WO2019210036A1 - Carboxylic acid adducted rosin polyol ester with fatty acid functionality and methods of producing the same - Google Patents

Abstract

Carboxylic acid adducted rosin polyol ester with fatty acid functionality compositions, methods of making the same, use of the same in adhesives, and methods or preparing the same are disclosed herein. The method of producing the carboxylic acid adducted rosin polyol ester with fatty acid functionality includes the steps of: adding and mixing a carboxylic acid (e.g., an α,β-unsaturated carboxylic acid) to a molten rosin to produce a carboxylic acid adducted rosin; esterifying the carboxylic acid adducted rosin by reaction with a polyol to produce a carboxylic acid adducted rosin polyol ester; and reacting the carboxylic acid adducted rosin polyol ester with a fatty acid material to produce the carboxylic acid adducted rosin polyol ester with fatty acid functionality.

Description

CARBOXYLIC ACID ADDUCTED ROSIN POLYOL ESTER WITH FATTY ACID

FUNCTIONALITY AND METHODS OF PRODUCING THE SAME

CROSS REFERENCE TO RELATED APPLICATION

[0001] This application claims the benefit of U.S. Application No. 62/663,070, filed on April 26, 2018, which is incorporated herein by reference in its entirety.

BACKGROUND

[0002] 1. Field of the Art

[0003] The present disclosure relates to carboxylic acid adducted rosin polyol ester with fatty acid functionality and method of producing the same; the use of carboxylic acid adducted rosin polyol ester with fatty acid functionality as tackifiers in adhesive compositions; the adhesive compositions produced thereby; and methods of producing the same.

[0004] 2. Description of Related Art

[0005] Hot melt adhesives (HMAs) and pressure sensitive polymer adhesives (PSAs) formulations include tackifying resins which increase the adhesion (i.e., the ability of the adhesive to form a lasting bond) of the adhesive to the substrate. These tackifiers tend to have low molecular weights (relative to the base polymer of the adhesive), as well as glass transition and softening temperatures above room temperature, which give the tackifiers unique amorphous properties. Tackifiers frequently account for a significant portion of the weight of a hot melt adhesive product as they can comprise up to 50% or more of the total mass of the product.

[0006] Heretofore, rosin ester tackifiers or oligomers have been successfully used to improve the adhesion properties of various polymer adhesive compositions. However, tall oil rosin esters have not generally been used in markets requiring low odor such as the hygiene market,-packaging, construction, graphic arts, automotive and other end uses that are sensitive to high odor due to odor issues originating from chemicals used in the kraft paper process (i.e., the extraction of rosin). It was found that adducting the rosin with acrylic acid followed by esterification with a polyhydric alcohol, such as trimethylolpropane, glycerin, pentaerythritol, or similar polyhydric alcohols, provides a resin with much improved odor characteristics when compared to typical non-acrylic acid modified rosin esters. Although the odor was much improved, the adhesive performance, e.g., in a diaper construction formulation, did not meet the required performance attributes. For example, when used in a standard diaper construction adhesive, the acrylic acid modified resin produced a“stiff’ adhesive which was undesirable for the adhesive application.

[0007] Therefore, in view of the above, it will be apparent that a need exists for: (a) an improved tackifying resin for adhesives, such as HMAs and PSAs; and (b) a rosin ester tackifier composition that has a low odor and the required adhesive performance attributes.

SUMMARY

[0008] In one aspect, there is provided a method of producing a carboxylic acid adducted rosin polyol ester with fatty acid functionality, which may be used as a tackifier in adhesives (such as hot melt adhesives (HMAs)). The method comprises: adding and mixing a carboxylic acid (such as an a,b-unsaturated carboxylic acid) to a molten rosin (e.g., reacting carboxylic acid with rosins, such as molten rosin) to produce a carboxylic acid adducted rosin; esterifying the carboxylic acid adducted rosin by reaction with a polyol to produce a carboxylic acid adducted rosin polyol ester; and reacting the carboxylic acid adducted rosin polyol ester with a fatty acid material to produce the carboxylic acid adducted rosin polyol ester with fatty acid functionality. [0009] In certain embodiments, the a,b-unsaturated carboxylic acid is at least one member selected from the group consisting of acrylic acid, maleic acid, maleic anhydride, fumaric acid, acrylic acid, methacrylic acid, or a combination thereof.

[0010] In further embodiments, the rosin is reacted with the polyol in the presence of an esterification catalyst.

[0011] In particular embodiments, the esterification catalyst is at least one of a phosphonate salt (such as calcium bismonoethyl(3,5-di-tert-butyl-4-hydroxy-benzyl)phosphonate, known commercially as BNX^® 1425), a phosphite ester, a phosphinic acid, an aryl sulfonic acid, or combinations thereof.

[0012] In other embodiments, the polyol is at least one member selected from the group consisting of triethyleneglycol, diethyleneglycol, pentaerythritol, glycerin, sorbitol, trimethylolpropane, 1, 4-cyclohexane dimethanol, l,4-butanediol, 1, 3-propanediol, and ethylene glycol used solely, or a combination thereof.

[0013] In a particular embodiment, the polyol is trimethylolpropane.

[0014] In additional embodiments, the fatty acid material is a saturated fatty acid.

[0015] In some embodiments, the fatty acid material is an unsaturated fatty acid.

[0016] In other embodiments, the fatty acid material is a C4-C40 saturated or unsaturated fatty acid.

[0017] In certain embodiments, the saturated fatty acid is stearic acid.

[0018] In some embodiments, the method further comprises adding an antioxidant.

[0019] In certain embodiments, the antioxidant is added to (or mixed or combined with) the molten rosin before the carboxylic acid. [0020] In certain other embodiments, esterifying the carboxylic acid adducted rosin includes the addition of an antioxidant.

[0021] In yet further embodiments, the antioxidant is selected from the group consisting of Irganox^® 1010, BNX-565, or a combination thereof.

[0022] In other embodiments, esterifying the carboxylic acid adducted rosin includes the addition of a disproportionation agent or catalyst.

[0023] In an embodiment, the disproportionation agent or catalyst is at least one of Rosinox^®, LOWINOX^® TBM-6, VULTAC^® 2, ETHANOX^® 328, alkylphenoldisulfide, alkylphenolsulfide, derivative thereof, and combinations thereof.

[0024] In yet other embodiments, the a,b-unsaturated carboxylic acid and rosin are added or combined in a ratio of carboxylic acid to rosin of about 1: 1 to about 1:30 (e.g., about 1: 15 to about 1:30 or about 1:24).

