinyl ethylene carbonate, cyclic carbonate with bis(4-glycidyloxy phenyl)phenyl phosphine oxide (BGPPO), and poly(propyleneglycol)diglycidylether,Rosin based Cylic carbonate, Cyclic bis-carbonate of DER 331, trimethylolpropanetricyclocarbonate, chlorine-contained aliphatic tricyclocarbonates, Cylic carbonate functionalized Polyhedral oligomeric silsesquioxanes (POSS), 4-((3-trimethoxysilyl)propoxy)methyl)1,3-dioxolan-2-one, and is preferably jeffsol® glycerine carbonate.

16. Ambient temperature curing/ coating formulations thereof as claimed in claims 1-15 adapted for clear coat or pigmented coat including one or more polymer blend, additives, fillers, extender and optionally pigments.

17. A method of providing ambient temperature curing/ coating formulations thereof as claimed in claims 1-16 said method comprising:
a) having (i) at least one ß-hydroxy carbamate-functional materialas ambient curing resin/ binder involving hydroxyl non-isocyanate polyurethane (HNIPU) binder ofselective amine hydrogen equivalent weight (AHEW) in the range of 600-1200 and having the following structure (I) below

(I)
wherein:n=2; x=0-4
R1,R2,R3, and R5comprises hydrogen or alkyl or aryl or aliphatic, cyclo aliphatic radicals that may include one or more hetero atom containing functionality; said alkyl, aryl, aliphatic or cyclo aliphatic radical may contain 1-30 or higher carbon atoms as linear and/or branched moieties;
R4 comprises residues of di and/or polyamine or amide-amine or imido-amine compound that may be aliphatic, aromatic, cyclo aliphatic, linear or branched moietiescontaining 1-30 or higher carbon atoms including one or more hetero atom containing functionality; and

b) having at least one (ii) hardener comprising at least one acid rich acrylic resin having acid value in the range of 18 to 50 mg/KOH per gm reactive with said hydroxyl non-isocyanate polyurethane (HNIPU).

c) mixing said binder (a) with said hardener(b) and allowing the mixture to react and dry at ambient temperature of -5 to 40 ?C optionally, with catalyst and preferably free of any catalyst to provide for said ambient temperature curing/ coating formulations thereof.

18. A method as claimed in claim 17 wherein said step (a) of having a binder comprising ambient temperature curable hydroxyl urethane oligomer and/or polymer (HNIPU) binder includes reacting polycyclic carbonate and/or cyclic carbonate with amines and/or imines in stoichiometric equivalents to yield a polymer with hydroxyurethane (PHU) groups having amine equivalent weight (AHEW) in the selective range of in the range of 600-1200.

19. A method as claimed in claim 18wherein said polycyclic carbonate and/or cyclic carbonate is sourced from reactions between aryl or alkyl carbonate and diol/glycol; cyclic ether and carbon dioxide; carbon dioxide and ring closed diol/ glycols as precursors to cyclic ethers also including epoxy, oxirane, glycidyl, oxetanes, oxanes based precursors to cyclic ethers.

20. A method as claimed in claim 18 wherein said polycyclic carbonate and/or cyclic carbonate are selected from jeffsol® glycerinecarbonate;ethylene carbonate, propylene carbonate, Glycerol Carbonate, cyclic (chloromethyl)-ethylene carbonate, 3,4-O-isopropylidene-D-mannitol-1,2:5,6-dicarbonate and D-mannitol-1,2:5,6-dicarbonate, isosorbide based bis-cyclic carbonate, 4-Phenyl-1,3-dioxolan-2-one, 4-Trifluoromethyl-1,3-dioxolan-2-one, bisphenol A polycarbonate,DivinylbenzeneDicarbonate, carbonated soybean, (CSBO) and carbonated linseed (CLSO) oils, cyclic limonene dicarbonate, terpene-based cyclic carbonates, carbonate-modified bis(4- glycidyloxy phenyl) phenyl phosphine oxide, cyclic carbonate polysiloxane compound, trimethylolpropanetricyclocarbonate, chlorine-contained aliphatic tricyclocarbonates, 2-oxo-1,3-dioxolan-4-yl)methyl N-allyl carbamate, 4-(2-oxo-1,3-dioxolan-4-yl)butyl N-allyl carbamate, 4-(allyloxymethyl)-1,3-dioxolan-2-one, (2-oxo-1,3-dioxolan-4-yl)methyl N-dodecylcarbamate, butanediolbiscycliccarbonates, 4-(2-oxo-1,3-dioxolan-4-yl)butyl N-dodecylcarbamate, diglyceroldicarbonate, trimethylol propane cylic carbonate derivative, vinyl carbonate, vinyl ethylene carbonate, cyclic carbonate with bis(4-glycidyloxy phenyl)phenyl phosphine oxide (BGPPO), and poly(propyleneglycol)diglycidylether,Rosin based Cylic carbonate, Cyclic bis-carbonate of DER 331, trimethylolpropanetricyclocarbonate, chlorine-contained aliphatic tricyclocarbonates, Cylic carbonate functionalized Polyhedral oligomeric silsesquioxanes (POSS), 4-((3-trimethoxysilyl)propoxy)methyl)1,3-dioxolan-2-one, and is preferably jeffsol® glycerine carbonate.

21. A method as claimed in claim 18 wherein said amine and/or imine is selected from IPDA (isophorone diamine); poly(ethylene imine); polyvinylamine; polyallylamine; dentriticpolypropyleneimine; chitosan and polylysine; 1,4-butane diamine; 1,6-hexamethylene diamine; 1,12-dodecane diamine; and isophorone diamine; alkylated phenolic polyamine (Phenalkamine); 2-methylpentamethylene, polyoxypropylene, diamine and polyoxypropylenetriamine diamine, metaxylenediamine, polyetheramineJeffamine EDR-148, diethylenetriamine, N,N-dimethyl-1,3-propanediamine, bis-(4,4'-aminocyclo hexyl)methane, tricyclodecanediamine (or 3(4), 8(9)-bis-(aminomethyl)tricyclo [5 .2 .l . l0]decane; 2-methylpentane-1,5-diamine; octylamine and hexylamine; polyalkylenamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine,pentaethylenehexamine,propylenediamine, dipropylenetriamine, N,N-bis (3-aminopropyl)-methylamine, 2,2,4- and/or 2,4,4 trimethylhexamethylenediamine, N,N'-bis-(3 -aminopropyl) ethylenediamine, neopentanediamine, 2-methyl-1,5 pentanediamine, 1,3-diaminopentane, andhexamethylenediamine; cycloaliphatic amines such as 1,2- or 1 ,3 -diaminocyclohexane, 1, 4-diamino-3, 6-diethylcyclohexane; 1,2-diamino-4-ethylcyclohexane; 1,4-diamino-3,6-diethyl-cyclohexane,1-cyclohexyl-3,4-diaminocyclohexane; 4,4'-diaminodicyclohexylmethane, propane, 2,2-bis-(4-aminocyclohexyl)-methane and –pro pane, 3,3'-dimethyl-4,4'-diaminodicyclohexyl-methane, 3-amino-1-cyclohexylaminopropane, 1,3- and 1,4-bis (amininomethyl)-cyclohexane; polyoxyalkylenaminessuchas poly(oxyethylenediamine), poly(oxyethylenetriamine), poly(oxypropylenediamine), and poly (oxypropylenetriamine); heterocyclic amines such as N-aminoethylpiperazine and 1,4-bis-(3'-aminopropyl) piperazine; and meta- and para-xylylenediamines, 3-aminopropyltriethoxysilane; polyethyleneglycol monoamine, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, cyclohexylamine, ethanol amine, benzyl amine, isopropyl amine, and is preferably IPDA (isophorone diamine).

