US 20150307754A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2015/0307754 A1 Combs et al. (43) Pub. Date: Oct. 29, 2015

(54) ADHESIVES THAT INCLUDE Publication Classification HIGHLY PLASTICIZED CELLULOSE ESTERS AND METHODS AND ARTICLES (51) Int. Cl. RELATING THERETO C09. IOI/2 (2006.01) C09, 7/04 (2006.01) (71) Applicant: Celanese Acetate LLC, Irving, TX (US) (52) U.S. Cl. CPC ...... C09J 101/12 (2013.01); C09J 7/045 (72) Inventors: Michael Combs, Pembroke, VA (US); (2013.01); C09J 220 1/606 (2013.01); C09J Wendy Bisset, Eggleston, VA (US); 2405/00 (2013.01) Lizbeth Milward, Blacksburg, VA (US); Adam Larkin, Dallas, TX (US); Naresh Budhavaram, Florence, KY (US) (57) ABSTRACT (73) Assignee: Celanese Acetate LLC, Irving, TX (US) Adhesives may include a base polymer composition, option ally a tackifying resin, optionally a wax, and optionally addi (21) Appl. No.: 14/302,550 tives (e.g., plasticizers, fillers, antioxidants, and the like, and combinations thereof), where the base polymer comprises a (22) Filed: Jun. 12, 2014 highly plasticized cellulose ester and optionally polymers traditionally used in pressure sensitive adhesives, hot melt Related U.S. Application Data pressure sensitive adhesives, or hot melt adhesives (e.g., eth (60) Provisional application No. 61/985,123, filed on Apr. ylene vinyl acetate copolymers, polysiloxanes, and polyure 28, 2014. thanes).

101

100a 102 Patent Application Publication Oct. 29, 2015 Sheet 1 of 2 US 2015/0307754 A1

101 100b 104

102 FIG. 1A FIG. 1B

105 100C to-- 100c 107 FIG. 1C

100eu C N-109 C N-110 108 C N-111 FIG. 1D

10Of 24

112

FIG. 1E Patent Application Publication Oct. 29, 2015 Sheet 2 of 2 US 2015/0307754 A1

105

100

95 889 O5O i 7 5

7 O

65

60 0.7 0.9 1.1 13 1.5 1.7 Intrinsic Viscosity

FIG.2 US 2015/0307754 A1 Oct. 29, 2015

ADHESIVES THAT INCLUDE disclosed is capable of considerable modifications, alter HGHLY PLASTICIZED CELLULOSE ations, combinations, and equivalents in form and function, ESTERS AND METHODS AND ARTICLES as will occur to those skilled in the art and having the benefit RELATING THERETO of this disclosure. 0006 FIGS. 1A-E provide illustrations of nonlimiting BACKGROUND examples of article configurations according to at least some embodiments described herein. 0001. The exemplary embodiments described herein 0007 FIG. 2 provides intrinsic viscosity as a function of relate to adhesive compositions, and methods and articles the melt temperature for highly-plasticized cellulose esters relating thereto. according to at least Some embodiments described herein. 0002 Adhesives are useful in several applications from arts and crafts (e.g., hot glue Sticks) to consumer products DETAILED DESCRIPTION (e.g., cigarette seamline adhesives and repositionable, adhe sive paper products like Sticky-notes) to packaging (e.g., ship 0008. The exemplary embodiments described herein ping box and cereal box adhesives). relate to PSA, HMPSA, and HMA that comprise highly 0003. There are several types of adhesives including pres plasticized cellulose esters (“HPCE), and methods and Sure sensitive adhesives, pressure sensitive hot melt adhesive, articles relating thereto. HPCE described herein may, in some hot melt adhesives, and drying adhesives. As used herein, embodiments, include a cellulose ester and a plasticizer, pressure-sensitive adhesives (“PSA) refer to adhesive com where the plasticizer is at about 15% or greater by weight of positions that are tacky at room temperature to the extent that the HPCE (e.g., about 15% to about 80% by weight of the a 4mil (the unit “mil” refers to a thousandth of an inch) coated HPCE). As used herein, the term “adhesive(s) of the present paper backing Sticks to the adhesive composition with no disclosure.” “adhesive(s) described herein.” or a derivative pressure applied (i.e., with only the weight of the 4 mil coated thereof refers generally to HMA, PSA, and HMPSA collec paper backing). In some instances, PSA may be a Viscous tively. As used herein, the term “plasticizer” refers to a com paste or putty. As used herein, hot melt pressure-sensitive pound that decreases the glass transition temperature (“T”) adhesives (“HMPSA) refer to adhesive compositions that of the polymer being plasticized. Sticks to a 4 mil coated paper backing at room temperature 0009. The cellulose ester and high concentration of plas with weight applied by a roller of 4.5 pounds or less. HMPSA ticizer in HPCE described herein may be more environmen may be tacky or non-tacky at room temperature. As used tally degradable (e.g., via both bulk erosion and chemical herein, hot melt adhesives (“HMA') refers to adhesive com degradation) than typical synthetic adhesive polymers like positions that Stick to a 4 mil coated paper backing when ethylene vinyl acetate copolymers, polysiloxanes, and poly heated and do not stick to the 4 mil coated paper backing at urethanes. Further, cellulose is a product of cellulose ester room temperature with weight applied by a roller of 4.5 decomposition, which may be considered a natural, environ pounds or less. As used herein, a 'drying adhesive' refers to mentally benign composition. an adhesive composition that is liquid at room temperature 0010 Additionally, caustic baths in recycling processes and often includes a solvent that evaporates to increase the would decompose the cellulose esters to cellulose, which is adhesive bond between the adhesive and a surface. Drying the product of caustic bath paper repulping or label removal. adhesives may, for example, be in the form of high viscosity Therefore, adhesives that include HPCE would minimally, if pastes or low viscosity fluids (e.g., spray adhesives). at all, impact caustic bath recycling processes. 0004 Common PSA HMPSA, and HMA utilize synthetic 0011. In some embodiments, the adhesives described polymers (e.g., ethylene vinyl acetate copolymers, polysilox herein may include a base polymer composition (which anes, and polyurethanes) in combination with additives like includes HPCE), optionally a tackifying resin, optionally a tackifiers, waxes, and fillers in varying concentrations and wax, and optionally additives (e.g., plasticizers, fillers, anti compositions for desired PSA, HMPSA, or HMA. However oxidants, and the like, and combinations thereof). In some formulated, these adhesives generally may have poor envi embodiments, the base polymer composition may be ronmental degradability and generally interfere with recy included in an adhesive described herein in an amount of cling processes. For example, in removing labels from glass about 20% to 100% by weight of the adhesive described bottles and repulping of paper products, a caustic bath is used herein. to degrade the paper product. Adhesives with synthetic poly 0012. In some embodiments, the base polymer composi mers like ethylene vinyl acetate copolymers, polysiloxanes, tion may include HPCE at 100% by weight of the base poly and polyurethanes generally stay intact when exposed to mer composition. In some embodiments, the base polymer caustic baths. Therefore, in Some instances, additional steps, composition may be a blend of HPCE and polymers tradi often costly, labor-intensive steps, are included in Such recy tionally used in PSA, HMPSA, or HMA. The inclusion of cling processes to account for the use of these adhesives. HPCE in such blends may increase the degradability and Further, in Some instances, depending on the amount of adhe recyclability of an adhesive that includes polymers tradition sive used and local recycling capabilities, the article may be ally used in PSA, HMPSA, or HMA (e.g., ethylene vinyl non-recyclable. Accordingly, PSA, HMPSA, and HMA hav acetate copolymers, polysiloxanes, and polyurethanes). ing increased environmental degradability and compatibility 0013. As used herein, the term “bio-derived refers to a with recycling processes may be useful. compound or portion thereof originating from a biological source or produced via a biological reaction. The bio-derived BRIEF DESCRIPTION OF THE DRAWINGS portion of an adhesive described herein refers to the mass percent that is bio-derived. 0005. The following figures are included to illustrate cer 0014. As used herein, the term “food-grade” refers to a tain aspects of the embodiments presented herein, and should material that has been approved for contacting (directly or not be viewed as exclusive embodiments. The subject matter indirectly) food, which may be classified as based on the US 2015/0307754 A1 Oct. 29, 2015

materials conformity to the requirements of the United 0022 HPCE described herein may, in some embodiments, States Pharmacopeia (“USP-grade'), the National Formulary include a cellulose ester and a plasticizer with the plasticizer (“NF-grade'), and/or the Food Chemicals Codex (“FCC at about 15% or greater by weight of the HPCE (e.g., about grade”). 15% to about 80% by weight of the HPCE). In some embodi 0.015. As used herein, the term “semi-volatile” refers to ments, the plasticizers may be present in the HPCE described compounds having a boiling point of about 260° C. to about herein in an amount ranging from a lower limit of about 15%, 400° C. 30%, 40%, 50%, or 60% by weight of the HPCE to an upper 0016. As used herein, the term “volatile” refers to com limit of about 80%, 70%, 60%, or 50% by weight of the pounds having a boiling point of about 50° C. to about 260° C. HPCE, wherein the amount may range from any lower limit to 0017. As used herein, the term “molecular weight” refers any upper limit and encompass any Subset therebetween (e.g., to a polystyrene equivalent number average molecular weight about 20% to about 40%). In some embodiments, cellulose esters may be present in the HPCE described herein in an (“M”). amount ranging from a lower limit of about 20%, 30%, 40%, 0.018. As used herein, the term “water-free” refers to a or 50% by weight of the HPCE to an upper limit of about 85%, composition having no more water than is naturally present at 70%, 60%, or 50% by weight of the HPCE, wherein the standard temperature and pressure with about 100% relative amount may range from any lower limit to any upper limit and humidity. As used herein, the term “substantially water-free” encompass any Subset therebetween. In some embodiments, refers to a composition having no more than about 1% by the HPCE described herein may consist essentially of cellu weight of water above the concentration of water that is lose ester and plasticizers. In some embodiments, the HPCE naturally present at Standard temperature and pressure with described herein may consist of cellulose ester and plasticiz 100% relative humidity. CS. 0019. It should be noted that when “about is used in 0023. In some embodiments, cellulose esters of the HPCE reference to a number in a numerical list, the term “about described herein may have ester substituents that include, but modifies each number of the numerical list. It should be noted are not limited to, C-Coaliphatic esters (e.g., acetate, pro that in some numerical listings of ranges. Some lower limits pionate, or butyrate), functional C-Coaliphatic esters (e.g., listed may be greater than Some upper limits listed. One Succinate, glutarate, maleate) aromatic esters (e.g., benzoate skilled in the art will recognize that the selected subset will or phthalate), Substituted aromatic esters, and the like, any require the selection of an upper limit in excess of the selected derivative thereof, and any combination. lower limit. Unless otherwise indicated, all numbers express 0024. In some embodiments, cellulose esters of the HPCE ing quantities of ingredients, properties such as molecular described herein may have a degree of substitution of the ester weight, reaction conditions, and so forth used in the present substituent ranging from a lower limit of about 0.5, 1.2, or 2 specification and associated claims are to be understood as to an upper limit of less than about 3, about 2.9, 2.7, or 2.5, being modified in all instances by the term “about.” Accord and wherein the degree of Substitution may range from any ingly, unless indicated to the contrary, the numerical param lower limit to any upper limit and encompass any Subset eters set forth in the following specification and attached therebetween. claims are approximations that may vary depending upon the 0025. In some embodiments, cellulose esters of the HPCE desired properties sought to be obtained by the embodiments described herein may have a molecular weight ranging from of the present invention. At the very least, and not as an a lower limit of about 10,000, 15,000, 25,000, 50,000, or attempt to limit the application of the doctrine of equivalents 85,000 to an upper limit of about 300,000, 200,000, 150,000, to the scope of the claim, each numerical parameter should at 125,000, 100,000, or 85,000, and wherein the molecular least be construed in light of the number of reported signifi weight may range from any lower limit to any upper limit and cant digits and by applying ordinary rounding techniques. encompass any Subset therebetween. As used herein, the term “molecular weight” refers to a polystyrene equivalent number I. Adhesive Compositions average molecular weight (M). 0020. In some embodiments, the adhesives described 0026. In some embodiments, cellulose esters of the HPCE herein may include a base polymer composition (which described herein may have an intrinsic viscosity ranging from includes HPCE), optionally a tackifying resin, and optionally a lower limit of about 0.5 dL/g, 0.7 dL/g, or 1.0 dL/g to an a wax. In some embodiments, the adhesives described herein upper limit of about 2.0 dL/g, 1.7 dL/g, 1.5 dL/g, or 1.3 dL/g, may optionally further include additives (e.g., plasticizers, and wherein the intrinsic viscosity may range from any lower fillers, antioxidants, and the like, and combinations thereof). limit to any upper limit and encompass any Subset therebe In some embodiments, the base polymer composition may be tween. Intrinsic viscosity may be measured by forming a included in an adhesive described herein in an amount of solution of 0.20 g/dL cellulose ester in 98/2 wit/wt acetone/ water and measuring the flow times of the Solution and the about 20% to 100% by weight of the adhesive described solvent at 30° C. in a #25 Cannon-Ubbelohde viscometer. herein. Then, the modified Baker-Philippoff equation may be used to 0021. In some embodiments, the base polymer composi determine intrinsic viscosity (“IV), which for this solvent tion may include HPCE at 100% by weight of the base poly system is Equation 1. mer composition. In some embodiments, the base polymer composition of the adhesives described herein may include HPCE at about 1% to about 99% by weight of the base k i Equation 1 polymer composition and an additional polymer (e.g., ethyl W = (antilog(logic)/k) - 1) where n = (), ene vinyl acetate, polyacrylamides, polyacrylates, styrene C i2 block co-polymers, and the like, and combinations thereof) at about 99% to about 1% by weight of the base polymer com t=the average flow time of solution (having cellulose ester) position. in seconds, t the average flow times of solvent in seconds, US 2015/0307754 A1 Oct. 29, 2015

k-solvent constant (10 for 98/2 wit/wt acetone/water), and -continued c-concentration (0.200 g/dL). Formula 5 0027. In some embodiments, cellulose esters described OH herein may be derived from any suitable cellulosic source. Suitable cellulosic sources may, in Some embodiments, N include, but are not limited to, Softwoods, hardwoods, cotton - Rio linters, Switchgrass, bamboo, bagasse, industrial hemp, wil %21. low, poplar, perennial grasses (e.g., grasses of the Miscanthus R12 R11 family), bacterial cellulose, seed hulls (e.g., soy beans), Formula 6 kudzu, and the like, and any combination thereof. Further, it NHR13 has been surprisingly discovered that the clarity of adhesives described herein does not appear to be substantially impacted N by the cellulosic source from which the cellulose esters are --R4 derived. This is unexpected because Some existing cellulose y-x1. ester products (that do not have adhesive properties) require R16 ORs high quality, expensive cellulosic sources (e.g., hardwoods Formula 7 with low hemicellulose content) to achieve high clarity. NHR 0028. In some embodiments, the cellulose ester may be N recycled from other cellulose ester materials. For example, --Rs cellulose acetate tow used in producing, for example, ciga 1. rette filters may be used for producing HPCE and the adhe R20%2 R19 sives described herein. Formula 8 0029 Plasticizers suitable for use in conjunction with the 21 N21 HPCE described herein may, in some embodiments, include, T- R21 but are not limited to, Sa S. S R22O Formula 9 Formula 1 C Nn Qexe R24 R23 Formula 10 R28 N R25 n Formula 2 O OR 2 R27 N R26 Formula 11 r R31 ex R OR3 R30 N Formula 12 O Formula 3 R32 OH R33 N N HR, --Rs AleXal 1. R6 ORs R36 R35 Formula 4 Formula 13 O R R40 R39 NN

