EP2970721A1 - Adhésifs thermofusibles et sensibles à la pression qui comprennent des esters de cellulose fortement plastifiés et procédés et articles associés - Google Patents

Adhésifs thermofusibles et sensibles à la pression qui comprennent des esters de cellulose fortement plastifiés et procédés et articles associés

Info

Publication number
EP2970721A1
EP2970721A1 EP14779331.9A EP14779331A EP2970721A1 EP 2970721 A1 EP2970721 A1 EP 2970721A1 EP 14779331 A EP14779331 A EP 14779331A EP 2970721 A1 EP2970721 A1 EP 2970721A1
Authority
EP
European Patent Office
Prior art keywords
adhesive
ester
plasticizer
hpce
cellulose ester
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP14779331.9A
Other languages
German (de)
English (en)
Other versions
EP2970721A4 (fr
Inventor
Michael Combs
Wendy Bisset
Lizbeth Milward
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Celanese Acetate LLC
Original Assignee
Celanese Acetate LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US13/796,005 external-priority patent/US20140262017A1/en
Priority claimed from US13/796,234 external-priority patent/US20140262018A1/en
Priority claimed from US13/795,779 external-priority patent/US20140262016A1/en
Priority claimed from US13/930,117 external-priority patent/US20140272131A1/en
Application filed by Celanese Acetate LLC filed Critical Celanese Acetate LLC
Publication of EP2970721A1 publication Critical patent/EP2970721A1/fr
Publication of EP2970721A4 publication Critical patent/EP2970721A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J101/00—Adhesives based on cellulose, modified cellulose, or cellulose derivatives
    • C09J101/08—Cellulose derivatives
    • C09J101/10—Esters of organic acids
    • C09J101/12—Cellulose acetate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/716—Degradable
    • B32B2307/7163—Biodegradable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2170/00—Compositions for adhesives
    • C08G2170/20—Compositions for hot melt adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2170/00—Compositions for adhesives
    • C08G2170/40—Compositions for pressure-sensitive adhesives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2401/00—Presence of cellulose

Definitions

  • the exemplary embodiments described herein relate to hot melt and pressure-sensitive adhesives that comprise highly-plasticized cellulose esters, and methods and articles relating thereto.
  • hot melt adhesive refers to an adhesive composition that is melted by heat, which at room temperature may be a solid, self-adhering solid, or a viscous liquid .
  • Hot melt adhesives are useful in several applications from arts and crafts (e.g. , hot glue sticks) to consumer products (e.g. , cigarette seam line adhesives) to packaging (e.g., shipping box and cereal box adhesives) .
  • Some of the desired properties of hot melt adhesives include low-temperature flexibility, high adhesion strength, wettability, water- resistance, optical clarity, and the ability to accept a wide variety of modifications and additives.
  • EVA-based adhesive ethylene vinyl acetate copolymer-based adhesive
  • EVA ethylene vinyl acetate copolymer-based adhesive
  • a wax ethylene vinyl acetate copolymer
  • tackifier ethylene vinyl acetate copolymer-based adhesive
  • EVA-based adhesives provide many of the desirable properties described above, including tailorability based on the vinyl acetate content of the EVA.
  • the components of EVA-based adhesives are derived from petroleum precursors, a recent push has been made to develop environmentally-friendly hot melt adhesives derived from renewable resources. BRIEF DESCRIPTION OF THE DRAWINGS
  • Figures 1A-E provide illustrations of nonlimiting examples of article configurations according to at least some embodiments described herein.
  • Figure 2 provides the melt temperature as a function of intrinsic viscosity for highly-plasticized cellulose ester hot melt adhesives according to at least some embodiments described herein.
  • the exemplary embodiments described herein relate to hot melt and pressure-sensitive adhesives that comprise highly-plasticized cellulose esters, and methods and articles relating thereto.
  • HPCE-adhesives include plasticizers and cellulose esters.
  • HPCE-adhesives may be hot melt adhesives, pressure sensitive hot melt adhesives, and pressure sensitive adhesives, which expands the applicability of these bio-derived and degradable adhesive compositions.
  • bio-derived refers to a compound or portion thereof originating from a biological source or produced via a biological reaction.
  • the bio-derived portion of the adhesive compositions described herein refers to the mass percent that is bio-derived . For example, a cellulose acetate produced from cellulose and a petroleum-derived acetic acid would be less than 100% bio-derived .
  • a 100% bio-derived cellulose acetate may be produced, for example, from acylation of cellulose with a bio- derived acid chloride (e.g., produced by reacting thionyl chloride with bio- derived acetic acid, which may be produced via a number of methods including those involving microbial fermentation) .
  • a bio- derived acid chloride e.g., produced by reacting thionyl chloride with bio- derived acetic acid, which may be produced via a number of methods including those involving microbial fermentation
  • the HPCE-adhesives described herein may be 100% bio-derived with the use of bio-derived plasticizers and cellulose derivatives that utilize bio-derived acids in the derivatization process.
  • the HPCE-adhesives described herein may, in some embodiments, have several advantageous properties like optical clarity, pressure-sensitive adhesive properties, high adhesion strength, and any combination thereof.
  • the adhesive strength of at least some embodiments of the H PCE-adhesives being comparable to that of EVA-based adhesives was unexpected .
  • the HPCE-adhesives described herein have a plurality of avenues through which the properties of the adhesive compositions (e.g. , tackiness, clarity, melt flow index, adhesive shear strength, degradability, and the like) can be tailored .
  • Examples of avenues for manipulating adhesive properties may include cellulose derivative composition, cellulose derivative molecular weight, cellulose derivative degree of substitution, plasticizer composition, plasticizer concentration, and the composition and concentrations of optional additives like tackifiers, fillers, antioxidants, and aromas.
  • the HPCE-adhesives described herein may be designed to be degradable over relatively short periods of time (e.g. , weeks) to longer periods of time (e.g., months to years) by manipulating the cellulose derivative composition, cellulose derivative molecular weight, plasticizer composition (e.g. , the volatility of the plasticizer), and the like. This may advantageously allow for articles and products that as a whole are more biodegradable than such articles and products utilizing other adhesives like urethanes and EVA-based adhesives.
  • the HPCE- adhesives described herein may be designed to be degradable over relatively short periods of time (e.g., weeks) to longer periods of time (e.g., months to years) .
  • the HPCE-adhesives described herein may, in some instances, be recyclable via repulping . This may advantageously enable articles and products that as a whole are more biodegradable and recyclable than such articles and products utilizing other hot melt adhesives like EVA-based adhesives.
  • the H PCE-adhesives described herein may be food- grade and utilize cellulose esters and plasticizers (e.g. , cellulose diacetate and triacetin) that are approved for use in conjunction with food applications (e.g. , food packaging) and other applications with an increased risk for oral ingestion by consumer (e.g. , cigarette adhesives) .
  • food-grade refers to a material that has been approved for contacting (directly or indirectly) food, which may be classified as based on the material's conformity to the requirements of the United States Pharmacopeia (“USP-grade”), the National Formulary (“NF-grade”), and/or the Food Chemicals Codex (“FCC-grade”) .
  • the HPCE-adhesives described herein may be suitable for high-speed coating/adhering methods because there is little to no dry time associated with their application and the melt flow properties of the adhesive composition can be tailored for fast coating processes. This is especially advantageous for laminate coatings and label application .
  • emulsion formulations that are used for adhesives and laminate coatings require drying through hundreds of feet of ovens to achieve the desired final product.
  • a brief heating may be performed to drive off plasticizer, but because the H PCE-adhesives described herein may include volatile to semi-volatile plasticizers, the time and distance associated with heating would be significantly less. Reducing the time and distance associated with heating would advantageously reduce energy costs and machinery footprint.
  • the components of at least some of the the H PCE-adhesives described herein are compatible with the current plastic recycling technologies (which allows for a 100% recyclable bottle) and glass bottle washing technologies (which allows for labels to be removed without additional steps and cost) .
  • Other technologies that provide this benefit includes some emulsion adhesives, however, as described above, their application when producing labeled bottles is more energy and labor intensive. Therefore, the adhesive compositions described herein provide for a more environmentally friendly adhesive from production (i.e. , from natural products) to application to recycling .