22. A method as claimed in claim 19 wherein said cyclic ether precursors for generation of polycyclic carbonate and/or cyclic carbonate includes precursors of epoxidized soybean oil; diglycidyl ether of bisphenols and cycloaliphatic diols, and poly-glycidyl terminated polyether oligomers/polymers thereof.

23. A method as claimed in claim 17 wherein said hardener component (ii) comprising said acid rich acrylic resin is selectively obtained from at least one acid-functional acrylic monomer and/or anhydride molecule as a source of acid and preferably includes MMA (methyl methacrylate), BA (butyl acrylate), Styrene and MAA (methacrylic acid) as a source of acid.

24. A method as claimed in claim 23 wherein said MAA comprising said hardener component (ii) is varied from 1.25% to about 2.5% by weightadapted for the desired acid value.

25. A method as claimed in claim 17 wherein said binder component (i) comprising ambient curing resin/ binder involving hydroxyl non-isocyanate polyurethane (HNIPU) binder having amine AHEW between 600-1200, is reacted with said hardener component (ii) comprising an acid rich acrylic resin having glycidyl functionality of 4-10 wt% on resin solids, free of any catalyst.

26.A method as claimed in claim 17 wherein saidbinder component (i) comprising ambient curing resin/ binder involving hydroxyl non-isocyanate polyurethane (HNIPU) binder having amine AHEW between 600-1200 is reacted with said hardener component (ii) comprising a blend of said acid rich acrylic resin and glycidyl functional resin, said glycidyl functional resin being present in amounts of 10 to 30wt.% with respect to said acid rich acrylic resin, at ambient temperature and preferably free of any catalyst.

27. A method as claimed in claim 17wherein said binder component (i) involving said HNIPU binder and said hardener component (ii) involving said acid rich acrylic resin is mixed from 50/50 (wt%) to about 70/30 (wt%).

28. A method as claimed in claim 17 providing for ambient temperature curing/ coating formulations based coating or curable formulations thereof as clear coat or pigmented coat including one or more polymer blend, additives, fillers, extender and optionally pigments.

Dated this the 11th of April, 2018 Anjan Sen
Of Anjan Sen and Associates
(Applicants Agent)
, Description:FIELD OF THE INVENTION

The present invention provides for ambient temperature curing/ coating formulations thereof comprising (i) at least one ß-hydroxy carbamate-functional material as ambient curing resin/ binder involving hydroxyl non-isocyanate polyurethane (HNIPU) binder ofselective amine hydrogen equivalent weight (AHEW) in the range of 600–1200 at least one (ii) hardener comprising at least one acid rich acrylic resin having acid value in the range of 18 to 50 mg/KOH per gmreactive with said hydroxyl non-isocyanate polyurethane (HNIPU) binder, adapted to provide tack free surface preferably in only after about 1-6 hrs with complete drying and hardness following only after 24h, at room and/or ambient temperature (~30°C) preferably free of catalyst and advantageously free of any involvement of isocyanate and imine.

BACKGROUND ART

Non-isocyanate polyurethane (NIPU) is an emerging polymer reporting diverse applications in material science as well as the paints and coating industry. In the paints and coating industry its application is visualized either as a base (i.e. binder or paint, to be curable by a hardener) or as a hardener (to cure a base), to finally provide a thermoset coating film. Both require cross-linking reaction through some of the functional groups of NIPU to provide otherwise polyurethane (PU) coating like performance. Unlike regular polyurethane coating, where the urethane linkage is formed as part of crosslinking reaction between a suitable polyol binder with polyisocyanate hardener, NIPU is generally a linear or branched thermoplastic binder already having polyurethane repeat units on the polymer backbone can be synthesized by a condensation polymerization of a poly-functional cyclic carbonate and a polyfunctional amine, wherein each repeat unit generates an open hydroxyl group and the terminals are amine. The amine terminal concentration can be optimized by designing the stoichiometry of poly functional cyclic carbonate and polyfunctional amine in the feed. Thus synthesized thermoplastic NIPU polymer has a considerable hydroxyl concentration like a polyol binder and certain amount of amine concentration like a polyamine hardener. The curing of NIPU binder through hydroxyl groupwith isocyanate hardener is not desirable as isocyanates are generally considered as toxic to an extent. On the other hand, crosslinking through the amine terminals with epoxy or acetoacetate route was not preferred due to reduction in durability especially in exterior applications, acid/alkali resistance etc. Curing through the amine groups with aldehyde, ketone, etc. was also not preferred due to intensification of colour, etc. then the only curing route for the NIPU left would be amino resin curing system, all of which either are either at elevated temperature or requiring high amount of catalyst and all involving formaldehyde.

It has been felt as a requirement in the state of the art of NIPU technology to develop an ambient temperature, catalyst-free curing system that would avoid all the above mentioned routes.

On this reference is drawn to the prevailing knowledge flowing from the state of the art, such as Progress in Organic Coatings 44 (2002) 161–183 by Zeno W. Wicks, Jr et al. disclosing a two package waterborne urethane systemsincluding water-reducible acrylic resins prepared from a combination of acrylic and methacrylic esters, sometimes styrene, a hydroxy-functional (meth)acrylate and (meth)acrylic acid. The non-functional monomers are selected to control the g of the resin and coating. A typical resin includes sufficient acid monomer and so the resin has an acid number of 35–60. The level of hydroxy-functional monomer controls the cross-link density of the coating. Molecular weights are commonly of the order of M¯ w = 35 000 and M¯ n = 15 000. Polymerization is carried out in a water-miscible solvent such as a glycol monoether. The resin is neutralized with an amine and diluted with water. The resin is not soluble in water and on dilution, a dispersion is obtained which is stabilized by the salt groups oriented on the surface. This prior art thus teaches a water borne two component PU involving a typical acrylic polyol binder where the -OH groups of the acrylic polyol binder is cured with a water-stable polyisocyanate.