R38 Nals R37 R 9 US 2015/0307754 A1 Oct. 29, 2015

-continued cyclic nitrogens that are independently H, C-C alkyl, aryl, Formula 14 C-C alkyl aryl, COOH, C-C alkyl carboxylate, acyl, C-C alkyl acyl, amine, C-C alkylamine, amide, or C-C, alkyl amide; triazole (1.2.3 or 12.4) with R substituents from each of the cyclic carbons or cyclic nitrogens that are inde pendently H, C-C alkyl, aryl, C-C alkyl aryl, COOH, C-C alkyl carboxylate, acyl, C-C alkyl acyl, amine, C-C, Formula 1 wherein R1 is H. C-C alkyl, aryl, or C-C alkyl alkyl amine, amide, or C-C alkyl amide; pyrrole with R aryl; Formula 2 wherein R2 is H. C-C alkyl, aryl, or C-C, substituents from each of the cyclic carbons or cyclic nitro alkyl aryl and R3 is H. C-C alkyl, aryl, C-C alkyl aryl, gens that are independently H, C-C alkyl, aryl, C-C alkyl acyl, or C-C alkyl acyl: Formula 3 wherein R4 and R6 are aryl, OH, C-C alkoxy, COOH, C-C alkyl carboxylate, independently H, C-C alkyl, aryl, C-C alkyl aryl, COOH, acyl, C-C alkyl acyl, amine, C-C alkyl amine, amide, or C-C alkyl carboxylate, acyl, C-C alkyl acyl, amine, C-C, C-C alkyl amide: piperidine with R substituents from each alkylamine, amide, or C-C alkyl amide and R5 is H. C-C, of the cyclic carbons or cyclic nitrogens that are indepen alkyl, aryl, C-C alkyl aryl, acyl, or C-C alkyl acyl: For dently H, C-C alkyl, aryl, C-C alkyl aryl, OH, C-C, mula 4 wherein R7 is H. C-C alkyl, aryl, C-C alkyl aryl, alkoxy, COOH, C-C alkyl carboxylate, acyl, C-C alkyl OH, C-C alkoxy, amine, or C-C alkyl amine and R8 and acyl, amine, C-C alkylamine, amide, or C-C alkylamide; R9 are independently H, C-C alkyl, aryl, C-C alkyl aryl, piperazine with R substituents from each of the cyclic carbons COOH, C-C alkyl carboxylate, acyl, C-C alkyl acyl, or cyclic nitrogens that are independently H, C-C alkyl, amine, C-C alkylamine, amide, or C-C alkyl amide; For aryl, C-C alkylaryl, OH, C-C alkoxy, COOH, C-C alkyl mula 5 wherein R10, R11, and R12 are independently H, carboxylate, acyl, C-C alkyl acyl, amine, C-C alkyl C-C alkyl, aryl, C-C alkyl aryl, COOH, C-C alkyl car amine, amide, or C-C alkyl amide: R44HN R45-NHR46 boxylate, acyl, C-C alkyl acyl, amine, C-C alkyl amine, where R44 and R46 are independently H, C-C alkyl, aryl, amide, or C-C alkyl amide; Formula 6 wherein R13 is H. C-C alkyl aryl, COOH, C-C alkyl carboxylate, acyl, C-C alkyl, aryl, or C-C alkyl aryl, R14 and R16 are inde C-C alkyl acyl, amine, C-C alkylamine, amide, or C-C, pendently H, C-C alkyl, aryl, C-C alkyl aryl, COOH, alkyl amide and R45 is C-Co alkyl, and combinations C-C alkyl carboxylate, acyl, C-C alkyl acyl, amine, C-C, thereof. As used herein, “alkyl refers to a substituent with C alkyl amine, amide, or C-C alkyl amide, and R15 is H. and H that may be linear or branched (e.g., t-butyl) and C-C alkyl, aryl, C-C alkyl aryl, acyl, or C-C alkyl acyl: saturated or unsaturated. As used herein, “aryl” refers to an Formula 7 wherein R17 is Hor C-C alkyland R18, R19, and aromatic ring that may include phenyl, naphthyl, and aro R20 are independently H, C-C alkyl, aryl, C-C alkylaryl, matic rings with heteroatoms. COOH, C-C alkyl carboxylate, acyl, C-C alkyl acyl, 0030 Examples of plasticizers suitable for use in conjunc amine, C-C alkylamine, amide, or C-C alkyl amide; For tion with the HPCE described herein may, in some embodi mula 8 wherein R21 is H. C-C alkyl, aryl, C-C alkyl aryl, ments, include, but are not limited to, triacetin, trimethyl COOH, C-C alkyl carboxylate, acyl, C-C alkyl acyl, phosphate, triethyl phosphate, tributyl phosphate, triphenyl amine, C-C alkyl amine, amide, or C-C alkyl amide and phosphate, triethyl citrate, acetyl trimethylcitrate, acetyl tri R22 is H. C-C alkyl, aryl, C-C alkylaryl, acyl, C-C alkyl ethyl citrate, acetyl tributyl citrate, tributyl-O-acetyl citrate, acyl, amine, or C-C alkyl amine; Formula 9 wherein R23 dibutyl phthalate, diaryl phthalate, diethyl phthalate, dim and R24 are independently H, C-C alkyl, aryl, C-C alkyl ethyl phthalate, di-2-methoxyethyl phthalate, di-octyl phtha aryl, COOH, C-C alkyl carboxylate, acyl, C-C alkyl acyl, late (and isomers), dibutyl tartrate, ethyl o-benzoylbenzoate, amine, C-C alkylamine, amide, or C-C alkyl amide; For ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glyco mula 10 wherein R25, R26, R27, and R28 are independently late, n-ethyltoluenesulfonamide, o-cresyl p-toluene H, C-C alkyl, aryl, C-C alkyl aryl, COOH, C-C alkyl Sulfonate, aromatic diol, Substituted aromatic diols, aromatic carboxylate, acyl, C-C alkyl acyl, amine, C-C alkyl ethers, tripropionin, polycaprolactone, glycerin, glycerin amine, amide, or C-C alkyl amide; Formula 1 1 wherein esters, diacetin, polyethylene glycol, polyethylene glycol R29, R30, and R31 are independently H, C-C alkyl, aryl, esters, polyethylene glycol diesters, di-2-ethylhexyl polyeth C-C alkyl aryl, COOH, C-C alkyl carboxylate, acyl, ylene glycolester, glycerolesters, diethylene glycol, polypro C-C alkyl acyl, amine, C-C alkyl amine, amide, or C-C, pylene glycol, polyglycoldiglycidyl ethers, dimethyl sulfox alkyl amide; Formula 12 wherein R32 is H. C-C alkyl, aryl, ide, N-methyl pyrollidinone, propylene carbonate, C-Co C-C alkylaryl, R33 is H. C-C alkyl, aryl, C-C alkylaryl, dicarboxylic acid esters, dimethyl adipate (and other dialkyl OH, C-C alkoxy, acyl, C-C alkyl acyl, amine, or C-C, esters), di-butyl maleate, di-octyl maleate, resorcinol alkyl amine, and R34, R35, and R36 are independently H, monoacetate, catechol, catechol esters, phenols, epoxidized C-C alkyl, aryl, C-C alkyl aryl, COOH, C-C alkyl car Soybean oil, castor oil, linseed oil, epoxidized linseed oil, boxylate, acyl, C-C alkyl acyl, amine, C-C alkyl amine, other vegetable oils, other seed oils, difunctional glycidyl amide, or C-C alkyl amide: Formula 13 wherein R37, R38, ether based on polyethylene glycol, alkyl lactones (e.g., R39, and R40 are independently H, C-C alkyl, aryl, C-C, Y-Valerolactone), alkylphosphate esters, aryl phosphate alkylaryl, COOH, C-C alkyl carboxylate, acyl, C-C alkyl esters, phospholipids, aromas (including some described acyl, amine, C-C alkylamine, amide, or C-C alkyl amide: herein, e.g., eugenol, cinnamyl alcohol, camphor, methoxy Formula 14 wherein R41 is H. C-C alkyl, aryl, C-C alkyl hydroxyacetophenone (acetovanillone), Vanillin, and ethyl aryl, OH, or C-C alkoxy and R42 and R43 are indepen Vanillin), 2-phenoxyethanol, glycol ethers, glycol esters, gly dently H, C-C alkyl, aryl, C-C alkyl aryl, COOH, C-C, col ester ethers, polyglycol ethers, polyglycol esters, ethylene alkyl carboxylate, acyl, C-C alkyl acyl, amine, C-C alkyl glycol ethers, propylene glycol ethers, ethylene glycol esters amine, amide, or C-C alkyl amide; triazine (1.2.3, 1.2.4, or (e.g., ethylene glycol diacetate), propylene glycol esters, 1.3.5) with R substituents from each of the cyclic carbons or polypropylene glycol esters, acetylsalicylic acid, acetami US 2015/0307754 A1 Oct. 29, 2015

