Waterborne coating composition based on water dispersible acrylic modified polyester

Abstract

A water dispersible acrylic modified polyester, which is the free-radical reaction product of: I. 45 to 90 wt.% of a saturated polyester, based on the total weight of (I) and (II), wherein said saturated polyester is free of an α,β-unsaturated monomer, and wherein the polyester has an acid number of 0 to 30 mg KOH / g, hydroxyl number of 5 to 50 mg KOH / g, a number average molecular weight of 2,000 to 30,000 g / mol, and a weight average molecular weight of 10,000 to 200,000 g / mol; and II. 10 to 55 wt.% of one or more ethylenically unsaturated monomers, based on the total weight of (I) and (II), wherein the one or more ethylenically unsaturated monomers comprises: i. methacrylic anhydride, acrylic anhydride or a combination thereof; and ii. optionally, one or more ethylenically unsaturated monomers other than (Il)(i).

Description

WATERBORNE COATING COMPOSITION BASED ON WATER DISPERSIBLE ACRYLIC MODIFIED POLYESTERTECHNICAL FIELDEmbodiments of the present disclosure generally relate to waterborne coating compositions based on water dispersible acrylic modified polyesters, and more particularly to hydrophobic saturated polyesters that are modified with ethylenically unsaturated monomers to enable water dispersibility. The aqueous dispersions thus prepared can be used for waterborne coating applications.BACKGROUND

[0001] Waterborne coatings based on polyesters may be achieved by using polyesters having enhanced hydrophilic properties, such as those with carboxyl (-COOH) or sulfo (-SO3) groups. Carboxyl-functional polyesters can be neutralized with a volatile amine to enable water dispersibility; the amine is subsequently vaporized when the coating is dried. The sulfo group typically is present as a sodium salt and will remain in the coating film, which can have detrimental effects on the water resistance of the coating. As for the carboxylic acid functionality regenerated after the amine is evaporated, it can still cause water sensitivity to the coating although it is not as damaging as a sodiosulfo salt (-SO3Na). Moreover, there exists other shortcomings for carboxyl-functional polyesters. The carboxyl-functional polyester can be made either by using an excess of carboxyl components or by reacting a polyester polyol with an anhydride. The former can produce higher molecular weight polyesters but suffer low hydroxyl functionality for crosslinking, while the latter cannot produce polyesters having higher molecular weights needed for certain applications, such as metal packaging. One way to resolve the aforementioned shortcomings is to eliminate the use of hydrophilic polyesters and instead use polyesters that are designed for organic solvent-based coatings. Those polyesters, however, are hydrophobic and not water dispersible.

[0002] Accordingly, there remains a desire for waterborne coatings that arebased on hydrophobic polyesters that are water dispersible to produce waterborne coatings having the desired properties, such as, for example, film clarity, solvent resistance, and acid resistance.SUMMARY

[0003] Disclosed in embodiments herein are water dispersible acrylic modified polyesters. The polyesters are the free-radical reaction product of the components comprising: I. 45 to 90 wt.% of a saturated polyester, based on the total weight of (I) and (II), wherein the saturated polyester is the reaction product of: i. 80 to 100 mol.% of a diol selected from the group consisting of 2, 2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD), 2-methyl-1,3-propanediol (MPdiol), 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, and combinations thereof, based on the total moles of (i) and (ii), ii. 0 to 20 mol.% of a triol, based on the total moles of (i) and (ii), ill.60 to 100 mol.% of an aromatic diacid, based on the total moles of (iii) and (iv), and iv. 0 to 40 mol.% of an aliphatic diacid, based on the total moles of (iii) and (iv), and wherein said saturated polyester is free of an α,β-unsaturated monomer, and wherein the polyester has an acid number of 0 to 30 mg KOH / g, hydroxyl number of 5 to 50 mg KOH / g, a number average molecular weight of 2,000 to 30,000 g / mol, and a weight average molecular weight of 10,000 to 200,000 g / mol; and II. 10 to 55 wt.% of one or more ethylenically unsaturated monomers, based on the total weight of (I) and (II), wherein the one or more ethylenically unsaturated monomers comprises: i. methacrylic anhydride, acrylic anhydride or a combination thereof; and ii. optionally, one or more ethylenically unsaturated monomers other than (II)(i).Further disclosed in one or more embodiments herein are aqueous dispersions. The aqueous dispersions comprise (a) an acrylic modified polyester; (b) an organic co-solvent; (c) a neutralizing agent; and (d) water; wherein the acrylic modified polyester is the free-radical reaction product of the components comprising: I. 45 to 90 wt.% of a saturated polyester, based on the total weight of (I) and (II), wherein the saturated polyester is the reaction product of: i. 80 to 100 mol.% of a diol selected from the group consisting of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD), 2-methyl-1,3-propanediol (MPdiol), 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, and combinations thereof, based on the total moles of (i) and (ii), ii. 0 to 20 mol.% of a triol, based on the total moles of (i) and (ii), ill.60 to 100 mol.% of an aromatic diacid, based on the total moles of (iii) and (iv), and iv. 0 to 40 mol.% of an aliphatic diacid, based on the total moles of (iii) and (iv), and wherein said saturated polyester is free of an α,β-unsaturated monomer, and wherein the polyester has an acid number of 0 to 30 mg KOH / g, hydroxyl number of 5 to 50 mg KOH / g, a number average molecular weight of 2,000 to 30,000 g / mol, and a weight average molecular weight of 10,000 to 200,000 g / mol; and II. 10 to 55 wt.% of one or more ethylenically unsaturated monomers, based on the total weight of (I) and (II), wherein the one or more ethylenically unsaturated monomers comprises: i. methacrylic anhydride, acrylic anhydride or a combination thereof; and ii. optionally, one or more ethylenically unsaturated monomers other than (II)(i).Further disclosed in one or more embodiments herein waterborne coating compositions. The waterborne coating compositions comprise (A) an acrylic modified polyester of the present invention in an amount of 60 to 95 weight percent, based on the total weight of (A) and (B); (B) a crosslinking agent in an amount of 5 to 40 weight percent, based on the total weight of (A) and (B); (C) an organic co-solvent in an amount of 10 to 30 weight %, based on the total weight of the coating composition; and (D) water in an amount of 30 to 60 weight percent, based on the total weight of the coating composition, wherein the acrylic modified polyester is the free-radical reaction product of the components comprising: I. 45 to 90 wt.% of a saturated polyester, based on the total weight of (I) and (II), wherein the saturated polyester is the reaction product of: i. 80 to 100 mol.% of a diol selected from the group consisting of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD), 2-methyl-1,3-propanediol (MPdiol), 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, and combinations thereof, based on the total moles of (i) and (ii), ii. 0 to 20 mol.% of a triol, based on the total moles of (i) and (ii), iii.60 to 100 mol.% of an aromatic diacid, based on the total moles of (iii) and (iv),and iv. 0 to 40 mol.% of an aliphatic diacid, based on the total moles of (iii) and (iv), and wherein said saturated polyester is free of an α,β-unsaturated monomer, and wherein the polyester has an acid number of 0 to 30 mg KOH / g, hydroxyl number of 5 to 50 mg KOH / g, a number average molecular weight of 2,000 to 30,000 g / mol, and a weight average molecular weight of 10,000 to 200,000 g / mol; and II. 10 to 55 wt.% of one or more ethylenically unsaturated monomers, based on the total weight of (I) and (II), wherein the one or more ethylenically unsaturated monomers comprises: i. methacrylic anhydride, acrylic anhydride or a combination thereof; and ii. optionally, one or more ethylenically unsaturated monomers other than (ll)(i).

[0004] Additional features and advantages of the embodiments will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from that description or recognized by practicing the embodiments described herein. It is to be understood that both the foregoing and the following description describe various embodiments and are intended to provide an overview or framework for understanding the nature and character of the claimed subject matter.DETAILED DESCRIPTIONReference will now be made in detail to embodiments of water dispersible acrylic modified polyesters, as well as aqueous dispersions or waterborne coating compositions containing the polyesters described herein. The water dispersible acrylic modified polyesters may be used in aqueous dispersions or waterborne coatings. Waterborne coatings may be used in metal packaging of food and beverage, such as interior and exterior can coatings, and other areas where waterborne coatings may be desirable (e.g., automotive OEM, auto refinish, transportation, aerospace, maintenance, marine, machinery and equipment, general metal, appliance, metal furniture, commercial construction, home construction, architectural coating applications, paints, and coil). In some embodiments, there is provided a metal can having an interior and exteriorsurface, wherein at least a portion of the interior or exterior surface is coated with the waterborne coating compositions described herein.Acrylic Modified Polyesters