  • the HPCE-adhesives described herein may comprise cellulose esters and plasticizers, wherein the plasticizers are present in an amount of about 15% or greater by weight of the HPCE-adhesive.
  • the plasticizers may be present in H PCE-adhesives described herein in an amount ranging from a lower limit of about 15%, 30%, 40%, 50%, or 60% by weight of the H PCE-adhesive to an upper limit of about 80%, 70%, 60%, or 50% by weight of the HPCE-adhesive, wherein the amount may range from any lower limit to any upper limit and encompass any subset therebetween, e.g. , about 20% to about 65% .
  • Cellulose esters suitable for use in conjunction with H PCE- adhesives described herein may, in some embodiments, have ester substituents that include, but are not limited to, C 1 -C 20 aliphatic esters (e.g. , acetate, propionate, or butyrate), functional Ci-C 20 aliphatic esters (e.g. , succinate, glutarate, maleate) aromatic esters (e.g. , benzoate or phthalate), substituted aromatic esters, and the like, any derivative thereof, and any combination thereof.
  • ester substituents include, but are not limited to, C 1 -C 20 aliphatic esters (e.g. , acetate, propionate, or butyrate), functional Ci-C 20 aliphatic esters (e.g. , succinate, glutarate, maleate) aromatic esters (e.g. , benzoate or phthalate), substituted aromatic esters, and the like, any derivative thereof, and any combination thereof.
  • Cellulose esters suitable for use in conjunction with H PCE- adhesives described herein may, in some embodiments, have a degree of substitution of the ester substituent ranging from a lower limit of about 0.5, 1.2, or 2 to an upper limit of less than about 3, about 2.9, 2.7, or 2.5, and wherein the degree of substitution may range from any lower limit to any upper limit and encompass any subset therebetween .
  • Cellulose esters suitable for use in conjunction with H PCE- adhesives described herein may, in some embodiments, have a molecular weight ranging from a lower limit of about 10,000, 15,000, 25,000, 50,000, or 85,000 to an upper limit of about 125,000, 100,000, or 85,000, and wherein the molecular weight may range from any lower limit to any upper limit and encompass any subset therebetween.
  • molecular weight refers to a polystyrene equivalent number average molecular weight (Mn).
  • Cellulose esters suitable for use in conjunction with HPCE- adhesives described herein may be derived from any suitable cellulosic source.
  • suitable cellulosic sources may, in some embodiments, include, but are not limited to, softwoods, hardwoods, cotton linters, switchgrass, bamboo, bagasse, industrial hemp, willow, poplar, perennial grasses (e.g. , grasses of the Miscanthus family), bacterial cellulose, seed hulls (e.g. , soy beans), and the like, and any combination thereof.
  • HPCE-adhesives described herein may be minimally to not impacted by the cellulosic source from which the cellulose esters are derived, which is unexpected because some existing cellulose ester products that do not have adhesive properties require high quality, expensive cellulosic sources (e.g., hardwoods with low hemicellulose content) to achieve high clarity.
  • Plasticizers suitable for use in conjunction with the embodiments described herein may, in some embodiments, include, but are not limited to, triacetin, trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, triethyl citrate, acetyl trimethyl citrate, acetyl triethyl citrate, acetyl tributyl citrate, tributyl-o-acetyl citrate, dibutyl phthalate, diaryl phthalate, diethyl phthalate, dimethyl phthalate, di-2-methoxyethyl phthalate, di-octyl phthalate (and isomers), dibutyl tartrate, ethyl o-benzoylbenzoate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, n- ethyltoluene
  • glycol ethers glycol esters, polyglycol ethers, polyglycol esters, ethylene glycol ethers, propylene glycol ethers, ethylene glycol esters (e.g . ethylene glycol diacetate), propylene glycol esters, polyethylene glycol esters, polypropylene glycol esters, and the like, any derivative thereof, and any combination thereof.
  • plasticizers may be food-grade plasticizers.
  • food-grade plasticizers may, in some embodiments, include, but are not limited to, triacetin, diacetin, tripropionin, trimethyl citrate, triethyl citrate, tributyl citrate, eugenol, cinnamyl alcohol, alkyl lactones (e.g. , ⁇ - valerolactone), methoxy hydroxy acetophenone (acetovanillone), vanillin, ethylvanillin, polyethylene glycols, 2-phenoxyethanol, glycol ethers, ethylene glycol ethers, propylene glycol ethers, and the like, and any combination thereof.
  • the HPCE-adhesives described herein may further comprise additives.
  • Additives suitable for use in conjunction with the HPCE-adhesives described herein may include, but are not limited to, tackifiers, crosslinkers, insolubilizers, starches, fillers, thickeners, rigid compounds, water- resistance additives, flame retardants, lubricants, softening agents, antibacterial agents, antifungal and/or antimicrobial agents, pigments, dyes, antioxidants, UV-stabilizers, resins, rosins, waxes, flowing agents, viscosity modifiers, aromas, and the like, and any combination thereof.
  • the additives may be present in HPCE- adhesives described herein in an amount ranging from a lower limit of about 0.1%, 1%, 5%, or 10% by weight of the HPCE-adhesive to an upper limit of about 75%, 60%, 45%, or 40% by weight of the HPCE-adhesive, wherein the amount may range from any lower limit to any upper limit and encompass any subset therebetween.
  • Tackifiers may, in some embodiments, increase the adhesive properties of the HPCE-adhesives described herein.
  • Tackifiers suitable for use in conjunction with the HPCE-adhesives described herein may, in some embodiments, include, but are not limited to, methylcellulose, ethylcellulose, hydroxyethylcellulose, carboxy methylcellulose, carboxy ethylcellulose, amides, diamines, polyesters, polycarbonates, silyl-modified polyamide compounds, polycarbamates, urethanes, natural resins, natural rosins, shellacs, acrylic acid polymers, 2-ethylhexylacrylate, acrylic acid ester polymers, acrylic acid derivative polymers, acrylic acid homopolymers, anacrylic acid ester homopolymers, poly(methyl acrylate), poly(butyl acrylate), poly(2-ethylhexyl acrylate), acrylic acid ester co-polymers, methacrylic acid derivative polymers, methacryl
  • tackifiers suitable for use in conjunction with the H PCE-adhesives described herein may be food-grade tackifiers.
  • food-grade tackifiers may, in some embodiments, include, but are not limited to, methylcellulose, ethylcellulose, hydroxyethylcellulose, carboxy methylcellulose, carboxy ethylcellulose, natural resins, natural rosins, and the like, and any combination thereof.
  • Crosslinkers may, in some embodiments, increase the adhesive properties and/or increase water-resistance of the HPCE-adhesives described herein .
  • Crosslinkers suitable for use in conjunction with the H PCE-adhesives described herein may, in some embodiments, include, but are not limited to, zirconium salts, boric acid, borate salts, ammonium zirconium carbonate, potassium zirconium carbonate, metal chelates (e.g. , zirconium chelates, titanium chelates, or aluminum chelates), formaldehyde crosslinkers, polyamide epichlorohydrin resin, crosslinkers containing N-methylol groups and/or etherified N-methylol groups (e.g.
  • ARKOFIX® an ultra-low formaldehyde crosslinking agent, available from Clariant
  • glyoxal urea glyoxal adduct crosslinkers, urea formaldehyde adduct crosslinkers, melamine formaldehyde, 4,5-dihydroxy-N, N'-dimethylolethyleneurea, hydroxymethylated cyclic ethyleneureas, hydroxymethylated cyclic propyleneureas, hydroxymethylated bicyclic glyoxal diurea, hydroxymethylated bicyclic malonaldehyde diureas, dialdehydes, protected dialdehydes, bisulfite protected aldehydes, isocyanates, blocked isocyanates, dimethyoxytetrahydrafuran, dicarboxylic acids, epoxides, diglycidyl ether, hydroxymethyl-substituted imidazolidinone, l,3-dimethyl
  • crosslinkers suitable for use in conjunction with the HPCE- adhesives described herein may be food-grade crosslinkers.
  • Water- resistance additives may, in some embodiments, increase the water-resistance properties of the H PCE-adhesives described herein, which may consequently yield articles capable of maintaining their mechanical properties in environments with higher water concentrations, e.g. , humid environments.