nophen, naproxen, imidazole, triethanolamine, benzoic acid, lactone), dibutyl maleate, di-octyl maleate, dibutyl tartrate, benzyl benzoate, salicylic acid, 4-hydroxybenzoic acid, pro eugenol, tributyl phosphate, tributyl-O-acetyl citrate, and pyl-4-hydroxybeonzoate, methyl-4-hydroxybeonzoate, resorcinol monoacetate. ethyl-4-hydroxybeonzoate, benzyl-4-hydroxybeonzoate, 0035. In some instances, two or more plasticizers may be butylated hydroxytoluene, butylated hydroxyanisol, sorbitol, used in HPCE composition. In some instances, it has been Xylitol, ethylene diamine, piperidine, piperazine, hexameth Surprisingly observed that two or more plasticizers may have ylene diamine, triazine, triazole, pyrrole, and the like, any synergistic effects. For the same total weight percent of total derivative thereof, and any combination thereof. plasticizer in the HPCE, HPCE with multiple plasticizers may have a greater melt flow index than HPCE with the individual 0031 Additional examples of plasticizers suitable for use plasticizers alone, which is an unexpected observation. in conjunction with the HPCE described herein may, in some 0036. In some embodiments, the base polymer composi embodiments, be nonionic Surfactants that include, but are tion of the adhesives described herein may include additional not limited to, polysorbates (e.g., TWEENR20 or polymers at about 1% to about 99% by weight of the base TWEENR80, available from Sigma Aldrich), sorbitan esters polymer composition and an additional polymer at about 99% (e.g., SPANR) products available from Sigma Aldrich), poly to about 1% by weight of the base polymer composition. ethoxylated aromatic hydrocarbons (e.g., TRITONR prod Additional polymers that may be blended with the HPCE to ucts available from Sigma Aldrich), polyethoxylated fatty form the base polymer composition may include, but are not acids, polyethoxylated fatty alcohols (e.g., BRIJ(R) products limited to, polyolefins, polyalphaolefins, polyesters, ethylene available from Sigma Aldrich), fluoroSurfactants, glucosides, vinyl acetate copolymers, polyvinyl acetate, polyvinyl alco and other nonionic Surfactants with hydrocarbon tails (e.g., hol (“PVOH), a polyethyleneimine, polyacrylates, poly C-C alkyl groups) and hydrophilic head groups with methacrylates, polyacrylamides, polyacrylonitriles, polyim hydroxyl and ester groups, and combinations thereof. It has ides, polyamides, polyvinyl chloride, polysiloxanes, been discovered that some nonionic Surfactants plasticize polyurethanes, polystyrene, polyetheramide copolymers, cellulose esters, alone or in combination with Small molecule styrene-butadiene copolymers, styrene-butadiene-styrene plasticizers. This is unexpected because traditional plasticiz copolymers, styrene-isoprene-styrene copolymers, styrene ers are Small molecules. By contrast, nonionic Surfactants are ethylene-butylene-styrene copolymers, styrene-ethylene bulky with long hydrocarbon tail groups and potentially large propylene-styrene copolymers, butyl rubber, polyisobuty head groups. For example, polyoxyethylene (20) Sorbitan lene, isobutylene-isoprene copolymers, acrylics, nitriles, and monolaurate, which is significantly larger than traditional combinations thereof. cellulose esterplasticizers like triacetin, has been observed to 0037. In some instances, the additional polymers blended plasticize cellulose ester. HPCE to form the base polymer composition may be suffi 0032. In some embodiments, the plasticizers may be food ciently hydrophobic that a compatibilizer is needed to pro grade plasticizers, which may be useful in producing adhe duce a homogeneous blend. Exemplary compatibilizers for sives described herein for use in applications where the adhe use in conjunction with HPCE may be nonionic surfactants sive may directly or indirectly contact food (e.g., food that include, but are not limited to, polysorbates (e.g., containers). Examples of food-grade plasticizers may, in TWEENR20 or TWEENR80, available from Sigma Ald Some embodiments, include, but are not limited to, triacetin, rich), sorbitan esters (e.g., SPANR) products available from diacetin, tripropionin, trimethylcitrate, triethylcitrate, tribu Sigma Aldrich), polyethoxylated aromatic hydrocarbons tyl citrate, eugenol, cinnamyl alcohol, alkyl lactones (e.g., (e.g., TRITONR products available from Sigma Aldrich), Y-Valerolactone), methoxy hydroxy acetophenone (acetova polyethoxylated fatty acids, polyethoxylated fatty alcohols nillone), Vanillin, ethylvanillin, polyethylene glycols, 2-phe (e.g., BRIJ(R) products available from Sigma Aldrich), fluoro noxyethanol, glycol ethers, ethylene glycol ethers, propylene Surfactants, glucosides, and other nonionic Surfactants with glycol ethers, polysorbate Surfactants, Sorbitan ester Surfac hydrocarbon tails (e.g., C-C alkyl groups) and hydrophilic tants, polyethoxylated aromatic hydrocarbons, polyethoxy head groups with hydroxyl and ester groups, and combina lated fatty acids, polyethoxylated fatty alcohols, and the like, tions thereof. Additional exemplary compatibilizers for use in and any combination thereof. conjunction with HPCE may be polymers that include, but are not limited to, polyethylene glycol less than about 2000 0033. In some embodiments, the plasticizers may be bio molecular weight. Combinations of the foregoing may also be derived, which may be useful in producing adhesive compo used. In some embodiments, compatibilizers may be present sitions that are bio-derived. For example, bio-derived triace in the adhesive composition in an amount of about 0.5% to tin, diacetin, tripropionin, glyceryl esters, may be produced about 20% by weight of the adhesives composition. from glycerol that is a byproduct of biodiesel. Other examples 0038 Tackifying resins may be useful in increasing the of plasticizers that may be bio-derived may include, but are room temperature tack of an adhesive described herein. In not limited to, Vanillin, acetovanillone, Y-Valerolactone, Some embodiments, a tackifying resin may be present in an eugenol, epoxidized soybean oil, castor oil, linseed oil, epoxi adhesive described herein in an amount ranging from a lower dized linseed oil, and dicarboxylic esters (e.g., dimethyl adi limit of 0%, about 1%. 5%, 10%, 20%, or 30% by weight of pate, dibutyl maleate). In some instances, aroma plasticizers the adhesive described herein to an upper limit of about 70%, may be extracts from natural products, and therefore, bio 60%, 50%, 40%, or 30% by weight of the adhesive described derived plasticizers. herein, and wherein the amount of tackifying resin may range 0034. In some embodiments, the plasticizers may be semi from any lower limit to any upper limit and encompass any volatile to volatile plasticizers. Examples of some preferred subset therebetween. semi-volatile to Volatile plasticizers may include, but are not 0039 Examples of tackifying resins suitable for use in limited to, glycerol esters, (e.g., triacetin, diacetin, monoace conjunction with the adhesives described hereinmay, in some tin), ethylene glycol diacetate, alkyl lactones (e.g., Y-Valero embodiments, include, but are not limited to, methylcellu US 2015/0307754 A1 Oct. 29, 2015 lose, ethylcellulose, hydroxyethylcellulose, carboxy methyl OKERINR) products, available from Astor Wax Corporation, cellulose, carboxyethylcellulose, amides, diamines, polyes PENRECOR) products, available from Pennzoil Products Co., ters, polycarbonates, silyl-modified polyamide compounds, R-7152 products, available from Moore & Munger, and polycarbamates, urethanes, natural resins, natural rosins, PARAFIN WAX 1297, available from International Waxes rosinesters (SYLVATAC(R) RE85 and SYLVALITER RE100, Ltd.), microcrystalline waxes (e.g., VICTORYR AMBER both esters of tall oil rosin, available from Arizona Chemical), WAX, available from Petrolite Corp, BARECOR ES-796 shellacs, acrylic acid polymers, 2-ethylhexylacrylate, acrylic Amber Wax, available from Bareco, and OKERINR 177, acid ester polymers, acrylic acid derivative polymers, acrylic available from Astro Wax Corporation), polyethylene waxes acid homopolymers, anacrylic acid ester homopolymers, (e.g., POLY WAX(R) products, available from Petrolite, Inc.), poly(methyl acrylate), poly(butyl acrylate), poly(2-ethyl polypropylene waxes, by-product polyethylene waxes, Fis hexyl acrylate), acrylic acid ester co-polymers, methacrylic cher-Tropsch waxes, and the like, and combinations thereof. acid derivative polymers, methacrylic acid homopolymers, In some embodiments, waxes may have a melting tempera methacrylic acid ester homopolymers, poly(methyl meth ture of about 45° C. to about 125° C. acrylate), poly(butyl methacrylate), poly(2-ethylhexyl meth 0045. In some embodiments, compatibilizers may be used acrylate), acrylamido-methyl-propane Sulfonate polymers, to more homogeneously incorporate waxes into an adhesive acrylamido-methyl-propane Sulfonate derivative polymers, described herein. Suitable compatibilizers may include those acrylamido-methyl-propane Sulfonate co-polymers, acrylic described above relative to the base polymer composition and acid/acrylamido-methyl-propane Sulfonate co-polymers, may be used at similar concentrations. benzyl coco di-(hydroxyethyl) quaternary amines, p-T-amyl 0046. In some instances, additives may be included in an phenols condensed with formaldehyde, dialkyl amino alkyl adhesive described herein. In some embodiments, an additive (meth)acrylates, acrylamides, N-(dialkyl amino alkyl) acry may be present in an adhesive described herein in an amount lamide, methacrylamides, hydroxy alkyl (meth)acrylates, ranging from a lower limit of 0%, about 1%. 5%, 10%, or 20% methacrylic acids, acrylic acids, hydroxyethyl acrylates, eth by weight of adhesive described herein to an upper limit of ylene vinyl acetate, vinyl acetate ethylene polymers, aliphatic about 40%, 30%, or 20% by weight of adhesive described hydrocarbons, cycloaliphatic hydrocarbons (e.g., EASTO herein, and wherein the amount of additive may range from TAC(R) products, available from Eastman Chemical Co.), aro any lower limit to any upper limit and encompass any Subset matic hydrocarbons, aromatically modified aliphatic hydro therebetween. carbons, cycloaliphatic hydrocarbons, hydrogenated versions 0047. Examples of additives suitable for use in conjunc of the foregoing hydrocarbons, terpenes, polyterpenes, modi tion with the adhesives described herein may, in some fied terpenes (e.g., phenolic modified terpene resins like embodiments, include, but are not limited to, plasticizers that SYLVARESTM TP96 and SYLVARESTM TP2040, available plasticize a component of an adhesive described herein other from Arizona Chemical), and the like, any derivative thereof, than the cellulose ester, antioxidants, pigments, adhesion pro and any combination thereof. moters (e.g., silanes and alkyl silanes), viscosity modifiers, 0040. In some embodiments, tackifiers suitable for use in lubricants, softening agents, antibacterial agents, antifungal conjunction with the adhesives described herein may befood agents, preservatives, flame retardants, corrosion inhibitors, grade tackifiers. Examples of food-grade tackifiers may, in dehydrators, aromas, and the like, and combinations thereof. Some embodiments, include, but are not limited to, methyl 0048 Fillers may, in some embodiments, increase the cellulose, ethylcellulose, hydroxyethylcellulose, carboxy rigidity and decrease the creep of an adhesive described methylcellulose, carboxyethylcellulose, natural resins, natu herein, which may consequently increase the mechanical ral rosins, and the like, and any combination thereof. rigidity of an article produced therewith. Examples of fillers 0041. In some embodiments, compatibilizers may be used may include, but are not limited to, coconut shellflour, walnut to more homogeneously incorporate tackifying resins into an shell flour, wood flour, wheat flour, soybean flour, gums, adhesive described herein. Suitable compatibilizers may protein materials, calcium carbonate, talc, Zeolite, clay, rigid include those described above relative to the base polymer compounds (e.g. lignin), thickeners, unreacted Starches, composition and may be used at similar concentrations. modified Starches (e.g., with modifications other than ester 0042. In some embodiments, the HPCE in the base poly modifications like hydroxyethyl starch, hydrolyzed starch, mercomposition may provide Sufficient tack Such that little to cationic starch, starch phosphate, oxidized Starch, and the no additional tackifying resins (e.g., about 5% or less weight like), waxy starches, cellulose nanofibrils, nanocrystalline of adhesive described herein) are required in an adhesive cellulose, glass microspheres, carbonates, talc, silica, sili described herein. cates, magnesium silicates, and the like, and any combination 0043. Waxes may be useful in lowering the melt viscosity, thereof. increasing adhesive strength, and increasing temperature 0049. In some embodiments, fillers suitable for use in resistance of an adhesive described herein. In some embodi conjunction with an adhesive described herein may be food ments, a wax may be present in an adhesive described herein grade fillers. Examples of food-grade fillers may, in some in an amount ranging from a lower limit of 0%, about 1%. 5%, embodiments, include, but are not limited to, coconut shell 10%, or 20% by weight of adhesive described herein to an flour, walnut shell flour, wood flour, wheat flour, soybean upper limit of about 40%, 30%, or 20% by weight of adhesive flour, gums, starches, protein materials, calcium carbonate, described herein, and wherein the amount of wax may range and the like, and any combination thereof. from any lower limit to any upper limit and encompass any 0050 Flame retardants suitable for use in conjunction subset therebetween. with an adhesive described herein may, in some embodi 0044 Examples of waxes suitable for use in conjunction ments, include, but are not limited to, silica, metal oxides, with the adhesives described herein may, in some embodi phosphates, catechol phosphates, resorcinol phosphates, ments, include, but are not limited to, paraffin waxes (e.g., borates, inorganic hydrates, aromatic polyhalides, and the PACEMAKER(R) products, available from Citgo Petroleum, like, and any combination thereof. US 2015/0307754 A1 Oct. 29, 2015

0051 Antifungal and/or antibacterial agents suitable for an adhesive described herein may, in some embodiments, use in conjunction with an adhesive described herein may, in include, but are not limited to, anthocyanin, ascorbic acid, Some embodiments, include, but are not limited to, polyene glutathione, lipoic acid, uric acid, resveratrol, flavonoids, car antifungals (e.g., natamycin, rimocidin, filipin, nystatin, otenes (e.g., beta-carotene), carotenoids, tocopherols (e.g., amphotericin B, candicin, and hamycin), imidazole antifun alpha-tocopherol, beta-tocopherol, gamma-tocopherol, and gals such as miconazole (available as MICATINR) from Well delta-tocopherol), tocotrienols, tocopherol esters (e.g., toco Spring Pharmaceutical Corporation), ketoconazole (com pherol acetate), ubiquinol, gallic acids, melatonin, secondary mercially available as NIZORAL(R) from McNeil consumer aromatic amines, benzofuranones, hindered phenols, Healthcare), clotrimazole (commercially available as polyphenols, hindered amines, organophosphorus com LOTRAMIN(R) and LOTRAMINAF(R) available from Merck pounds, thioesters, benzoates, lactones, hydroxylamines, and CANESTENR) available from Bayer), econazole, omo butylated hydroxytoluene (“BHT), butylated hydroxyani conazole, bifonazole, butoconazole, fenticonazole, isocona sole (“BHA), hydroquinone, and the like, and any combina Zole, oxiconazole, Sertaconazole (commercially available as tion thereof. ERTACZOR) from OrthoDematologics), sulconazole, and 0056. In some embodiments, antioxidants suitable for use tioconazole; triazole antifungals such as fluconazole, itra in conjunction with an adhesive described herein may be conazole, isaVuconazole, raVuconazole, posaconazole, Vori food-grade antioxidants. Examples of food-grade antioxi conazole, terconazole, and albaconazole), thiazole antifun dants may, in some embodiments, include, but are not limited gals (e.g., abafungin), allylamine antifungals (e.g., to, ascorbic acid, vitamin A, tocopherols, tocopherol esters, terbinafine (commercially available as LAMISIL(R) from beta-carotene, flavonoids, BHT, BHA, hydroquinone, and the Novartis Consumer Health, Inc.), naftifine (commercially like, and any combination thereof. available as NAFTINR) available from Merz Pharmaceuti 0057 Viscosity modifiers may, in some embodiments, be cals), and butenafine (commercially available as LOTRA advantageous in modifying the melt flow index of an adhesive MINULTRAR) from Merck), echinocandinantifungals (e.g., described herein and/or modify the viscosity of an adhesive anidulafungin, caspofungin, and micafungin), polygodial, described herein. Viscosity modifiers suitable for use in con benzoic acid, ciclopirox, tolnaftate (e.g., commercially avail junction with an adhesive described herein may, in some able as TINACTINR) from MDS Consumer Care, Inc.), unde embodiments, include, but are not limited to, polyethylene cylenic acid, flucytosine, 5-fluorocytosine, griseofulvin, glycols, polypropylene glycols, glycerin, and the like, and haloprogin, caprylic acid, and any combination thereof. any combination thereof, which, in some embodiments, may 0052 Preservatives suitable for use in conjunction with an be a food-grade viscosity modifier. adhesive described herein may, in Some embodiments, 0.058 Aromas suitable for use in conjunction with the include, but are not limited to, benzoates, parabens (e.g., the adhesives described herein may, in some embodiments, propyl-4-hydroxybeonzoate series), and the like, and any include, but are not limited to, spices, spice extracts, herb combination thereof. extracts, essential oils, Smelling salts, Volatile organic com 0053 Pigments and dyes suitable for use in conjunction pounds, Volatile Small molecules, methyl formate, methyl with an adhesive described herein may, in some embodi acetate, methyl butyrate, ethyl acetate, ethyl butyrate, ments, include, but are not limited to, plant dyes, vegetable isoamyl acetate, penty1 butyrate, pentyl pentanoate, octyl dyes, titanium dioxide, silicon dioxide, tartrazine, E102. acetate, myrcene, geraniol, nerol, citral, citronellal, cit phthalocyanine blue, phthalocyanine green, quinacridones, ronellol, linalool, nerolidol, limonene, camphor, terpineol. perylene tetracarboxylic acid di-imides, dioxazines, perino alpha-ionone, thujone, benzaldehyde, eugenol, isoeugenol, nes disazo pigments, anthraquinone pigments, carbon black, cinnamaldehyde, ethyl maltol, Vanilla, Vannillin, cinnamyl metal powders, iron oxide, ultramarine, calcium carbonate, alcohol, anisole, anethole, estragole, thymol, furaneol. kaolin clay, aluminum hydroxide, barium Sulfate, Zinc oxide, methanol, rosemary, lavender, citrus, freesia, apricot blos aluminum oxide, CARTASOLR dyes (cationic dyes, avail soms, greens, peach, jasmine, rosewood, pine, thyme, oak able from Clariant Services) in liquid and/or granular form moss, musk, Vetiver, myrrh, blackcurrant, bergamot, grape (e.g., CARTASOL(R) Brilliant Yellow K-6G liquid, CARTA fruit, acacia, passiflora, sandalwood, tonka bean, mandarin, SOLOR. Yellow K-4GL liquid, CARTASOL(R) Yellow K-GL neroli, violet leaves, gardenia, red fruits, ylang-ylang, acacia liquid, CARTASOL(R) Orange K-3GL liquid, CARTASOL(R) farnesiana, mimosa, tonka bean, woods, ambergris, daffodil, Scarlet K-2GL liquid, CARTASOL(R) Red K-3BN liquid, hyacinth, narcissus, black currant bud, iris, raspberry, lily of CARTASOL(R) Blue K-5R liquid, CARTASOL(R) Blue K-RL the Valley, sandalwood, Vetiver, cedarwood, neroli, Straw liquid, CARTASOL(R) Turquoise K-RL liquid/granules, berry, carnation, oregano, honey, civet, heliotrope, caramel, CARTASOL(R) Brown K-BL liquid), FASTUSOL(R) dyes (an coumarin, patchouli, dewberry, helonial, coriander, pimento auxochrome, available from BASF) (e.g., Yellow 3GL, Fas berry, labdanum, cassie, aldehydes, orchid, amber, orris, tusol C Blue 74L), and the like, any derivative thereof, and tuberose, palmarosa, cinnamon, nutmeg, moss, styrax, pine any combination thereof. apple, foxglove, tulip, wisteria, clematis, ambergris, gums, 0054. In some embodiments, pigments and dyes suitable resins, civet, plum, castoreum, civet, myrrh, geranium, rose for use in conjunction with an adhesive described herein may violet, jonquil, spicy carnation, galbanum, petitgrain, iris, be food-grade pigments and dyes. Examples of food-grade honeysuckle, pepper, raspberry, benzoin, mango, coconut, pigments and dyes may, in Some embodiments, include, but hesperides, castoreum, osmanthus, mousse de chene, nectar are not limited to, plant dyes, vegetable dyes, titanium diox ine, mint, anise, cinnamon, orris, apricot, plumeria, marigold, ide, and the like, and any combination thereof. rose otto, narcissus, tolu balsam, frankincense, amber, orange 0055 Antioxidants may, in some embodiments, mitigate blossom, bourbon Vetiver, opopanax, white musk, papaya, oxidation and/or chemical degradation of an adhesive Sugar candy, jackfruit, honeydew, lotus blossom, muguet, described herein during storage, transportation, and/or imple mulberry, absinthe, ginger, juniper berries, spicebush, peony, mentation. Antioxidants suitable for use in conjunction with violet, lemon, lime, hibiscus, white rum, basil, lavender, bal US 2015/0307754 A1 Oct. 29, 2015