[0005] In embodiments herein, the water dispersible acrylic modified polyester is the free-radical reaction product of: (I) 45 to 90 wt.% of a saturated polyester, and (II) 10 to 55 wt.% of one or more ethylenically unsaturated monomers, based on the total weight of (I) and (II). All individual values and subranges are included and disclosed herein. For example, in some embodiments, the amount of saturated polyester ranges from a lower limit of 45, 47.5, 50, 55, 60, 65, or 70 to an upper limit of 90, 87.5, 85, 82.5, 80, 75, or 70 wt.%, and the amount of one or more ethylenically unsaturated monomers ranges from a lower limit of 10, 12.5, 15, 17.5, 20, 25, or 30 to an upper limit of 55, 52.5, 50, 45, 40, 35, or 30 wt.%, based on the total weight of (I) and (II). In other embodiments, the amount of saturated polyester ranges from a lower limit of 47.5, 52.5, 57.5, 62.5, 67.5, or 72.5 to an upper limit of 87.5, 82.5, 77.5, 72.5, 67.5, 62.5, or 57.5 wt.%, and the amount of one or more ethylenically unsaturated monomers ranges from a lower limit of 12.5, 17.5, 22.5, 27.5, 32.5, 37.5, or 42.5 to an upper limit of 52.5, 47.5, 42.5, 37.5, 32.5, or 27.5 wt.%, based on the total weight of (I) and (II).The free-radical reaction is carried out by feeding the acrylic monomers (II)(i and ii) to a solution of the saturated polyester (I) in an organic solvent along with a free-radical initiator at an elevated temperature to polymerize the ethylenically unsaturated monomers. Without wishing to be bound by theory, it has been hypothesized that the acrylic moiety is grafted onto polyester through the reaction of the hydroxyl groups on the polyester with one or more ethylenically unsaturated monomers (methacrylate anhydride, acrylate anhydride, or combinations thereof (II)(i)), followed by chain extension of the acrylic moieties by free-radical polymerization. The resulting acrylic grafted polyester surprisingly is capable of forming the desirable aqueous dispersion upon neutralization of the carboxyl groups.

[0006] The saturated polyesters described herein can be prepared fromdicarboxylic acids and polyols incorporated into the polyester polymer as their corresponding residues. The saturated polyester is the reaction product of: a polyol component, and a dicarboxylic acid component. The term “polyester”, as used herein, is intended to include “copolyesters” and is understood to mean a synthetic polymer prepared by the reaction of one or more difunctional carboxylic acids and / or multifunctional carboxylic acids with one or more difunctional hydroxyl compounds and / or multifunctional hydroxyl compounds, as referred to above as comprised of a dicarboxylic acid component and a polyol component. The term “polyol” as used herein includes, but is not limited to, diols, glycols, and / or multifunctional hydroxyl compounds. The term “residue”, as used herein, means any organic structure incorporated into a polymer through a polycondensation and / or an esterification reaction from the corresponding monomer. The term “repeating unit”, as used herein, means an organic structure having a dicarboxylic acid residue and a diol residue bonded through an ester group. Thus, for example, the dicarboxylic acid residues may be derived from a dicarboxylic acid monomer or its associated acid halides, esters, salts, anhydrides, and / or mixtures thereof. Furthermore, as used herein, the term “diacid” or “dicarboxylic acid” includes multifunctional acids. As used herein, therefore, the term “dicarboxylic acid” is intended to include dicarboxylic acids and any derivative of a dicarboxylic acid, including its associated acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, and / or mixtures thereof, useful in a reaction process with a diol to make a polyester. The stoichiometry of the polyol components and dicarboxylic acid components can be adjusted as needed to obtain the desired acid number (and / or hydroxyl number) in the final saturated polyester.

[0007] In one or more embodiments herein, the saturated polyester may be the reaction product of: (i) 80 to 100 mol.% of a diol and ii. 0 to 20 mol.% of a triol, based on the total moles of (i) and (ii), and ill. 60 to 100 mol.% of an aromatic diacid and iv. 0 to 40 mol.% of an aliphatic diacid, based on the total moles of (iii) and (iv). All individual values and subranges are included and disclosed herein. For example, in some embodiments, the saturated polyester is the reaction product of: (i) 80, 82.5, 85, 87.5, or 90 to 100, 99.5, 99.0, or 98.5mol.% of a diol and ii. 0, greater than 0, 0.5, 1.0, or 1.5 to 20, 17.5, 15, 12.5, or 10 mol.% of a triol, based on the total moles of (i) and (ii), and ill. 60, 65, 70, 75, 80, 85, or 90 to 100, 99.0, 97.5, 97, or 95 mol.% of an aromatic diacid and iv. 0, greater than 0, 1.0, 2.5, 3, or 5 to 40, 35, 30, 25, 20, 15, or 10 mol.% of an aliphatic diacid, based on the total moles of (iii) and (iv). In further embodiments, the saturated polyester is the reaction product of: (i) 85 or 90 to 100 or 99.0 mol.% of a diol and ii. 0, greater than 0, or 1.0 to 15 or 10 mol.% of a triol, based on the total moles of (i) and (ii), and iii. 85 or 90 to 100 or 97.5 mol.% of an aromatic diacid and iv. 0, greater than 0, or 2.5 to 15 or 10 mol.% of an aliphatic diacid, based on the total moles of (iii) and (iv).In embodiments herein, the diol is selected from the group consisting of 2, 2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD), 2-methyl-1,3-propanediol (MPdiol), 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, and combinations thereof. In one or more embodiments herein, the diol (l)(i) may be a combination of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD), 1,4-cyclohexanedimethanol, and 2-methyl-1,3-propanediol (MPdiol). In one or more embodiments herein, the diol (l)(i) may be a combination of 2, 2, 4, 4-tetramethyl-1,3-cyclobutanediol (TMCD) in an amount of 20-60 mol.%, 1,4-cyclohexanedimethanol in an amount of 30-60 mol.%, and 2-methyl-1,3-propanediol (MPdiol) in an amount of 5-40 mol.%, based on the total moles of the diols. All individual values and subranges are included and disclosed herein. For example, in some embodiments, the diol (l)(i) may be a combination of 2, 2, 4, 4-tetramethyl-1,3-cyclobutanediol (TMCD) in an amount of from 25, 30, 35 to 60, 55, or 50 mol.%, 1,4-cyclohexanedimethanol in an amount of from 30, 32.5 or 35 to 60, 55, 50, or 47.5 mol.%, and 2-methyl-1,3-propanediol (MPdiol) in an amount of 5, 7.5, or 10 to 40, 35, 30, or 25 mol.%, based on the total moles of the diols.

[0008] In one or more embodiments herein, the diol (l)(i) may be a combination of 1,4-cyclohexanedimethanol and 2-methyl-1,3-propanediol (MPdiol). In one or more embodiments herein, the diol (l)(i) may be a combination of 1,4-cyclohexanedimethanol in an amount of 30-60 mol.% and 2-methyl-1,3-propanediol (MPdiol)in an amount of 40-70 mol.%, based on thetotal moles of the diols. All individual values and subranges are included and disclosed herein. For example, in some embodiments, the diol (l)(i) may be a combination of,4-cyclohexanedimethanol in an amount of from 30, 32.5, or 35 to 60, 55, 50, or 47.5 mol.% and 2-methyl-1,3-propanediol (MPdiol) in an amount of from 40, 45, 50, or 55 to 70, 67.5, or 65 mol.%, based on the total moles of the diols.

[0009] In one or more embodiments herein, the triol (l)(ii) may include 1,1,1-trimethylol propane, 1,1,1 -trimethylolethane, glycerin, and mixtures thereof. In some embodiments, the triol (l)(ii) is 1,1,1 -trimethylolpropane (TMP). In other embodiments, the triol (l)(ii) is TMP in combination with 1,1,1 -trimethylolethane and / or glycerin.

[0010] In one or more embodiments herein, the aromatic diacid (l)(iii) may include isophthalic acid (or dimethyl isophthalate), terephthalic acid (or dimethyl terephthalate), phthalic acid, and mixtures thereof. In some embodiments, the aromatic diacid (l)(iii) is a combination of isophthalic acid and terephthalic acid. In some embodiments herein, the aromatic diacid (l)(iii) is a combination of isophthalic acid and terephthalic acid, wherein the isophthalic acid is in an amount of 50-80 mol.% and terephthalic acid is in an amount of 20-50 mol.%, based on the total moles of the aromatic diacids. All individual values and subranges are included and disclosed herein. For example, in some embodiments, the aromatic diacid (l)(iii) is a combination of isophthalic acid and terephthalic acid, wherein the isophthalic acid is in an amount of from 50, 55, 60, 62.5, 65, or 67.5 to 80, 75, or 72.5 mol.% and terephthalic acid is in an amount of from 20, 25, or 27.5 to 50, 45, 40, 35, or 32.5 mol.%, based on the total moles of the aromatic diacids.

[0011] In one or more embodiments herein, the aliphatic diacid (l)(iv) may include hexahydrophthalic anhydride, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, dodecanedioic acid, sebacic acid, succinic acid, adipic acid, and mixtures thereof. In some embodiments, the aliphatic diacid (I) (iv) is dodecanedioic acid, sebacic acid, succinic acid, adipic acid, and mixtures thereof. In some embodiments, the aliphatic diacid (l)(iv) is adipic acid.