CN 101531757teaches a vegetable oil based onisomeric cyanate radical polyurethane acrylic ester and a preparation method thereof belong to the field of photosensitive high polymer material. The adoption of isocyanate for preparing polyurethane acrylic ester results in great toxic and side effects and other problems. It is taught that carbonate esterified vegetable oil derivatives mixed with 2-10 parts of solvent, and heated to 80-90 ?with stirring, dropwise addition of hydroxy primary amine or secondary amine or a hydroxyl compound, is added and the reaction progress was determined by the infrared spectroscopy, when the characteristic peak of 1805 cm-1 of the ring shaped carbonate decreases and disappears, while 1704, 1545 cm-1 characteristic carbamate peak appearsfor vegetable oil based hydroxyalkyl carbamate ester which is reacted with 3-8 parts of acrylic acid, acrylic acid and esterification catalyst 0.01-0.03% of the total mass of the three polymerization inhibitor and vegetable-oil based accounting hydroxyalkyl carbamate acrylate and 10-35% of the total mass of the solvent, mixing and heated to 78-110 ?, when at the boiling state, there is no longer moisture removal, the reaction is completed, heated to 90-100 ?, removal of water and excess acrylic acid under reduced pressure by a pump provides vegetable oil-based non-isocyanato urethane acrylate.

This prior art thus teaches synthesis of an acrylated macromonomer by doing a standard esterification reaction between the -OH groups of the hydroxy-carbamate groups of NIPU and an acrylic acid at elevated temperature in presence of esterification catalyst and in presence of polymerization inhibitor, so that the carbamate acrylate macromonomer is formed, is stable and is not polymerized. It is indicative that the polymerizable acrylic groups of this macromonomer shall later be cured, most likely by UV curing, to deliver a coating.

CN 103483905 teaches UV-curable is composed of (by wt.%) non-isocyanate polyurethane acrylate oligomer 32-42, epoxy resin acrylate oligomer 16-24, reactive diluent 18-32, photoinitiator 3-6, nano-silica 2-4, additive 1-2 and pigment 6-12, wherein this prior art provides a preparation method of the UV-curable ink and the UV-curable ink does not contain polyisocyanate group, has environmental friendliness, can be light-cured rapidly, and has good gloss, excellent adhesion strength, excellent mechanical property and high oil resistance.Ethylene carbonate: 1,6-ethylenediamine: zinc acetate catalyst reaction affords polyurethane oligomer A, i.e., having hydroxyl end groups; which product A with acrylic anhydride provides non-isocyanate urethane acrylate oligomer, that may be further blended with epoxy acrylate oligomer is an epoxy resin. This prior art is thus about using a NIPU-acrylate macromonomer that is blended with another epoxy-acrylate macromonomer and then together cured under UV curing in presence of photo-initiators.

CN104744670 relates toan epoxy acrylate prepolymer and an application thereof. The prepolymer is prepared from the following raw materials in parts by weight: 2-10 parts of cyclic carbonate, 4-20 parts of binary polyether amine, 50-70 parts of epoxy resin, 10-30 parts of acrylic acid, 0.01-0.1 part of a polymerization inhibitor and 0.1-0.5 part of a catalyst. A preparation process of the epoxy acrylate prepolymer comprises the following steps: (1) preparing an aliphatic dihydroxyl compound; (2) preparing modified epoxy resin; and (3) performing acrylic acid esterification and end sealing. The epoxy acrylate prepolymer prepared by using the method provided by the this prior art can be applied to ultraviolet curing coatings, can be rapidly cured under ultraviolet light, has high film coating hardness, good adhesive force and excellent flexibility after being cured, also has good acid resistance, good alkali resistance and certain wear resistance, and can also be applied to decoration of printing inks, adhesives as well as metal and plastic surfaces.

CN 105505136A provides a UV coating prepared from cyclic carbonate synthesized polyurethane. The UV coating is processed from, by weight, 35-45 parts of epoxy acrylate, 10-20 parts of non-isocyanate polyurethane, 20-25 parts of acrylic acid activated monomers, 0.8-1.2 parts of pentaerythritol, 6-8 parts of silicon oxide nano-particles, 2-3 parts of toluylene biphenyl sodium disulfonate, 2-2.5 parts of photoinitiator, 2.5-3.5 parts of antifoaming agent, 1.5-2.5 parts of US surface improver and 4-8 parts of ABK accelerant. This prior art provides a preparation method of the UV coating which is green, environmentally friendly and free of toxicity and has good yellowing resistance; besides, the adhesive force, abrasive resistance and other properties of the coating that also achieves a good effect in terms of application to exterior walls and buildings.

CN 107177035A provides a polyurethane prepolymer which is novel environment-friendly non-isocyanate polyurethane, does not contain an isocyanate group has no pollution to the environment and has no damages to human health. The low-viscosity ultraviolet-cured composition can be widely used for preparing ultraviolet-cured polyurethane coating, 3D (Three Dimensional) printing photosensitive resin, ultraviolet-cured polyurethane ink or an ultraviolet-cured polyurethane adhesive. Preparation of the polyurethane prepolymers is taught comprising: a), a carbonate compound and a cyclic amine compound reacted in the presence of catalyst under an inert gas, to obtain a first reaction intermediate; b) step a) to obtain a first reaction intermediate and an acrylic compound reacted in the presence of a polymerization inhibitor, to obtain the polyurethane prepolymer.The above preparation method includes under step b) the glycidyl acrylic compound is methacrylic acid or methacrylic acid; the polymerization inhibitor is p-hydroxy anisole, to hydroquinone or di-t-butyl-4-methylphenol.
Hence in most of the above prior arts the polymerizable acrylic groups of the macromonomer are later cured, most likely by UV curing, to deliver a coating.

US005916960A relates to a water-based, storage stable coating composition which is self-curing at room temperature. More particularly, this prior art relates to a water based coating composition of a polyurethane and a self curing acrylic polymer which can be applied to various substrates, such as wood, and particularly teaches a water-based, self-curing storage-stable coating composition comprising: (1) an aqueous dispersion of a self-curing vinyl polymer prepared by addition polymerization; (2) a polyurethane dispersion prepared by chain extension of a prepolymer reaction product of a diisocyanate and one or more polyols, at least one polyol being a carboxy-substituted polyol, the polyurethane dispersion being neutralized with ammonia or ammonium hydroxide; and (3) a water-soluble catalyst for initiating cross-linking of said vinyl polymer aqueous dispersion; wherein the aqueous dispersion of a self-curing vinyl polymer has been polymerized before being mixed with the neutralized polyurethane dispersion. This prior art is thus about having a vinyl polymer (that may include acrylic polymer also) comprised of active methylene containing monomers, which is mixed with PUD dispersion and neutralized by amines, wherein the active methylene groups will slowly cure with the amine present in neutralization upon evaporation of water and pH getting lowered. Presence of epoxy in the acrylic polymer backbone suggests that the epoxy to react with the monomeric / oligomeric amine neutralizers to provide secondary amine functionality, which can further self-cure with the active methylene during film formation.