samics, fo-ti-tieng, osmanthus, karo karunde, white orchid, only the weight of the 4 mil coated paper backing). In some calla lilies, white rose, rhubrum lily, tagetes, ambergris, ivy, instances, tacky compositions may include HPCE where the grass, seringa, Spearmint, clary sage, cottonwood, grapes, concentration of plasticized is about 40% or greater by weight brimbelle, lotus, cyclamen, orchid, glycine, tiare flower, gin of the HPCE. ger lily, green osmanthus, passion flower, blue rose, bay rum, 0063. In some embodiments, the adhesives described cassie, Africantagetes, Anatolian rose, Auvergne narcissus, herein may be non-tacky at room temperature. In some British broom, British broom chocolate, Bulgarian rose, Chi instances, tacky compositions may include HPCE where the nese patchouli, Chinese gardenia, Calabrian mandarin, concentration of plasticized is about 60% or less by weight of Comoros Island tuberose, Ceylonese cardamom, Caribbean the HPCE. passion fruit, Damascena rose, Georgia peach, white 0064. The presence or absence of tack in the adhesives Madonna lily, Egyptian jasmine, Egyptian marigold, Ethio described herein at room temperature may be modified by the pian civet, Farnesian cassie, Florentine iris, French jasmine, concentration and composition of plasticizer, the composi French jonquil, French hyacinth, Guinea oranges, Guyana tion of the cellulose esters, the concentration of additional wacapua, Grasse petitgrain, Grasse rose, Grasse tuberose, components like tackifiers, waxes, or additional polymers, Haitian Vetiver, Hawaiian pineapple, Israeli basil, Indian san and the like. Therefore, the foregoing plasticizer concentra dalwood, Indian Ocean Vanilla, Italianbergamot, Italian iris, tions may be viewed as general guidelines and not limiting as Jamaican pepper, May rose, Madagascarylang-ylang, Mada to the presence or absence of tack in the adhesives described gascar Vanilla, Moroccan jasmine, Moroccan rose, Moroccan herein. oakmoss, Moroccan orange blossom, Mysore Sandalwood, 0065. The characteristics of the adhesives described Oriental rose, Russian leather, Russian coriander, Sicilian herein may be tailored by adjusting the changing the ratios of mandarin, South African marigold, South American tonka individual components and changing the physical and chemi bean, Singapore patchouli, Spanish orange blossom, Sicilian cal properties of individual components (especially the com lime, Reunion Island Vetiver, Turkish rose, Thai benzoin, ponents of the HPCE). Examples of such properties may Tunisian orange blossom, Yugoslavian oakmoss, Virginian include, but are not limited to, the composition of the ester cedarwood, Utahyarrow, West Indian rosewood, and the like, substituents of the cellulose esters, the degree of substitution and any combination thereof. of the ester substituent of the cellulose esters, the molecular 0059. In some instances, a component of an adhesive weight of the cellulose esters, the composition of the plasti described herein may perform more than one function in the cizers in the HPCE, and the like, and any combination thereof. adhesive described herein. For example, BHT and BHA are Further, the amount of plasticizer in the HPCE may be tai both antioxidants and plasticizers for cellulose ester. Addi lored to achieve the desired characteristics of the adhesives tionally, nonionic Surfactants may, in some instances, func described herein. Accordingly, the physical and chemical tion as both plasticizers and compatibilizers. In another properties of individual components of the adhesive example, aromas like eugenol, cinnamyl alcohol, camphor, described herein may be changed to achieve PSA HMPSA, methoxy hydroxy acetophenone (acetovanillone), Vanillin, or HMA as desired. This allows for increasing the environ and ethylvanillin may also plasticize cellulose ester. In yet mental degradability and recyclability of an adhesive over a another example, benzoates and parabens (e.g., the propyl-4- variety of applications. hydroxybeonzoate series) may be both preservatives and 0066. The characteristics of the adhesives described plasticizers for cellulose ester. herein that may be tailored to achieve a desired PSA, 0060. In some embodiments, an adhesive described herein HMPSA, or HMA may include, but are not limited to, glass may be substantially water-free. As used herein, the term transition temperature, melt flow index, melt viscosity, adhe “water-free” refers to a composition having no more water sive strength, degradability, clarity, and the like, and any than is naturally present at Standard temperature and pressure combination thereof. with 100% relative humidity. As used herein, the term “sub 0067. In some embodiments, an adhesive described herein stantially water-free” refers to a composition having no more may have a glass transition temperature of about 190° C. or than about 1% by weight of water above the concentration of less. In some embodiments, an adhesive described herein may water that is naturally present at standard temperature and have a glass transition temperature ranging from a lower limit pressure with 100% relative humidity. of not measurable, about -75° C., -70° C., -61C., -55°C., 0061. In some embodiments, the adhesive compositions 10° C., 75° C., 120° C., 130° C., or 150° C. to an upper limit described herein may be at least in part bio-derived adhesive of about 190° C., 175° C., or 150° C., and wherein the glass compositions. In some embodiments, the amount of the adhe transition temperature may range from any lower limit to any sive composition that is bio-derived may range from a lower upper limit and encompass any Subset therebetween. limit of about 2%. 5%, 10%, 25%, 50%, 75%, or 90% to an 0068. In some embodiments, an adhesive described herein upper limit of about 100%, 99%. 95%, 90%, 75%, or 50%, may have no detectible glass transition temperature. As used and wherein the amount of the adhesive composition that is herein, the term “no detectable glass transition temperature' bio-derived may range from any lower limit to any upper limit and derivatives thereof refers to material having no detectable and encompasses any Subset therebetween. heat flow event (as measured by DSC), which may be caused by the plasticized material having no glass transition tem II. Adhesive Properties perature or the heat flow broadening to an extent that the glass 0062. In some embodiments, the adhesives described transition temperature is not detectable. herein may be tacky at room temperature. As used herein, the 0069. The glass transition temperature of an adhesive term “tacky' refers to a composition that is tacky at room described herein may be measured by differential scanning temperature to the extent that a 4 mil (the unit “mil” refers to calorimetry. Factors that affect the glass transition tempera a thousandth of an inch) coated paper backing Sticks to the ture of an adhesive described herein may include, but are not adhesive composition with no pressure applied (i.e., with limited to, plasticizer concentration in the HPCE (e.g., a US 2015/0307754 A1 Oct. 29, 2015

higher concentration of plasticizer may decrease the glass method Agives a measure of the adherence, when peeled at transition temperature), HPCE concentration in the adhesive 180° angle, to a standard steel panel or to other surfaces of described herein (e.g., a higher concentration of HPCE may interest (e.g., corrugated board or glass) for a single-coated decrease the glass transition temperature), the composition of tape. This test method provides a mean for assessing the the cellulose ester and the additional polymer blended with uniformity of the adhesion of a given type of adhesive. In this the HPCE, and the like, and combinations thereof. method, a strip is applied to a standard test panel (or other 0070. In some embodiments, an adhesive described herein surface of interest) with controlled pressure. The tape is may have a melt flow index (with a 300 sec melt time) ranging peeled from the panel at 180° angle at a specified rate with a from a lower limit of about 0 g/10 min, 5 g/10 min, 25 g/10 1 kN load cell, during which the force required to effect peel min, 29 g/10 min, 35 g/10 min, or 40 g/10 min (at 150° C./0.5 is measured. kg measured in accordance with ASTM D1238) to an upper 0077. In some embodiments, an adhesive described herein limit of about 150 g/10 min, 125 g/10 min, 100 g/10 min, 80 may have a peel adhesion (using with a 4 mil coated paper g/10 min, 70 g/10 min, 60 g/10 min, 50 g/10 min, or 40 g/10 backing) ranging from a lower limit of about 0.1 lb/in, 0.25 min (at 150° C./0.5 kg measured in accordance with ASTM 1b/in, 0.5 lb/in, 1 lb/in, 2 lb/in, 3 lb/in, 4 lb/in, or 5 lb/in to an D1238), and wherein the melt flow index may range from any upper limit of about 25 lb/in, 201b/in, 15 lb/in, or 10 lb/in, and lower limit to any upper limit and encompass any Subset wherein the peel adhesion may range from any lower limit to therebetween. In some instances where the melt flow index at any upper limit and encompass any Subset therebetween. 150° C./500 g is greater than 150 g/10 min, the melt flow Depending on the Substrate, in Some instances, the Substrate index may be measured at 150° C./100 g and range from a may fail (e.g., tear) before failure of the adhesive described lower limit of about 5 g/10 min, 25 g/10 min, 29 g/10 min, 35 herein. g/10 min, or 40 g/10 min (at 150° C./100 g measured in accordance with ASTM D1238) to an upper limit of about 86 0078. In some embodiments, an adhesive described herein g/10 min, 80 g/10 min, 70 g/10 min, 60 g/10 min, 50 g/10 min, may increase in peel adhesion over time when applied to a or 40 g/10 min (at 150°C/100g measured in accordance with Substrate or Surface. A measurement of a change in peel ASTM D1238), and wherein the melt flow index may range adhesion over time may be analyzed by comparing the from any lower limit to any upper limit and encompass any 24-hour peel adhesion to the 72-hour peel adhesion. As used subset therebetween. In some embodiments, an adhesive herein, the "72-hr percent increase in peel adhesion' is cal described herein may have a melt flow index that is higher culated by (peel adhesion at 72 hours-peel adhesion at 24 than can be measured at 150° C./100 g (e.g., greater than hours)/(peel adhesion at 24 hours)* 100. In some instances, an about 86 g/10 min at 150° C./100 g). adhesive described herein may have a 72-hr percent increase 0071 Factors that affect the melt flow index of an adhesive in peel adhesion ranging from a lower limit of about 3%. 5%, described herein may include, but are not limited to, plasti or 10% to an upper limit of about 300%, 150%, 75%, or 25%, cizer concentration in the HPCE (e.g., a higher concentration and wherein the percent increase in peel adhesion may range of plasticizer may increase the melt flow index), HPCE con from any lower limit to any upper limit and encompass any centration in the adhesive described herein (e.g., a higher subset therebetween. concentration of HPCE may increase the melt flow index), the 007.9 The lap shear strength of an adhesive described composition of the cellulose ester and the additional polymer herein can be measured by testing lap shears by tension load blended with the HPCE, and the like, and combinations ing with a 1 kN load cell by a method that includes placing a thereof. specimen (two substrates with a 1 inch by 1 inch overlap and 0072 The melt viscosity of an adhesive described herein 3 mm thick glue line) in the grips of the testing machine so may be measure by rheometers (rotational, or capillary). that each end of the specimen is in contact with the grip 0073. In some embodiments, an adhesive described herein assemble, applying the loading immediately to the specimen may have a melt viscosity measure at 150° C. and 100s' at the rate of 800 lb force of shear permin, and continuing the ranging from a lower limit of about 500cP, 1,000 cB, 2,500 cF. load to failure of the adhesive or substrate. Adhesives failure or 5,000 cp to an upper limit of 200,000 cB, 150,000 cB. is recorded as the lap shear strength, and Substrate failure is 50,000 cF. 10,000 cB, and wherein the melt viscosity may recorded as Substrate failure. In some instances, Substrate range from any lower limit to any upper limit and encompass failure for a 4 mil coated paper has been observed at about 17 any subset therebetween. kgf. This value may change depending on the Substrate and 0074 Factors that affect the melt viscosity of an adhesive size of the glue line. described herein may include, but are not limited to, plasti 0080. In some embodiments, an adhesive described herein cizer concentration in the HPCE (e.g., a higher concentration may have a lap shear strength (using with a 4 mil coated paper of plasticizer may decrease the melt viscosity), HPCE con backing) ranging from a lower limit of about 0.2 kgf, 0.5 kgf, centration in the adhesive described herein (e.g., a higher 1 kgf, 2 kgf, 4 kgf, or 6 kgf to an upper limit of about 17 kgf, concentration of HPCE may increase the melt viscosity), the 15 kgf, 10 kgf, 8 kgf, 6 kgf, or 4 kgf, and wherein the lap shear composition of the cellulose ester and the additional polymer strength may range from any lower limit to any upper limit blended with the HPCE, and the like, and combinations and encompass any Subset therebetween. In some instances, thereof. the 4 mil coated paper may fail before the adhesive described 0075. The adhesive strength of adhesives described herein herein fails. In some embodiments, an adhesive described may be measured by peel adhesion and/or lap shear strength herein may have a lap shear strength (using an aluminum or testing mechanisms. stainless steel Substrate) ranging from a lower limit of about 0076 Peel adhesion can be measured by ASTM 3330/D 0.2 kgf, 0.5 kgf, 1 kgf, 2 kgf, 5 kgf, or 10 kgf to an upper limit Method A (Standard test method for peel adhesion of PSA of about 50 kgf, 30 kgf, 20 kgf, 15 kgf, or 10 kgf, and wherein tape (180° Peel)) and tested on a surface of interest (e.g., the lap shear strength may range from any lower limit to any corrugated cardboard, glass, stainless steel panels). Test upper limit and encompass any Subset therebetween. US 2015/0307754 A1 Oct. 29, 2015