[0025] In some embodiments, the carboxylic acid adducted rosin and the polyol are added or combined in a ratio of carboxylic adducted rosin to polyol of about 3: 1 to about 20: 1 (e.g., about 3: 1 to about 10: 1 or about 6: 1).

[0026] In particular embodiments, the carboxylic acid adducted rosin polyol ester and the fatty acid material are added or combined in a ratio of carboxylic acid adducted rosin polyol ester to fatty acid material of about 5: 1 to about 200: 1 (e.g., about 30: 1 to about 55: 1 or about 41: 1).

[0027] In another aspect, there is provided an acrylic acid adducted rosin polyol ester with fatty acid functionality produced by the method of the present disclosure.

[0028] Further aspects, features, and advantages of the present invention will be apparent to those of ordinary skill in the art upon reading the following Detailed Description of the Preferred

Embodiments. DETAILED DESCRIPTION

[0029] The following is a detailed description of the disclosure provided to aid those skilled in the art in practicing the present disclosure. Those of ordinary skill in the art may make modifications and variations in the embodiments described herein without departing from the spirit or scope of the present disclosure. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. The terminology used in the description of the disclosure herein is for describing particular embodiments only and is not intended to be limiting of the disclosure. All publications, patent applications, patents, figures and other references mentioned herein are expressly incorporated by reference in their entirety.

[0030] The present disclosure provides a carboxylic acid adducted rosin polyol ester with fatty acid functionality with the surprising and unexpected low odor and improved rheological characteristics compared to other experimental low odor rosin based tackifiers. In addition, the present disclosure provides a method of producing the inventive modified rosin resin tackifier. Further, the present disclosure provides a thermoplastic adhesive composition which preferably comprises: (a) a polymer material; and (b) the inventive modified rosin resin tackifier.

[0031] Where a range of values is provided, it is understood that each intervening value, to the tenth of the unit of the lower limit unless the context clearly dictates otherwise (such as in the case of a group containing a number of carbon atoms in which case each carbon atom number falling within the range is provided), between the upper and lower limit of that range and any other stated or intervening value in that stated range is encompassed within the disclosure. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges is also encompassed within the invention, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either both of those included limits are also included in the invention.

[0032] The following terms are used to describe the present invention. In instances where a term is not specifically defined herein, that term is given an art-recognized meaning by those of ordinary skill applying that term in context to its use in describing the present invention.

[0033] The articles "a" and "an" as used herein and in the appended claims are used herein to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article unless the context clearly indicates otherwise. By way of example, "an element" means one element or more than one element.

[0034] The phrase "and/or," as used herein in the specification and in the claims, should be understood to mean "either or both" of the elements so conjoined, i.e., elements that are conjunctively present in some cases and disjunctively present in other cases. Multiple elements listed with "and/or" should be construed in the same fashion, i.e., "one or more" of the elements so conjoined. Other elements may optionally be present other than the elements specifically identified by the "and/or" clause, whether related or unrelated to those elements specifically identified. Thus, as a non-limiting example, a reference to "A and/or B", when used in conjunction with open-ended language such as "comprising" can refer, in one embodiment, to A only (optionally including elements other than B); in another embodiment, to B only (optionally including elements other than A); in yet another embodiment, to both A and B (optionally including other elements); etc.

[0035] As used herein in the specification and in the claims, "or" should be understood to have the same meaning as "and/or" as defined above. For example, when separating items in a list, "or" or "and/or" shall be interpreted as being inclusive, i.e., the inclusion of at least one, but also including more than one, of a number or list of elements, and, optionally, additional unlisted items. Only terms clearly indicated to the contrary, such as "only one of or "exactly one of," or, when used in the claims, "consisting of," will refer to the inclusion of exactly one element of a number or list of elements. In general, the term "or" as used herein shall only be interpreted as indicating exclusive alternatives (i.e., "one or the other but not both") when preceded by terms of exclusivity, such as "either," "one of," "only one of," or "exactly one of."

[0036] In the claims, as well as in the specification above, all transitional phrases such as "comprising," "including," "carrying," "having," "containing," "involving," "holding," "composed of," and the like are to be understood to be open-ended, i.e., to mean including but not limited to. Only the transitional phrases "consisting of and "consisting essentially of shall be closed or semi- closed transitional phrases, respectively, as set forth in the 10 United States Patent Office Manual of Patent Examining Procedures, Section 2111.03.

[0037] As used herein in the specification and in the claims, the phrase "at least one," in reference to a list of one or more elements, should be understood to mean at least one element selected from anyone or more of the elements in the list of elements, but not necessarily including at least one of each and every element specifically listed within the list of elements and not excluding any combinations of elements in the list of elements. This definition also allows that elements may optionally be present other than the elements specifically identified within the list of elements to which the phrase "at least one" refers, whether related or unrelated to those elements specifically identified. Thus, as a nonlimiting example, "at least one of A and B" (or, equivalently, "at least one of A or B," or, equivalently "at least one of A and/or B") can refer, in one embodiment, to at least one, optionally including more than one, A, with no B present (and optionally including elements other than B); in another embodiment, to at least one, optionally including more than one, B, with no A present (and optionally including elements other than A); in yet another embodiment, to at least one, optionally including more than one, A, and at least one, optionally including more than one, B (and optionally including other elements); etc.

[0038] It should also be understood that, unless clearly indicated to the contrary, in any methods claimed herein that include more than one step or act, the order of the steps or acts of the method is not necessarily limited to the order in which the steps or acts of the method are recited.

[0039] The term“compound”, as used herein, unless otherwise indicated, refers to any specific chemical compound disclosed herein and includes tautomers, regioisomers, geometric isomers, and where applicable, stereoisomers, including optical isomers (enantiomers) and other steroisomers (diastereomers) thereof. It is noted that in describing the present compounds, numerous substituents and variables associated with same, among others, are described. It is understood by those of ordinary skill that molecules which are described herein are stable compounds as generally described hereunder.

[0040] The term“rosin” or“rosin acids” refers to mixtures of several related carboxylic acids such as abietic acid, neoabietic acid, dehydroabietic acid, palustric acid, levopimaric acid, pimaric acid and isopimaric acids found in tree resins. Nearly all resin acids have the same basic skeleton: three fused ring fused with the empirical formula C19H29COOH.

[0041] The term“modified rosin” refers to rosin acids chemically modified by a modification as described herein.