US 7829631B2 provides a crosslinkable waterborne coating composition useful for providing protective coating to wood and other substrates, wherein the coating composition includes a vinyl addition latex polymer having a first crosslinkable functional group and a polyurethane dispersion having a second crosslinkable functional end group. The coating composition is preferably essentially formaldehyde free. Further it is taught therein a composition comprising:a vinyl addition latex polymer having a first crosslinkable functional group; a polyurethane dispersion having a second crosslinkable functional end group; and
a crosslinker comprising a diacetone, acetoacetoxyl or dihydrazide compound, or combination thereof;wherein the composition is in the form of a waterborne coating composition; and the first crosslinkable functional group of the vinyl addition latex polymer and the second crosslinkable functional end group of the polyurethane dispersion self-crosslink via polymer-to-crosslinker reaction of the vinyl addition polymer with the crosslinker and polymer-to-crosslinker reaction of the polyurethane dispersion with the crosslinker at low temperature upon coalescence.

US20020103319A1 teaches water-soluble, ß-hydroxy carbamate-functional materials and coating compositions, especially waterborne coating compositions, containing the carbamate-functional materials, and particularly provides a coating prepared from the coating composition together with at last one crosslinker which is reactive with carbamate functionality, and is a melamine formaldehyde resin.

Reference is further drawn to Poussard, L., et al. advancemententitled ‘Non-Isocyanate Polyurethanes from Carbonated Soybean Oil Using Monomeric or Oligomeric Diamines To Achieve Thermosets or Thermoplastics’ Macromolecules, 2016, 49, pp 2162–2171. Elastomeric NIPUs derived from oligoamides and CSBO (Cyclic carbonate of Soybean Oil)thatexhibited better rigidity, an improved elongation at break (erup to 400%), and a higher thermal stability (T95 wt % > 350 °C) than those of starting oligoamides.

US2011/0313091A1 discloses the ambient temperature curable isocyanate free composition containing polycarbamate and aldehyde cross linker and acid catalyst.

US4520167 teaches amino-aldehyde diluent cross linker for hydroxyl polyurethane structures that cures at elevated temperatures.

US8143346 and US8450413/ 2003A relates to fast curable NIPU and HNIPU polymeric nanocompositions that are derived upon crosslinking a mixture comprising of natural or modified nano-claywith either a monomer(s)/ oligomer(s) bearing cyclic carbonate group(s) or amixture of the latter with an epoxy resin, with a hardenerbearing aminogroups.

US6001925 A, describes amodified melamine-formaldehyde resins prepared by reacting melamine with formaldehyde at a F:M molar ratio in the range of about 1.55:1-2.5:1 in the presence of about 1-10 wt % dicyandiamide and about 1-10 wt % sorbitol based on the total weight of resin solids. The resins are used to impregnate substrates in the preparation of decorative laminates.

deRuiter, B., et al., teaches a two-step curing processes for coating applications in Progress in Organic Coatings, 2006,55, pp.154-159 teaching coating formed through metal-ligand supramolecular interaction wherein the processrefersto the combination of a covalent cationic crosslinkingstepandasupramolecular,reversiblecross-linkingstep(through metal–ligand interaction) leading to a class of coatings with unprecedented rheological properties, with potential applications as“self-healing” coatings.

Montaranl, D., et al. in Epoxy-Based Networks Combining Chemical and Supramolecular Hydrogen-Bonding CrosslinksJournal of Polymer Science: Part A: Polymer Chemistry, 2010, 48, pp 1133-1141 discloses certain groups combine the supramolecular chemistry of heterocyclic ureas with the chemistry of epoxides to synthesize new crosslinked materials incorporating both chemical and supramolecular hydrogen-bonded links.

Han, J.T et al. in Fabrication of Superhydrophobic Surface from a Supramolecular Organosilane with Quadruple Hydrogen Bonding. J. AM. CHEM. SOC. 2004, 126, pp4796-4797 describes a method to fabricate a superhydrophobic surface by the simple sol-gel process at room temperature using a supramolecular organosilane having quadruple hydrogen bonds.

Schubert, U. S. et al. in Combination of supramolecular cross-linking with covalent cross-linking through epoxide ring-opening including gel studies in E-Polymers, 2003, 053, pp 1-13 discloses terpolymers based on poly(methyl methacrylate), containing terpyridinemoieties as well as epoxide groups, synthesized via free-radical polymerization wherein the products were cross-linked non-covalently with iron(II) ions and covalently by treatment with AlCl3.

Liu, R et al. in Synthesis and properties of UV-curable self-healing oligomer inProgress in Organic Coatings, 2016, 101, pp 122-129 describes a UV-curable self-healing oligomer was designed on the basis of a quadrupolar hydrogen bond system. The oligomer is formed by reacting a mixture of a hydrogen bonding group and a photosensitive monomer with three-arm polyols.

US20160230035, describes floor coating compositions containing supramolecular polymers.

It would be apparent from the above state of the art on NIPU polymers that most prior teachings on such NIPU polymers indicate acrylic double bond containing prepolymers or polymerizable acrylic groups containing macromonomers that is UV cured in presence or absence of photoinitiator (the acrylic double bond polymerizes during curing), whereas for some NIPU polymers active methylene group containing monomers are used to facilitate film formation, and some uses melamine formaldehyde resin for curing to deliver a coating.
Further it is also known that curing of NIPU can be done with epoxy rich acrylic resin or alkyd resin under ambient condition. In another way the curing of NIPU can be done using polyaldehyde like glyoxal, CHADA any isomer of cyclohexane dicarboxaldehydeetc. through imine formation at ambient temperature. Other way the curing of NIPU can also be possible through amino resin curing route. In another way the curing of NIPU can be done through isocyante route at room temperature or through ester formation at elevated temperature. All these routes are not preferred due to durability or colour issue. To avoid all these undesired routes of crosslinking of NIPU to provide a thermoset coating film it is thus a longfelt requirement in the state of the art of NIPU technology and more specifically HNIPU, hydroxyl non-isocyanate polyurethane,to develop an ambient temperature, preferably catalyst-free curing system that would avoid the involvement of isocyanate and imine and further all of the above mentioned routes.

OBJECTS OF THE INVENTION

It is thus the primary object of the present invention to provide for ambient temperature, curing systempreferably catalyst-free curing systems involving hydroxyl non-isocyanate polyurethane(HNIPU), which HNIPU would be curable simply by acid rich acrylic resin free of any acrylic double bond available for polymerization during curing.