0081 Factors that affect the adhesive strength of an adhe the haze), the composition of the cellulose ester and the sive described herein may include, but are not limited to, additional polymer blended with the HPCE, and the like, and plasticizer concentration in the HPCE (e.g., a higher concen combinations thereof. tration of plasticizer may decrease the lap shear strength but may increase tack and peel adhesion), HPCE concentration in III. Methods of Producing Adhesives Described Herein the adhesive described herein (e.g., a higher concentration of I0086 Producing adhesives described herein may, in some HPCE may lap shear strength), the composition of the cellu embodiments, involve blending the components of the adhe lose ester and the additional polymer blended with the HPCE, sive described herein (e.g., the HPCE, the optional additional the environmental conditions (e.g., temperature), and the like, polymer, the optional tackifying resins, the optional waxes, and combinations thereof. and the optional additives). In some instances, blending may 0082. As used herein, the term “degradation' includes involve high-shear mixing processes. In some instances, both mechanical and chemical degradation. In some embodi blending may be performed at an elevated temperature (e.g., ments, an adhesive described herein may degrade to a greater a temperature above room temperature). In some instances, extent for a given time frame than a comparable adhesive the components of the adhesive may be heated before and composition where the HPCE is replaced with a cellulose during blending. Some embodiments may involve a combi diacetate material plasticized with 20% triacetin. In some nation of the foregoing. embodiments, an adhesive described herein may degrade by I0087. In some embodiments, additives may be incorpo about 5% or greater by weight than a cellulose diacetate rated into an adhesive described herein the mixing step. In material plasticized with 20% triacetin in a procedure per Some embodiments, additives may be incorporated into an formed according to EN 13432 “Requirements for Packaging adhesive described herein after the mixing step by, for Recoverable through Composting and Biodegradation—Test example, via absorption. Absorption may, in some embodi Scheme and Evaluation Criteria for the Final Acceptance of ments, be advantageous for the incorporation of volatile addi Packaging.” In some embodiments, an adhesive described tives and/or Small molecule additives (e.g., some fragrances, herein may degrade by an amount ranging from a lower limit aromas, dyes, and pigments). of about 5%, 10%, or 15% to an upper limit of about 300%, I0088. In some instances, the HPCE may be produced 200%, 100%, 50%, 40%, or 30% by weight than a compa before combining the HPCE with the other components of the rable adhesive composition where the HPCE is replaced with adhesive described herein. Producing an adhesive described a cellulose diacetate material plasticized with 20% triacetin in herein may involve at least one of mixing, compounding, a procedure performed according to EN 13432 “Require high-shear mixing, heating, or preheating the cellulose ester ments for Packaging Recoverable through Composting and and/or the plasticizer. Biodegradation Test Scheme and Evaluation Criteria for I0089. In some instance, the HPCE may be mixed, com the Final Acceptance of Packaging, and wherein the degra pounded, etc. with a compatibilizer before adding the addi dation may range from any lower limit to any upper limit and tional polymer to the adhesive described herein. encompass any Subset therebetween. 0090 Some embodiments may involve using an adhesive 0083) Factors that affect the degradability of an adhesive described herein immediately after production/mixing for an described herein may include, but are not limited to, plasti application (e.g., applying the adhesive described herein to a cizer concentration in the HPCE (e.g., a higher concentration Substrate so as to form a laminate surface on the Substrate). of plasticizer may increase the degradability), HPCE concen 0091. In some embodiments, a portion of an adhesive tration in the adhesive described herein (e.g., a higher con described herein may be produced, formed into pellets, pil centration of HPCE may increase the degradability), the com lows, or other forms and coated with the remaining compo position of the cellulose ester and the additional polymer nents of the adhesive. For example, HPCE may be produced blended with the HPCE, and the like, and combinations and coated with or encased by an additional polymer Such that thereof. when the produced coated HPCE is melted and mixed, the desired adhesive described herein is produced. 0084. The haze (a measure of clarity) of an adhesive 0092 Additional embodiments may involve forming an described herein can be measured with properly sized speci adhesive described herein into a desired form. Depending on mens Substantially plane-parallel Surfaces (e.g., flat without its characteristics, an adhesive described herein may be in the wrinkling) free of dust, scratches, and particles of about 0.85 form of a paste, a putty, pellets, or a molded shape (e.g., a glue mm in thickness using an UltraScan Pro from Hunter Lab with stick or an adhesive sheet). It should be noted that the term D65 Illuminant/10° observer. In some embodiments, an adhe “sheet’ should not be interpreted to be limited in thickness, sive described herein may have a haze ranging from a lower width or length, and encompasses films, layers, and the like. limit of about 3, 5, 15, 20, or 25 to an upper limit of about 100 Forming an adhesive described herein into a desired form (i.e., intentionally opaque), 85,70, 60, or 40, and wherein the may, in some embodiments, be a consequence of production haze may range from any lower limit to any upper limit and of the adhesive (e.g., a paste or a putty). In some embodi encompass any Subset therebetween. In some instances, the ments, forming an adhesive described herein into a desired haze value may be significantly larger than the preferred form may involve methods like extruding, injection molding, ranges above (e.g., about 100) when additives like titanium blow molding, over molding, compression molding, casting, dioxide are used in significant quantities to produce an calendaring, near net shape molding, melt casting, and the opaque adhesive. Additionally, pigments and dyes may affect like, any hybrid thereof, and any combination thereof. the haze of the adhesive. 0093. In some embodiments, an adhesive described herein 0085 Factors that affect the clarity of an adhesive in sheet form may have a thickness ranging from a lower limit described herein may include, but are not limited to, HPCE of about 15 microns, 20 microns, 30 microns, 50 microns, or concentration in the adhesive described herein (e.g., a higher 100 microns to an upper limit of about 1200 microns, 800 concentration of HPCE may decrease the clarity and increase microns, 400 microns, 200 microns, or 100 microns, and US 2015/0307754 A1 Oct. 29, 2015

wherein the thickness may range from any lower limit to any adhered to other surfaces, or a toilet paper or paper towel roll upper limit and encompasses any subset therebetween. While where the outermost sheet is adhered to the roll). In some these thicknesses may be preferred, one skilled in the art, with embodiments, the first Surface and the second Surface may the benefit of this disclosure, should understand that the thick correspond to a first Substrate and a second Substrate, respec nesses described are not limiting to the structure of a sheet tively. In some embodiments, the first surface and the second described herein and thicknesses outside these ranges may be Surface may correspond to the same Substrate (e.g., a single achieved. piece of paper rolled into a cylinder and adhered to itself 0094. In some embodiments, an adhesive described herein along a seamline). In some embodiments, articles described in laminate form on a substrate may be produced by applying herein may be extended to three or more Surfaces, including an adhesive melt to the Substrate (e.g., via melt casting); and hundreds or thousands of Surfaces (e.g., adhesive bookbind allowing the adhesive melt to cool, thereby yielding the lami ings), without departing from the spirit of this disclosure. nate on the Substrate. In some embodiments, the laminate 0101. In some embodiments, the articles described herein may be Smooth and Substantially non-tacky at room tempera may be designed with the first Surface and the second Surface ture. In some embodiments, the laminate may be tacky at adhered in any Suitable configuration. Examples of Suitable room temperature (e.g., for self-adhesive articles) and may configurations may, in some embodiments, include, but are optionally have a second Substrate applied to the laminate not limited to, those illustrated in FIG. 1. FIG. 1A illustrates (e.g., to protect the adhesive laminate or to layer the self a first substrate 101 and a second substrate 102 adhered adhesive articles). together with an adhesive described herein 100a in a stacked 0095. In some embodiments, a laminate may have a thick configuration. FIG. 1B illustrates a first substrate 103 and a ness ranging from a lower limit of about 15 microns, 20 second substrate 104 adhered together an adhesive described microns, 30 microns, 50 microns, or 100 microns to an upper herein 100b in a side-by-side configuration. FIG. 1C illus limit of about 500 microns, 400 microns, 300 microns, 200 trates a first substrate 105, a second substrate 106, and a third microns, or 100 microns, and wherein the thickness may substrate 107 adhered together with an adhesive described range from any lower limit to any upper limit and encom herein 100c, 100d in a stacked configuration where each passes any subset therebetween. While these thicknesses may substrate 105,106,107 has different sizes. FIG. 1D illustrates be preferred, one skilled in the art, with the benefit of this a plurality of Substrates in a hybrid configuration, wherein disclosure, should understand that the thicknesses described substrates 109,110,111 are each embedded at one end in an are not limiting to the structure of a laminate described herein adhesive described herein 100e which further adheres sub and thicknesses outside these ranges may be achieved. strates 109,110,111 to substrate 108. FIG. 1E illustrates a 0096. In some instances, a higher concentration of HPCE substrate 112 rolled and adhered to itself at a seam with an in an adhesive described herein may increase the flow of the adhesive described herein 100f. One skilled in the art with the adhesive melt at lower temperatures, which may produce benefit of this disclosure should recognize that FIGS. 1A-1E laminates with more uniform thickness and allow for thinner are merely examples of possible configurations of articles laminates that tend to be more flexible. More uniform thick described herein and that a multitude of other configurations nesses may provide for higher quality articles and, in some are possible and within the bounds of this disclosure. instances, higher clarity laminates. 0097. Some embodiments may further involve treating the 0102) Exemplary examples of articles or applications that laminate to reduce the concentration of plasticizer in the may utilize an adhesive described herein may, in some laminate. Treating may involve drying, heating, applying embodiments, include, but are not limited to, Smoking articles vacuum, and the like, and any combination thereof. Reducing (e.g., cigarettes), envelopes, larger mailing envelopes, tape, the concentration of the plasticizer may increase the stiffness cardboard packaging (e.g., mailing packages and food con tainers like cereal boxes and frozen dinner containers), books, and chemical resistance of the laminate. notebooks, magazines, Sticky-notes, corrugated boxes, deco 0098. Some embodiments may further involve treating the rative boxes, paper bags, grocery bags, folding cartons, card laminate to change surface chemistry of the laminate. For board rolls (e.g., for toilet paper or paper towels), seamlines example, a caustic bath may be utilized to produce a laminate on toilet paper and paper towels that prevent unrolling, wrap with a superhydrophilic surface. ping paper, wallpaper, paper honeycomb, emery boards, elec IV. Articles Comprising Adhesives Described Herein and tric insulation paper, air filters, papier-maché articles, carpets, Methods Relating Thereto dartboards, furniture or components thereof (e.g., carpet and/ or fabric coated headboards, chairs, stools, edge banding, and 0099. Some embodiments may involve applying an adhe laminated wood), picture frames, medical garments (e.g., sive described herein to a Surface. In some instances, the disposable gowns and Surgical masks), bandages, therapeutic adhesive described herein may be exposed to the local envi patches, feminine hygiene products, diapers, shoes, clothing ronment and not necessarily adhering two or more surfaces (e.g., binding), glues for labels (e.g., self-adhesive labels and together. For example, an iron-on design or heat-activated HM or HMPSA glues for labels (e.g., replacing casein window tint may be have an adhesive disposed on one side glues)), self-adhesive stamps, self-adhesive window covering that may later be heated to adhere to a second surface. films (e.g., protective films for glass or other Substrates), 0100 Some embodiments may involve adhering a first self-adhesive window coverings (e.g., decorative window surface to a second surface with an adhesive described herein. Stickers, window films, and window tinting), heat activated In some embodiments, at least one of the Surfaces may be films, light films, light filters, iron-on designs, Substrates with releasable from the adhesive (e.g., an envelope with an adhe laminated Surfaces (e.g., laminated paper, laminated business sive between the paper and a release strip, a roll of tape where cards, a laminated paper board, or a protective covering the adhesive preferably adheres to one side of the tape, or a directly laminated onto a Surface like glass), a coated Sub stack of self-adhesive notes or paper where each note is indi strate, automobiles or components thereof (e.g., temperature vidually removable from the stack and capable of being or sound insulation adhesively secured in place), electronics US 2015/0307754 A1 Oct. 29, 2015

(e.g., for insulation or containment), and the like. In some polymer foams, polystyrene foam, polyurethane foam, instances, adhesives described herein may have adhesive frothed polyurethane, and Soy-based foams), and the like, and strength at lower temperatures, which may be related to the any combination thereof. glass transition temperature, and allow for applications or 0106 By way of nonlimiting example, an article (e.g., a uses in cold environments like sealing frozen-food packag cigarette paper or a paper towel roll) may comprise two Sur ing, aerospace applications, low temperature electronics, and faces of a single Substrate (e.g., a tipping paper or a card the like. board) adhered together (e.g., at a seamline) with an adhesive described herein. 0103 Substrates or surfaces suitable for use in conjunc 0107. By way of another nonlimiting example, an article tion with articles described herein may, in some embodi (e.g., a cardboard container for shipping or containing food) ments, include, but are not limited to, fibers, woven fiber may comprise two Surfaces adhered together with an adhesive Substrates, nonwoven fiber Substrates, foamed Substrates, described herein. solid substrates, and the like, any hybrid thereof, and any 0108) By way of yet another nonlimiting example, an combination thereof. article (e.g., a food container) may comprise two Surfaces 0104 Substrates or surfaces suitable for use in conjunc (e.g., a cardboard container and a cellulose diacetate film (like tion with articles described herein may, in some embodi CLARIFOIL(R)) adhered together with an adhesive described ments, comprise materials that include, but are not limited to, herein. ceramics, natural polymers, synthetic polymers, metals, natu 0109. By way of another nonlimiting example, an article ral materials, carbons, and the like, and any combination (e.g., window tints or window coverings) may comprise a first thereof. Examples of ceramics may, in Some embodiments, Surface (e.g., a polyester film) with an adhesive described include, but are not limited to, glass, quartz, Silica, alumina, herein disposed thereon so as to allow for adherence to a Zirconia, carbide ceramics, boride ceramics, nitride ceramics, second Surface (e.g., a glass Surface or other similar transpar and the like, and any combination thereof. Examples of natu ent Surface). In some embodiments, the article may comprise, ral polymers may, in Some embodiments, include, but are not in order, the first surface, the adhesive described herein, and a limited to, cellulose, starch, polylactic acid, polyhydroxy peelable layer that can be removed before adherence to the alkonates, polyhydroxybutyrates, and the like, any derivative second Surface. In some embodiments, the article may com thereof, and any combination thereof. Examples of synthetic prise an adhesive described herein that is smooth and sub polymers may, in some embodiments, include, but are not stantially non-tacky at room temperature such that a peelable limited to, cellulose diacetate, cellulose triacetate, synthetic layer is not required and the adhesive may be exposed to air. bamboo, rayon, acrylic, aramid, nylon, polyolefins, polyeth In Such embodiments, heat may be utilized in adhering the ylene, polypropylene (including biaxially oriented polypro first surface to the second surface. pylene Substrates), polyethylene terephthalate, polyesters, 0110. By way of yet another nonlimiting example, an polyamides, Zylon, polyolefin copolymers (e.g., ethylene article (e.g., an iron-on design, heat activated film, or lami vinyl acetate), polysulfides, polyethers (including liquid crys nated card) may comprise a surface or Substrate (e.g., paper, talline polymer, polyoxomethylene), and the like, any deriva a fabric, or a polymer film) with an adhesive described herein tive thereof, and any combination thereof. Examples of met disposed thereon. In some instances, the article may then be als may, in Some embodiments, include, but are not limited to, adhered to another surface (e.g., applying heat so as to adhere steel, stainless steel, aluminum, copper, and the like, any alloy an iron-on design or heat activated film to another Surface like thereof, and any combination thereof. Examples of natural a piece of clothing or other fabric). In some embodiments, the materials may, in some embodiments, include, but are not article may be formed by applying an adhesive melt to the limited to, wood, grass, animal hide, and the like, and any Surface or Substrate and allowing the adhesive melt to cool So combination thereof. Examples of carbons may, in some as to form a laminate on the Surface or Substrate. embodiments, include, but are not limited to, carbon fibers, 0111. By way of nonlimiting example, an article (e.g. a and the like, any derivative thereof, and any combination labelled bottle) may comprise a first Surface (e.g., a plastic or thereof. glass container) to which an adhesive described herein may 0105 Exemplary examples of substrates suitable for use be applied for use in adhering a second Surface (e.g., a paper in conjunction with the articles described hereinmay, in some label, a plastic label, or a CLARIFOIL(R) label) to the first embodiments, include, but are not limited to, paper, card Surface. In some instances, the adhesive described herein may board, card stock, sand paper, bond paper, wallpaper, wrap be on the second surface before application to the first surface. ping paper, cotton paper, tipping paper, bleached paper, col The adhesive described herein may have unique advantages ored paper, construction paper, sisal paper, coated paper, wax in relation to recycling of the bottles. For example, the com paper, CLARIFOILR) (cellulose diacetate film, available ponents of at least some of the adhesive described herein, from Celanese Corporation), woven fabrics, continuous fila especially the HPCE portion of the adhesive, may be com ment nonwoven fabrics, carded nonwoven fabrics, tow, fiber patible with the current plastic recycling technologies (which bundles, twill, twine, rope, carpet, carpet backing, leather, allows for a 100% recyclable bottle) and glass bottle washing animal hide, insulation, wood and/or grass derived Substrates technologies (which allows for labels to be removed in a (e.g., wood veneers, particle board, fiberboard, medium-den caustic bath without additional steps and cost). sity fiberboard, high-density fiberboard, oriented strand 0112 Some embodiments described herein may involve board, cork, hardwoods (e.g., balsa wood, beech, ash, birch, adhering two or more surfaces together using an adhesive Brazil wood, cherry, chestnut, elm, hickory, mahogany, described herein. In some embodiments, adhering may maple, oak, rosewood, teak, walnut, locust, mango, alder, and involve heating the adhesive described herein and/or applying the like), Softwoods (e.g., pine, fir, spruce, cedar, hemlock, pressure to the adhesive described herein. and the like), rough lumber, finished lumber, natural fibrous 0113. In some embodiments, adhering surfaces together material, and bamboo), foam Substrates (e.g., memory foams, may involve heating an adhesive described herein to yield an US 2015/0307754 A1 Oct. 29, 2015