[0012] In some embodiments herein, said diol (l)(i) is a combination of 2.2.4.4-tetramethyl-1,3-cyclobutanediol (TMCD) in an amount of 20-60 mol.%, 1.4-cyclohexanedimethanol (1,4-CHDM) in an amount of 30-60 mol.%, and 2-methyl-1,3-propanediol (MPdiol) in an amount of 5-40 mol.%, based on the total moles of the diols; said aromatic diacid (ll)(i) is a combination of isophthalic acid is in an amount of 50-80 mol.% and terephthalic acid is in an amount of 20-50 mol.%, based on the total moles of the aromatic diacids; and said aliphatic diacid (ll)(ii) is adipic acid.

[0013] In some embodiments herein, said diol (l)(i) is a combination of 2.2.4.4-tetramethyl-1,3-cyclobutanediol (TMCD) in an amount of 20-60 mol.%, 1.4-cyclohexanedimethanol (1,4-CHDM) in an amount of 30-60 mol.%, and 2-methyl-1,3-propanediol (MPdiol) in an amount of 5-40 mol.%, based on the total moles of the diols; said triol (l)(ii) is trimethylolpropane (TMP); said aromatic diacid (ll)(i) is a combination of isophthalic acid is in an amount of 50-80 mol.% and terephthalic acid is in an amount of 20-50 mol.%, based on the total moles of the aromatic diacids; and said aliphatic diacid (ll)(ii) is adipic acid.

[0014] In embodiments herein, the saturated polyester (I) is free of an α,β-unsaturated monomer. As used herein, the term “free of” denotes a polyester that contains either an insignificant amount of or no reactive double bonds from unsaturated monomers in the polyester. An insignificant amount means that the residues of unsaturated monomers in the saturated polyester is less than 1.0 (alternatively, less than 0.5, 0.1 or 0.01 ) wt.%. Thus, the saturated polyester is free of an α,β-unsaturated monomer. Examples of α,β-unsaturated monomers include maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, and itaconic acid.

[0015] In embodiments herein, the saturated polyester has an acid number of 0 to 30 mg KOH / g, hydroxyl number of 5 to 50 mg KOH / g, number average molecular weight of 2,000 to 30,000 g / mol, and weight average molecular weight of 10,000 to 200,000 g / mol. All individual values and subranges are included and disclosed herein. For example, in some embodiments, the saturated polyester has an acid number of from 0 or 1 to 30, 25, 20, 15, 12.5 or 10 mg KOH / g, hydroxyl number of from 5 or 6 to 50, 45, 40, 35, 30, 25, or 20OL‘9JB|XjOBL|J9lU |Xx8l||Xl|J9-g ‘9JB|XjOB |Xx9l]|Xl]}9-g ‘9JB|XjOB |XL|J9XXOI]}91U -g ‘9JB|XjOBL|J9lU |XxOL|-U ‘9JB|XjOB |Xx9l|-U ‘9JB|XjOBL|J9Ull |Xjnq-U ‘9JB|XjOB |Xjnq-u ‘OJB|XJOB |Xqjo ‘9jB|XjoBqj9iu |Xqjo ‘OJB|XJOB iXqjoiu ‘OJB|XJOBL|J9UJ 0£ iXqjoiu opnpui XBLU (||)(||) jo S9|diuBX -gpijpXquB OI|XJOBL|19IU si (i)(||) ‘sjuoiuipoqiuo oiuos u| '(i)(| |) UBL J jgqjo SJOLUOUOLU pojBjnjBSun XnBOiuoiXqjg OJOLU JO ouo ‘X||Buoijdo (H) puB ijoojgqj uoijBuiqiuoo B O ‘opupXquB OI|XJOB ‘opupXquB 9i|XjoBqj9iu (i):jo SJSISUOO ‘(ll) SJOLUOUOLU pojBjnjBSun X||BOiuo|Xqio OJOLU JO OUO oqj ‘uiojoq sjuoiuipoqiuo OJOLU JO OUO u| [6U00] 93■opixo uij|Xjnqip ‘OJBIBXO snouuBjs ‘piOB oiouuBjS|Xjnq ‘ojBOUBxoqiXqjo -g-suj uiiiXjnq opnpui spunodiuoo UIJ oiqBjins jo so|diuBX ‘(igi ®JOZXJ_ ‘■B’o) OJBUBJIJ iXinqBJjoi pus ‘(ojBuojooBiXjooBjsiq opixodojdosiip luniuBjij ‘OJBUBJIJ |Xd0jd0SIBJJ9J ‘(31 ®JOZX1 ‘-B’O) OpiXOdOjdOS ojBUILUBIOUBqjOUj) ( l)uuniuBi!i ‘(101 @JOZXI ‘-B'o) opixoiXxoqiXqjo 03 -3 (Al) n! UBi!i opnioui spunodiuoo luniuBiu oiqBjins jo so|diuBX

[8100] uij JO luniuBjii uo possq si ISX|BJBO oi|j ‘luoiuipoqwo QUO u| 30 sojnixiiu puB ‘opixojpXq unipos JO opixojpXq luniqiii qiiM spunodiuoo iunuiiun|B jo suoiiBuiqiuoo ‘spunodiuoo iunuiiun|B ‘spunodiuoo q so OUI|B>||B ‘lunipos pus luniqin X|jB|noi Bd g|. ‘S|Bjoiu i|B^|B ‘luniuBiujoB ‘OSOUBBUBLU ‘i|Bqoo ‘XuoiuiiuB ‘ouiz ‘iuni||B6 ‘uij ‘luniuBin uo psssq osoqj opnioui SJSX|BIBO oiqBjins jo so|diuBX qsXiBiBO B jo oouosojd oqj ui pozisoqjuXs oq XBLU JojsoX|od pojBjnjBS oi|i [ZLOO]Oo08-09 JO ‘Oo08-99 ‘Oo08-09 ‘O0O6-OZ ‘Oo06-99 ‘Oo06-09 ‘Oo06-99 ‘0o06-09 ‘Oo06-9fr ‘OoOO k -99 ‘OoOO I- -09 ‘OoOO k -99 ‘OoOO k -09 ‘OoOO L -9fr ‘O0O8 0 L -O ‘Oo06-0 ‘OoOO 1.-017 ‘O0OL I.-OI7 ‘OoOL -08 ‘OoOI4-03 ‘OcOL L-OI- JO (61) sjnjBJodiuoj UOIJISUBJJ SSB|6 B OABLI XBLU J9jsoX|od pojBjnjBS oqj ‘sjuoiuipoqius QLUOS ui ‘0|diuBX9 jog 'uigjgq pgsopsip pus pgpnpui BJB sgBusjqns pus sgn|BA iBnpiAipui nv ’OoOJ I--0 jo (61) gjnjBjgdiugj UOIJISUBJJ SSB|6 B 9ABL| XBLU JojsoX d pojBjnjBS oqj ‘upjoq sjuoiuipoqiuo oiuos u| [9U00] 9■|0LU / 6 000‘09 JO ‘000‘9Z ‘000‘00J ‘000‘09 ‘000‘003 oj 000‘93 JO ‘000‘03 ‘000‘OL JO jqBiOM jB|no9|Oiu OBBJOAB jq BIO puB ‘ |Oiu / 6009‘Z L JO ‘000‘03 ‘000‘93 ‘000‘08 oj 009‘Z JO ‘000‘9 ‘000‘3 LUOJJ JO jqBiOM jB|noo|Oiu OBBJOAB jgqiunu ‘6 / HOM BLULOOM999Z8isobutyl acrylate, isobutyl methacrylate, n-octyl acrylate, n-octyl methacrylate, iso-octyl acrylate, and iso-octyl methacrylate. 2-hydroxyethyl (meth)acrylate, 2- hydroxypropyl (meth)acrylate, acrylic acid, methacrylic acid, glycidyl (meth)acrylate, acetoacetoxy ethyl methacrylate, acetoacetoxy ethyl acrylate, styrene, and combinations thereof. In some embodiments, (ll)(ii) is selected from the group consisting of methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, styrene, and combinations thereof.

[0020] In some embodiments, the one or more ethylenically unsaturated monomers (II) is (consists of) (ll)(i) methacrylic anhydride. In some embodiments, the one or more ethylenically unsaturated monomers (II) is (consists of) a combination of (ll)(i) methacrylic anhydride (MAN) and (ll)(ii) butyl acrylate (BA) at a weight ratio of 70-80 (MAN) / 20-30 (BA). In other embodiments, the one or more ethylenically unsaturated monomers (II) is (consists of) a combination of methacrylic anhydride (MAN) and methyl methacrylate (MMA) at a weight ratio of 70-80 (MAN) / 20-30 (MMA). In further embodiments, the one or more ethylenically unsaturated monomers (II) is (consists of) a combination of methacrylic anhydride (MAN) in an amount of 70-90 weight %, butyl acrylate (BA) in an amount of 5-15 weight %, and 2- hydroxyethyl methacrylate (HEMA) in an amount of 5-15 weight %, based on the total weight of the one or more ethylenically unsaturated monomers (II).