It is another object of the present invention to provide for said ambient temperature, curing system comprising said HNIPU as curing based resin and hardener composition comprising acid rich acrylic resin that would not cause any durability and colour issues and would provide for a thermoset coating through simple curing, the curing system being free of any isocyanate, formaldehyde and imine as requirements for curing.

It is yet another object of the present invention to provide for said acid rich acrylic resin curableHNIPU system that would not require any epoxy or aldehyde as curing agent and yet would facilitate significant curing in the absence of any catalyst at room temperature, that would also favourably impart good solvent resistance and hardnessof the films.

It is still another object of the present invention to provide for said acid rich acrylic resin curableHNIPU system that would be curable without any catalyst system and would be applicable in various paint applications including wood finish or industrial application such that preferably when applied on wood panel would enable tack free wood surface only after 1h with complete drying and hardness after 24h at room and/or ambient temperature (~30?C).

SUMMARY OF THE INVENTION

Thus according to the basic aspect of the present invention there is provided an ambient temperature curing/ coating formulations thereof comprising
(i) at least one ß-hydroxy carbamate-functional material as ambient curing resin/ binder involving hydroxyl non-isocyanate polyurethane (HNIPU)binder ofselective amine hydrogen equivalent weight (AHEW) in the range of 600–1200and having the following structure (I) below

(I)

wherein:n=2; x=0-4
R1,R2,R3, and R5comprises hydrogen or alkyl or aryl or aliphatic, cyclo aliphatic radicals that may include one or more hetero atom containing functionality; said alkyl, aryl, aliphatic or cyclo aliphatic radical may contain 1-30 or higher carbon atoms as linear and/or branched moieties;
R4 comprises residues of di and/or polyamine or amide-amine or imido-amine compound that may be aliphatic, aromatic, cyclo aliphatic, linear or branched moietiescontaining 1-30 or higher carbon atoms including one or more hetero atom containing functionality; and

at least one (ii) hardener comprising at least one acid rich acrylic resin having acid value in the range of 18 to 50 mg/KOH per gm reactive with said hydroxyl non-isocyanate polyurethane (HNIPU) binder, preferably free of any catalyst.

Preferably said ambient temperature curing/ coating formulations thereof is either a coating comprising ambient cured reaction product of said (i) and (ii), or, is a formulation comprising ambient curing ready to apply said (i) and (ii) as components of a formulation favoring generation of said coating.

More preferably, in said ambient temperature curing/ coating formulations thereof curing and subsequent drying is due to curing between the acid part of acrylic resin and the hydroxyl part of HNIPU wherein said acrylic resin is devoid of any acrylic double bondfor polymerization during curing.

According to another preferred aspect of the present invention there is provided said ambient temperature curing/ coating formulations thereof wherein said ß-hydroxy carbamate-functional material as ambient curing resin/binder involves said hydroxyl non-isocyanate polyurethane (HNIPU) binder end capped with phthalic anhydride having residual amine AHEW above 800 and upto 1200.

Preferably in said ambient temperature curing/ coating formulations thereof said hardener (ii) comprises said acid rich acrylic resin selectively obtained of at least one acid-functional acrylic monomer and/or anhydride molecule as a source of acid.

According to another preferred aspect of the present invention there is provided said ambient temperature curing/ coating formulations thereof wherein said (i) comprising ambient curing resin/ binder involving hydroxyl non-isocyanate polyurethane (HNIPU) binder hasamine AHEW between 600 and 1200 and wherein said hardener (ii) comprises an acid rich acrylic resin having glycidyl functionality of 4-10 wt% on resin solid.

According to yet another preferred aspect of the present invention there is providedsaid ambient temperature curing/ coating formulations thereof wherein said (i) comprising ambient curing resin/ binder involving hydroxyl non-isocyanate polyurethane (HNIPU) binder has amine AHEW between 600-1200; and said hardener (ii) comprises a blend of said acid rich acrylic resin and glycidyl functional resin, said glycidyl functional resin being present in amounts of 10-30 wt.% with respect to said acid rich acrylic resin.

According to another preferred aspect of the present invention there is provided said ambient temperature curing/ coating formulations thereof wherein said (i) HNIPU binder and said (ii) hardener of acid rich acrylic resin is mixed from 50/50 (wt%) to about 70/30 (wt%).

Preferably, said ambient temperature curing/ coating formulations thereof has 30% to about 40% by weight solid.

Advantageously, said ambient temperature curing/ coating formulations thereof has viscosity from J to about P in gardener scale; wherein the touch dried film was formed only after 20min; and wherein the dried film has gloss of 45 to 85 gloss unit measured at 60°.

Preferably in said ambient temperature curing/ coating formulations thereof said component (i) involving (HNIPU) binder have aromatic content chemically connected with said HNIPU binder and is sourced from the groups selected from the group consisting of one or more aromatic polyamines, one or more aromatic epoxy resins, one or more epoxy functional polymers, one or more benzene ring containing polymers, one or more polyanhydrides, one or more anhydride functional polymers and combinations thereof.

According to another preferred aspect of the present invention there is providedsaid ambient temperature curing/ coating formulations thereof wherein said component (i) involving (HNIPU) binder comprises amines and/or imine reacted polycyclic carbonate and/or cyclic carbonate based (HNIPU) binder, said polycyclic carbonate and/or cyclic carbonate includes reaction products of at least one aryl or alkyl carbonate and diol/glycol; cyclic ether and carbon dioxide; carbon dioxide and ring closed diol/ glycols as precursors to cyclic ethers also including epoxy, oxirane, glycidyl, oxetanes, oxanes based precursors to cyclic ethers.