adhesive melt; applying the adhesive melt to a first Surface; acetate, a polyvinyl alcohol, a polyethyleneimine, a polyacry and adhering a second Surface to the first Surface with the late, a polymethacrylate, a polyacrylamide, a polyacryloni adhesive. trile, a polyimide, a polyamide, polyvinyl chloride, a polysi 0114. In some embodiments wherein an adhesive loxane, a polyurethane, polystyrene, a polyetheramide described herein is tacky, adhering Surfaces together may copolymer, a styrene-butadiene copolymer, a styrene-butadi involve applying an adhesive described herein to a first Sur ene-styrene copolymer, a styrene-isoprene-styrene copoly face; and adhering a second Surface to the first Surface with mer, a styrene-ethylene-butylene-styrene copolymer, a sty the adhesive disposed thereon. rene-ethylene-propylene-styrene copolymer, butyl rubber, 0115. In some embodiments, adhering surfaces together polyisobutylene, a isobutylene-isoprene copolymer, an may involve disposing an adhesive sheet between a first Sur acrylic, a nitrile, and a combination thereof; face and a second Surface; and heating the adhesive sheet so as I0120 C. a method that includes applying an adhesive of to adhere the first surface and the second surface together. Embodiment A to a surface of a substrate; and 0116 Embodiments disclosed herein may include: an 0121 D. an article that includes an adhesive of Embodi adhesive comprising (1) a base polymer composition (e.g., at ment A disposed on a Surface of a Substrate. about 20% to about 100% by weight of the adhesive) that includes HPCE (a cellulose ester and a plasticizers at 15% or 0.122 Each of embodiments A, B, C, and D may have one greater by weight of the HPCE) and an additional polymer at or more of the following additional elements in any combi a weight ratio of about 1:99 to about 100:0, (2) optionally a nation: Element 1: the adhesive further including a tackifying tackifying resin (e.g., at 0% to about 70% by weight of the resin; Element 2: Element 1 wherein the tackifying resin is adhesive), (3) optionally a wax (e.g., at 0% to about 40% by present in an amount of at about 1% to about 70% by weight weight of the adhesive), and (4) optionally an additive (e.g., at of the adhesive: Element 3: the adhesive further including 0% to about 40% by weight of the adhesive). Embodiments about 5% or less of a tackifying resin by weight of the adhe disclosed herein may also include: mixing the components of sive; Element 4: the adhesive further including a wax; Ele one of the foregoing adhesive to produce the adhesive. ment 5: Element 4 wherein the wax is present in an amount of Embodiments disclosed herein may also include: applying at at about 1% to about 40% by weight of the adhesive: Element least one of one of the foregoing adhesives to a surface. 6: the adhesive further including an additive: Element 7: Embodiments disclosed herein may also include: adhering Element 6 wherein the additive is present in an amount of at two or more surfaces together with at least one of one of the about 1% to about 40% by weight of the adhesive; Element 8: foregoing adhesives. Embodiments disclosed herein may also the adhesive further including a tackifying resin in an amount include: an article that includes at least one substrate with at of at about 1% to about 70% by weight of the adhesive; a wax least one of the foregoing adhesives disposed on at least a is present in an amount of at about 1% to about 40% by weight of the adhesive; and an additive is present in an amount of at portion of a surface of the substrate. about 1% to about 40% by weight of the adhesive; Element 9: 0117 Embodiments Disclosed Herein Include: wherein the plasticizer comprises a nonionic Surfactant; Ele 0118 A. an adhesive that includes a base polymer compo ment 10: wherein the highly plasticized cellulose ester sition that includes a highly plasticized cellulose ester and an includes the plasticizer at about 40% to about 80% by weight additional polymer, the highly plasticized cellulose ester at of the highly plasticized cellulose ester; Element 11: wherein about 1% to about 99% by weight of the base polymer, the the plasticizer comprises at least one plasticizer described additional polymer at about 1% to about 99% by weight of the herein; Element 12: wherein the plasticizer comprises a mix base polymer, the highly plasticized cellulose ester compris ture of two or more plasticizers; Element 13: wherein the ing a cellulose ester and a plasticizer at about 15% or greater adhesive is a pressure sensitive adhesive; Element 14: by weight of the highly plasticized cellulose ester, and the wherein the adhesive is a hot melt pressure sensitive adhesive; additional polymer being selected from the group consisting Element 15: wherein the adhesive is a hot melt adhesive; of a polyolefin, a polyalphaolefin, a polyester, an ethylene Element 16: wherein the base polymer consists essentially of vinyl acetate copolymer, a polyvinyl acetate, a polyvinyl the highly plasticized cellulose ester and the additional poly alcohol, a polyethyleneimine, a polyacrylate, a poly mer; and Element 17: wherein the base polymer consists of methacrylate, a polyacrylamide, a polyacrylonitrile, a poly the highly plasticized cellulose ester and the additional poly imide, a polyamide, polyvinyl chloride, a polysiloxane, a mer. By way of non-limiting example, exemplary combina polyurethane, polystyrene, a polyetheramide copolymer, a tions applicable to A, B, C, D include: Element 3 in combi styrene-butadiene copolymer, a styrene-butadiene-styrene nation with Element 13 and optionally Element 12, Element copolymer, a styrene-isoprene-styrene copolymer, a styrene 9, or both; Element 3 in combination with Element 14 and ethylene-butylene-styrene copolymer, a styrene-ethylene optionally Element 12, Element 9, or both; Element 8 in propylene-styrene copolymer, butyl rubber, polyisobutylene, combination with Element 13 and optionally Element 12, a isobutylene-isoprene copolymer, an acrylic, a nitrile, and a Element 9, or both; Element 8 in combination with Element combination thereof; 14 and optionally Element 12, Element 9, or both; Element 8 0119 B. a method that includes blending a highly plasti in combination with Element 15 and optionally Element 12, cized cellulose ester and an additional polymer the highly Element 9, or both; and Element 16 or Element 17 in combi plasticized cellulose ester at about 1% to about 99% by nation with Element 10, Element 12, or a combination thereof weight of the blend, the additional polymer at about 1% to and one of Elements 13-15. about 99% by weight of the blend, the highly plasticized cellulose ester comprising a cellulose ester and a plasticizer at (0123 Embodiments Disclosed Herein Include: about 15% or greater by weight of the highly plasticized 0.124 E. an adhesive that includes a base polymer compo cellulose ester, and the additional polymer being selected sition that consists essentially of a highly plasticized cellulose from the group consisting of a polyolefin, a polyalphaolefin, ester comprising a cellulose ester and a plasticizer at about a polyester, an ethylene vinyl acetate copolymer, a polyvinyl 15% or greater by weight of the highly plasticized cellulose US 2015/0307754 A1 Oct. 29, 2015

ester, and at least one selected from the group consisting of a acetates tested were CA-1 having a degree of Substitution of tackifying resin, a wax, and any combination thereof. about 2.5 and a molecular weight (M) of about 78,000, CA-2 0.125 F. a method that includes blending a highly plasti having a degree of substitution of about 2.4 and a M., of about cized cellulose ester and at least one selected from the group 44,000, and CA-3 having a degree of substitution of about 2.4 consisting of a tackifying resin, a wax, and any combination and a M, of about 62,000. The characteristics of the adhesive thereof samples and control cellulose acetate samples without plas 012.6 G. a method that includes applying an adhesive of ticizer were measured and are reported in Table 2. Embodiment E to a surface of a substrate; and 0127 H. an article that includes an adhesive of Embodi TABLE 1 ment E disposed on a Surface of a Substrate. 0128. Each of embodiments E, F, G, and H may have one Cellulose Acetate Plasticizer or more of the following additional elements in any combi Sample Composition Composition Wt 96 Plasticizer nation: Element 18: the adhesive further including a tackify CA-1 CA-1 O ing resin; Element 19: Element 18 wherein the tackifying HPCE-1 CA-1 triacetin 2O HPCE-2 CA-1 triacetin 40 resin is present in an amount of at about 1% to about 70% by HPCE-3 CA-1 triacetin 60 weight of the adhesive: Element 20: the adhesive further HPCE-4 CA-1 tributyl phosphate 2O including about 5% or less of a tackifying resin by weight of HPCE-5 CA-1 tributyl phosphate 40 the adhesive; Element 21: the adhesive further including a HPCE-6 CA-1 tributyl phosphate 60 CA-2 CA-2 O wax: Element 22: Element 21 wherein the wax is present in an HPCE-7 CA-2 triacetin 60 amount of at about 1% to about 40% by weight of the adhe HPCE-8 CA-2 triacetin 70 sive; Element 23: the adhesive further including an additive: HPCE-9 CA-2 tributyl phosphate 60 Element 24: Element 23 wherein the additive is present in an CA-3 CA-3 O amount of at about 1% to about 40% by weight of the adhe HPCE-10 CA-3 triacetin 60 HPCE-11 CA-2 eugenol 50 sive; Element 25: the adhesive further including a tackifying HPCE-12 CA-2 ethylvanillin 50 resin in an amount of at about 1% to about 70% by weight of HPCE-13 CA-2 triacetin and 62 (92:8 the adhesive; a wax is present in an amount of at about 1% to ethylvanillin triacetin:ethylvanillin) about 40% by weight of the adhesive; and an additive is HPCE-14 CA-2 triacetin and 64 (84:16) present in an amount of at about 1% to about 40% by weight ethylvanillin of the adhesive; Element 26: wherein the plasticizer com HPCE-15 CA-2 acetovanillone 50 prises a nonionic surfactant; Element 27: wherein the highly HPCE-16 CA-2 triacetin and 62 (92:8) plasticized cellulose ester includes the plasticizer at about acetovanillone 40% to about 80% by weight of the highly plasticized cellu lose ester; Element 28: wherein the plasticizer comprises at least one plasticizer described herein; Element 29: wherein TABLE 2 the plasticizer comprises a mixture of two or more plasticiz Complex ers: Element 30: wherein the adhesive is a pressure sensitive Viscosity adhesive; Element 31: wherein the adhesive is a hot melt Sample Description MP (o C.) T (° C.) (Pa *s) pressure sensitive adhesive; Element 32: wherein the adhe CA-1 white flake 167-2074 sive is a hot melt adhesive; and Element 33: wherein the base HPCE-1 clear; stiff; brittle 8O 93,777 polymer consists of the highly plasticized cellulose ester. By HPCE-2 clear; flexible; tacky -SS 7,187 way of non-limiting example, exemplary combinations appli HPCE-3 clear; flexible: 150 -53 2,417 cable to E, F, G, H include: Element 20 in combination with stretchy; very tacky HPCE-4 clear; stiff brittle 1662 Ole 122,456 Element 30 and optionally Element 29, Element 26, or both; detected Element 20 in combination with Element 31 and optionally HPCE-5 clear; stiff with 1802 14 56,004 Element 29, Element 26, or both; Element 25 in combination some flexibility with Element 30 and optionally Element 29, Element 26, or HPCE-6 clear; flexible; tacky 18O 12 13,661 CA-2 white flake 167-207 both; Element 25 in combination with Element 31 and option HPCE-7 clear; flexible: -44 4,037 ally Element 29, Element 26, or both; Element 25 in combi stretchy; tacky nation with Element 32 and optionally Element 29, Element HPCE-8 gel-like -61 4,037 26, or both; and Element 33 in combination with Element 27, HPCE-9 clear; flexible 15 23,230 CA-3 white flake 167-2074 Element 29, or a combination thereof and one of Elements HPCE-10 clear; flexible: -57 30-32. stretchy; tacky 0129. To facilitate a better understanding of the embodi HPCE-11 clear; coloured: -43 ments described herein, the following examples of preferred tacky; flexible HPCE-12 hard; glass-like: -35 or representative embodiments are given. In no way should clear-yellow the following examples be read to limit, or to define, the scope HPCE-13 clear; flexible -53 of the disclosure. HPCE-14 clear; flexible -51 HPCE-15 hard; glass-like: -34 EXAMPLES clear yellow HPCE-16 clear; flexible -52 Example 1 Flow onset point as measured by visual inspection upon heating, *Glass transition temperature as measured by TA Instruments DSC Q2000. 0130. A plurality of adhesive samples was prepared by Complex viscosity at 140°C. by TA Instruments Rheometer Discovery HR-2. compounding cellulose acetate and a plasticizer in the Literature values for cellulose acetate. amounts and compositions detailed in Table 1. The cellulose US 2015/0307754 A1 Oct. 29, 2015 15