[0021] In one or more embodiments herein, the acrylic modified polyester has an acid number of 30-200 mgKOH / g. All individual values and subranges are included and disclosed herein. For example, in some embodiments, the acrylic modified polyester has an acid number of 50-150 or 70-120 mgKOH / g.

[0022] The acrylic modified polyester may be prepared by: (1) reacting the reactants (l)(i), (l)(ii), (l)(iii), and (l)(iv) under polycondensation conditions to produce the saturated polyester (I); and (2) reacting under solution free-radical polymerization conditions of the polyester made in step (1) with one or more ethylenically unsaturated monomers (II).

[0023] The reaction in step (2) may be conducted under solution free-radical polymerization conditions at a temperature of about 50 to 150° C under inert atmosphere in the presence of a free radical initiator. The free-radical initiator may be in a suspension, such as in an alcohol.

[0024] The free-radical initiator employed in this second step is selected from organic peroxides or azo compounds, such as benzoyl peroxide, t-butyl hydroperoxide, t-butyl peroxide, t-butyl peroxybenzoate, azobisisobutyronitrile, and 2,2'-azobis(2,4-dimethyl)-valeronitrile.

[0025] Suitable solvents for free-radical solution polymerization are water miscible solvents including n-butanol, sec-butanol, isobutanol, isopropanol, n-propanol, ethanol, ethylene glycol monobutyl ether, propylene glycol n-butyl ether, propylene glycol methyl ether, propylene glycol monopropyl ether, dipropylene glycol methyl ether, diacetone alcohol, dibasic ester (DBE, a mixture of dimethyl succinate (19-30%), dimethyl glutarate (50-75%), and dimethyl adipate (10-25%)), ethylene glycol monopropyl ether (EP), n-butyl propionate (BPP), n-butylpyrrolidone (NBP), and combinations thereof. After free-radical polymerization, solvents may be partially or completely removed to afford the acrylic-modified polyester at a desired % solids, such as, for example, 50 to 100, 60 to 90, or 70 to 80 % solids.Aqueous Dispersions

[0026] Also disclosed herein are aqueous dispersions. The aqueous dispersions comprise: an acrylic modified polyester as described herein; an organic co-solvent; a neutralizing agent; and water. The aqueous dispersion may be prepared by neutralizing the acrylic modified polyester prepared by free-radical acrylic polymerization in the presence of the saturated polyester in an organic solvent. After neutralization, water was added to the mixture to yield an aqueous dispersion. Alternatively, the neutralizing agent and water can be added together to the solution of the acrylic modified polyester in an organic solvent. Thus, the aqueous dispersions described herein contain one or more aforementioned organic co-solvents in addition to water.

[0027] The resulting aqueous dispersion may contain undispersed resin solids, which can be removed by filtration to yield a dispersion free of particulate substances. In some embodiments, the aqueous dispersion contains no more than 1 wt.% of undispersed resin solids, based on the total weight of the dispersion, before filtering the dispersion.

[0028] The neutralizing agent may be an amine or an inorganic base. Exemplary amines may include ammonia, trimethylamine, diethylamine, monoethanolamine, monoisopropanolamine, morpholine, ethanolamine, diethanolamine, triethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N-methyldiethanolamine and the like. In some embodiments, the neutralizing agent is an amine selected from the group consisting of ammonia, trimethylamine, diethylamine, monoethanolamine, monoisopropanolamine, morpholine, ethanolamine, diethanolamine, triethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N-methyldiethanolamine, and combinations thereof.

[0029] As previously noted herein, the organic co-solvent may be a water miscible solvent, such as n-butanol, sec-butanol, isobutanol, isopropanol, n-propanol, ethanol, ethylene glycol monobutyl ether, propylene glycol n-butyl ether, propylene glycol methyl ether, propylene glycol monopropyl ether, dipropylene glycol methyl ether, diacetone alcohol, dibasic ester (DBE, a mixture of dimethyl succinate (19-30%), dimethyl glutarate (50-75%), and dimethyl adipate (10-25%)), ethylene glycol monopropyl ether (EP), n-butyl propionate (BPP), n-butylpyrrolidone (NBP), and combinations thereof.

[0030] In some embodiments, the organic co-solvent is a combination of ethylene glycol monobutyl ether (EB) and dibasic ester (DBE) at a ratio of 65-85 (EB) / 15-35 (DBE), and wherein DBE is a mixture of dimethyl succinate (19-30%), dimethyl glutarate (50-75%), and dimethyl adipate (10-25 %). In other embodiments, the organic co-solvent is a combination of ethylene glycol monopropyl ether (EP) and dibasic ester (DBE) at a ratio of 65-75 (EP) / 25-35 (DBE), and wherein DBE is a mixture of dimethyl succinate (19-30%), dimethyl glutarate (50-75%), and dimethyl adipate (10-25 wt.%). In further embodiments, the organic co-solvent is a combination of ethylene glycolmonopropyl ether (EP) and n-butyl propionate (BPP) at a ratio of 75-85 (EP) / 15-25 (BPP). In even further embodiments, the organic co-solvent is n-butylpyrrolidone (NBP).Waterborne Coating Composition

[0031] Also disclosed herein are waterborne coating compositions. The waterborne coating compositions comprise: A. the acrylic modified polyester as described herein in an amount of 60 to 95 weight percent, based on the total weight of (A) and (B); B. a crosslinking agent in an amount of 5 to 40 weight percent, based on the total weight of (A) and (B); C. an organic co-solvent in an amount of 10 to 30 weight percent, based on the total weight of the coating composition; and D. water in an amount of 30 to 60 weight percent, based on the total weight of the coating composition. All individual values and subranges are included and disclosed herein. For example, in some embodiments, the waterborne coating compositions comprise: A. the acrylic modified polyester as described herein in an amount of from 65 to 95, 70 to 95, 75 to 95, or 80 to 95 weight percent, based on the total weight of (A) and (B); B. a crosslinking agent in an amount of from 5 to 35, 5 to 30, 5 to 25, or 5 to 20 weight percent, based on the total weight of (A) and (B); C. an organic co-solvent in an amount of from 12.5 to 30, 12.5 to 27.5, 15 to 30, or 15 to 25 weight percent, based on the total weight of the coating composition; and D. water in an amount of from 35 to 60, 40 to 60, or 45 to 60 weight percent, based on the total weight of the coating composition.

[0032] The organic co-solvent (C) are as previously described herein. The crosslinker (B) may be one or more selected from the group consisting of resole phenolic resin, isocyanate, amino resin, and p-hydroxyalkylamide crosslinkers. Selection of the crosslinker may depend on whether the polymer is hydroxyl-functional (e.g., resole phenolic resin, isocyanate, or amino resin crosslinkers) or carboxyl-functional (e.g., [3-hydroxyalkylamide crosslinkers).

[0033] In some embodiments, the crosslinking agent is a β-hydroxyalkylamide. In other embodiments, the crosslinking agent is a β-hydroxyalkylamide selected from the group consisting of bis(N, N'-dihydroxyethyl)adipamide, bis(N, N'-dihydroxypropyl)adipamide, or a mixture thereof. Commercially available [3-hydroxyalkylamides include bis(N, N'-dihydroxyethyl)adipamide (Primid® XL-552), bis(N, N'-dihydroxypropyl)adipamide (Primid® QM-1260), and Primid® SF-4510 available from EMS-GRILTECH. Also commercially available is Megamid XL from MEGARA RESINS-ANASTASIOS FANIS S. A.

[0034] In some embodiments, the crosslinking agent is a resole phenolic resin. In other embodiments, the crosslinking agent is a resole phenolic resin selected from the group consisting of phenolic resin based on cresol and formaldehyde; resole phenolic resin based on unsubstituted phenol and formaldehyde; resole phenolic resin based on m-cresol, p-cresol, and formaldehyde; and combinations thereof.

[0035] Resole phenolic resins contain the residues of un-substituted phenol and / or meta-substituted phenols. These particular resole resins can exhibit good reactivity with said acrylic modified polyester (A). In some embodiments, the amount of the resole phenolic resin is at least 50 wt.% or greater than 60 wt.% or greater than 70 wt.% or greater than 80 wt.% or greater than 90 wt.% based on the total weight of all cross-linker compounds.

[0036] The resole phenolic resin present in the crosslinking composition contains methylol groups on the phenolic rings. Phenolic resins having methylol functionalities are referred to as resole type phenolic resins. As is known in the art, the methylol group (--CH2OH) may be etherated with an alcohol and present as -CH2OR, wherein R is Ci-Cs alkyl group, in order to improve resin properties such as storage stability and compatibility. For purpose of the description, the term “methylol” used herein includes both - CH2OH and -CH2OR and an un-substituted methylol group is CH2OH. Said methylol groups (either -CH2OH or -CH2OR) are the end groups attached to the resole resins. The methylol groups are formed during the resole resin synthesis and can further react with another molecule to form ether or methylene linkages leading to macromolecules.