  • Water-resistance additives suitable for use in conjunction with the HPCE-adhesives described herein may, in some embodiments, include, but are not limited to, waxes, polyolefins, insolublizers, ethylene vinyl acetate, vinyl acetate ethylene polymers, octenyl succinyls, alkenyl succinyls, and the like, and any combination thereof.
  • water-resistance additives suitable for use in conjunction with the HPCE-adhesives described herein may be food-grade water-resistance additives.
  • food-grade water-resistance additives may, in some embodiments, include, but are not limited to, waxes, polyolefins, ethylene vinyl acetate, vinyl acetate ethylene polymers, and the like, and any combination thereof.
  • Fillers may, in some embodiments, increase the rigidity of the HPCE-adhesives described herein, which may consequently increase the mechanical rigidity of an article produced therewith .
  • Fillers suitable for use in conjunction with the HPCE-adhesives described herein may, in some embodiments, include, but are not limited to, coconut shell flour, walnut shell flour, wood flour, wheat flour, soybean flour, gums, starches, protein materials, calcium carbonate, talc, zeolite, clay, rigid compounds (e.g. lignin), thickeners, and the like, and any combination thereof.
  • fillers suitable for use in conjunction with the HPCE-adhesives described herein may be food-grade fillers.
  • food-grade fillers may, in some embodiments, include, but are not limited to, coconut shell flour, walnut shell flour, wood flour, wheat flour, soybean flour, gums, starches, protein materials, calcium carbonate, and the like, and any combination thereof.
  • Flame retardants suitable for use in conjunction with the H PCE- adhesives described herein may, in some embodiments, include, but are not limited to, silica, metal oxides, phosphates, catechol phosphates, resorcinol phosphates, aromatic polyhalides, borates, inorganic hydrates, and the like, and any combination thereof.
  • Antifungal and/or antimicrobial agents suitable for use in conjunction with the HPCE-adhesives described herein may, in some embodiments, include, but are not limited to, polyene antifungals (e.g. , natamycin, rimocidin, filipin, nystatin, amphotericin B, candicin, and hamycin), imidazole antifungals such as miconazole (available as MICATIN® from WellSpring Pharmaceutical Corporation), ketoconazole (commercially available as NIZORAL® from McNeil consumer Healthcare), clotrimazole (commercially available as LOTRAMIN® and LOTRAMIN AF® available from Merck and CANESTEN® available from Bayer), econazole, omoconazole, bifonazole, butoconazole, fenticonazole, isoconazole, oxiconazole, sertaconazole (commercially available as ERTACZO® from OrthoDematologics),
  • allylamine antifungals e.g. , terbinafine (commercially available as LAMISIL® from Novartis Consumer Health, Inc.), naftifine (commercially available as NAFTIN® available from Merz Pharmaceuticals), and butenafine (commercially available as LOTRAMIN ULTRA® from Merck), echinocandin antifungals (e.g.
  • anidulafungin caspofungin, and micafungin
  • polygodial benzoic acid
  • ciclopirox tolnaftate (e.g., commercially available as TINACTIN® from MDS Consumer Care, Inc.)
  • undecylenic acid flucytosine, 5-fluorocytosine, griseofulvin, haloprogin, octynoic acid, and any combination thereof.
  • Pigments and dyes suitable for use in conjunction with the HPCE-adhesives described herein may, in some embodiments, include, but are not limited to, plant dyes, vegetable dyes, titanium dioxide, silicon dioxide, tartrazine, E102, phthalocyanine blue, phthalocyanine green, quinacridones, perylene tetracarboxylic acid di-imides, dioxazines, perinones disazo pigments, anthraquinone pigments, carbon black, metal powders, iron oxide, ultramarine, calcium carbonate, kaolin clay, aluminum hydroxide, barium sulfate, zinc oxide, aluminum oxide, CARTASOL® dyes (cationic dyes, available from Clariant Services) in liquid and/or granular form (e.g., CARTASOL® Brilliant Yellow K-6G liquid, CARTASOL® Yellow K-4GL liquid, CARTASOL® Yellow K-GL liquid, CARTASOL® Orange K-3GL liquid, CARTASOL® Scarlet
  • pigments and dyes suitable for use in conjunction with the H PCE-adhesives described herein may be food-grade pigments and dyes.
  • food-grade pigments and dyes may, in some embodiments, include, but are not limited to, plant dyes, vegetable dyes, titanium dioxide, and the like, and any combination thereof.
  • Antioxidants may, in some embodiments, mitigate oxidation and/or chemical degradation of the HPCE-adhesives described herein during storage, transportation, and/or implementation .
  • Antioxidants suitable for use in conjunction with the HPCE-adhesives described herein may, in some embodiments, include, but are not limited to, anthocyanin, ascorbic acid, glutathione, lipoic acid, uric acid, resveratrol, flavonoids, carotenes (e.g., beta- carotene), carotenoids, tocopherols (e.g., alpha-tocopherol, beta-tocopherol, gamma-tocopherol, and delta-tocopherol), tocotrienols, tocopherol esters (e.g.
  • antioxidants suitable for use in conjunction with the HPCE-adhesives described herein may be food-grade antioxidants.
  • food-grade antioxidants may, in some embodiments, include, but are not limited to, ascorbic acid, vitamin A, tocopherols, tocopherol esters, beta-carotene, flavonoids, and the like, and any combination thereof.
  • Viscosity modifiers may, in some embodiments, be advantageous in modifying the melt flow index of the HPCE-adhesives described herein and/or modify the viscosity of HPCE-adhesives described herein that are in a paste or putty form.
  • Viscosity modifiers suitable for use in conjunction with the HPCE-adhesives described herein may, in some embodiments, include, but are not limited to, polyethylene glycols, polypropylene glycols, and the like, and any combination thereof, which, in some embodiments, may be a food-grade viscosity modifier.
  • Aromas suitable for use in conjunction with the HPCE-adhesives described herein may, in some embodiments, include, but are not limited to, spices, spice extracts, herb extracts, essential oils, smelling salts, volatile organic compounds, volatile small molecules, methyl formate, methyl acetate, methyl butyrate, ethyl acetate, ethyl butyrate, isoamyl acetate, pentyl butyrate, pentyl pentanoate, octyl acetate, myrcene, geraniol, nerol, citral, citronellal, citronellol, linalool, nerolidol, limonene, camphor, terpineol, alpha-ionone, thujone, benzaldehyde, eugenol, isoeugenol, cinnamaldehyde, ethyl maltol, vanilla,
  • HPCE-adhesives described herein may be food-grade HPCE-adhesives that comprise food-grade cellulose esters and food- grade plasticizers and optionally further comprise food-grade additives.
  • the HPCE-adhesives described herein may comprise cellulose esters (e.g., having an ester substituent described herein, a degree of substitution described herein, a molecular weight described herein, from a cellulosic source described herein, and a combination thereof), plasticizers (e.g. , one or more specific plasticizers describe herein, food-grade plasticizers described herein, aroma plasticizers described herein, and a combination thereof), and optionally additives described herein (e.g.
  • the physical and chemical properties of cellulose esters and plasticizers described herein may be tailored to achieve the desired characteristics of the HPCE-adhesives.
  • properties may include, but are not limited to, the composition of the ester substituents of the cellulose esters, the degree of substitution of the ester substituent of the cellulose esters, the molecular weight of the cellulose esters, the composition of the plasticizers, and the like, and any combination thereof.
  • the amount of plasticizer in the HPCE-adhesives described herein may be tailored to achieve the desired characteristics of the HPCE-adhesives.
  • HPCE-adhesives described herein may include, but are not limited to, flow onset point, glass transition temperature, melt flow index, adhesive strength, degradability, clarity, and the like, and any combination thereof.
  • tailoring the flow onset point of the HPCE-adhesives described herein may be achieved by, inter alia, changing the plasticizer concentration (e.g. , decreasing the concentration to increase the flow onset point), changing plasticizer composition, changing the degree of substitution or composition of the cellulose ester, and changing the molecular weight of the cellulose ester (e.g. , decreasing molecular weight to decrease the flow onset point).
  • the HPCE-adhesives described herein may have a flow onset point of about 220°C or less. In some embodiments, the HPCE-adhesives described herein may have a flow onset point ranging from a lower limit of about 50°C, 70°C, 80°C, 100°C, 110°C, 130°C, or 150°C to an upper limit of about 220°C, 200°C, 170°C, 150°C, 130°C, or 110°C, and wherein the flow onset point may range from any lower limit to any upper limit and encompass any subset therebetween. In some embodiments, the HPCE- adhesives described herein may have no flow onset point.