Example 2 TABLE 3

0131 Samples HPCE-3, HPCE-6, HPCE-7, and HPCE-9 Cellulose were tested for adherence between a glass Surface and a Acetate cardboard Surface. A portion of the sample was added to a Compo glass slide and heated to between 60° C. and 100° C. Then a Sample sition Plasticizer Composition Wt 96 Plasticizer piece of cardboard was applied to the adhesive, which was PC E-17 CA-4 diacetin 60 then allowed to cool. The cardboard piece was then peeled PC E-18 CA-4 triacetin 60 from the glass slide. PC E-19 CA-1 diacetin 60 PC CA-4 diacetin an 62 (92:8 0132) Adhesion was achieved in all samples. Upon trying acetylsalicylic acid diacetin:acetylsalicylic to separate the two substrates, the cardboard pieces adhered acid) with samples HPCE-3, HPCE-6, and HPCE-7 were unable to PC E-21 CA-4 triacetin an 62 (92:8) acetylsalicylic acid be peeled without rupturing the cardboard. The cardboard PC E-22 CA-4 triacetin and butylated 62 (92:8) piece adhered with sample HPCE-9 was able to be cleanly hydroxytoluene peeled from the glass slide. PC E-23 CA-4 diacetin and butylated 62 (92:8) hydroxytoluene PC E-24 CA-4 triacetin and butylated 62 (92:8) Example 3 hydroxyanisol PC CA-4 diacetin and butylated 62 (92:8) 0.133 HPCE-7 was tested for thermal stability by storing hydroxyanisol in a freezer for over 24 hours two paper Surfaces glued PC E-26 CA-4 triacetin and benzoic 62 (92:8) together. Once warmed to room temperature, the paper Sur aci faces were manually pulled and remained adhered together. PC E-27 CA-4 diacetin and benzoic 62 (92:8) Further, the seam where the HPCE-7 adhered to the two paper aci surfaces remained flexible after the temperature cycling. This PC E-28 CA-4 triacetin an 62 (92:8) example appears to demonstrate, to at least some extent, the SYLVATAC (RRE85 PC E-29 CA-4 diacetin an 62 (92:8) temperature stability of at least some of the adhesive SYLVATAC (RRE85 described herein. PC E-30 CA-4 triacetin an 62 (92:8) SYLVALITE OR RE100 Example 4 PC E-31 CA-4 diacetin an 62 (92:8) SYLVALITE OR RE100 0134 Mixes of CA with intrinsic viscosities from 0.8 to PC E-32 CA-2 triacetin an 62 (92:8) 1.6 and triacetin content to CA ratio of 1:1 and 0.8:1 were SYLVATAC (RRE85 prepared. The mixes were analyzed for the changes in melt PC E-33 CA-2 triacetin an 62 (92:8) temperature as a function of intrinsic viscosity. As shown in SYLVALITE OR RE100 PC E-34 CA-4 diacetin and ethyl 62 (92:8) FIG. 2, a substantially linear relationship was observed where vanillin increased intrinsic viscosity yields a linear increase in melt PC E-35 CA-2 triacetin and ethyl 62 (92:8) temperature. Further, a higher plasticizer concentration vanillin yields a lower melt temperature at the same intrinsic viscosity. PC E-36 CA-4 diacetin and Salicylic 62 (92:8) This example appears to demonstrate the ability to tailor the acid flow onset temperature response by controlling intrinsic vis PC E-37 CA-4 triacetin and xylitol 62 (92:8) PC E-38 CA-4 triacetin and sorbitol 62 (92:8) cosity or plasticizer concentration of HPCE. PC E-39 CA-2 triacetin and xylitol 62 (92:8) PC E-40 CA-2 triacetin and sorbitol 62 (92:8) Example 5 PC E-41 CA-2 triacetin and gamma 62 (92:8) 0135 An adhesive melt was prepared by compounding Valerolactone cellulose diacetate (40% by weight of the adhesive melt) with triacetin plasticizer (60% by weight of the adhesive melt) and placing the compounded mixture in an oven for about 5 min TABLE 4 at 140°C. The adhesive melt was then coated to one surface? Melt Flow Index side of a card-stock paper Substrate and allowed to cool So as Sample Description T (° C.) to yield a laminate film on the paper Surface. The coated (g 10 min) substrate was subjected to an additional heating step at 140° CA-4 white flake 167-207 7 PC E-17 clear; flexible; stretchy -69 40 C. for 2-3 minutes. The laminate film was glossy, flexible, and PC E-18 clear; flexible; stretchy -53 31 well adhered to the surface precluding the need for both film PC E-19 clear; hard -66 16 and laminating adhesive. PC E-2O clear; flexible: -66 57 stretchy; tacky PC E-21 clear; flexible: -54 49 Example 6 stretchy; tacky PC E-22 clear-yellow; flexible; -SS 0136. A plurality of adhesive samples were prepared by stretchy compounding cellulose acetate and a plasticizer in the PC E-23 clear-yellow; flexible; -63 56 amounts and compositions detailed in Table 3. The cellulose stretchy acetates tested were CA-2 from Example 1 and CA-4 having PC E-24 clear-yellow; flexible; -SS stretchy; tacky a degree of substitution of about 2.4, a M., of about 60,000, PC clear-yellow; flexible; -62 46 and an intrinsic viscosity of about 1.36 dL/g. The character stretchy; tacky istics of the adhesive samples and control cellulose acetate PC E-26 clear-yellow; flexible; -56 51 samples without plasticizer were measured and are reported S tretchy; tacky in Table 4. US 2015/0307754 A1 Oct. 29, 2015

TABLE 4-continued TABLE 6-continued Melt Flow Index Melt Flow Index Sample Description T. (° C.) (g 10 min) Sample Plasticizer T (° C.) (g 10 min) HPCE-27 clear-yellow; flexible: -59 67 HPCE-43 50 wt % acetylsalicylic acid -21 less than 1 Stretc.ny; tacky HPCE-44 60 wt % acetylsalicylic acid -32 less than 1 HPCE-28 yellow; flexible -54 45 HPCE-45 33 wt % diacetin and -57 125 HPCE-29 yellow; flexible -61 38 33 wt % acetylsalicylic acid HPCE-30 white; flexible: -54 68 HPCE-46 49.5 wt % diacetin and -59 1OO Stretc.ny; tacky 16.5 wt % acetylsalicylic acid HPCE-31 white; flexible: 47 HPCE-47 16.5 wt % diacetin and -48 1OO Stretc.ny; tacky 49.5 wt % acetylsalicylic acid HPCE-32 white; flexible: -53 278 Stretc.ny; tacky Glass transition temprature as measured by TA Instruments DSC Q2000. HPCE-33 white; flexible: -53 218 Melt flow index measured at 150° C. with a 500 g weight, Stretc.ny; tacky HPCE-34 clear-yellow; flexible: -68 81 Stretc.ny; tacky Example 9 HPCE-35 clear; flexible: -54 348 Stretc.ny; tacky 0.139. This example appears to demonstrate the synergistic HPCE-36 clear-yellow; flexible: -63 8O effect on melt flow index using multiple plasticizers in the Stretc.ny; tacky adhesives described herein. A plurality of adhesive samples HPCE-37 clear; flexible -51 44 were prepared by compounding cellulose acetate (CA-4 of HPCE-38 clear; flexible -56 41 HPCE-39 clear; flexible -SS Example 6) and a plasticizer in the amounts and compositions HPCE-40 clear; flexible -54 detailed in Table 7. The characteristics of the adhesive samples were measured and are reported in Table 7. Glass transition temprature as measured by TA Instruments DSC Q2000. Melt flow index measured at 150° C. with a 500 g weight, Literature values for cellulose acetate. TABLE 7 Melt flow index measured at 150°C, with a 100 g weight, Melt Flow Index Sample Plasticizer T (° C.) (g 10 min) Example 7 HPCE-17 60 wt.% diacetin -69 40 HPCE-48 60 wt.% triethylcitrate -56 15 0.137 Some of the adhesive compositions from Tables 1 HPCE-49 30 wt.% diacetin and -61 45 and 3 were tested for peel adhesion by ASTM 3330/D Method 30 wt % triethylcitrate HPCE-42 62 wt.% diacetin -68 82 A (180° Peel) after a 24 hour dwell time conditioned at 22°C. HPCE-79 62 wt.o imidazole -50 less than 1 and 60% relative humidity. The adhesive strength was mea HPCE-51 57 wt.% diacetin and -62 109 Sured on stainless steel, glass, and corrugated cardboard and 5 wt % imidazole is presented in Table 5. Glass transition temprature as measured by TA Instruments DSC Q2000. Melt flow index measured at 150°C, with a 500 g weight, TABLE 5 180° Peel Example 10 180° Peel 180° Peel Corrugated Adhesive Stainless Steel Glass Cardboard 0140. This example appears to demonstrate the use of Thickness Substrate 24hr. Substrate 24hr. Substrate 24hr. amines as plasticizers in the adhesives described herein. A (mil) Dwell Time Dwell Time Dwell Time plurality of adhesive samples were prepared by compounding Sample (mil) Mean (Ibfin) Mean (Ibfin) Mean (Ibfin) cellulose acetate (CA-4 of Example 6) and a plasticizer in the HPCE-14 1.5 3.0 2.6 1.7 amounts and compositions detailed in Table 8. The charac HPCE-16 5 1.7 2.4 1.4 teristics of the adhesive samples were measured and are HPCE-41 1.5 O.8 1.7 1.7 reported in Table 8.

TABLE 8 Example 8 Sample Plasticizer T. (° C.) 0138 A plurality of adhesive samples were prepared by HPCE-17 60 wt % diacetin -69 compounding cellulose acetate (CA-4 of Example 6) and a HPCE-50 60 wt % imidazole -53 plasticizer in the amounts and compositions detailed in Table HPCE-51 57 wt.% diacetin and -62 5 wt % imidazole 6. The characteristics of the adhesive samples were measured HPCE-52 50 wt % ethylene diamine Ole and are reported in Table 6. detected HPCE-53 50 wt % piperidine Ole TABLE 6 detected HPCE-54 50 wt % piperazine -60 Melt Flow Index HPCE-55 50 wt % hexanediamine -65 Sample Plasticizer T (° C.) (g 10 min) Glass transition temprature as measured by TA Instruments DSC Q2000. HPCE-17 60 wt % diacetin -69 40 HPCE-42 62 wt % diacetin -68 82 HPCE-20 57 wt % diacetin and -66 57 Example 11 5 wt % acetylsalicylic acid 0.141. This example appears to demonstrate the effect of tackifiers on the properties of the adhesives described herein. US 2015/0307754 A1 Oct. 29, 2015 17

A plurality of adhesive samples were prepared by compound Example 13 0143. This example appears to demonstrate the effect of ing cellulose acetate (CA-4 of Example 6 or CA-5 (a blend of cellulosic source on the properties of the adhesives described two cellulose acetates both having a degree of substitution of herein. A plurality of adhesive samples were prepared by about 2.3 and each an intrinsic viscosity of about 1.27 dL/g compounding cellulose acetate from different cellulosic and 1.21 dL/g), a plasticizer, and tackifiers (terpenephenolic sources. CA-4 and CA-5 described in Examples 6 and 11, respectively, were prepared with acetate grade cellulose, resins, SYLVARESTMTP96 and SYLVARESTM TP2040 and which has an alpha-cellulose content of greater than 94%. rosin esters, SYLVALITETMRE 100XL, available from Ari CA-6 was prepared to have similar degree of substitution and molecular weight as CA-4 but with viscose grade cellulose Zona Chemical) in the amounts and compositions detailed in starting material, which has an alpha-cellulose content of Table 9. The characteristics of the adhesive samples were about 90% to about 94%. The adhesive formulations and measured and are reported in Table 9. characteristics are provided in Table 11. TABLE 9

Melt Flow Index Sample Cellulose Plasticizer Tackifier T (C.) (g/10 min) HPCE-56 CA-4 57 wt % 5 wt % -68 516 iacetin SYLVARESTM TP96 HPCE-57 CA-4 57 wt % 5 wt % -68 626 iacetin SYLVARESTM TP2O40 HPCE-58 CA-5 S1 wt % 5 wt % -66 498 iacetin SYLVARESTM TP2O40 HPCE-59 CA-5 57 wt % 5 wt % Ole 108 iacetin SYLVALITETM detected RE 1 OOXL HPCE-60 CA-5 S1 wt % 5 wt % -62 118 iacetin SYLVALITETM RE 1 OOXL HPCE-61 CA-5 47.12 wt % 4.88 wt % -62 58 iacetin SYLVALITETM RE 1 OOXL HPCE-62 CA-5 42 wt % 30 wt % -61 3O8 iacetin SYLVALITETM RE 1 OOXL HPCE-63 CA-5 32.24 wt % 29.76 wt % -61 326 iacetin SYLVALITETM RE 1 OOXL Glass transition temprature as measured by TA Instruments DSC Q2000. Melt flow index measured at 150° C. with a 500 g weight, Melt flow index measured at 150°C, with a 100 g weight,

Example 12 0142. This example appears to demonstrate the effect of nonionic Surfactants on the properties of the adhesives described herein. A plurality of adhesive samples were pre pared by compounding cellulose acetate (CA-5 of Example 11), a plasticizer, tackifiers, and surfactant (GLY COMUL(R) L., Sorbitan monolaurate, available from Lonza) in the amounts and compositions detailed in Table 10. The charac teristics of the adhesive samples were measured and are reported in Table 10. TABLE 10 MFI Sample Cellulose Plasticizer Tackifier Surfactant T (C.) (g/10 min)

HPCE- CA-5 57 wt % 5 wt % Owt % Ole 10 59 diacetin SYLVALITETM detected RE 1 OOXL HPCE- CA-5 43.89 wt % 18.8 wt % 5 wt % -65 48 64 diacetin SYLVALITETM RE 1 OOXL

Glass transition temprature as measured by TA Instruments DSC Q2000. Melt flow index measured at 150° C. with a 100 g weight, US 2015/0307754 A1 Oct. 29, 2015 18

TABLE 11

MFI Sample Cellulose Plasticizer Tackifier T (C.) (g/10 min) HPCE-17 CA-4 60 wt % O% -69 406 iacetin HPCE-42 CA-4 62 wt % O% -68 826 iacetin HPCE.-65 CA-6 60 wt % O% -67 756 iacetin HPCE-66 CA-6 62 wt % O% -66 1016 iacetin HPCE-59 CA-5 57 wt % 5 wt % Ole 108 iacetin SYLVALITETMRE detected OOXL HPCE-60 CA-5 S1 wt % 5 wt % -62 118 iacetin SYLVALITETMRE OOXL HPCE-61 CA-5 47.12 wt % 4.88 wt % -62 58 iacetin SYLVALITETMRE OOXL HPCE-67 CA-6 57 wt % 5 wt % -72 448 iacetin SYLVALITETMRE OOXL HPCE-68 CA-6 S1 wt % 5 wt % -SS 378 iacetin SYLVALITETMRE OOXL HPCE-69 CA-6 47.12 wt % 4.88 wt % -66 278 iacetin SYLVALITETMRE OOXL Glass transition temprature as measured by TA Instruments DSC Q2000. Melt flow index measured at 150° C. with a 500 g weight, Melt flow index measured at 150° C. with a 100 g weight,