[0037] The resole phenolic resin may contain the residues of un-substituted phenols or meta-substituted phenols. When starting with phenol or meta-substituted phenols to make a resole, the para and ortho positions are both available for bridging reactions to form a branched network with final methylol end groups on the resin being in the para or ortho positions relative to the phenolic hydroxyl group. To make the phenolic resole, a phenol composition is used as a starting material. The phenol composition contains un-substituted and / or meta-substituted phenols. The amount of un-substituted, metasubstituted, or a combination of the two, that is present in the phenol compositions used as a reactant to make the phenolic resole resin, is at least 50 wt.%, or at least 60 wt.%, or at least 70 wt.%, or at least 75 wt.%, or at least 80 wt.%, or at least 85 wt.%, or at least 90 wt.%, or at least 95 wt.%, or at least 98 wt.%, based on the weight of the phenol composition used as a reactant starting material.

[0038] The phenol composition is reacted with a reactive compound such as an aldehyde at an aldehyde:phenol molar ratio (using aldehyde as an example) of greater than 1:1, or at least 1.05:1, or at least 1.1:1, or at least 1.2:1, or at least 1.25:1, or at least 1.3:1, or at least 1.35:1, or at least 1.4:1, or at least 1.45:1, or at least 1.5:1, or at least 1.55:1, or at least 1.6:1, or at least 1.65:1, or at least 1.7:1, or at least 1.75:1, or at least 1.8:1, or at least 1.85:1, or at least 1.9:1, or at least 1.95:1, or at least 2:1. The upper amount of aldehyde is not limited and can be as high as 30:1, but generally is up to 5:1, or up to 4:1, or up to 3:1, or up to 2.5:1. In some embodiments, the ratio of aldehyde:phenol is at least 1.2:1 or more, or 1.4:1 or more or 1.5:1 or more, and typically up to 3:1. These ratios may also apply to the aldehyde / unsubstituted phenol or meta¬ substituted phenol ratio.

[0039] The resole phenolic resin can contain an average of at least 0.3, or at least 0.4, or at least 0.45, or at least 0.5, or at least 0.6, or at least 0.8, or at least 0.9 methylol groups per one phenolic hydroxyl group, and “methylol” includes both -CH2OH and -CH2OR.

[0040] The phenolic resin obtained by the condensation of phenols with aldehydes of the general formula (RCHO)n, where R is hydrogen or a hydrocarbon group having 1 to 8 carbon atoms and n is 1, 2, or 3. Examples include formaldehyde, paraldehyde, acetaldehyde, glyoxal, propionaldehyde,furfuraldehyde, or benzaldehyde. In some embodiments, the phenolic resin is the reaction product of phenols with formaldehyde.At least a part of the crosslinker in (B) comprises a resole type phenolic resin that is prepared by reacting either un-substituted phenol or meta-substituted phenol or a combination thereof with an aldehyde. The unsubstituted phenol is phenol (CeHsOH). Examples of meta-substituted phenols include m-cresol, m-ethylphenol, m-propylphenol, m-butylphenol, moctylphenol, m-alkylphenol, m-phenylphenol, m-alkoxyphenol, 3,5-xylenol, 3,5-diethyl phenol, 3,5-dibutyl phenol, 3,5-dialkylphenol, 3,5-dicyclohexyl phenol, 3,5-dimethoxy phenol, 3-alkyl-5-alkyoxy phenol, and the like.

[0041] Although other substituted phenol compounds can be used in combination with said un-substituted phenols or meta-substituted phenols for making phenolic resins, it is desirable that at least 50%, or at least 70%, or at least 80%, or at least 90%, or at least 95%, or at least 98%, or at least 100% of the phenolic compounds used to make the resole resin are unsubstituted phenol or meta-substituted phenol. In some embodiments, the resole phenolic resin used in this invention comprises residues of m-substituted phenol. In some embodiments, the crosslinking agent is a resole phenolic resin selected from the group consisting of resole phenolic resin based on cresol and formaldehyde; resole phenolic resin based on unsubstituted phenol and formaldehyde; resole phenolic resin based on m-cresol, p-cresol, and formaldehyde; and combinations thereof.

[0042] Examples of suitable commercial phenolic resins include, but are not limited to, PHENODUR® PR 516 / 60B (based on cresol and formaldehyde) available from Allnex, PHENODUR® PR 371 / 70B (based on unsubstituted phenol and formaldehyde) also available from Allnex, and CURAPHEN 40-856 B60 (based on m-cresol, p-cresol, and formaldehyde) available from Bitrez.

[0043] In one or more embodiments herein, the resole phenolic resins are heat curable. In one or more embodiments herein, the resole phenolic resins are not made by the addition of bisphenol A, F, or S (collectively “BPA”). In one or more embodiments herein, the resole phenolic resins are soluble in alcohol. In one or more embodiments herein, the resole phenolic resins can be liquid at25°C. In one or more embodiments herein, the resole phenolic resins have a weight average molecular weight from 200 to 2000 g / mol (alternatively, from 300 to 1000, from 400 to 800, or from 500 to 600 g / mol).

[0044] In some embodiments, the crosslinking agent is an isocyanate crosslinker. The isocyanate crosslinker suitable for this invention may be a blocked or unblocked isocyanate type. Examples of suitable isocyanate crosslinkers include, but are not limited to, 1,6-hexamethylene diisocyanate, methylene bis(4-cyclohexyl isocyanate), and isophorone diisocyanate. In some embodiments, the crosslinking agent is an isocyanate crosslinker selected from the group consisting of isophorone diisocyanate (IPDI) or blocked IPDI. Commercial examples are available from COVESTRO as Desmodur® BL 2078 / 2, or Bayhydur® 3100 available from COVESTRO is a hydrophilic aliphatic polyisocyanate based on hexamethylene diisocyanate (HDI), which is particularly suitable for waterborne formulations.

[0045] In some embodiments, the crosslinking agent is an amino resin. The amino resin (crosslinker or cross-linking agent) can be a melamine¬ formaldehyde type or benzoguanamine-formaldehyde type cross-linking agent, i.e., a cross-linking agent having a plurality of -N(CH2OR3)2 functional groups, wherein R3is C1 -C4 alkyl, such as methyl.

[0046] In general, the amino cross-linking agent may be selected from compounds of the following formulae, wherein R3is independently Ci -C4 alkyl:

[0047] Exemplary amino resins suitable as crosslinking agents may include hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylbenzoguanamine, tetrabutoxymethylbenzoguanamine, tetramethoxymethylurea, mixed butoxy / methoxy substituted melamines, and the like. In some embodiments, the crosslinking agent is an amino resin selected from the group consisting of hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylbenzoguanamine, tetrabutoxymethylbenzoguanamine, tetramethoxymethylurea, mixed butoxy / methoxy substituted melamines, or a mixture thereof. Suitable commercial amino resins include Maprenal BF 987 (n-butylated benzoquanamine-formaldelhyde resin available from Ineos), CYMEL® 1123 (highly methylated / ethylated benzoguanamine-formaldehyde resin available from Allnex), CYMEL® 1158 (butylated melamine-formaldehyde resin with amino functionality available from Allnex) CYMEL® 325 (methylated high imino melamine resin available from Allnex), CYMEL® 327 (methylated high imino melamine / formaldehyde amino crosslinker available from Allnex), and other benzoguanamine-formaldehyde and melamine-formaldehyde type resins.

[0048] In one or more embodiments herein, the crosslinking agent (B) may be a mixture of an amino resin in an amount of 20-80 weight % and isocyanate in an amount of 80-20 weight %, based on the total weight of the crosslinkers. All individual values and subranges are included and disclosed herein. For example, in some embodiments, the crosslinking agent (B) is a mixture of an amino resin in an amount of from 25, 30, 35, 40, 45 or 50 to 80, 75, or 70 weight % and isocyanate in an amount of 75, 70, 65, 60, 55, or 55 to 20, 25, or 30 weight %, based on the total weight of the crosslinkers.

[0049] In one or more embodiments herein, the crosslinking agent (B) may be a mixture of a resole phenolic resin in an amount of 70-90 weight % and isocyanate in an amount of 10-30 weight %, based on the total weight of the crosslinkers. All individual values and subranges are included and disclosed herein. For example, in some embodiments, the crosslinking agent (B) may be a mixture of a resole phenolic resin in an amount of 70-90, 75-90, or 80-90 weight % and isocyanate in an amount of 10-30, 10-25, or 10-20 weight %, based on the total weight of the crosslinkers. As an example, the crosslinking agent (B) may be a mixture of CURAPHEN 40-856 B60 available from Bitrez and blocked isophorone diisocyanate (I P DI).

[0050] In any thermosetting compositions, one or more crosslinking catalysts may also be included. Representative crosslinking catalysts include from carboxylic acids, sulfonic acids, tertiary amines, tertiary phosphines, tin compounds, or combinations of these compounds. Some specific examples of crosslinking catalysts include p-toluenesulfonic acid, phosphoric acid, the NACURE™ 155, 5076, and 1051 catalysts sold by King Industries, BYK 450, 470, available from BYK-Chemie U. S. A., methyl tolyl sulfonimide, p- toluenesulfonic acid, dodecylbenzene sulfonic acid, dinonylnaphthalene sulfonic acid, and dinonylnaphthalene disulfonic acid, benzoic acid, triphenylphosphine, dibutyltindilaurate, and dibutyltindiacetate.