  • the HPCE-adhesives described herein may exhibit visual flow under a gravitation load (i.e., no additional load) at a temperature ranging from a lower limit of about 75°C, 100°C, 125°C, or 150°C to an upper limit of about 220°C, 200°C, 175°C, or 150°C, and wherein the flow onset point may range from any lower limit to any upper limit and encompass any subset therebetween.
  • a gravitation load i.e., no additional load
  • Tailoring the glass transition temperature of the HPCE-adhesives described herein may alter the physical characteristics of the HPCE-adhesive at ambient conditions, e.g. , stiff or flexible, brittle or pliable, smooth or tacky, and the like, and any combination thereof.
  • tacy refers to a composition that is at least sticky to the touch at room temperature.
  • HPCE-adhesives having no detectable glass transition temperature may be more tacky and flexible than those having a glass transition temperature.
  • no detectable glass transition temperature and derivatives thereof refers to material having no detectable heat flow event (as measured by DSC), which may be caused by the plasticized material having no glass transition temperature or the heat flow broadening to an extent that the glass transition temperature is not detectable.
  • HPCE-adhesives having higher glass transition temperatures may be more stiff and/or brittle than those having moderate to low glass transition temperatures.
  • tailoring the glass transition temperature of the HPCE-adhesives described herein may be achieved by, inter alia, changing the plasticizer concentration (e.g., increasing the concentration to decrease the glass transition temperature), changing the composition of the plasticizer, changing the molecular weight, and changing the degree of substitution of the cellulose ester (e.g., in some instances, increasing the degree of substitution to decrease the glass transition temperature).
  • the HPCE-adhesives described herein may have a glass transition temperature of about 190°C or less. In some embodiments, the HPCE-adhesives described herein may have a glass transition temperature ranging from a lower limit of not measurable, about -61°C, -55°C, 10°C, 75°C, 120°C, 130°C, or 150°C to an upper limit of about 190°C, 175°C, or 150°C, and wherein the glass transition temperature may range from any lower limit to any upper limit and encompass any subset therebetween.
  • the glass transition temperature of an HPCE-adhesive can be measured by either differential scanning calorimetry or rheology.
  • the glass transition temperature value may fall outside the preferred range described herein for different plasticizers used to produce HPCE-adhesive samples. Accordingly, within the scope of the embodiments described herein, the glass transition can be manipulated based on the composition and concentration of additives included in the HPCE-adhesives.
  • melt flow index of HPCE-adhesives described herein may enable the use of the HPCE-adhesives over a wide variety of applications.
  • lower melt flow index HPCE-adhesives may be useful in applications where shape is retained until heating (e.g. , window films, glue sticks, and pelletized HPCE-adhesives)
  • higher melt flow index HPCE- adhesives may be useful in applications where pliable or even spreadable HPCE- adhesives are desired (e.g. , for creating thin films for self-adhesive stamps and envelopes).
  • tailoring the melt flow index of the HPCE- adhesives described herein may be achieved by, inter alia, changing the plasticizer composition, changing the plasticizer concentration (e.g. , increasing the concentration to decrease the melt flow index), changing the molecular weight of the cellulose ester (e.g., decreasing molecular weight to decrease the melt flow index), and changing the composition and/or concentration of additives (e.g., increasing crosslinker concentration to increase the melt flow index).
  • the HPCE-adhesives described herein may have a melt flow index ranging from a lower limit of about 25 g/10 min, 29 g/10 min, 35 g/10 min, or 40 g/10 min (at 130°C/2.16 kg) to an upper limit of about 86 g/10 min, 80 g/10 min, 70 g/10 min, 60 g/10 min, 50 g/10 min, or 40 g/10 min (at 125°C/500 g), and wherein the melt flow index may range from any lower limit to any upper limit and encompass any subset therebetween.
  • melt flow index of the HPCE-adhesives described herein may fall outside the ranges described herein depending on, inter alia, the additive (e.g., fillers, tackifiers, and the like), included in the adhesive.
  • the HPCE-adhesives described herein may have a melt flow index that is higher than can be measured at 125°C/500 g (e.g. , greater than about 86 g/10 min at 125°C/500 g kg).
  • HPCE-adhesives described herein may enable the use of the HPCE-adhesives over a wide variety of applications. For example, a lower adhesive strength may be useful in semipermanent adhesive applications (e.g. , between substrates with lower mechanical properties as in sticky-notes or peelable protective coatings), while higher adhesive strength may be useful in permanent to semi-permanent applications between substrates with higher mechanical properties (e.g. , adhering the cardboard packaging of mailing boxes or laminating applications).
  • semipermanent adhesive applications e.g. , between substrates with lower mechanical properties as in sticky-notes or peelable protective coatings
  • higher adhesive strength may be useful in permanent to semi-permanent applications between substrates with higher mechanical properties (e.g. , adhering the cardboard packaging of mailing boxes or laminating applications).
  • higher adhesive strength may be useful in forming a film (or coating) on a substrate (e.g., laminating paper, glass, metal, and the like such that the HPCE-adhesive forms a protective coating/laminate on the substrate).
  • tailoring the adhesive strength of the HPCE- adhesives described herein may be achieved by, inter alia, changing the plasticizer composition, changing the plasticizer concentration (e.g. , increasing the concentration to decrease the adhesive strength), changing the molecular weight of the cellulose ester (e.g., decreasing molecular weight to decrease the adhesive strength), and changing the composition and/or concentration of additives (e.g., increasing crosslinker and/or tackifier concentration to increase the adhesive strength).
  • the HPCE-adhesives described herein may have an adhesive shear strength ranging from a lower limit of about 0.2 kgf, 0.5 kgf, 1 kgf, 2 kgf, or 4 kgf to an upper value limited by the force required to tear the substrate, and wherein the adhesive shear strength may range from any lower limit to any upper limit and encompass any subset therebetween.
  • the HPCE-adhesives described herein may have an adhesive shear strength ranging from a lower limit of about 0.2 kgf, 0.5 kgf, 1 kgf, 2 kgf, or 4 kgf to an upper limit of about 10 kgf, 8 kgf, 8 kgf, 6 kgf, or 4 kgf, and wherein the adhesive shear strength may range from any lower limit to any upper limit and encompass any subset therebetween.
  • the adhesive shear strength of an HPCE-adhesive can be measured by testing lap shears by tension loading with a 1 kN load cell by a method that includes placing a specimen in the grips of the testing machine so that each end is in contact with the grip assemble, applying the loading immediately to the specimen at the rate of 800 lb force of shear per min, and continuing the load to failure. Substrate failure was observed above the strength of 8 kgf for paper substrates and a glue line less than 3 mm thick. This value may change depending on the substrate and size of the glue line.
  • Tailoring the degradability of HPCE-adhesives described herein may contribute to the overall degradability of products and articles comprising the HPCE-adhesives.
  • tailoring the degradability of the HPCE-adhesives described herein may be achieved by, inter alia, changing the plasticizer composition (e.g., utilizing a plasticizer that biodegrades or dissipates into the environment at a higher rate to increase the degradability), changing the plasticizer concentration (e.g. , increasing the concentration to increase the degradability), changing the degree of substitution of the cellulose ester (e.g. , decreasing the degree of substitution to increase the degradability), and changing the composition and/or concentration of additives (e.g. , increasing antioxidant and/or stabilizer concentration to decrease the degradability).
  • changing the plasticizer composition e.g., utilizing a plasticizer that biodegrades or dissipates into the environment at a higher rate to increase the degradability
  • changing the plasticizer concentration e
  • the HPCE-adhesives described herein may degrade to a greater extent than a cellulose diacetate material plasticized with 20% triacetin. In some embodiments, the HPCE-adhesives may degrade by about 5% or greater by weight than a cellulose diacetate material plasticized with 20% triacetin in a procedure performed according to EN13432 "Requirements for Packaging Recoverable through Composting and Biodegradation - Test Scheme and Evaluation Criteria for the Final Acceptance of Packaging." In some embodiments, the HPCE-adhesives may degrade by an amount ranging from a lower limit of about 5%, 10%, or 15% to an upper limit of about 300%, 200%, 100%, 50%, 40%, or 30% by weight than a cellulose diacetate material plasticized with 20% triacetin in a procedure performed according to EN 13432 "Requirements for Packaging Recoverable through Composting and Biodegradation - Test Scheme and Evaluation Criteria for the Final Acceptance of Packaging,"
  • the clarity of the HPCE-adhesives described herein may be important in some applications, e.g., high clarity (or low haze) may be necessary when the HPCE-adhesives are used in conjunction with high clarity (or low haze) films (e.g. , window tints or CLARIFOIL® packaging) or high clarity laminate films (e.g. , laminate or protective coatings on substrates like paper, glass, metal, polymer films).