[0042] As used herein,“polyol” refers to a compound that contains multiple hydroxyl groups, i.e., two or more hydroxyl groups.

[0043] As used herein,“adduct” refers to a direct addition of two or more distinct molecules, resulting in a single reaction product containing all atoms of each of the distinct molecules. [0044] In one aspect, there is provided a method of producing a carboxylic acid adducted rosin polyol ester with fatty acid functionality, which may be used as a tackifier. The method comprises: adding and mixing (e.g., reacting) an a,b-unsaturated carboxylic acid to a molten rosin to produce a carboxylic acid adducted rosin; esterifying the carboxylic acid adducted rosin by reacting with a polyol to produce a carboxylic acid adducted rosin polyol ester; and reacting the carboxylic acid adducted rosin polyol ester with a fatty acid material to produce the carboxylic acid adducted rosin polyol ester with fatty acid functionality.

[0045] The a,b-unsaturated carboxylic acid and rosin may be combined or added or mixed in a ratio of carboxylic acid to rosin of about 1: 1 to about 1:30 (e.g., about 1: 15 to about 1:30 or about 1:24). For example, the ratio of carboxylic acid to rosin is about 1: 1 to about 1:30, about 1:5 to about 1:30, about 1: 10 to about 1:30, about 1: 15 to about 1:30, about 1:20 to about 1:30, about 1:25 to about 1:30, about 1:5 to about 1:25, about 1: 10 to about 1:25, about 1: 15 to about 1:25, about 1:20 to about 1:25, about 1:5 to about 1:20, about 1: 10 to about 1:20, about 1: 15 to about 1:20, about 1:5 to about 1: 15, about 1: 10 to about 1: 15, or about 1:5 to about 1: 10.

[0046] The carboxylic acid adducted rosin and the polyol may be combined or added or mixed in a ratio of carboxylic adducted rosin to polyol of about 3: 1 to about 20: 1 (e.g., about 3: 1 to about 10: 1 or about 6: 1). For example, the ratio of carboxylic adducted rosin to polyol is about 3: 1 to about 20: 1, about 5: 1 to about 20: 1, about 10: 1 to about 20: 1, about 15: 1 to about 20: 1, about 3: 1 to about 15: 1, about 5: 1 to about 15: 1, about 10: 1 to about 15: 1, about 3: 1 to about 10: 1, about 5: 1 to about 10: 1, or about 3: 1 to about 5: 1.

[0047] The carboxylic acid adducted rosin polyol ester and the fatty acid material may be combined or added or mixed in a ratio of carboxylic acid adducted rosin polyol ester to fatty acid material of about 5: 1 to about 200: 1 (e.g., about 30: 1 to about 55: 1 or about 41: 1). For example, the ratio of carboxylic acid adducted rosin polyol ester to fatty acid material is about 5:1 to about 200:1, about 25:1 to about 200:1, about 50:1 to about 200:1, about 75:1 to about 200:1, about 100:1 to about 200:1, about 125: 1 to about 200:1, about 150: 1 to about 200:1, about 175: 1 to about 200:1, about 5:1 to about 175:1, about 25:1 to about 175:1, about 50:1 to about 175:1, about 75:1 to about 175:1, about 100:1 to about 175:1, about 125:1 to about 175:1, about 150:1 to about 175:1, about 5:1 to about 150:1, about 25:1 to about 150:1, about 50:1 to about 150:1, about 75:1 to about 150:1, about 100:1 to about 150:1, about 125:1 to about 150:1, about 5:1 to about 125:1, about 25:1 to about 125:1, about 50:1 to about 125:1, about 75:1 to about 125:1, about 100:1 to about 125:1, about 5:1 to about 100:1, about 25:1 to about 100:1, about 50:1 to about 100:1, about 75:1 to about 100:1, about 5:1 to about 75:1, about 25:1 to about 75:1, about 50:1 to about 75:1, about 5:1 to about 50:1, or about 25:1 to about 50:1.

[0048] In some embodiments, the a,b-unsaturated carboxylic acid is at least one of acrylic acid, maleic acid, maleic anhydride, fumaric acid, acrylic acid, methacrylic acid, or combinations thereof.

[0049] The rosin may be reacted with the polyol in the presence of an esterification catalyst. Esterification catalysts and stabilizers for rosin esters are known in the art. An example of an esterification catalyst that may be used in the inventive method is phosphonic acid, P-[[3,5-bis(l,l-dimethylethyl)-4-hydroxyphenyl]methyl]-, monoethyl ester, calcium salt (2:1). This composition is commercially available from, e.g., Mayzo under the name BNX^® 1425. For example, the esterification catalyst may be at least one of a phosphonate salt (such as calcium bismonoethyl(3,5-di-tert-butyl-4-hydroxy-benzyl)phosphonate, known commercially as BNX^® 1425), a phosphite ester, a phosphinic acid, an aryl sulfonic acid, or combinations thereof. [0050] Many different polyols are known and used in the art to react with the carboxylic core of the rosin structure, thus producing rosin esters. For example, the polyol can be at least one of triethyleneglycol, diethyleneglycol, pentaerythritol, glycerin, sorbitol, trimethylolpropane, 1,4- cyclohexane dimethanol, l,4-butanediol, 1, 3-propanediol, and ethylene glycol used solely, or as a combination thereof. For example, the polyol may be trimethylolpropane, pentaerythritol, glycerin, cyclohexane dimethanol, or a combination thereof.

[0051] In additional embodiments, the fatty acid material is at least one saturated fatty acid (such as stearic acid) (e.g., at least two, at least three, or at least four saturated fatty acids).

[0052] In other embodiments, the fatty acid material is at least one unsaturated fatty acid (at least two, at least three, or at least four unsaturated fatty acids).