Preferably said ambient temperature curing/ coating formulations thereof is provided wherein said amine and/or imine is selected from IPDA (isophorone diamine); poly(ethylene imine); polyvinylamine; polyallylamine; dentriticpolypropyleneimine; chitosan and polylysine; 1,4-butane diamine; 1,6-hexamethylene diamine; 1,12-dodecane diamine; and isophorone diamine; alkylated phenolic polyamine (Phenalkamine); 2-methylpentamethylene, polyoxypropylene, diamine and polyoxypropylenetriamine diamine, metaxylenediamine, polyetheramineJeffamine EDR-148, diethylenetriamine, N,N-dimethyl-1,3-propanediamine, bis-(4,4'-aminocyclo hexyl)methane, tricyclodecanediamine (or 3(4), 8(9)-bis-(aminomethyl)tricyclo [5 .2 .l . l0]decane; 2-methylpentane-1,5-diamine; octylamine and hexylamine; polyalkylenamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine,pentaethylenehexamine,propylenediamine, dipropylenetriamine, N,N-bis (3-aminopropyl)-methylamine, 2,2,4- and/or 2,4,4 trimethylhexamethylenediamine, N,N'-bis-(3 -aminopropyl) ethylenediamine, neopentanediamine, 2-methyl-1,5 pentanediamine, 1,3-diaminopentane, andhexamethylenediamine; cycloaliphatic amines such as 1, 2- or 1,3 -diaminocyclohexane, 1, 4-diamino-3, 6-diethylcyclohexane; 1,2-diamino-4-ethylcyclohexane; 1,4-diamino-3,6-diethyl-cyclohexane,1-cyclohexyl-3,4-diaminocyclohexane; 4,4'-diaminodicyclohexylmethane, propane, 2,2-bis-(4-aminocyclohexyl)-methane and –pro pane, 3,3'-dimethyl-4,4'-diaminodicyclohexyl-methane, 3-amino-1-cyclohexylaminopropane, 1,3- and 1,4-bis (amininomethyl)-cyclohexane; polyoxyalkylenaminessuchas poly(oxyethylenediamine), poly(oxyethylenetriamine), poly(oxypropylenediamine), and poly (oxypropylenetriamine); heterocyclic amines such as N-aminoethylpiperazine and 1,4-bis-(3'-aminopropyl) piperazine; and meta- and para-xylylenediamines, 3-aminopropyltriethoxysilane;polyethyleneglycol monoamine, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, cyclohexylamine, ethanol amine, benzyl amine, isopropyl amine, and is preferably IPDA (isophorone diamine).

Preferably said ambient temperature curing/ coating formulations thereof is provided wherein said cyclic ether precursors to polycyclic carbonate and/or cyclic carbonate includes precursors of epoxidized soybean oil; diglycidyl ether of bisphenols and cycloaliphatic diols, and poly-glycidyl terminated polyether oligomers/polymers thereof.

More preferably said ambient temperature curing/ coating formulations thereof is provided wherein said polycyclic carbonate and/or cyclic carbonate are selected from jeffsol® glycerinecarbonate; ethylene carbonate, propylene carbonate, Glycerol Carbonate, cyclic (chloromethyl)-ethylene carbonate, 3,4-O-isopropylidene-D-mannitol-1,2:5,6-dicarbonate and D-mannitol-1,2:5,6-dicarbonate, isosorbide based bis-cyclic carbonate, 4-Phenyl-1,3-dioxolan-2-one, 4-Trifluoromethyl-1,3-dioxolan-2-one, bisphenol A polycarbonate,DivinylbenzeneDicarbonate, carbonated soybean, (CSBO) and carbonated linseed (CLSO) oils, cyclic limonene dicarbonate, terpene-based cyclic carbonates, carbonate-modified bis(4- glycidyloxy phenyl) phenyl phosphine oxide, cyclic carbonate polysiloxane compound, trimethylolpropanetricyclocarbonate, chlorine-contained aliphatic tricyclocarbonates, 2-oxo-1,3-dioxolan-4-yl)methyl N-allyl carbamate, 4-(2-oxo-1,3-dioxolan-4-yl)butyl N-allyl carbamate, 4-(allyloxymethyl)-1,3-dioxolan-2-one, (2-oxo-1,3-dioxolan-4-yl)methyl N-dodecylcarbamate, butanediolbiscycliccarbonates, 4-(2-oxo-1,3-dioxolan-4-yl)butyl N-dodecylcarbamate, diglyceroldicarbonate, trimethylol propane cylic carbonate derivative, vinyl carbonate, vinyl ethylene carbonate, cyclic carbonate with bis(4-glycidyloxy phenyl)phenyl phosphine oxide (BGPPO), and poly(propyleneglycol)diglycidylether,Rosin based Cylic carbonate, Cyclic bis-carbonate of DER 331, trimethylolpropanetricyclocarbonate, chlorine-contained aliphatic tricyclocarbonates, Cylic carbonate functionalized Polyhedral oligomeric silsesquioxanes (POSS), 4-((3-trimethoxysilyl)propoxy)methyl)1,3-dioxolan-2-one, and is preferably jeffsol® glycerine carbonate.

Advantageously said ambient temperature curing/ coating formulations thereof is adapted for clear coat or pigmented coat including one or more polymer blend, additives, fillers, extender and optionally pigments.

According to another aspect of the present invention there is provided a method of providing ambient temperature curing/ coating formulations thereof said method comprising:
a) having (i) at least one ß-hydroxy carbamate-functional material as ambient curing resin/ binder involving hydroxyl non-isocyanate polyurethane (HNIPU) binder of selective amine hydrogen equivalent weight (AHEW) in the range of 600-1200 and having the following structure (I) below

(I)
wherein:n=2; x=0-4
R1,R2,R3, and R5comprises hydrogen or alkyl or aryl or aliphatic, cyclo aliphatic radicals that may include one or more hetero atom containing functionality; said alkyl, aryl, aliphatic or cyclo aliphatic radical may contain 1-30 or higher carbon atoms as linear and/or branched moieties;
R4 comprises residues of di and/or polyamine or amide-amine or imido-amine compound that may be aliphatic, aromatic, cyclo aliphatic, linear or branched moieties containing 1-30 or higher carbon atoms including one or more hetero atom containing functionality; and

b) having at least one (ii) hardener comprising at least one acid rich acrylic resin having acid value in the range of 18 to 50 mg/KOH per gm reactive with said hydroxyl non-isocyanate polyurethane (HNIPU).

c) mixing said binder (a) with said hardener(b) and allowing the mixture to react and dry at ambient temperature of -5 to 40 ?C optionally, with catalyst and preferably free of any catalyst to provide for said ambient temperature curing/ coating formulations thereof.

Preferably in said method said step (a) of having a binder comprising ambient temperature curable hydroxyl urethane oligomer and/or polymer (HNIPU) binder includes reacting polycyclic carbonate and/or cyclic carbonate with amines and/or imines in stoichiometric equivalents to yield a polymer with hydroxyurethane (PHU) groups having amine equivalent weight (AHEW) in the selective range of in the range of 600-1200.

More preferably, in said method said polycyclic carbonate and/or cyclic carbonate is sourced from reactions between aryl or alkyl carbonate and diol/glycol; cyclic ether and carbon dioxide; carbon dioxide and ring closed diol/ glycols as precursors to cyclic ethers also including epoxy, oxirane, glycidyl, oxetanes, oxanes based precursors to cyclic ethers.