  • tailoring the clarity of the HPCE- adhesives described herein may be achieved by, inter alia, changing the plasticizer concentration (e.g. , increasing the concentration to decrease the clarity/increasing the haze) and changing the composition and/or concentration of additives (e.g. , increasing the filler concentration to decrease the clarity/ increase the haze).
  • the HPCE-adhesives described herein may have a haze ranging from a lower limit of about 2, 5, 7, 10, 15, 20, or 25 to an upper limit of about 45, 40, 35, 30, or 25, and wherein the haze may range from any lower limit to any upper limit and encompass any subset therebetween.
  • the haze of an HPCE-adhesive can be measured with properly sized specimens having substantially plane-parallel surfaces (e.g. , flat without wrinkling) free of dust, scratches, particles and a thickness of about 0.85mm using an UtraScan Pro from Hunter Lab with D65 Illuminant/10 o observer.
  • the haze value may fall outside the preferred ranges described herein for different thickness of an HPCE-adhesive sample.
  • the haze value may be significantly larger than the preferred ranges above (e.g. , about 100) when additives like titanium dioxide are used in significant quantities to produce an opaque HPCE-adhesive.
  • pigments and dyes may affect the haze of the HPCE-adhesive. Accordingly, within the scope of the embodiments described herein, the haze may range from about 2 to about 100, including subsets therebetween, depending on the composition and concentration of additives included in the HPCE-adhesives.
  • HPCE-adhesives described herein may involve producing HPCE-adhesives described herein, which may involve compounding cellulose esters described herein and plasticizers described herein at a suitable concentration, which may optionally involve heating (e.g. , forming an HPCE- adhesive melt).
  • Some embodiments may involve using the HPCE-adhesives immediately for an application (e.g. , applying an HPCE-adhesive melt to a substrate so as to form a laminate surface on the substrate), while other embodiments may involve forming the HPCE-adhesives into a desired form .
  • the HPCE-adhesives described herein may be in a desired form, e.g.
  • a paste e.g. , a putty, pellets, or a molded shape ⁇ e.g. , a glue stick or an adhesive sheet.
  • sheet should not be interpreted to be limited in thickness and encompasses films, layers, and the like.
  • HPCE-adhesives in sheet form may comprise plasticizers in an amount ranging from a lower limit of about 30%, 35%, or 40% to an upper limit of about 70%, 55%, or 40% by weight of the HPCE-adhesive, and wherein the amount may range from any lower limit to any upper limit and encompasses any subset therebetween.
  • the HPCE-adhesives in sheet form may be smooth and substantially non-tacky at room temperature.
  • the HPCE-adhesives in sheet form may be heated to initiate adhesion to a surface(s) (e.g. , iron-on designs or laminating sheets disposed between one or two substrates).
  • the sheet may be disposed on one or between two release liners that are easily removed and serves to protect the sheet from adhering to another surface.
  • a release liner may be useful to mitigate an HPCE- adhesive in sheet form from adhering to itself when in a roll, especially an HPCE- adhesive in sheet form with higher plasticizer concentrations.
  • HPCE-adhesives in sheet form may have a thickness ranging from a lower limit of about 15 microns, 20 microns, 30 microns, 50 microns, or 100 microns to an upper limit of about 1200 microns, 800 microns, 400 microns, 200 microns, or 100 microns, and wherein the thickness may range from any lower limit to any upper limit and encompasses any subset therebetween. While these thicknesses may be preferred, one skilled in the art, with the benefit of this disclosure, should understand that the thicknesses described are not limiting to the structure of a sheet described herein and thicknesses outside these ranges may be achieved.
  • HPCE-adhesives may be particularly advantageous as a laminate on a substrate in that the HPCE-adhesive may function as both the adhesive and the film (i.e. , not requiring a second adhesive to adhere to a surface and cooling to a laminate form).
  • HPCE-adhesives in laminate form on a substrate may be produced from an HPCE-adhesive melt comprising plasticizers in an amount ranging from a lower limit of about 30%, 35%, or 40% to an upper limit of about 75%, 60%, 50%, or 45% by weight of the HPCE- adhesive melt, and wherein the amount may range from any lower limit to any upper limit and encompasses any subset therebetween .
  • the plasticizer concentration in the melt and subsequent heating to drive off additional plasticizer may each be tuned to provide a H PCE-adhesive in laminate form with varying properties (e.g. , flexibility and rigidity) .
  • the H PCE-adhesives in laminate form on a substrate may be produced by applying an H PCE-adhesive melt to the substrate (e.g. , via melt casting); and allowing the HPCE-adhesive melt to cool, thereby yielding the laminate on the substrate.
  • the HPCE-adhesives in laminate form on a substrate may be smooth and substantially non-tacky at room temperature.
  • the H PCE- adhesive melt may comprise HPCE-adhesive that is tacky at room temperature and melted to increase the flow of the HPCE-adhesive.
  • the H PCE-adhesive melt may comprise H PCE-adhesive that is non-tacky at room temperature and melted to allow for the flow of the HPCE-adhesive.
  • a higher plasticizer concentration may be preferred to increase the flow of the HPCE-adhesive melt at lower temperatures.
  • a H PCE-adhesive melt with increased flow may yield laminates with more uniform thickness and allow for thinner laminates, which tend to be more flexible. More uniform thicknesses provide for higher quality articles and, in some instances, higher clarity laminates.
  • Some embodiments may further involve treating the laminate to reduce the concentration of plasticizer in the laminate. Treating may involve drying, heating, applying vacuum, and the like, and any combination thereof. Reducing the concentration of the plasticizer may increase the stiffness, clarity, and chemical resistance of the laminate.
  • Some embodiments may further involve treating the laminate to change surface chemistry of the laminate.
  • a caustic bath may be utilized to produce a laminate with a superhydrophilic surface.
  • HPCE-adhesives in laminate form on a substrate may have a thickness ranging from a lower limit of about 15 microns, 20 microns, 30 microns, 50 microns, or 100 microns to an upper limit of about 500 microns, 400 microns, 300 microns, 200 microns, or 100 microns, and wherein the thickness may range from any lower limit to any upper limit and encompasses any subset therebetween . While these thicknesses may be preferred, one skilled in the art, with the benefit of this disclosure, should understand that the thicknesses described are not limiting to the structure of a laminate described herein and thicknesses outside these ranges may be achieved.
  • HPCE-adhesives in pellet form or molded shapes may comprise plasticizers in an amount ranging from a lower limit of about 30%, 35%, or 40% to an upper limit of about 65%, 55%, or 45% by weight of the HPCE-adhesive, and wherein the amount may range from any lower limit to any upper limit and encompasses any subset therebetween.
  • HPCE-adhesives in pellet form or molded shapes may be tacky.
  • the HPCE-adhesives in pellet form or molded shapes may be smooth and substantially non-tacky at room temperature.
  • the suitable amount of plasticizer in the HPCE-adhesives to achieve pellet form or molded shapes may depend on, inter alia, the degree of substitution of the cellulose esters, the composition of the cellulose esters, the molecular weight of the cellulose esters, and the composition of the plasticizers.
  • HPCE-adhesives in a paste or putty form may comprise plasticizers in an amount of about 40% or greater by weight of the HPCE-adhesive.
  • HPCE-adhesives in a paste or putty form may comprise plasticizers in an amount of about 40%, 45%, 50%, or 60% to an upper limit of about 80%, 75%, 70%, 65%, or 60% by weight of the HPCE-adhesive, and wherein the amount may range from any lower limit to any upper limit and encompasses any subset therebetween.
  • HPCE-adhesives in a paste or putty form may be tacky.
  • HPCE-adhesives in a paste or putty form may be smooth and substantially non- tacky.