Example 14 Example 15 0144. This example appears to demonstrate the effect of 0145 This example appears to demonstrate the ability to nonionic Surfactants on the properties of the adhesives produce adhesives with base polymers that include HPCE and described herein. A plurality of adhesive samples were pre traditional adhesive polymers (e.g., ethylene vinyl acetate pared by compounding cellulose acetate (CA-5 of Example copolymer (“EVA') and polyvinyl alcohol (“PVOH)). Inter 11), a plasticizer, tackifiers, and Surfactant in the amounts and estingly, in these exemplary adhesive compositions, compati compositions detailed in Table 12. The characteristics of the bilizers were not required. A plurality of adhesive samples adhesive samples were measured and are reported in Table were prepared by compounding cellulose acetate (CA-5 of 12. Example 11), a plasticizer, and an additional polymer in the TABLE 12 T MFIS Sample Plasticizer Tackifier Surfactant (° C.) (g/10 min) HPCE-70 37.62 wt % 25 wt % 5 wt % -63 31 iacetin SYLVALITE TM BRIT L23 RE 10OXL (30% (w/v) in HO HPCE-71 37.62 wt % 25 wt % 5 wt % -64 41 iacetin SYLVALITE TM SIDERCEL SF E 10OXL 140 HPCE-72 37.62 wt % 25 wt % 5 wt % -62 31 iacetin SYLVALITE TM TRITONX-100 E 10OXL HPCE-73 37.62 wt % 25 wt % 5 wt % -63 17 iacetin SYLVALITE TM POLY FOX PF E 10OXL 151N HPCE-74 37.62 wt % 25 wt % 5 wt % -64 41 iacetin SYLVALITETM GLYCOSPERSE RE 10OXL L-2OKFG HPCE-75 39.60 wt % 264 wt % Owt % -66 11 iacetin SYLVALITE TM RE 10OXL Glass transition temprature as measured by TA Instruments DSC Q2000. Melt flow index measured at 150° C. with a 100 g weight, US 2015/0307754 A1 Oct. 29, 2015 19 amounts and compositions detailed in Table 13. The charac ing a cellulose ester and a plasticizer at about 15% or teristics of the adhesive samples were measured and are greater by weight of the highly plasticized cellulose reported in Table 13. ester, and the additional polymer being selected from the group consisting of a polyolefin, a polyalphaolefin, a TABLE 13 polyester, an ethylene vinyl acetate copolymer, a poly vinyl acetate, a polyvinyl alcohol, a polyethyleneimine, Additional MFI a polyacrylate, a polymethacrylate, a polyacrylamide, a Sample Cellulose Plasticizer Polymer (° C.) (g 10 min) polyacrylonitrile, a polyimide, a polyamide, polyvinyl HPCE-76 38% CA-5 57% 5% EVA -62 61 chloride, a polysiloxane, a polyurethane, polystyrene, a diacetin (28% vinyl polyetheramide copolymer, a styrene-butadiene copoly acetate) HPCE-77 38% CA-5 57% 59, PVOH -65 40 mer, a styrene-butadiene-styrene copolymer, a styrene diacetin (98.4% isoprene-styrene copolymer, a styrene-ethylene-buty hydrolysis) lene-styrene copolymer, a styrene-ethylene-propylene HPCE-78 38% CA-5 57% 59, PVOH -63 34 styrene copolymer, butyl rubber, polyisobutylene, a diacetin (88% hydrolysis) isobutylene-isoprene copolymer, an acrylic, a nitrile, and a combination thereof. Glass transition temprature as measured by TA Instruments DSC Q2000. 2. The adhesive of claim 1 further comprising: Melt flow index measured at 150°C, with a 100 g weight, a tackifying resin. 0146 Therefore, this disclosure is well adapted to attain 3. The adhesive of claim 2, wherein the tackifying resin is the ends and advantages mentioned as well as those that are present in an amount of at about 1% to about 70% by weight inherent therein. The particular embodiments disclosed of the adhesive. above are illustrative only, as the embodiments described 4. The adhesive of claim 1 further comprising: herein may be modified and practiced in different but equiva about 5% or less of a tackifying resin by weight of the lent manners apparent to those skilled in the art having the adhesive. benefit of the teachings herein. Furthermore, no limitations 5. The adhesive of claim 1 further comprising: are intended to the details of construction or design herein a Wax. shown, other than as described in the claims below. It is 6. The adhesive of claim 5, wherein the wax is present in an therefore evident that the particular illustrative embodiments amount of at about 1% to about 40% by weight of the adhe disclosed above may be altered, combined, or modified and S1V. all such variations are considered within the scope and spirit 7. The adhesive of claim 1 further comprising: of the disclosure. The embodiments illustratively disclosed an additive. herein suitably may be practiced in the absence of any ele 8. The adhesive of claim 7, wherein the additive is present ment that is not specifically disclosed herein and/or any in an amount of at about 1% to about 40% by weight of the optional element disclosed herein. While compositions and adhesive. methods are described in terms of "comprising.” “contain 9. The adhesive of claim 1 further comprising: ing.” or “including various components or steps, the com a tackifying resin in an amount of at about 1% to about 70% positions and methods can also “consist essentially of or by weight of the adhesive; “consist of the various components and steps. All numbers a wax is present in an amount of at about 1% to about 40% and ranges disclosed above may vary by Some amount. by weight of the adhesive; and Whenever a numerical range with a lower limit and an upper an additive is present in an amount of at about 1% to about limit is disclosed, any number and any included range falling 40% by weight of the adhesive. within the range is specifically disclosed. In particular, every 10. The adhesive of claim 1, wherein the plasticizer com range of values (of the form, “from about a to about b or, prises at least one selected from the group consisting of equivalently, “from approximately a to b,” or, equivalently, Formula 1 wherein R1 is H. C-C alkyl, aryl, or C-C alkyl “from approximately a-b') disclosed herein is to be under aryl; Formula 2 wherein R2 is H. C-C alkyl, aryl, or C-C, stood to set forth every number and range encompassed alkyl aryl and R3 is H. C-C alkyl, aryl, C-C alkyl aryl, within the broader range of values. Also, the terms in the acyl, or C-C alkyl acyl: Formula 3 wherein R4 and R6 are claims have their plain, ordinary meaning unless otherwise independently H, C-C alkyl, aryl, C-C alkyl aryl, COOH, explicitly and clearly defined by the patentee. Moreover, the C-C alkyl carboxylate, acyl, C-C alkyl acyl, amine, C-C, indefinite articles 'a' or “an as used in the claims, are alkylamine, amide, or C-C alkyl amide and R5 is H. C-C, defined herein to mean one or more than one of the element alkyl, aryl, C-C alkyl aryl, acyl, or C-C alkyl acyl: For that it introduces. If there is any conflict in the usages of a mula 4 wherein R7 is H. C-C alkyl, aryl, C-C alkyl aryl, word or term in this specification and one or more patent or OH, C-C alkoxy, amine, or C-C alkyl amine and R8 and other documents that may be incorporated herein by refer R9 are independently H, C-C alkyl, aryl, C-C alkyl aryl, ence, the definitions that are consistent with this specification COOH, C-C alkyl carboxylate, acyl, C-C alkyl acyl, should be adopted. amine, C-C alkylamine, amide, or C-C alkyl amide; For The invention claimed is: mula 5 wherein R10, R11, and R12 are independently H, 1. An adhesive comprising: C-C alkyl, aryl, C-C alkyl aryl, COOH, C-C alkyl car a base polymer composition that includes a highly plasti boxylate, acyl, C-C alkyl acyl, amine, C-C alkyl amine, cized cellulose ester and an additional polymer, the amide, or C-C alkyl amide; Formula 6 wherein R13 is H. highly plasticized cellulose ester at about 1% to about C-C alkyl, aryl, or C-C alkylaryl, R14 and R16 are inde 99% by weight of the base polymer, the additional poly pendently H, C-C alkyl, aryl, C-C alkyl aryl, COOH, mer at about 1% to about 99% by weight of the base C-C alkyl carboxylate, acyl, C-C alkyl acyl, amine, C-C, polymer, the highly plasticized cellulose ester compris alkyl amine, amide, or C-C alkyl amide, and R15 is H. US 2015/0307754 A1 Oct. 29, 2015 20

C-C alkyl, aryl, C-C alkylaryl, acyl, or C-C alkyl acyl: Formula 7 wherein R17 is Hor C-C alkyland R18, R19, and Formula 1 R20 are independently H, C-C alkyl, aryl, C-C alkylaryl, COOH, C-C alkyl carboxylate, acyl, C-C alkyl acyl, amine, C-C alkylamine, amide, or C-C alkyl amide; For mula 8 wherein R21 is H. C-C alkyl, aryl, C-C alkyl aryl, COOH, C-C alkyl carboxylate, acyl, C-C alkyl acyl, amine, C-C alkyl amine, amide, or C-C alkyl amide and R22 is H. C-C alkyl, aryl, C-C alkylaryl, acyl, C-C alkyl Formula 2 acyl, amine, or C-C alkyl amine; Formula 9 wherein R23 and R24 are independently H, C-C alkyl, aryl, C-C alkyl aryl, COOH, C-C alkyl carboxylate, acyl, C-C alkyl acyl, amine, C-C alkylamine, amide, or C-C alkyl amide; For mula 10 wherein R25, R26, R27, and R28 are independently H, C-C alkyl, aryl, C-C alkyl aryl, COOH, C-C alkyl carboxylate, acyl, C-C alkyl acyl, amine, C-C alkyl Formula 3 amine, amide, or C-C alkyl amide; Formula 1 1 wherein R29, R30, and R31 are independently H, C-C alkyl, aryl, C-C alkyl aryl, COOH, C-C alkyl carboxylate, acyl, C-C alkyl acyl, amine, C-C alkyl amine, amide, or C-C, alkyl amide; Formula 12 wherein R32 is H. C-C alkyl, aryl, C-C alkylaryl, R33 is H. C-C alkyl, aryl, C-C alkylaryl, OH, C-C alkoxy, acyl, C-C alkyl acyl, amine, or C-C, Formula 4 alkyl amine, and R34, R35, and R36 are independently H, C-C alkyl, aryl, C-C alkyl aryl, COOH, C-C alkyl car boxylate, acyl, C-C alkyl acyl, amine, C-C alkyl amine, amide, or C-C alkyl amide: Formula 13 wherein R37, R38, R39, and R40 are independently H, C-C alkyl, aryl, C-C, alkylaryl, COOH, C-C alkyl carboxylate, acyl, C-C alkyl acyl, amine, C-C alkylamine, amide, or C-C alkylamide; Formula 14 wherein R41 is H. C-C alkyl, aryl, C-C alkyl Formula 5 aryl, OH, or C-C alkoxy and R42 and R43 are indepen dently H, C-C alkyl, aryl, C-C alkyl aryl, COOH, C-C, alkyl carboxylate, acyl, C-C alkyl acyl, amine, C-C alkyl amine, amide, or C-C alkyl amide; triazine (1.2.3, 1.2.4, or 1.3.5) with R substituents from each of the cyclic carbons or cyclic nitrogens that are independently H, C-C alkyl, aryl, C-C alkyl aryl, COOH, C-C alkyl carboxylate, acyl, Formula 6 C-C alkyl acyl, amine, C-C alkyl amine, amide, or C-C, alkyl amide; triazole (1.2.3 or 12.4) with R substituents from each of the cyclic carbons or cyclic nitrogens that are inde pendently H, C-C alkyl, aryl, C-C alkyl aryl, COOH, C-C alkyl carboxylate, acyl, C-C alkyl acyl, amine, C-C, alkyl amine, amide, or C-C alkyl amide; pyrrole with R substituents from each of the cyclic carbons or cyclic nitro Formula 7 gens that are independently H, C-C alkyl, aryl, C-C alkyl aryl, OH, C-C alkoxy, COOH, C-C alkyl carboxylate, acyl, C-C alkyl acyl, amine, C-C alkyl amine, amide, or C-C alkyl amide: piperidine with R substituents from each of the cyclic carbons or cyclic nitrogens that are indepen dently H, C-C alkyl, aryl, C-C alkyl aryl, OH, C-C, alkoxy, COOH, C-C alkyl carboxylate, acyl, C-C alkyl Formula 8 acyl, amine, C-C alkylamine, amide, or C-C alkylamide; piperazine with R substituents from each of the cyclic carbons or cyclic nitrogens that are independently H, C-C alkyl, aryl, C-C alkylaryl, OH, C-C alkoxy, COOH, C-C alkyl carboxylate, acyl, C-C alkyl acyl, amine, C-C alkyl amine, amide, or C-C alkyl amide: R44HN R45-NHR46 Formula 9 where R44 and R46 are independently H, C-C alkyl, aryl, C-C alkyl aryl, COOH, C-C alkyl carboxylate, acyl, C-C alkyl acyl, amine, C-C alkyl amine, amide, or C-C, alkyl amide and R45 is C-C alkyl; and combinations thereof US 2015/0307754 A1 Oct. 29, 2015

-continued polyglycol ethers, polyglycol esters, ethylene glycol ethers, Formula 10 propylene glycol ethers, ethylene glycol esters, propylene R2s N R25 glycol esters, polypropylene glycol esters, acetylsalicylic acid, acetaminophen, naproxen, imidazole, triethanolamine, benzoic acid, benzylbenzoate, salicylic acid, 4-hydroxyben R27D N C R26 Zoic acid, propyl-4-hydroxybeonzoate, methyl-4-hydroxy beonzoate, ethyl-4-hydroxybeonzoate, benzyl-4-hydroxy Formula 11 beonzoate, butylated hydroxytoluene, butylated R31 hydroxyanisol, Sorbitol, xylitol, ethylene diamine, piperi dine, piperazine, hexamethylene diamine, triazine, triazole, R30 N pyrrole, any derivative thereof, and any combination thereof. Formula 12 12. The adhesive of claim 1, wherein the plasticizer com O prises a nonionic surfactant. 13. An article comprising the adhesive of claim 1 disposed R32 on a substrate. R33 14. The article of claim 13, wherein the adhesive is a pressure sensitive adhesive, the substrate comprises paper, N and the article is repositionable. --Rs 15. The article of claim 13, wherein the adhesive is a al pressure sensitive adhesive, the substrate comprises paper, R36 R35 and the article is not repositionable. Formula 13 16. The article of claim 13, wherein the adhesive is a hot R40 melt pressure sensitive adhesive and the substrate comprises paper, and wherein the substrate is adhered to a glass surface R39 or a polymer surface. 17. The article of claim 13, wherein the substrate comprises r cellulose diacetate. R3s Nals R37 Formula 14 18. An adhesive comprising: R41 a base polymer composition that consists of a highly plas 1 ticized cellulose ester comprising a cellulose ester and a plasticizer at about 15% or greater by weight of the highly plasticized cellulose ester; and R43 R42. at least one selected from the group consisting of a tacki fying resin, a wax, and any combination thereof. 11. The adhesive of claim 1, wherein the plasticizer com 19. An method comprising: prises at least one selected from the group consisting of: blending a highly plasticized cellulose ester and an addi triacetin, trimethyl phosphate, triethyl phosphate, tributyl tional polymer, the highly plasticized cellulose ester at phosphate, triphenyl phosphate, triethyl citrate, acetyl trim about 1% to about 99% by weight of the blend, the ethyl citrate, acetyl triethyl citrate, acetyl tributyl citrate, additional polymer at about 1% to about 99% by weight tributyl-O-acetyl citrate, dibutyl phthalate, diaryl phthalate, of the blend, the highly plasticized cellulose ester com diethyl phthalate, dimethyl phthalate, di-2-methoxyethyl prising a cellulose ester and a plasticizer at about 15% or phthalate, di-octyl phthalate, dibutyl tartrate, ethyl o-ben greater by weight of the highly plasticized cellulose Zoylbenzoate, ethyl phthalyl ethylglycolate, methyl phthalyl ester, and the additional polymer being selected from the ethylglycolate, n-ethyltoluenesulfonamide, o-cresyl p-tolu group consisting of a polyolefin, a polyalphaolefin, a enesulfonate, aromatic diol, substituted aromatic diols, aro polyester, an ethylene vinyl acetate copolymer, a poly matic ethers, tripropionin, polycaprolactone, glycerin, glyc vinyl acetate, a polyvinyl alcohol, a polyethyleneimine. erinesters, diacetin, polyethylene glycol, polyethylene glycol a polyacrylate, a polymethacrylate, a polyacrylamide, a esters, polyethylene glycol diesters, di-2-ethylhexyl polyeth polyacrylonitrile, a polyimide, a polyamide, polyvinyl ylene glycol ester, glycerolesters, diethylene glycol, polypro chloride, a polysiloxane, a polyurethane, polystyrene, a pylene glycol, polyglycoldiglycidyl ethers, dimethyl sulfox polyetheramide copolymer, a styrene-butadiene copoly ide, N-methyl pyrollidinone, propylene carbonate, C-Co mer, a styrene-butadiene-styrene copolymer, a styrene dicarboxylic acid esters, dimethyl adipate, di-butyl maleate, isoprene-styrene copolymer, a styrene-ethylene-buty di-octyl maleate, resorcinol monoacetate, catechol, catechol lene-styrene copolymer, a styrene-ethylene-propylene esters, phenols, epoxidized soybean oil, castor oil, linseed styrene copolymer, butyl rubber, polyisobutylene, a oil, epoxidized linseed oil, other vegetable oils, other seed isobutylene-isoprene copolymer, an acrylic, a nitrile, oils, difunctional glycidyl ether based on polyethylene gly and a combination thereof. col, alkyl lactones (e.g., Y-Valerolactone), alkylphosphate 20. The method of claim 19, wherein the blending involves esters, aryl phosphate esters, phospholipids, aromas, 2-phe high-shear mixing. noxyethanol, glycol ethers, glycol esters, glycol ester ethers, ck ck ci: ck ck