[0053] In certain embodiment, the fatty acid material is at least one (or at least two, at least three, or at least four) C4-C40 saturated or unsaturated fatty acid. For example, the fatty acid material is at least one (or at least two, at least three, or at least four) C6-C26 saturated or unsaturated fatty acid. The fatty acid material may include a C4-C40, C4-C35, C4-C30, C4-C25, C4-C20, C4-C15, C10-C40, C10-C35, C10-C30, C10-C25, C10-C20, C10-C15, C15-C40, 05- C35, C15-C30, C15-C25, C15-C20, C20-C40, C20-C35, C20-C30, C20-C25, C25-C40, C25-C35, C25-C30, C30-C40, C30-C35, or C35-C40 saturated fatty acid. The fatty acid material may include a C4-C40, C4-C35, C4-C30, C4-C25, C4-C20, C4-C15, C10-C40, C10-C35, C10-C30, C10-C25, C10-C20, C10-C15, C15-C40, C15-C35, C15-C30, C15-C25, C15-C20, C20-C40, C20- C35, C20-C30, C20-C25, C25-C40, C25-C35, C25-C30, C30-C40, C30-C35, or C35-C40 unsaturated fatty acid. [0054] The method may further comprise adding an antioxidant (e.g., at least one of Irganox^® 1010, BNX-565 or a combination thereof), which may be added to the molten rosin before the carboxylic acid or after esterifying the carboxylic acid adducted rosin.

[0055] During esterifying the carboxylic acid adducted rosin, one or more disproportionation agent or catalyst (such as Rosinox^®, LOWINOX^® TBM-6, VULTAC^® 2, ETHANOX^® 328, alkylphenoldisulfide, alkylphenolsulfide, derivative thereof, and combinations thereof) may be added. Alternatively, or in addition to adding a disproportionation agent/catalyst during esterification, the rosin or adducted rosin may be pretreated with one or more disproportionation agent or catalyst.

[0056] The method may further comprise melting the rosin, e.g., by heating the rosin to 200°C to about 260°C (e.g., about 220°C). The melting/heating may be performed under a chemically inert gas blanket (e.g., nitrogen, argon, helium, neon, krypton, xenon, or radon). The a,b- unsaturated carboxylic acid is added to the molten rosin. An antioxidant may be added to the molten resin prior to the addition of the a,b-unsaturated carboxylic acid, at the same time as the addition of a,b-unsaturated carboxylic acid, or after the addition of the a,b-unsaturated carboxylic acid. For example, Irganox^® 1010 may be added. The antioxidant may be added to the rosin at a ratio of molten rosin to antioxidant of about 300: 1 to about 450: 1 (e.g., about 385: 1). The a,b- unsaturated carboxylic acid may be added at a rate of about 0.2 g/min to about 3.0 g/min (e.g., about 0.5 g/min to about 2.0 g/min or about 1 g/min). The carboxylic acid and molten rosin may be mixed or stirred for about 45 minutes to about 10 hours (e.g., about 1.5 hours to about 4.5 hours or about 3 hours), which may be performed at about 200°C to about 260°C (e.g., 220°C)

[0057] The method may further comprise cooling the carboxylic acid adducted rosin to about room temperature (e.g., about l8°C to about 28°C or about 23°C) to about 200°C. The carboxylic acid adducted rosin may have at least one of a Gardner color of no greater than 6.0 (neat) (e.g., no greater than 5.7), an acid number value of no greater than 215 mg KOH/g (e.g., no greater than 195 mg KOH/g), a softening point of no greater than 97°C (e.g., no greater than 93.5°C), or a combination thereof.

[0058] The method may comprise melting or heating the carboxylic adducted rosin to about l60°C to about 2lO°C to melt or maintain the molten state of the carboxylic adducted rosin. The polyol is added to the molten carboxylic acid adducted rosin. Furthermore, during this esterification step, at least one of an (i) esterification catalyst (e.g., at least one of a phosphonate salt [such as calcium bismonoethyl(3,5-di-tert-butyl-4-hydroxy-benzyl)phosphonate, known commercially as BNX^® 1425], a phosphite ester, a phosphinic acid, an aryl sulfonic acid, or combinations thereof), (ii) a disproportionation agent or catalyst (e.g., at least one of Rosinox^®, LOWINOX^® TBM-6, VULTAC^® 2, ETHANOX^® 328, alkylphenoldisulfide, alkylphenolsulfide, derivative thereof, and combinations thereof), or (iii) a combination thereof, may be added. The carboxylic acid adducted rosin and the esterification catalyst may be combined or mixed or added in a ratio of carboxylic acid adducted rosin to esterification catalyst of about 175: 1 to about 300: 1 (e.g., about 235: 1). The carboxylic acid adducted rosin and the disproportionation agent may be combined or mixed or added in a ratio of carboxylic acid adducted rosin to disproportionation agent or catalyst of about 275: 1 to about 375: 1 (e.g., about 333: 1).

[0059] After the addition of the polyol (with or without the esterification catalyst and/or disproportionation agent/catalyst), the mixture may be heated to about 240°C to about 335°C (e.g., about 275°C). The esterification mixture (i.e., the mixture that comprises the carboxylic acid adducted rosin and at least one polyol) is mixed for about 15 minutes to 3 hours (e.g., about 30 minutes to about 2 hours or about 1 hour), which may be performed under a blanket of chemically inert gas (e.g., nitrogen, argon, helium, neon, krypton, xenon, or radon). The esterification mixture may be further mixed for an additional about 30 minutes to about 5 hours (e.g., about 1 hour to about 3 hours or about 2 hours) under inert gas sparging or until the acid number value is no greater than 30, during which time generated water may be removed. The carboxylic acid adducted rosin polyol ester may then be cooled to about l60°C to about 2lO°C (e.g., about l80°C).

[0060] The fatty acid material (e.g., a C6-C26 fatty acid or stearic acid) may be added under a chemically inert gas blanket (e.g., nitrogen, argon, helium, neon, krypton, xenon, or radon). The carboxylic acid adducted rosin polyol ester-fatty acid mixture may be heated to about 240°C to about 325°C for about 1 hour to about 10 hours (e.g., about 2 hours to about 5 hours or about 4 hours) or until the acid number value was below 15. Sparging with a chemically inert gas may be performed during the mixing of the carboxylic acid adducted rosin polyol ester-fatty acid mixture.

[0061] The carboxylic acid adducted rosin polyol ester with fatty acid functionality may be cooled to about l60°C to about 220°C (e.g., about l80°C), an antioxidant added (e.g., Irganox^® 1010), and mixed (e.g., for at least 3 minutes or at least 5 minutes). The carboxylic acid adducted rosin polyol ester with fatty acid functionality (with or without the antioxidant) is cooled to room temperature (e.g., about l8°C to about 28°C). For example, the carboxylic acid adducted rosin polyol ester with fatty acid functionality and the antioxidant may be mixed or combined or added at a ratio of carboxylic acid adducted rosin polyol ester with fatty acid functionality to antioxidant of about 350: 1 to about 450: 1 (e.g., about 397: 1).