[0051] The crosslinking catalyst can depend on the type of crosslinker that is used in the coating composition. For example, the crosslinker can comprise a melamine or "amino" crosslinker and the crosslinking catalyst can comprise p-toluenesulfonic acid, phosphoric acid, unblocked and blocked dodecylbenzene sulfonic (abbreviated herein as “DDBSA”), dinonylnaphthalene sulfonic acid (abbreviated herein as “DNNSA”) and dinonylnaphthalene disulfonic acid (abbreviated herein as “DNNDSA”). Some of these catalysts are available commercially under trademarks such as, for example, NACURE™ 155, 5076, 1051, 5225, and XC-296B (available from King Industries), BYK-CATALYSTS™ (available from BYK-Chemie USA), and CYCAT™ catalysts (available from Cytec Surface Specialties). The coating compositions described herein can comprise one or more isocyanatecrosslinking catalysts such as, for example, FASCAT™ 4202 (dibutyltindilaurate), FASCAT™ 4200 (dibutyltindiacetate, both available from Arkema), DABCO™ T-12 (available from Air Products) and K-KAT™ 348, 4205, 5218, XC-6212™ non-tin catalysts (available from King Industries), and tertiary amines. The coating composition can contain an acid or base catalyst in an amount ranging from 0.1 to 2 weight %, based on the total weight of any of the aforementioned curable polyester resins and the crosslinker composition.EXAMPLESExample 1. Synthesis of Saturated Polyesters

[0052] The polyols are produced using a resin kettle reactor setup controlled with automated control software. The compositions are produced on a 3.5 mole scale using a 2 L kettle with overhead stirring and a partial condenser topped with total condenser and Dean Stark trap. The monomers include isophthalic acid (IPA), terephthalic acid (TPA), adipic acid (AD), 1,4-cyclohexane dimethanol (CHDM), 2,2,4,4-tetramethy-1,3-lcyclobutanediol (TMCD), 2-methyl-1,3-propanediol (MPdiol), and trimethylolpropane (TMP). The monomers are added to the reactor which is then completely assembled. The Fascat 4100 (monobutyltin oxide, available from PMC Organometallix Inc.) is added via the sampling port after the reactor had been assembled and blanketed with nitrogen for the reaction. The reaction mixture is heated without stirring from room temperature to 150 °C using a set output controlled through the automation system. Once the reaction mixture is fluid enough, the stirring is started to encourage even heating of the mixture. At 150 °C, the control of heating is switched to automated control and the temperature is ramped to 230 °C over the course of 4 h. The reaction is held at 230 °C for 1 h and then heated to 240 °C over the course of 1 h. The reaction is then held at 240 °C and sampled every 1-2 h upon clearing until the desired acid value is reached. It should be noted that the glycol excesses are determined empirically for the lab reactor and may be different depending on the partial condenser and reactor design used. The glycol acid ratio is also manipulated to enable achieving the same molecular weight with simply different acid and hydroxyl endlevels. Table 1 shows an example of saturated polyester resin (PE-1) made by this method using a resin kettle reactor.Table 1. The charge sheet of the saturated polyester resin (PE-1) made using a resin rig reactor.Charge WeightRaw Material Moles Equivalents Weight (including % Excess excess, g)IPA 2.2750 4.5500 377.95 377.95 0TPA 1.0500 2.1000 174.44 174.44 0 Adipic Acid 0.1750 0.3500 25.57 25.57 0 TMCD 1.4221 2.8442 205.08 229.69 121,4-CHDM 1.3510 2.7020 194.83 194.83 0 MPdiol 0.7111 1.4221 64.07 65.99 3TMP 0.0711 0.2133 9.54 10.11 6(Catalyst) ConcentrationFascat 4100 400 ppm 0.76

[0053] Using the same method as described above, a series of polyesters with various compositions is synthesized. Table 2 lists their compositions. Table 2. Saturated polyesters with various compositionsMole Ratio Based on Total Mole Ratio Based Alcohols on Total Acids(%) (%)PolyesterCHDM TMCD MP Diol TMP IPA TPA AD resinPE-1 38 40 20 2 65 30 5PE-2 43 45 10 2 70 30 0PE-3 45 45 10 0 70 30 0PE-4 38 0 60 2 65 30 5

[0054] Table 3 lists the resin properties of the saturated polyesters. Glass transition temperature (Tg) is determined using a Q2000 differential scanning calorimeter (DSC) from TA Instruments, New Castle, DE, US, at a scan rate of 20°C / min. Number average molecular weight (Mn) and weight average molecular weight (Mw) are measured by gel permeation chromatography (GPC) using polystyrene equivalent molecular weight. Acid number (AN) is measured by using a procedure based on ASTM D7253-16 entitled “Standard Test Method for Polyurethane Raw Materials: Determination of Acidity as Acid Number for Polyether Polyols,” and hydroxyl number (OHN) is measured using a procedure based on ASTM E222-1 entitled “Standard Test Methods for Hydroxyl Groups Using Acetic Anhydride.”Table 3. Resin properties of saturated polyestersPolyesterAN OHN Tg (°C) Mn Mw resinPE-1 4 15 78 10800 35900 PE-2 4 18 92 9300 26900 PE-3 3 7 97 15600 32600 PE-4 10 12 44 10500 43988Example 2: Synthesis of Methacrylic Anhydride-Modified Polyester Resin by Free-Radical Solution Polymerization

[0055] In a heated 500 mL round-bottom flask equipped with a water condenser is dissolved 45 g of the polyester resin (PE-1) from Example 1 in 45 g of organic solvents (EB 31.5 g and DBE 18.5 g). The mixture is heated to about 120 °C and stirred under nitrogen atmosphere. A solution of the initiator (t-butyl peroctoate, 1 g) in methacrylic anhydride (11.25 g) is prepared. This initiator / monomer solution is added dropwise to the reaction mixture over 0.5 hour. The reaction mixture is then held at 120 °C for 1 hour to produce methacrylic anhydride-modified polyester resin (MR-1).

[0056] Using the same method as described above, various combinations of acrylic monomers and polyester resins are used for solution free-radical polymerization to prepare acrylic modified polyesters, as listed in tables 4-6.Example 3: Preparation of Aqueous Dispersions of Acrylic Modified Polyesters

[0057] The polymer solution (20 g) prepared in Example 2 is charged to a 250 mL round-bottom flask and heated to 90°C, followed by the addition of N, N-dimethylethanolamine (DMEA) as the neutralizing agent (90-100% neutralization). The mixture is then held at for 15 minutes, and deionized water is gradually added over 30 minutes (-25% solids). The mixture is allowed to cool to room temperature and the resulting dispersion is collected. Other aqueous dispersions are also prepared according to the same procedures by using the acrylic modified polyesters prepared in Example 2, and the dispersion results are shown in tables 4-6.