Preferably in said method said polycyclic carbonate and/or cyclic carbonate are selected from jeffsol® glycerinecarbonate;ethylene carbonate, propylene carbonate, Glycerol Carbonate, cyclic (chloromethyl)-ethylene carbonate, 3,4-O-isopropylidene-D-mannitol-1,2:5,6-dicarbonate and D-mannitol-1,2:5,6-dicarbonate, isosorbide based bis-cyclic carbonate, 4-Phenyl-1,3-dioxolan-2-one, 4-Trifluoromethyl-1,3-dioxolan-2-one, bisphenol A polycarbonate,DivinylbenzeneDicarbonate, carbonated soybean, (CSBO) and carbonated linseed (CLSO) oils, cyclic limonene dicarbonate, terpene-based cyclic carbonates, carbonate-modified bis(4- glycidyloxy phenyl) phenyl phosphine oxide, cyclic carbonate polysiloxane compound, trimethylolpropanetricyclocarbonate, chlorine-contained aliphatic tricyclocarbonates, 2-oxo-1,3-dioxolan-4-yl)methyl N-allyl carbamate, 4-(2-oxo-1,3-dioxolan-4-yl)butyl N-allyl carbamate, 4-(allyloxymethyl)-1,3-dioxolan-2-one, (2-oxo-1,3-dioxolan-4-yl)methyl N-dodecylcarbamate, butanediolbiscycliccarbonates, 4-(2-oxo-1,3-dioxolan-4-yl)butyl N-dodecylcarbamate, diglyceroldicarbonate, trimethylol propane cylic carbonate derivative, vinyl carbonate, vinyl ethylene carbonate, cyclic carbonate with bis(4-glycidyloxy phenyl)phenyl phosphine oxide (BGPPO), and poly(propyleneglycol)diglycidylether,Rosin based Cylic carbonate, Cyclic bis-carbonate of DER 331, trimethylolpropanetricyclocarbonate, chlorine-contained aliphatic tricyclocarbonates, Cylic carbonate functionalized Polyhedral oligomeric silsesquioxanes (POSS), 4-((3-trimethoxysilyl)propoxy)methyl)1,3-dioxolan-2-one, and is preferably jeffsol® glycerine carbonate.

More preferably in said method said amine and/or imine is selected from IPDA (isophorone diamine); poly(ethylene imine); polyvinylamine; polyallylamine; dentriticpolypropyleneimine; chitosan and polylysine; 1,4-butane diamine; 1,6-hexamethylene diamine; 1,12-dodecane diamine; and isophorone diamine; alkylated phenolic polyamine (Phenalkamine); 2-methylpentamethylene, polyoxypropylene, diamine and polyoxypropylenetriamine diamine, metaxylenediamine, polyetheramineJeffamine EDR-148, diethylenetriamine, N,N-dimethyl-1,3-propanediamine, bis-(4,4'-aminocyclo hexyl)methane, tricyclodecanediamine (or 3(4), 8(9)-bis-(aminomethyl)tricyclo [5 .2 .l . l0]decane; 2-methylpentane-1,5-diamine; octylamine and hexylamine; polyalkylenamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine,pentaethylenehexamine,propylenediamine, dipropylenetriamine, N,N-bis (3-aminopropyl)-methylamine, 2,2,4- and/or 2,4,4 trimethylhexamethylenediamine, N,N'-bis-(3 -aminopropyl) ethylenediamine, neopentanediamine, 2-methyl-1,5 pentanediamine, 1,3-diaminopentane, andhexamethylenediamine; cycloaliphatic amines such as 1,2- or 1 ,3 -diaminocyclohexane, 1, 4-diamino-3, 6-diethylcyclohexane; 1,2-diamino-4-ethylcyclohexane; 1,4-diamino-3,6-diethyl-cyclohexane,1-cyclohexyl-3,4-diaminocyclohexane; 4,4'-diaminodicyclohexylmethane, propane, 2,2-bis-(4-aminocyclohexyl)-methane and –pro pane, 3,3'-dimethyl-4,4'-diaminodicyclohexyl-methane, 3-amino-1-cyclohexylaminopropane, 1,3- and 1,4-bis (amininomethyl)-cyclohexane; polyoxyalkylenaminessuchas poly(oxyethylenediamine), poly(oxyethylenetriamine), poly(oxypropylenediamine), and poly (oxypropylenetriamine); heterocyclic amines such as N-aminoethylpiperazine and 1,4-bis-(3'-aminopropyl) piperazine; and meta- and para-xylylenediamines, 3-aminopropyltriethoxysilane; polyethyleneglycol monoamine, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, cyclohexylamine, ethanol amine, benzyl amine, isopropyl amine, and is preferably IPDA (isophorone diamine).

According to another preferred aspect of the present invention there is provided said method said cyclic ether precursors for generation of polycyclic carbonate and/or cyclic carbonate includes precursors of epoxidized soybean oil; diglycidyl ether of bisphenols and cycloaliphatic diols, and poly-glycidyl terminated polyether oligomers/polymers thereof.

Preferably in said method said hardener component (ii) comprising said acid rich acrylic resinis selectively obtained from at least one acid-functional acrylic monomer and/or anhydride molecule as a source of acid and preferably includes MMA (methyl methacrylate), BA (butyl acrylate), Styrene and MAA (methacrylic acid) as a source of acid.

More preferably in said method said MAA comprising said hardener component (ii) is varied from 1.25% to about 2.5% by weightadapted for the desired acid value.

According to another preferred aspect of the present invention there is provided said binder component (i) comprising ambient curing resin/ binder involving hydroxyl non-isocyanate polyurethane (HNIPU) binder havingamine AHEW between 600-1200, is reacted with said hardener component (ii) comprising an acid rich acrylic resin having glycidyl functionality of 4-10 wt% on resin solids, free of any catalyst.

Preferably in said method saidbinder component (i) comprising ambient curing resin/ binder involving hydroxyl non-isocyanate polyurethane (HNIPU) binder having amine AHEW between 600-1200 is reacted with said hardener component (ii) comprising a blend of said acid rich acrylic resin and glycidyl functional resin, said glycidyl functional resin being present in amounts of 10 to 30 wt.% with respect to said acid rich acrylic resin, at ambient temperature and preferably free of any catalyst.

More preferably in said method said binder component (i) involving said HNIPU binder and said hardener component (ii) involving said acid rich acrylic resin is mixed from 50/50 (wt%) to about 70/30 (wt%).

Advantageously said method providing for ambient temperature curing/ coating formulations based coating or curable formulations thereof is provided as clear coat or pigmented coat including one or more polymer blend, additives, fillers, extender and optionally pigments.

DETAILED DESCRIPTION OF THE INVENTION
As discussed hereinbefore, the present invention provides for curing base resin and hardener composition comprising acid rich acrylic (solvent based, NVM 50-70%) resin having selective acid value in the range of 18 to 50 mg/KOH per gm when blended with hydroxyl non-isocyanate polyurethane (HNIPU) of selective amine hydrogen equivalent wt. (AHEW) in the range of 600–1200, preferably free of any catalyst and applied on wood panel could surprisingly provide for a tack free surface preferably wood surface after only 1h and complete dying and hardness followed only after 24h, at room and/or ambient temperature (~30°C).