[0062] In an embodiment, the carboxylic acid adducted rosin polyol ester with fatty acid functionality (with or without antioxidant) has at least one of a Gardner color of about 3.5 (neat) or less (e.g., about 3.1 or less), an acid number value of 12.0 mg KOH/g or less (e.g., about 10.8 mg KOH/g or less), a softening point of l00°C or less (e.g., about 95.3°C or less), or a combination thereof.

[0063] As mentioned above, a carboxylic acid adducted rosin polyol ester with fatty acid functionality is provided by the present disclosure that is produced by the method of the present disclosure.

[0064] As also mentioned above, a thermoplastic adhesive composition is provided by the present disclosure that comprises a polymer material and a tackifier (i.e., the carboxylic acid adducted rosin polyol ester with fatty acid functionality). A method of producing a thermoplastic adhesive composition is also provided by the present disclosure. The method comprising: (1) producing the tackifier according to the method of producing a carboxylic acid adduced rosin polyol ester with fatty acid functionality of the present disclosure or supplying the same, and (2) mixing the tackifier with the polymer material.

[0065] Many different polymer materials for use in thermoplastic adhesive compositions are known and used in the art, and one skilled in the art would appreciate exemplary polymers that may be used in the thermoplastic adhesive of the present disclosure. For example, the polymer material may be at least one of a copolymer, a block polymer, or a combination thereof. The polymer material may be one or more of poly(styrene -block-butadiene-block-styrene) (SBS) polymer, styrenic block copolymer (SBC), Styrene ethylene butylene styrene (SEBS), styrene- ethylene/propylene-styrene (SEPS), styrene-isoprene-styrene (SIS), or a combination thereof.

[0066] The method may further comprise adding at least one of oil or plasticizer (e.g., naphthenic oil), an antioxidant, or a combination thereof. For example, the antioxidant is BNX® 1010 and the oil maybe naphthenic oil, paraffinic oil, synthetic oil, or any other acceptable plasticizers. [0067] The method may further comprise at least one of the following: adding the oil in an amount of about 10% to about 30% of the thermoplastic adhesive composition; adding the antioxidant in an amount of about 0.1% to about 2.5% of the thermoplastic adhesive composition; adding the polymer in an amount of about 10% to about 30% of the thermoplastic adhesive composition; adding the tackifier in an amount of about 40% to about 80% of the thermoplastic adhesive composition; or a combination thereof.

[0068] The oil may be present (i.e., added) in an amount of about 10% to about 30% of the thermoplastic adhesive composition.

[0069] Additionally, the antioxidant may be present (i.e., added) in an amount of about 0.1% to about 2.5% of the thermoplastic adhesive composition.

[0070] Furthermore, the polymer may be present (i.e., added) in an amount of about 10% to about 30% of the thermoplastic adhesive composition.

[0071] The tackifier may be present (i.e., added) in an amount of about 40% to about 80% of the thermoplastic adhesive composition.

[0072] By way of example, but not by way of limitation, the inventive thermoplastic adhesive composition can be prepared by adding the composition components, preferably one at a time, to a heated mixing vessel, preferably with a full sized agitator, under a chemically inert gas (e.g., nitrogen, argon, helium, neon, krypton, xenon, or radon) atmosphere. Preferably, the inventive tackifier is added and then the polymer material.

[0073] The components of the inventive adhesive composition will preferably be mixed until a smooth, clear, homogeneous blend is formed. The material can then, for example, be removed from the mixing vessel and extruded or otherwise processed to an acceptable physical form, such as a chip or a pellet. This product can be used, for example, in hot melt adhesive applications by adding the chips or pellets to a hot melting tank and pumping the melted product through a nozzle for application of the material to the surface of any type of article, item or structure. The surface of a second article, item, or structure is then pressed against or otherwise applied the treated surface of the first article to thereby bond the second article to the first article.

[0074] As discussed above, a thermoplastic adhesive composition is provided by the present disclosure that is produced according to the method of the present disclosure. That is, the thermoplastic adhesive composition may comprise: a tackifier (i.e., the carboxylic acid adducted rosin polyol ester with fatty acid functionality of the present disclosure) in an amount of about 40% to about 80% of the thermoplastic adhesive composition, and a polymer in an amount of about 10% to about 30% of the thermoplastic adhesive composition. The composition may further comprise at least one of: oil in an amount of about 10% to about 30% of the thermoplastic adhesive composition, an antioxidant in an amount of about 0.1% to about 2.5% of the thermoplastic adhesive composition, or a combination thereof.

[0075] Although the chemical structure of the carboxylic acid adducted rosin polyol ester with fatty acid functionality provided by the present disclosure has not yet been determined, the inventive product, as formed by the inventive production method, is highly compatible with polymer materials to produce stable, smooth, and clear compositions with lower odor relative to other rosin based tackifiers and similar rheological adhesive properties compared to standard adhesive formulations with hydrocarbon tackifiers used in these applications.

[0076] Moreover, these results for the inventive carboxylic acid adducted rosin polyol ester with fatty acid functionality are surprising and unexpected. To our knowledge, these are the first rosin ester based compounds to provide adhesive properties equivalent to non-resin based tackifiers with low odor. Typical rosin ester tackifiers provide poor adhesive properties. [0077] The following examples are intended to illustrate, but in no way limit, the invention as claimed.

EXAMPLES

[0078] Materials and Methods.

[0079] Instrumentation: TA-DHR-2 equipped with an enclosed oven and a nitrogen cooling system capable of cooling to -90 °C. 8 mm parallel plate geometry used in most analysis.

[0080] General Procedures: Pre-run calibrations including rotational mapping, gas temperature compensation, and zero gap were completed prior to examining the compositions. The linear viscoelastic range is first determined for the material before the method is created. Testing is performed at an acceptable % strain which lies within the linear region of the linear viscoelastic range. For most adhesives, a general ramp procedure is as follows: a start temperature of about 150-160 °C followed by a cooling rate of < 2 °C/min to a minimum temperature of -30 °C was used for the majority of testing. A 2.5% strain rate and an oscillatory frequency of 1 Hz were used for most applications. Control samples were used for comparison.

[0081] In one focus area, hygiene, the importance of rheological data points is as follows. Tg indicates the point at which a polymeric product transitions from a solid glassy material to an amorphous flexible product. For nonwoven based products, the lower the Tg of the adhesive, the better from an adhesive performance perspective. The rheological data obtained on each adhesive at both 25 °C and 40°C are important to understand the wettability and strength of the adhesives at both room temperature and human body temperature. G’ value indicates the relative strength or elastic nature of the adhesive. The G” is an indicator of the flow characteristics or wet-out of the adhesive film to different substrates. [0082] The adhesive formulations were prepared in accordance with Table 1 and the results for each example and control are shown in Table 2.