  • the suitable amount of plasticizer in the HPCE-adhesives to achieve a paste or putty form may depend on, inter alia, the degree of substitution of the cellulose esters, the composition of the cellulose esters, the molecular weight of the cellulose esters, and the composition of the plasticizers.
  • Forming the HPCE-adhesives into a desired form may, in some embodiments, be a consequence of compounding, e.g. , a paste or a putty. Forming the HPCE-adhesives into a desired form may, in some embodiments, involve methods like extruding, injection molding, blow molding, over molding, compression molding, casting, calendaring, near net shape molding, melt casting, and the like, any hybrid thereof, and any combination thereof.
  • additives may be incorporated into HPCE-adhesives by inclusion in the compounding step. In some embodiments, additives may be incorporated into HPCE-adhesives after the compounding step by, for example, absorption. Absorption may, in some embodiments, be advantageous for the incorporation of volatile additives and/or small molecule additives, e.g., some fragrances, aromas, dyes, and pigments.
  • an article may comprise a first surface having an HPCE-adhesive described herein disposed thereon such that the HPCE- adhesive is exposed to the local environment (e.g., a window tint, window film, light films, light filters, iron-on designs, laminates, substrate coatings, peelable layers or films, and the like).
  • a window tint, window film, light films, light filters, iron-on designs, laminates, substrate coatings, peelable layers or films, and the like e.g., a window tint, window film, light films, light filters, iron-on designs, laminates, substrate coatings, peelable layers or films, and the like.
  • an article may comprise a first surface adhered to a second surface with an HPCE-adhesive described herein.
  • at least one of the surfaces may be chosen so as to be releasable (e.g. , a peelable layer) from the HPCE-adhesive, e.g., an envelope with an adhesive between the paper and a release strip.
  • the first surface and the second surface may correspond to a first substrate and a second substrate, respectively.
  • the first surface and the second surface may correspond to a single substrate, e.g. , a single piece of paper rolled into a cylinder and adhered to itself.
  • articles described herein may be extended to three or more surfaces, including hundreds or thousands of surfaces (e.g. , adhesive book bindings), without departing from the spirit of this disclosure.
  • the articles described herein may be designed with the first surface and the second surface adhered in any suitable configuration.
  • suitable configurations may, in some embodiments, include, but are not limited to, those illustrated in Figure 1.
  • Figure 1A illustrates a first substrate 101 and a second substrate 102 adhered together with an HPCE-adhesive 100a in a stacked configuration.
  • Figure IB illustrates a first substrate 103 and a second substrate 104 adhered together with an HPCE- adhesive 100b in a side-by-side configuration.
  • Figure 1C illustrates a first substrate 105, a second substrate 106, and a third substrate 107 adhered together with an HPCE-adhesive 100c, lOOd in a stacked configuration where each substrate 105,106,107 has different sizes.
  • Figure ID illustrates a plurality of substrates in a hybrid configuration, wherein substrates 109,110,111 are each embedded at one end in an HPCE-adhesive lOOe which further adheres substrates 109,110,111 to substrate 108.
  • Figure IE illustrates a substrate 112 rolled and adhered to itself at a seam with an HPCE- adhesive lOOf.
  • HPCE-adhesives and at least one fibrous substrate (or surface) as described herein may, in some embodiments, include, but are not limited to, smoking articles ⁇ e.g., cigarettes), envelopes, tape, cardboard packaging ⁇ e.g. , mailing packages and food containers like cereal boxes and frozen dinner containers), books, notebooks, magazines, sticky-notes, corrugated boxes, decorative boxes, paper bags, grocery bags, wrapping paper, wallpaper, paper honeycomb, emery boards, electric insulation paper, air filters, papier-mache articles, carpets, dartboards, furniture or components thereof ⁇ e.g., carpet and/or fabric coated headboards, chairs, and stools), picture frames, medical garments ⁇ e.g.
  • Substrates or surfaces suitable for use in conjunction with articles described herein may, in some embodiments, include, but are not limited to, fibers, woven fiber substrates, nonwoven fiber substrates, foamed substrates, solid substrates, and the like, any hybrid thereof, and any combination thereof.
  • Substrates or surfaces suitable for use in conjunction with articles described herein may, in some embodiments, comprise materials that include, but are not limited to, ceramics, natural polymers, synthetic polymers, metals, natural materials, carbons, and the like, and any combination thereof.
  • ceramics may, in some embodiments, include, but are not limited to, glass, quartz, silica, alumina, zirconia, carbide ceramics, boride ceramics, nitride ceramics, and the like, and any combination thereof.
  • Examples of natural polymers may, in some embodiments, include, but are not limited to, cellulose, and the like, any derivative thereof, and any combination thereof.
  • Examples of synthetic polymers may, in some embodiments, include, but are not limited to, cellulose diacetate, cellulose triacetate, synthetic bamboo, rayon, acrylic, aramid, nylon, polyolefins, polyethylene, polypropylene (including biaxially oriented polypropylene substrates), polyethylene terephthalate, polyesters, polyamides, zylon, and the like, any derivative thereof, and any combination thereof.
  • Examples of metals may, in some embodiments, include, but are not limited to, steel, stainless steel, aluminum, copper, and the like, any alloy thereof, and any combination thereof.
  • Examples of natural materials may, in some embodiments, include, but are not limited to, wood, grass, animal hide, and the like, and any combination thereof.
  • Examples of carbons may, in some embodiments, include, but are not limited to, carbon fibers, and the like, any derivative thereof, and any combination thereof.
  • Exemplary examples of substrates suitable for use in conjunction with the articles described herein may, in some embodiments, include, but are not limited to, paper, cardboard, card stock, sand paper, bond paper, wallpaper, wrapping paper, cotton paper, tipping paper, bleached paper, colored paper, construction paper, sisal paper, coated paper, wax paper, CLARIFOIL® (cellulose diacetate film, available from Celanese Corporation), woven fabrics, continuous filament nonwoven fabrics, carded nonwoven fabrics, tow, fiber bundles, twill, twine, rope, carpet, carpet backing, leather, animal hide, insulation, wood and/or grass derived substrates ⁇ e.g., wood veneers, particle board, fiberboard, medium-density fiberboard, high-density fiberboard, oriented strand board, cork, hardwoods (e.g., balsa wood, beech, ash, birch, Brazil wood, cherry, chestnut, elm, hickory, mahogany, maple, oak, rosewood, teak
  • an article e.g., a cigarette paper or a paper towel roll
  • a single substrate e.g. , a tipping paper or a cardboard
  • adhered together e.g., at a seam line
  • an article e.g., a cardboard container for shipping or containing food
  • an article e.g., a food container
  • an article e.g. , window tints or window coverings
  • a first surface e.g., a polyester film
  • HPCE-adhesives described herein disposed thereon so as to allow for adherence to a second surface (e.g. , a glass surface or other similar transparent surface)
  • the article may comprise, in order, the first surface, the HPCE-adhesives, and a peelable layer that can be removed before adherence to the second surface.
  • the article may comprise HPCE-adhesives that are smooth and substantially non-tacky at room temperature such that a peelable layer is not required and the H PCE-adhesives may be exposed to air.
  • heat may be utilized in adhering the first surface to the second surface.
  • an article e.g. , an iron-on design, heat activated film or laminated card
  • a surface or substrate e.g., paper, a fabric, or a polymer film
  • H PCE-adhesives disposed thereon .
  • the article may then be adhered to another surface (e.g. , applying heat so as to adhere an iron-on design or heat activated film to another surface like a piece of clothing or other fabric).
  • the article may be formed by applying an HPCE-adhesive melt to the surface or substrate and allowing the HPCE-adhesive melt to cool so as to form a laminate on the surface or substrate.
  • Some embodiments described herein may involve adhering two or more surfaces together using HPCE-adhesives described herein .
  • adhering may involve heating the H PCE-adhesives and/or applying pressure to the HPCE-adhesives.
  • adhering surfaces together may involve heating an HPCE-adhesive described herein to yield an adhesive melt; applying the adhesive melt to a first surface; and adhering a second surface to the first surface with the adhesive.
  • HPCE-adhesives described herein may be suitable for producing adhesive melts
  • HPCE-adhesives used for producing adhesive melts may comprise plasticizers in an amount of about 15% to about 70% by weight of the adhesive composition.