[0058] The particle size of the aqueous dispersion is measured by dynamic light scattering on a Zetasizer Nano-ZS (Malvern Instrument). The aqueous dispersion thus prepared may contain undispersed resin solids, which can be removed by filtration to yield a dispersion free of particulate substances. It is desirable that the aqueous dispersion contains no more than 1 weight % of undispersed resin solids, based on the total weight of the dispersion, before filtration.Table 4. Aqueous dispersion results of methacrylic anhydride-modified polyester resins (EB = Ethylene glycol monobutyl ether, DBE = Dibasic ester mixture, BPP = n-Butyl propionate, NBP = n-Butylpyrrolidone).WeightMethacryliccontent of Undispersed anhydride- Particle Polyester methacrylic resin before modified Solvents size resin anhydride in filtration polyester (nm) the modified (weight %) resinresinEB / DBEMR-1 PE-1 20% <1 % 152 (70 / 30)EB / DBEMR-2 PE-1 15% <1 % 250 (80 / 20)EB / DBEMR-3 PE-1 30% <1 % 204 (80 / 20)EB / DBEMR-4 PE-1 40% <1 % 168 (80 / 20)EB / DBEMR-5 PE-1 50% <1 % 184 (80 / 20)EB / DBEMR-6 PE-2 20% <1 % 158 (70 / 30)EB / DBEMR-7 PE-2 30% <1 % 146 (80 / 20)EB / DBEMR-8 PE-3 30% <1 % 749 (80 / 20)EB / DBEMR-9 PE-4 20% <1 % 182 (70 / 30)EP / DBEMR-10 PE-1 20% <1 % 234 (70 / 30)EP / BPPMR-11 PE-1 30% <1 % 370 (80 / 20)MR-12 PE-1 20% NBP <1 % 486Table 5. Aqueous dispersion results of comparative methacrylic anhydride-modified polyester resins (EB = Ethylene glycol monobutyl ether, DBE = Dibasic ester mixture, EP = Ethylene glycol monopropyl ether, PM = Propylene glycol monomethyl ether, DE Acetate = Diethylene glycol monoethyl ether acetate, MAK = Methyl n-amyl ketone, DPM = Di(propylene glycol) methyl ether).WeightComparativecontent of Undispersed acrylic- Polyester methacrylic resin before modified Solventsresin anhydride in filtration polyesterthe modified (weight %) resinresinCMR-1 PE-1 20% EB >1%CMR-2 PE-1 20% EP >1%CMR-3 PE-1 20% PM >1%CMR-4 PE-1 20% DE Acetate >1%CMR-5 PE-1 20% MAK >1%CMR-6 PE-1 20% DPM >1%CMR-7 PE-1 20% Xylene >1%PM / DBECMR-8 PE-1 20% >1%(70 / 30)PM / MAKCMR-9 PE-1 20% >1%(70 / 30)DPM / MAKCMR-10 PE-1 20% >1%(70 / 30)EP / MAKCMR-11 PE-1 20% >1%(70 / 30)EB / DBECMR-12 PE-1 15% >1%(70 / 30)EB / DBECMR-13 PE-1 15% >1%(60 / 40)WeightComparativecontent of Undispersed acrylic- Polyester methacrylic resin before modified Solventsresin anhydride in filtration polyesterthe modified (weight %) resinresinEB / DBECMR-14 PE-1 10% >1%(80 / 20)EB / DBECMR-15 PE-1 20% >1%(80 / 20)EB / DBECMR-16 PE-2 20% >1%(80 / 20)Table 6. Aqueous dispersion results of acrylic-modified polyester resins with mixtures of acrylic monomers (EB = Ethylene glycol monobutyl ether, DBE = Dibasic ester mixture, MPK = Methyl n-propyl ketone, DPM = Di(propylene glycol) methyl ether, NBP = n-Butylpyrrolidone; MAA = Methacrylic acid, BA = Butyl acrylate, MMA = Methyl methacrylate, HEMA = 2-Hydroxyethyl methacrylate, MAN = Methacrylic anhydride).WeightAcrylic- content Undisperse Mixtures ofmodifie of acrylic d resin Partici Polyest Solvent acrylic monomersd monomer before e size er resin s and their weightpolyest s in the filtration (nm) ratioser resin modified (weight %)resinMAA / BA / MMA / HEMMR-1 PE-1 40% EB >1% / MA (40 / 10 / 40 / 10)MAA / BA / MMA / HEMMR-2 PE-1 40% MPK >1% / MA (40 / 25 / 25 / 10)MAA / BA / MMA / HEMMR-3 PE-1 20% DPM >1% / MA (30 / 10 / 50 / 10)87655WQ01WeightAcrylic- content Undisperse Mixtures ofmodifie of acrylic d resin Partici Polyest Solvent acrylic monomersd monomer before e size er resin s and their weightpolyest s in the filtration (nm) ratioser resin modified (weight %)resinMAA / BA / MMA / HEMMR-4 PE-1 40% DPM >1% / MA (40 / 10 / 40 / 10)MAA / BA / MMA / HEMMR-5 PE-1 40% NBP >1% / MA (40 / 25 / 25 / 10)EB / DBEMMR-6 PE-1 20% MAN / BA (75 / 25) <1% 1017 (80 / 20)EB / DBEMMR-7 PE-1 30% MAN / MMA (75 / 25) <1% 291 (80 / 20)EB / DBE MAN / BA / HEMAMMR-8 PE-1 30% <1% 427 (70 / 30) (80 / 10 / 10)Example 4. Preparation of Waterborne Coating Formulations

[0059] Waterborne coating formulations are prepared by using Primid QM 1260 as the crosslinker. Primid QM 1260 is a hydroxyalkylamide crosslinker available from EMS-GRILTECH. A food grade approved BYK-392 from BYK is chosen as polyacrylate defoamer. An empty glass jar with a lid is labeled and pre-weighted to record the tare weight. For each formulation, Primid QM 1260, BYK-392, and solvent (butanol and DI water) are weighed out respectively and added to the resin solution in order. Primid QM 1260 is reduced in DI water with 25% solid and BYK-392 is reduced in butanol (1:9 ratio) with 5.2% solid. Once it is completed, the glass jar containing the formulation is then rolled overnight with slight agitation at ambient conditions.

[0060] Table 7 lists coating formulations using an aqueous dispersion prepared in Example 3. Table 8 lists comparative coating formulations using an aqueous dispersion prepared in Example 3. Table 9 and 10 list coating properties of the films made from the formulations.Example 5. Coating Preparation and Testing

[0061] Aluminum substrate panels are supplied by Q-lab - 0.19 mm thickness. The substrates are coated by casting wet films with wire wound rods, RDS 7 (available from R. D. Specialties, Inc.). This yielded a final dry film weight approximately 3-4 grams / m2 for clear coatings. The coated panels are placed in a rack to hold them vertically in an oven for cure. A Despatch forced air oven is preheated to a setting temperature of 210 °C. The coated panels in a rack are then placed into the oven for 3 minutes of bake cycle time in order to allow the coatings to be baked at 195 °C Peak Metal Temperature (PMT) for 90 seconds. In conclusion of baking cycle, the panel rack is removed from oven and allowed to cool back to ambient conditions. A Sencon SI9600 coating thickness gauge is used to confirm the dry film weight of the applied coatings.

[0062] Methyl Ethyl Ketone (MEK) Double Rubs: The resistance to MEK solvent is measured using a MEK rub test machine (Gardco MEK Rub Test Machine AB-410103EN with 1 kg block). This test is carried out similar to ASTM D7835. MEK solvent resistance is reported as the number of double rubs a coated panel can take before the coating starts to be removed. For example, one back-and-forth motion constitutes one double rub. A maximum of 100 double rubs is set as the upper limit for each evaluation.

[0063] Sterilization Resistance Testing: A coated coupon measuring 1.5" widex3" long is cut from the coated panel. The coupons are then placed in 16 oz wide mouth Le Parfait glass jar half filled with the food simulant where half the coupon is above food simulant liquid, and the other half is submerged in food simulant liquid. Two different simulants are evaluated:• DI water: 100% deionized water.• Citric acid: 1 % citric acid, 99% deionized water.

[0064] The jars with properly closed top are placed in an autoclave, Priorclave Model PNA / QCS / EH150, for 1 hr at 121 °C. Once the retort process is finished, the autoclave is allowed to depressurize to ambient conditions. After the completion of sterilization cycle, the glass jars containing the test coupons are then removed from the autoclave. The coupons are removed from the jarsand wash under water and blotted dry with paper towels. Typically, the retort performance is rated on a scale of 0 (worst) to 5 (best) using a visual observation. For each food simulant, the retort performance is rated on (1) blush at vapor phase, (2) blush at liquid phase, (3) roughness at vapor phase, (4) roughness at liquid phase and (5) crosshatch adhesion (following ASTM D 3359) at liquid phase, respectively. An overall retort performance is reported as Total Retort % is calculated by:Total Retort %_ Sum of rating (1) to (5) from DI water + _ S_um of rating (1) to (5)from 1% citric acidx 100%

[0065] Each retort rating in this experiment is an average rating from 2 replicates.Table 7. Clear Coating FormulationsF-1 F-2Solids / Active WeightComponent Weight (g)% (g)Resin (MR-1) 25% 16.96 16.07Primid QM 1260 - 25% in DI25% 1.00 2.00waterDI water 0% 5.75 5.00BYK 392 - 10% in Butanol 5.2% 0.50Solvent (Butanol) 0% 1.29 1.43Total weight 25.00 25.00Calculation:% Total solids 20.00% 20.00%% HAA crosslinker on total binder 5.00% 10.00%% Total water 59.92% 58.14%% Total organic solvent 20.08% 21.76%Table 8. Clear Coating Properties1% Citric acid MEK Double Rubs DI water Retort %Retort % F-1 27 70% 78%F-2 40 80% 80%Table 9. Comparative Clear Coating FormulationsCF-1 CF-2 CF-3 Solids / Active Weight Weight Weight Component% (g) (g) (g) Resin (MR-1) 25% 16.96 16.07 16.07 Primid QM 1260 - 25%25% 1.00 2.00 2.00 in DI waterDI water 0% 2.50 2.50 5.00 Solvent (Butanol) 0% 4.54 4.43 1.93 Total weight 25.00 25.00 25.00 Calculation:% Total solids 20.00% 20.00% 20.00% % HAA crosslinker on total binder 5.00% 10.00% 10.00% % Total water 46.92% 48.14% 58.14% % Total organic solvent 33.08% 31.86% 21.86%Table 10. Clear Coating Properties1%MEK CitricDI waterDouble acid Note Retort %Rubs Retort%Solution phase CF-1separation1%MEK CitricDI waterDouble acid Note Retort %Rubs Retort%Solution phaseCF-2separationSolution phaseCF-3separation

[0066] As shown in Tables 7-10, the inventive coatings show no solution phase separation whereas the comparative coatings do have solution phase separation.