[0083] Table 1. Adhesive Formulation

[0084] Table 2. Comparison of Comparative Examples 1-3 and the Inventive Example

[0085] Evaluation of Odor. A proprietary threshold odor panel method was utilized to differentiate the samples based on odor. In the method, a series of five concentrations of equal interval per sample were collected, including a blank control. The concentrations were divided in a way that allowed the middle sample (sample #3) to be detected 50% of the time by the average panelist.

[0086] Once concentrations have been determined, the sample is ground into a powder and the designated weights for the five samples are weighed in a closable vial. To mitigate the propensity for panelist bias, each of the samples were then diluted with an odorless medium, such as sand, to a predetermined final weight. For example, a concentration array consisting of 0 g to 4 g (in 1 g increments) of sample with a predetermined final weight of 5 g would be diluted with sand to reach the final predetermined weight.

[0087] Once samples were prepared, they were placed in an oven at 50° C for a period of at least 30 minutes before odor panel testing. The odor panel typically consisted of at least four members who had been evaluated and trained for odor detection and consistency. A standardized method of odor evaluation was used for each sample in ascending order of concentration. The panelist maintained the sample three inches from their nose (approximately resting on the chin) and took three short sniffs to check for detection. Once odor was detected, the panelist designates the sample as first detection and continues with the sample array. In some cases, a faint detection followed by a definite detection was noted.

[0088] Once the concentration array was completed, the threshold detections of all panelist were collected. In the case of faint detection followed by definite detection, the two concentrations were averaged. An average of all concentrations was then averaged to render the odor detection threshold of the sample. Table 3 is an example of a typical odor panel test. Note that the lower the odor detection threshold, the lower the odor of the sample (i.e., higher values indicate a higher concentration of resin was required for odor detection).

[0089] Table 3. Results from a typical odor panel test

[0090] Exemplary formulation. To a 3 L four- neck round bottom flask equipped with an air driven agitator, condenser, nitrogen inlet tube, and thermocouple was added Ingevity rosin (1540 g, 5.1 mol). The solid rosin was heated to 220 °C under N₂ blanket to melt followed by the addition of Irganox^® 1010 (4.0 g, 0.0034 mol). To the molten mixture was added acrylic acid (56 g, 0.78 mol) at a rate of approximately 1 g/min via a fluid metering pump. After the addition of acrylic acid was complete, the mixture was stirred at 220 °C for 3 hour. The acrylic acid adducted rosin was cooled to 180 °C, discharged into aluminum pans, and cooled to room temperature to provide a resin with a Gardner color of 5.7 (neat) (Gardner Color Scale performed according to a standard method ASTM D6166 12(2016)), an acid number value of 195 mg KOH/g, and a softening point of 93.5 °C.

[0091] To a 2 L four- neck round bottom flask equipped with an air driven agitator, condenser, Dean-Stark apparatus, nitrogen inlet tube, and thermocouple was added acrylic acid adducted rosin (832.37 g). The solid was heated to 180 °C to melt followed by the addition of BNC^®-1425 (3.5 g, 0.005 mol), Rosinox^® (2.5 g), and trimethylolpropane (139.13 g, 1.04 mol). The mixture was heated to 275 °C under N₂ blanket and stirred for approximately 1 hour before initiating a N₂ sparge. The mixture was stirred for an additional 2 hour (removing water as it was generated) or until the acid number value reached a value at or below 30. The resin was cooled to 180 °C under N₂ blanket and stearic acid (20.0 g, 0.07 mol) was added. The temperature of the mixture was increased to 275 °C and N₂ sparging was continued for approximately 4 hour or until the acid number value was below 15. The resin was cooled to 180 °C under N₂ blanket and Irganox^® 1010 (2.5 g, 0.002 mol) was added. After stirring for at least 5 minute, the resin was discharged and allowed to cool to room temperature to provide the Inventive Example with a Gardner color of 3.1 (neat), an acid number value of 10.8 mg KOH/g, and a softening point of 95.3 °C. [0092] Comparative Example 1. To a 3 L four-neck round bottom flask equipped with an air driven agitator, condenser, nitrogen inlet tube, and thermocouple was added Ingevity rosin (1532 g, 5.07 mol). The solid rosin was heated to 220 °C under N₂ blanket to melt followed by the addition of Irganox^® 1010 (4.0 g, 0.0034 mol). To the molten mixture was added acrylic acid (64 g, 0.89 mol) at a rate of approximately 1 g/min via a fluid metering pump. After the addition of acrylic acid was complete, the mixture was stirred at 220 °C for 3 hours. The acrylic acid adducted rosin was cooled to 180 °C, discharged into aluminum pans, and cooled to room temperature to provide a resin with a Gardner color of 6.2 (neat), an acid number value of 199 mg KOH/g, and a softening point of 95.5 °C.

[0093] To a 2 L four-neck round bottom flask equipped with an air driven agitator, condenser, Dean-Stark apparatus, nitrogen inlet tube, and thermocouple was added acrylic acid adducted rosin (1019.91 g). The solid was heated to 180 °C to melt followed by the addition of BNX^® 1425 (4.2 g, 0.006 mol), Rosinox^® (3.0 g), and trimethylolpropane (169.89 g, 1.27 mol). The mixture was heated to 275 °C under N₂ blanket and stirred for approximately 1 hour before initiating a N₂ sparge. The mixture was stirred for an additional 6-8 hours (removing water as it was generated) or until the acid number value reached a value below 15. The resin was cooled to 180 °C and Irganox^® 1010 (3.0 g, (0.003 mol) was added. After stirring for at least 5 min, the resin was discharged and allowed to cool to room temperature to provide Comparative Example 1 Resin with a Gardner color of 3.5 (neat), an acid number value of 11.7 mg KOH/g, and a softening point of 99.5 °C.