  • adhering surfaces together may involve applying the HPCE- adhesive to a first surface; and adhering a second surface to the first surface with the HPCE-adhesive.
  • adhering surfaces together may involve disposing an adhesive sheet between a first surface and a second surface; and heating the adhesive sheet so as to adhere the first surface and the second surface together.
  • Embodiments disclosed herein include :
  • B a method that includes compounding at least a cellulose ester and a plasticizer to yield an adhesive melt, the plasticizer included in an amount of about 30% to about 75% by weight of the adhesive melt; applying the adhesive melt to a substrate; allowing the adhesive melt to cool so as to yield a laminate on the substrate; and treating the laminate with at least one selected from the group consisting of heat, vacuum, a caustic bath, and any combination thereof.
  • Each of embodiments A and B may have one or more of the following additional elements in any combination : Element 1 : the cellulose ester having a degree of substitution between about 0.5 and less than about 3; Element 2 : the adhesive having a flow onset point between about 70°C and about 220°C; Element 3 : the adhesive having a glass transition temperature between about -61°C and about 190°C; Element 4: the adhesive having no detectable glass transition temperature; Element 5 : the substrate comprising at least one selected from the group consisting of a ceramic, a natural polymer, a synthetic polymer, a metal, a natural material, carbon, and any combination thereof; Element 6: the cellulose ester comprising at least one organic ester substituent selected from the group consisting of a C 1 -C 2 0 aliphatic ester, a functional Ci-C 20 aliphatic ester, acetate, propionate, butyrate, succinate, glutarate, maleate, an aromatic ester,
  • glycol ethers glycol esters, polyglycol ethers, polyglycol esters, ethylene glycol ethers, propylene glycol ethers, ethylene glycol esters (e.g .
  • Element 10 the method further comprising producing an article selected from the group consisting of a laminated card, a laminated paper, a laminated business card, a laminated paper board, a heat activated film, a coated substrate, an iron-on design, and a substrate with a laminated surface;
  • the adhesive further comprising at least one additive selected from the group consisting of crossl inkers, insolubilizers, starches, fillers, thickeners, rigid compounds, water- resistance additives, flame retardants, lubricants, softening agents, antibacterial agents, antifungal and/or antimicrobial agents, pigments, dyes, antioxidants, UV-stabilizers, resins, rosins, waxes, flowing agents, viscosity modifiers, aromas, and any combination thereof;
  • Element 12 Element 12 wherein the additive is
  • exemplary combinations applicable to A and B include : Element 1 in combination with Element 2; Element 1 in combination with Element 3; Element 1 in combination with Element 4; Element 1 in combination with Element 8; Element 2 in combination with Element 3; Element 2 in combination with Element 4; Element 2 in combination with Element 8; Element 3 in combination with Element 8; Element 4 in combination with Element 8; Element 1 in combination with at least two of Elements 2, 3, 5, 6, 7, and 8; Element 2 in combination with at least two of Elements 3, 5, 6, 7, and 8; Element 3 in combination with at least two of Elements 5, 6, 7, and 8; Element 1 in combination with at least two of Elements 2, 4, 5, 6, 7, and 8; Element 2 in combination with at least two of Elements 4, 5, 6, 7, and 8; Element 4 in combination with at least two of Elements 5, 6, 7, and 8; Element 9 in combination with any of the foregoing; Element 10 in combination with any of the foregoing; Element
  • Embodiments disclosed herein also include :
  • an article that includes a substrate with a laminate disposed on at least a portion of a surface of the substrate, wherein the laminate comprises a cellulose ester and a plasticizer in the amount of about 30% to about 75% by weight of the laminate.
  • Embodiment C may have one or more of the Elements 1 and 5-9 disclosed above.
  • exemplary combinations applicable to C include : Element 1 in combination with Element 5; Element 1 in combination with Element 6; Element 1 in combination with Element 7; Element 1 in combination with Element 8; Element 8 in combination with Element 5; Element 8 in combination with Element 6; Element 8 in combination with Element 7; Element 1 in combination with at least two of Elements 5-9; Element 8 in combination with at least two of Elements 5-7 and 9; and so on.
  • D a method that includes heating an adhesive to yield an adhesive melt, the adhesive comprising a cellulose ester and a plasticizer, the plasticizer included in an amount of about 15% to about 60% by weight of the adhesive; applying the adhesive melt to a first surface; and adhering a second surface to the first surface with the adhesive;
  • an adhesive that includes a cellulose ester; and a plasticizer in an amount of about 15% to about 60% by weight of the adhesive.
  • Each of embodiments D, E, and F may have one or more of the following additional elements in any combination :
  • Element 101 the adhesive having a visual flow with a gravitational load at a temperature of about 75°C and about 220°C;
  • Element 102 the adhesive has a glass transition temperature between about 10°C and about 190°C or the adhesive having the adhesive having no detectable glass transition temperature;
  • Element 103 the cellulose ester having a degree of substitution between about 0.5 and about 2.9;
  • Element 104 the cellulose ester comprising at least one organic ester substituent selected from the group consisting of a C 1 -C 2 0 aliphatic ester, a functional Ci-C 20 aliphatic ester, acetate, propionate, butyrate, succinate, glutarate, maleate, an aromatic ester, a substituted aromatic ester, any derivative thereof, and any combination thereof;
  • Element 105 the cellulose ester having a molecular weight between about 10,000 and about 125,000;
  • alkylphosphate esters alkylphosphate esters, aryl phosphate esters, phospholipids, aromas (including some described herein, e.g., eugenol, cinnamyl alcohol, camphor, methoxy hydroxy acetophenone (acetovanillone), vanillin, and ethylvanillin), 2-phenoxyethanol, glycol ethers, glycol esters, polyglycol ethers, polyglycol esters, ethylene glycol ethers, propylene glycol ethers, ethylene glycol esters (e.g . ethylene glycol diacetate), propylene glycol esters, polyethylene glycol esters, polypropylene glycol esters, any derivative thereof, and any combination thereof.
  • aromas including some described herein, e.g., eugenol, cinnamyl alcohol, camphor, methoxy hydroxy acetophenone (acetovanillone), vanillin, and ethy
  • Each of embodiments D and E may have one or more of the following additional elements in any combination :
  • Element 108 the first surface and/or the second surface comprising at least one selected from the group consisting of a ceramic, a natural polymer, a synthetic polymer, a metal, a natural material, carbon, and any combination thereof;
  • Element 109 producing an article selected from the group consisting of a smoking article, a cigarette, tape, cardboard packaging, a mailing package, a food container, a cereal box, a frozen dinner container, a book, a notebook, a magazine, a corrugated box, a decorative box, a paper bag, a grocery bag, paper honeycomb, an emery board, electric insulation paper, an air filter, a carpet, a dartboard, furniture or a component thereof, carpet or fabric coated headboard, a chair, a stool, a picture frame, a medical garment, a disposable gown, a surgical mask, a window film, window tinting, a light film, and
  • exemplary combinations applicable to D, E, and F include: Elements 101 and 102 in combination; Elements 102 and 103 in combination; Elements 101 and 103 in combination; Elements 101, 102, and 103 in combination; Element 106 in combination with any one or more of Elements 101-105, 107; and so on.
  • exemplary combinations applicable to D and E include: Elements 101 and 102 in combination; Elements 102 and 103 in combination; Elements 101 and 103 in combination; Elements 101, 102, and 103 in combination; Element 106 in combination with any one or more of Elements 101-105, 107; any of the foregoing in combination with Element 108; any of the foregoing in combination with Element 109; and so on.
  • G a method that includes applying an adhesive that is tacky at an ambient temperature to a first surface, the adhesive comprising a cellulose ester and a plasticizer, the plasticizer included in an amount of about 40% or greater by weight of the adhesive; and adhering a second surface to the first surface with the adhesive;
  • H a method that includes compounding at least a cellulose ester and a plasticizer to yield an adhesive that is tacky, the plasticizer included in an amount of about 40% or greater by weight of the cellulose ester;
  • an adhesive that includes a cellulose ester; and a plasticizer in an amount of about 40% or greater by weight of the cellulose ester, wherein the adhesive is tacky.