[0067] The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as “40 mm” is intended to mean “about 40 mm.”

[0068] Every document cited herein, if any, including any cross- referenced or related patent or application and any patent application or patent to which this application claims priority or benefit thereof, is hereby incorporated herein by reference in its entirety unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art with respect to any invention disclosed or claimed herein or that it alone, or in any combination with any other reference or references, teaches, suggests or discloses any such invention. Further, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.

[0069] While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art thatvarious other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims

What is claimed is:

1. A water dispersible acrylic modified polyester, which is the free-radical reaction product of:

1. 45 to 90 wt.% of a saturated polyester, based on the total weight of (I) and (II), wherein the saturated polyester is the reaction product of:i. 80 to 100 mol.% of a diol selected from the group consisting of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD), 2-methyl-1,3- propanediol (MPdiol), 1,4-cyclohexanedimethanol, 1,3- cyclohexanedimethanol, 1,2-cyclohexanedimethanol, and combinations thereof, based on the total moles of (i) and (ii),ii. 0 to 20 mol.% of a triol, based on the total moles of (i) and (ii), ill. 60 to 100 mol.% of an aromatic diacid, based on the total moles of (iii) and (iv), andiv. 0 to 40 mol.% of an aliphatic diacid, based on the total moles of (iii) and (iv), andwherein said saturated polyester is free of an α,β-unsaturated monomer, and wherein the polyester has an acid number of 0 to 30 mg KOH / g, hydroxyl number of 5 to 50 mg KOH / g, a number average molecular weight of 2,000 to 30,000 g / mol, and a weight average molecular weight of 10,000 to 200,000 g / mol; andII. 10 to 55 wt.% of one or more ethylenically unsaturated monomers, based on the total weight of (I) and (II), wherein the one or more ethylenically unsaturated monomers comprises:i. methacrylic anhydride, acrylic anhydride or a combination thereof; andii. optionally, one or more ethylenically unsaturated monomers other than (ll)(i).

2. The acrylic modified polyester of claim 1, wherein the acrylic modified polyester has an acid number of 30-200 mgKOH / g.

3. The acrylic modified polyester of claims 1 or 2, wherein the diol (l)(i) is a combination of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) in an amount of 20-60 mol.%, 1,4-cyclohexanedimethanol in an amount of 30-60 mol.%, and 2-methyl-1,3-propanediol (MPdiol) in an amount of 5-40 mol.%, based on the total moles of the diols.

4. The acrylic modified polyester of claims 1 or 2, wherein the diol (l)(i) is a combination of 1,4-cyclohexanedimethanol in an amount of 30-60 mol.% and 2-methyl-1,3-propanediol (MPdiol)in an amount of 40-70 mol.%, based on the total moles of the diols.

5. The acrylic modified polyester of claims 1-4, wherein the triol (l)(ii) is trimethylolpropane (TMP).

6. The acrylic modified polyester of claims 1 -5, wherein the aromatic diacid (l)(iii) is a combination of isophthalic acid and terephthalic acid.

7. The acrylic modified polyester of claim 6, wherein the isophthalic acid is in an amount of 50-80 mol.% and terephthalic acid is in an amount of 20-50 mol.%, based on the total moles of the aromatic diacids.

8. The acrylic modified polyester of claims 1 -7, wherein the acrylic modified polyester comprises greater than 0 to 40 mol.% of the aliphatic diacid (l)(iv), and wherein the aliphatic diacid (l)(iv) is adipic acid.

9. The acrylic modified polyester of claims 1-8, wherein (ll)(ii) is selected from the group consisting of methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, styrene, and combinations thereof.

10. The acrylic modified polyester of claims 1-9, wherein the one or more ethylenically unsaturated monomer (II) is methacrylic anhydride.

11. The acrylic modified polyester of claims 1-9, wherein the one or more ethylenically unsaturated monomer (II) is a combination of methacrylic anhydride (MAN) and butyl acrylate (BA) at a weight ratio of 70-80 (MAN) / 20-30 (BA).

12. The acrylic modified polyester of claims 1-9, wherein the one or more ethylenically unsaturated monomer (II) is a combination of methacrylic anhydride (MAN) and methyl methacrylate (MMA) at a weight ratio of 70-80 (MAN) / 20-30 (MMA).

13. The acrylic modified polyester of claims 1-9, wherein the one or more ethylenically unsaturated monomer (II) is a combination of methacrylic anhydride (MAN) in an amount of 70-90 weight %, butyl acrylate (BA) in an amount of 5-15 weight %, and 2-hydroxyethyl methacrylate (HEMA) in an amount of 5-15 weight %, based on the total weight of the one or more ethylenically unsaturated monomers (II).

14. The acrylic modified polyester of claim 1, wherein said diol (l)(i) is a combination of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) in an amount of 20-60 mol.%, 1,4-cyclohexanedimethanol (1,4-CHDM) in an amount of 30- 60 mol.%, and 2-methyl-1,3-propanediol (MPdiol) in an amount of 5-40 mol.%, based on the total moles of the diols; said triol (l)(ii) is trimethylolpropane (TMP); said aromatic diacid (ll)(i) is a combination of isophthalic acid in an amount of 50-80 mol.% and terephthalic acid in an amount of 20-50 mol.%, based on the total moles of the aromatic diacids; and the acrylic modified polyester comprises greater than 0 to 40 mol.% of the aliphatic diacid (l)(iv), and said aliphatic diacid (l)(iv)is adipic acid.

15. An aqueous dispersion comprising:a. the acrylic modified polyester of any one of claims 1 -14;b. an organic co-solvent;c. a neutralizing agent; andd. water.

16. The aqueous dispersion of claim 15, wherein the dispersion contains no more than 1 weight % of undispersed resin solids, based on the total weight of the dispersion, before filtering the dispersion.

17. The aqueous dispersion of claims 15 or 16, wherein the organic co¬ solvent is a combination of ethylene glycol monobutyl ether (EB) and dibasic ester (DBE) at a ratio of 65-85 (EB) / 15-35 (DBE), and wherein DBE is a mixture of dimethyl succinate (19-30%), dimethyl glutarate (50-75%), and dimethyl adipate (10-25 %).

18. The aqueous dispersion of claims 15 or 16, wherein the organic co¬ solvent is a combination of ethylene glycol monopropyl ether (EP) and dibasic ester (DBE) at a ratio of 65-75 (EP) / 25-35 (DBE), and wherein DBE is a mixture of dimethyl succinate (19-30%), dimethyl glutarate (50-75%), and dimethyl adipate (10-25 wt.%).

19. The aqueous dispersion of claims 15 or 16, wherein the organic co¬ solvent is a combination of ethylene glycol monopropyl ether (EP) and n-butyl propionate (BPP) at a ratio of 75-85 (EP) / 15-25 (BPP).

20. The aqueous dispersion of claims 15 or 16, wherein the organic cosolvent is n-butylpyrrolidone (NBP).

21. The aqueous dispersion of claims 15-20, wherein the neutralizing agent is an amine selected from the group consisting of ammonia, trimethylamine, diethylamine, monoethanolamine, monoisopropanolamine, morpholine,ethanolamine, diethanolamine, triethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N-methyldiethanolamine, and combinations thereof.

22. A waterborne coating composition comprising:A. the acrylic modified polyester of any one of claims 1-14 in an amount of 60 to 95 weight percent, based on the total weight of (A) and (B);B. a crosslinking agent in an amount of 5 to 40 weight percent, based on the total weight of (A) and (B);C. an organic co-solvent in an amount of 10 to 30 weight percent, based on the total weight of the coating composition; andD. water in an amount of 30 to 60 weight percent, based on the total weight of the coating composition.

23. The waterborne coating composition of claim 22, wherein the crosslinking agent is one or more selected from the group consisting of resole phenolic resin, isocyanate, amino resin, and p-hydroxyalkylamide crosslinkers.

24. The waterborne coating composition of claim 22, wherein the crosslinking agent is a β-hydroxyalkylamide selected from the group consisting of bis(N, N'-dihydroxyethyl)adipamide, bis(N, N'-dihydroxypropyl)adipamide, or a mixture thereof.

25. The waterborne coating composition of claim 22, wherein the crosslinking agent is a resole phenolic resin selected from the group consisting of resole phenolic resin based on cresol and formaldehyde; resole phenolic resin based on unsubstituted phenol and formaldehyde; resole phenolic resin based on m-cresol, p-cresol, and formaldehyde; and combinations thereof.

26. The waterborne coating composition of claim 22, wherein the crosslinking agent is an isocyanate crosslinker selected from the group consisting of isophorone diisocyanate (I PDI) or blocked IPDI.

27. The waterborne coating composition of claim 22, wherein the crosslinking agent is an amino resin selected from the group consisting of hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylbenzoguanamine, tetrabutoxymethylbenzoguanamine, tetramethoxymethylurea, mixed butoxy / methoxy substituted melamines, or a mixture thereof.

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