[0094] Comparative Example 2. To a 3 L four-neck round bottom flask equipped with an air driven agitator, condenser, nitrogen inlet tube, and thermocouple was added Ingevity rosin (1540 g, 5.1 mol). The solid rosin was heated to 220 °C under N₂ blanket to melt followed by the addition of Irganox^® 1010 (4.0 g, 0.0034 mol). To the molten mixture was added acrylic acid (56 g, 0.78 mol) at a rate of approximately 1 g/min via a fluid metering pump. After the addition of acrylic acid was complete, the mixture was stirred at 220 °C for 3 hours. The acrylic acid adducted rosin was cooled to 180 °C, discharged into aluminum pans, and cooled to room temperature to provide a resin with a Gardner color of 5.7 (neat), an acid number value of 195 mg KOH/g, and a softening point of 93.5 °C.

[0095] To a 2 L four-neck round bottom flask equipped with an air driven agitator, condenser, Dean-Stark apparatus, nitrogen inlet tube, and thermocouple was added acrylic acid adducted rosin (852.37 g). The solid was heated to 180 °C to melt followed by the addition of BNC^®-1425 (3.5 g, 0.005 mol), Rosinox^® (2.5 g), and trimethylolpropane (139.13 g, 1.04 mol). The mixture was heated to 275 °C under N₂ blanket and stirred for approximately 1 hour before initiating a N₂ sparge. The mixture was stirred for an additional 6-8 hours (removing water as it was generated) or until the acid number value reached a value below 15. The resin was cooled to 180 °C and Irganox^® 1010 (2.5 g, 0.002 mol) was added. After stirring for at least 5 minutes, the resin was discharged and allowed to cool to room temperature to provide Comparative Example 2 Resin with a Gardner color of 3.1 (neat), an acid number value of 10.1 mg KOH/g, and a softening point of 101.7 °C.

[0096] Comparative Example 3. To a 3 L four-neck round bottom flask equipped with an air driven agitator, condenser, nitrogen inlet tube, and thermocouple was added Ingevity rosin (1548 g, 5.13 mol). The solid rosin was heated to 220 °C under N₂ blanket to melt followed by the addition of Irganox^® 1010 (4.0 g, 0.0034 mol). To the molten mixture was added acrylic acid (48 g, 0.67 mol) at a rate of approximately 1 g/min via a fluid metering pump. After the addition of acrylic acid was complete, the mixture was stirred at 220 °C for 3 hour. The acrylic acid adducted rosin was cooled to 180 °C, discharged into aluminum pans, and cooled to room temperature to provide a resin with a Gardner color of 5.9 (neat), an acid number value of 193 mg KOH/g, and a softening point of 92.7 °C.

[0097] To a 2 L four-neck round bottom flask equipped with an air driven agitator, condenser, Dean-Stark apparatus, nitrogen inlet tube, and thermocouple was added acrylic acid adducted rosin (853.35 g). The solid was heated to 180 °C to melt followed by the addition of BNC^®-1425 (3.5 g, 0.005 mol), Rosinox^® (2.5 g), and trimethylolpropane (138.15 g, 1.03 mol). The mixture was heated to 275 °C under N₂ blanket and stirred for approximately 1 hour before initiating a N₂ sparge. The mixture was stirred for an additional 6-8 hours (removing water as it was generated) or until the acid number value reached a value below 15. The resin was cooled to 180 °C and Irganox^® 1010 (2.5 g, 0.002 mol) was added. After stirring for at least 5 min, the resin was discharged and allowed to cool to room temperature to provide Comparative Example 3 Resin with a Gardner color of 3.3 (neat), an acid number value of 12.7 mg KOH/g, and a softening point of 99.9 °C.

[0098] Discussion of Examples. Tall oil rosin esters are generally not used in the domestic hygiene market due to odor issues originating from chemicals used in the kraft paper process. It was determined that adducting the rosin with acrylic acid followed by esterification with a polyhydric alcohol such as trimethylolpropane, glycerin, pentaerythritol, or similar polyhydric alcohols provides a resin with much improved odor characteristics when compared to typical non acrylic acid modified rosin esters. However, although the odor was much improved, the adhesive performance was poor. For example, the adhesive performance in a diaper construction formulation, does not meet the required performance attributes because when used in a standard diaper construction adhesive, the resin produced a“stiff’ adhesive, which is undesirable for the adhesive application.

[0099] It was suspected that the molecular structure of the rosin ester was too large due to the acrylic acid modification, therefore; several resins (Comparative Examples 2-3) were prepared with lower amounts of acrylic acid. The formulated adhesives of the lower acrylic acid modified resins were evaluated via rheology and compared to adhesives prepared using a standard hydrocarbon resin as well as a standard pentaerythritol based rosin ester. As shown in Table 2 above, the Tg of the test adhesives were >4 °C higher than that of the control. The majority of G’ and G” at 25 °C and 40 °C were also higher values.

[0100] Other resin chemistries were then evaluated to form a“softer” finished adhesive, while retaining the desired physical properties of the resin such as 95-100 °C softening points. It was surprisingly discovered that the addition of a small amount of stearic acid to the acrylic acid/trimethylolpropane formulation retained the low odor aspect of the resin, while improving the rheological characteristics. See Table 2. The Tg and the G’ and G” of the adhesive prepared with the Inventive Example Resin were much closer to that of the control adhesive. It is thought that the stearic acid incorporation into the rosin ester structure increases the aliphatic character, thus compensating for the larger structure associated with acrylic acid modification. As a result, the resin can provide an adhesive that more closely resembles the rheological characteristics of the control adhesive.

[0101] Specific Embodiments

[0102] According to an aspect, the present disclosure provides a method of producing a carboxylic acid adducted rosin polyol ester with fatty acid functionality, the method comprising: adding and mixing an alpha, beta-unsaturated carboxylic acid to a molten rosin to produce a carboxylic acid adducted rosin; esterifying the adducted rosin by reaction with a polyol to produce a carboxylic acid adducted rosin polyol ester; and reacting the carboxylic acid adducted rosin polyol ester with a fatty acid material to produce the carboxylic acid adducted rosin polyol ester with fatty acid functionality.

[0103] In any aspect or embodiment described herein, the alpha, beta-unsaturated carboxylic acid is at least one of acrylic acid, maleic acid, maleic anhydride, fumaric acid, acrylic acid, methacrylic acid, or a combination thereof.

[0104] In any aspect or embodiment described herein, the alpha, beta-unsaturated carboxylic acid is acrylic acid.

[0105] In any aspect or embodiment described herein, the rosin is reacted with the polyol in the presence of an esterification catalyst.

[0106] In any aspect or embodiment described herein, the esterification catalyst is at least one of a phosphonate salt, a phosphite ester, a phosphinic acid, an aryl sulfonic acid, or a combination thereof.