Preferably the acid rich acrylic resin is selectively obtained of at least one acid-functional acrylic monomer and/or anhydride molecule as a source of acid.

According to another embodiment of the present invention, it was found that when glycidyl functionalities are borne on the acid-rich acrylic polymer up to a level of 4-10 wt% on resin solids providing for epoxy equivalent wt. (EEW) in the range of 1200-1800 similar curing results were obtained by blending this polymer with the NIPU in similar proportions as above.

It was thus significantly found by the present invention that said acid-rich acrylic resin having selective acid value 18 to 45 mg/KOH per gm, and free of any acrylic double bond available for polymerization during curing, was a sufficient condition to provide said ambient curing solution with HNIPU and the glycidyl functionality was not a necessary condition.

It was also found that only glycidyl functional acrylic resin with glycidyl functionalities borne in said resin upto a level of 4-10 wt% on resin solid, and even when employed at any other wt% without incorporation of selective levels of acid in the acrylic resin backbone was not able to give tack free surface even after 24h.

It was also found that having glycidyl functionality below and beyond the above said levels in the acrylic polymer of selective acid value either gives tacky surface or reduces the pot life of the blends, respectively.
While glycidyl functionality below the mentioned lower limit causes film tackiness, glycidyl functionality beyond mentioned upper limits, reduces pot life and gloss across all acid values of the acrylic polymer. Further to the aforesaid beyond said above mentioned levels of glycidyl functionality in the acrylic polymer reduces surface gloss of the NIPU based coating at both 20 and 60 degree angles, apart from reducing pot life.

Further to the above it was also found by the present invention that blending a glycidyl functional resin with said acid-rich acrylic at 10 to 30wt.% with respect to the acrylic polymer was able to give tack free surface only after 4h. Similar results were obtained with the glycidyl-functional acrylic resin as mentioned above. In case of the aforesaid using more than 50 wt.% of the glycidyl-functional resin was counter-productive to drying.

Similar effects on drying and hardness was found with makingacetoacetate functionality available in the acid-rich acrylic hardener either as a blend or grafted in the same way as the glycidyl functionality was made available in earlier examples.

Finally it was found that irrespective of glycidyl or acetoacetate functionalities being available in the acrylic hardener system, an acid value of the acrylic resin less than 17 mg KOH/g was notable to provide a tack-free cured film. On the other hand availability of glycidyl or acetoacetate functionalities was not necessary conditions for the acid-rich acrylic hardener system of the present invention.

EXAMPLES:

Example 1: It was found from several re-runs that only when hydroxyl non-isocyanate polyurethane (HNIPU) binder ofselective amine hydrogen equivalent weight (AHEW) in the range of 600–1200 is employed together with at least one acid rich acrylic resin having acid value in the range of 18 to 50 mg/KOH per gm the same combination when coated on a surface could provide for a tack free surface preferably within 1-6 hrs only and preferably without the involvement of any catalyst. Whereas HINPU with amine equivalent wt. 200, 400 and 500 prepared and cured with the same acid functional acrylic lead to unsatisfactory drying performance and tacky surface evenafter 12h.

Example 2: Table2:-Column 1in the table below showing changing AHEW

Sr. No. Amine hydrogen Equivalentwt. (AHEW) of the HNIPU base binder Acid Value of Acrylic Resin(18-50 mg-KOH/g) Epoxy Equivalent(epoxy equivalent wt.) of Acrylic resin Remarks
1 200 25 1400 Tacky Surface after 12h
2 500 25 1400 Tacky Surface after 12h
3 800 25 1400 Tack free surface after 6h
4 1200 25 1400 Tack free surface after 6h

Example 3: Table 3:-Column 3in the table below showing changing EEW

Sr. No. Amine hydrogen Equivalentwt. (AHEW) of the HNIPU base binder Acid Value of Acrylic Resin(18-50 mg-KOH/g) Epoxy Equivalent(epoxy equivalent wt.) of Acrylic resin Remarks
1 800 25 800 Tacky Surface after 12h
2 800 25 1400 Tack free surface after 6h
800 25 1800 Tack free surface after 8h
3 800 25 2000 Tack free surface after 12h

Preferably, Table 2 further reveals that incorporation of glycidyl functionality in the acid rich acrylic resinhaving said select acid value in the range of 18 to 50 mg/KOH per gmand such said glycidyl functionality providing for epoxy equivalent of acrylic resin in the range of about 1400 impacted to impart a tack free surface in only after 6 hrs. Hence the acrylic binder having EEW in between 1200-1800 gives the best drying but any value beyond this range provides a tacky surface.
Further Table 3 results infers that the involvement of the glycidyl functionalityin said acid rich acrylic resin involves a limiting range showing desired activity which is lost when the EEW is higher (higher than 6 to 15 wt.% as stated above which now may require revision) and is thus counter-productive to drying.

Further experiments were run by blending 10 to 30 wt.% of glycidyl functional resin with respect to the acid rich acrylic polymer to cure the HNIPU binder at ambient temperature and preferably free of catalyst and it was found that said binder HNIPU having AHEW 600-1200 provided for excellent drying performances giving satisfactory drying and hardness while AHEW below 500 lead to non-drying surfaces even after 12h.

Thus while the curing of NIPU can be done with epoxy rich acrylic resin or alkyd resin under ambient condition, wherein while another way the curing of NIPU can be done using polyaldehyde like glyoxal, CHADA etc. through imine formation at ambient temperature, and wherein the other way of curing NIPU can also be possible through amino resin curing route, and while the curing of NIPU can be done through isocyante route at room temperature or through ester formation at elevated temperature and as all these routes were not preferred due to durability or colour issue, thus to avoid all these undesired routes of crosslinking of NIPU to provide a thermoset coating film, it was thus possible for the present advancement to provide for simple curing between acid rich acrylic resin and HNIPU, free of any involvement of isocyanate and imine at ambient temperature preferably free of any catalyst.
The catalyst may or may not be added depending on drying time vs. open time requirements of the formulation.
The acid rich acrylic resin without any epoxy grafting was prepared and when blended with HNIPU with selective acid levels curing at ambient temperature was observed from the increasing viscosity and hardness of the film.
Advantageously, in addition to the above acrylic curing HNIPU system of the present invention without any epoxy or aldehyde as curing agent developed significant curing in the complete absence of any catalyst at room temperature, imparting good solvent resistance of the films. Furthermore the hardness of the film is as equivalent with acid rich acrylic-epoxy/NIPU curing system. More advantageously, the added advantage of simple curing effect from an acid rich acrylic with HNIPU is hitherto before unknown.