[0107] In any aspect or embodiment described herein, the polyol is at least one of triethyleneglycol, diethyleneglycol, pentaerythritol, glycerin, sorbitol, trimethylolpropane, 1 ,4- cyclohexane dimethanol, l,4-butanediol, 1, 3-propanediol, ethylene glycol used solely, or a combination thereof.

[0108] In any aspect or embodiment described herein, the polyol is trimethylolpropane.

[0109] In any aspect or embodiment described herein, the fatty acid material is a C4 to C40 saturated and/or unsaturated fatty acid.

[0110] In any aspect or embodiment described herein, the fatty acid material is a C6-C26 saturated and/or unsaturated fatty acid. [0111] In any aspect or embodiment described herein, the saturated fatty acid is stearic acid.

[0112] In any aspect or embodiment described herein, esterifying the carboxylic acid adducted rosin includes the addition of a disproportionation agent or catalyst.

[0113] In any aspect or embodiment described herein, the disproportionation agent or catalyst is at least one of Rosinox^®, LOWINOX^® TBM-6, VULTAC^® 2, ETHANOX^® 328, alkylphenoldisulfide, alkylphenolsulfide, or derivatives thereof, or a combination thereof .

[0114] In any aspect or embodiment described herein, the carboxylic acid and rosin are added in a ratio of carboxylic acid to rosin of about 1: 1 to about 1:30.

[0115] In any aspect or embodiment described herein, the ratio of carboxylic acid to rosin is about 1:24.

[0116] In any aspect or embodiment described herein, the carboxylic acid adducted rosin and the polyol are added in a ratio of carboxylic adducted rosin to polyol of about 3: 1 to about 20: 1.

[0117] In any aspect or embodiment described herein, the ratio of carboxylic adducted rosin to polyol is about 6: 1.

[0118] In any aspect or embodiment described herein, the carboxylic acid adducted rosin polyol ester and the fatty acid material are added in a ratio of carboxylic acid adducted rosin polyol ester to fatty acid material of about 5: 1 to about 200: 1.

[0119] In any aspect or embodiment described herein, the ratio of carboxylic acid adducted rosin polyol ester to fatty acid material is about 30: 1 to about 55: 1.

[0120] According to a further aspect, the present disclosure provides a carboxylic acid adducted rosin polyol ester with fatty acid functionality produced by the method of the present disclosure.

[0121] As would be understood by those of skill in the art, certain quantities, amounts, and measurements are subject to theoretical and/or practical limitations in precision, which are inherent to some of the instruments and/or methods. Therefore, unless otherwise indicated, it is contemplated that claimed amounts encompass a reasonable amount of variation.

[0122] It is understood that the detailed examples and embodiments described herein are given by way of example for illustrative purposes only, and are in no way considered to be limiting to the invention. Various modifications or changes in light thereof will be suggested to persons skilled in the art and are included within the spirit and purview of this application and are considered within the scope of the appended claims. For example, the relative quantities of the ingredients may be varied to optimize the desired effects, additional ingredients may be added, and/or similar ingredients may be substituted for one or more of the ingredients described. Additional advantageous features and functionalities associated with the systems, methods, and processes of the present invention will be apparent from the appended claims.

Claims

CLAIMS What Is Claimed Is:

1. A method of producing a carboxylic acid adducted rosin polyol ester with fatty acid functionality, the method comprising:

mixing an alpha, beta-unsaturated carboxylic acid to a molten rosin to produce a carboxylic acid adducted rosin;

esterifying the adducted rosin by reaction with a polyol to produce a carboxylic acid adducted rosin polyol ester; and

reacting the carboxylic acid adducted rosin polyol ester with a fatty acid material to produce the carboxylic acid adducted rosin polyol ester with fatty acid functionality.

2. The method of claim 1, wherein the alpha, beta-unsaturated carboxylic acid is at least one of acrylic acid, maleic acid, maleic anhydride, fumaric acid, acrylic acid, methacrylic acid, or a combination thereof.

3. The method of claim 1, wherein the alpha, beta-unsaturated carboxylic acid is acrylic acid.

4. The method of claim 1, wherein the rosin is reacted with the polyol in the presence of an esterification catalyst.

5. The method of claim 4, wherein the esterification catalyst is at least one of a phosphonate salt, a phosphite ester, a phosphinic acid, an aryl sulfonic acid, or a combination thereof.

6. The method of claim 1, wherein the polyol is at least one of triethyleneglycol, diethyleneglycol, pentaerythritol, glycerin, sorbitol, trimethylolpropane, 1, 4-cyclohexane dimethanol, l,4-butanediol, 1, 3-propanediol, ethylene glycol used solely, or a combination thereof.

7. The method of claim 1, wherein the polyol is trimethylolpropane.

8. The method of claim 1, wherein the fatty acid material is a C4 to C40 saturated and/or unsaturated fatty acid.

9. The method of claim 1, wherein the fatty acid material is a C6-C26 saturated and/or unsaturated fatty acid.

10. The method of claim 8, wherein the saturated fatty acid is stearic acid.

11. The method of claim 1, wherein esterifying the carboxylic acid adducted rosin includes the addition of a disproportionation agent or catalyst.

12. The method of claim 11, wherein the disproportionation agent or catalyst is at least one of ROSINOX, LOWINOX, TBM-6, VULTAC 2, ETHANOX 328, alkylphenoldisulfide, alkylphenolsulfide, or derivatives thereof, or a combination thereof .

13. The method of claim 1, wherein the carboxylic acid and rosin are added in a ratio of carboxylic acid to rosin of about 1:1 to about 1:30.

14. The method of claim 13, wherein the ratio of carboxylic acid to rosin is about 1:24.

15. The method of claim 1, wherein the carboxylic acid adducted rosin and the polyol are added in a ratio of carboxylic adducted rosin to polyol of about 3:1 to about 20:1.

16. The method of claim 15, wherein the ratio of carboxylic adducted rosin to polyol is about 6:1.

17. The method of claim 1, wherein the carboxylic acid adducted rosin polyol ester and the fatty acid material are added in a ratio of carboxylic acid adducted rosin polyol ester to fatty acid material of about 5:1 to about 200:1.

18. The method of claim 17, wherein the ratio of carboxylic acid adducted rosin polyol ester to fatty acid material is about 30:1 to about 55:1.

19. A carboxylic acid adducted rosin polyol ester with fatty acid functionality produced by the method of any of claims 1-18.