  • each of embodiments G, H, and I may have one or more of the following additional elements in any combination :
  • Element 201 the adhesive has a flow onset point of about 110°C or less;
  • Element 202 the adhesive has a glass transition temperature about 130°C or less or the adhesive having the adhesive having no detectable glass transition temperature;
  • Element 203 the cellulose ester has a degree of substitution between about 1.5 and about 2.8;
  • Element 204 the cellulose ester comprising at least one organic ester substituent selected from the group consisting of a C1-C20 aliphatic ester, a functional C1-C20 aliphatic ester, acetate, propionate, butyrate, succinate, glutarate, maleate, an aromatic ester, a substituted aromatic ester, any derivative thereof, and any combination thereof;
  • Element 205 the cellulose ester having a molecular weight between about 10,000 and about 125,000;
  • Element 206 the plasticizer being a food-grade plasticizer; and
  • glycol ethers glycol esters, polyglycol ethers, polyglycol esters, ethylene glycol ethers, propylene glycol ethers, ethylene glycol esters (e.g . ethylene glycol diacetate), propylene glycol esters, polyethylene glycol esters, polypropylene glycol esters, any derivative thereof, and any combination thereof.
  • Each of embodiments G and H may have one or more of the following additional elements in any combination :
  • Element 209 compounding the cellulose ester and the plasticizer so as to produce the adhesive;
  • Element 210 the first surface and/or the second surface comprising at least one selected from the group consisting of a ceramic, a natural polymer, a synthetic polymer, a metal, a natural material, carbon, and any combination thereof;
  • Element 211 producing an article selected from the group consisting of a smoking article, a cigarette, an envelope, tape, cardboard packaging, a mailing package, a food container, a cereal box, a frozen dinner container, a book, a notebook, a magazine, a sticky-note, a corrugated box, a decorative box, a paper bag, a grocery bag, wrapping paper, wallpaper, paper honeycomb, an emery board, electric insulation paper, an air filter, a papier-mache article, a carpet,
  • exemplary combinations applicable to G, H, and I include : Elements 201 and 202 in combination; Elements 202 and 203 in combination; Elements 201 and 203 in combination; Elements 201, 202, and 203 in combination; Element 206 in combination with any one or more of Elements 201-205, 207; and so on.
  • exemplary combinations applicable to G and H include: Elements 201 and 202 in combination; Elements 202 and 203 in combination; Elements 201 and 203 in combination; Elements 201, 202, and 203 in combination; Element 206 in combination with any one or more of Elements 201-205, 207; any of the foregoing in combination with Element 210; any of the foregoing in combination with Element 211; and so on.
  • J a method that includes disposing an adhesive sheet between a first surface and a second surface, the adhesive sheet comprising an adhesive that comprises a cellulose ester and a plasticizer, the plasticizer included in an amount of about 30% to about 60% by weight of the adhesive; and heating the adhesive sheet so as to adhere the first surface to the second surface;
  • K a method that includes compounding at least a cellulose ester and a plasticizer to yield an adhesive, the plasticizer included in an amount of about 30% to about 60% by weight of the adhesive; and forming the adhesive into an adhesive sheet;
  • L an adhesive sheet that includes a cellulose ester; and a plasticizer in an amount of about 30% to about 60% by weight of the adhesive.
  • Each of embodiments J, K, and L may have one or more of the following additional elements in any combination :
  • Element 301 the adhesive having a flow onset point between about 75°C and about 180°C;
  • Element 302 the adhesive having a glass transition temperature between about 10°C and about 190°C or the adhesive having the adhesive having no detectable glass transition temperature;
  • Element 303 the cellulose ester having a degree of substitution between about 1.5 and about 2.7;
  • Element 304 the cellulose ester comprising at least one organic ester substituent selected from the group consisting of a Ci-C 2 o aliphatic ester, a functional Ci-C 20 aliphatic ester, acetate, propionate, butyrate, succinate, glutarate, maleate, an aromatic ester, a substituted aromatic ester, any derivative thereof, and any combination thereof;
  • Element 305 the cellulose ester having a molecular weight between about 10,000 and about 125,000;
  • Element 306 the plasticizer being
  • alkylphosphate esters alkylphosphate esters, aryl phosphate esters, phospholipids, aromas (including some described herein, e.g., eugenol, cinnamyl alcohol, camphor, methoxy hydroxy acetophenone (acetovanillone), vanillin, and ethylvanillin), 2-phenoxyethanol, glycol ethers, glycol esters, polyglycol ethers, polyglycol esters, ethylene glycol ethers, propylene glycol ethers, ethylene glycol esters (e.g . ethylene glycol diacetate), propylene glycol esters, polyethylene glycol esters, polypropylene glycol esters, any derivative thereof, and any combination thereof.
  • aromas including some described herein, e.g., eugenol, cinnamyl alcohol, camphor, methoxy hydroxy acetophenone (acetovanillone), vanillin, and ethy
  • Each of embodiments J and K may have one or more of the following additional elements in any combination :
  • Element 308 the first surface and/or the second surface comprising at least one selected from the group consisting of a ceramic, a natural polymer, a synthetic polymer, a metal, a natural material, carbon, and any combination thereof;
  • Element 309 producing an article selected from the group consisting of an envelope, tape, cardboard packaging, a mailing package, a food container, a cereal box, a frozen dinner container, a book, a notebook, a magazine, a corrugated box, a decorative box, a paper bag, a grocery bag, electric insulation paper, an air filter, furniture or a component thereof, carpet or fabric coated headboard, a chair, a stool, and a picture frame; and
  • Element 310 absorbing an additive into the adhesive sheet, wherein the additive comprises at least one selected from the group consisting of a crosslinker, a lubricant, a softening agent, an antibacterial agent, an
  • exemplary combinations applicable to J, K, and L include : Elements 301 and 302 in combination; Elements 302 and 303 in combination; Elements 301 and 303 in combination; Elements 301, 302, and 303 in combination; Element 306 in combination with any one or more of Elements 301-305, 307; and so on.
  • exemplary combinations applicable to J and K include : Elements 301 and 302 in combination; Elements 302 and 303 in combination; Elements 301 and 303 in combination; Elements 301, 302, and 303 in combination; Element 306 in combination with any one or more of Elements 301-305, 307; any of the foregoing in combination with Element 308; any of the foregoing in combination with Element 309; and so on.
  • Example 1 A plurality of HPCE-adhesive samples were prepared by compounding cellulose acetate and a plasticizer in the amounts and compositions detailed in Table 1.
  • the cellulose acetates tested were CA-1 having a degree of substitution of about 2.5 and a molecular weight (M n ) of about 78,000, CA-2 having a degree of substitution of about 2.4 and a M n of about 44,000, and CA-3 having a degree of substitution of about 2.4 and a M n of about 62,000.
  • the characteristics of the HPCE-adhesive samples and control cellulose acetate samples without plasticizer were measured and are reported in Table 2.
  • composition Composition Composition
  • Example 2 Samples HPCE-3, HPCE-6, HPCE-7, and HPCE-9 were tested for adherence between a glass surface and a cardboard surface. A portion of the sample was added to a glass slide and heated to between 60°C and 100°C. Then a piece of cardboard was applied to the adhesive, which was then allowed to cool . The cardboard piece was then peeled from the glass slide.
  • Example 3 H PCE-7 was tested for thermal stability by storing in a freezer for over 24 hours two paper surfaces glued together. Once warmed to room temperature, the paper surfaces were manually pulled and remained adhered together. Further, the seam where the HPCE-7 adhered to the two paper surfaces remained flexible after the temperature cycling . This example demonstrates, to at least some extent, the temperature stability of HPCE- adhesives.
  • Example 4 Mixes of CA with intrinsic viscosities from 0.8 to 1.6 and triacetin content to CA ratio of 1 : 1 and 0.8 : 1 were prepared . The mixes were analyzed for the changes in melt temperature as a function of intrinsic viscosity. As shown in Figure 2, a substantially linear relationship was observed where increased intrinsic viscosity yields a linear increase in melt temperature. Further, a higher plasticizer concentration yields a lower melt temperature at the same intrinsic viscosity. This example demonstrates the ability to tailor the flow onset temperature response by controlling intrinsic viscosity or plasticizer concentration of H PCE-adhesives.
  • Example 5 An adhesive melt was prepared by compounding 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 at 140°C. The adhesive melt was then coated to one surface/side of a card-stock paper substrate and allowed to cool so as to yield a laminate film on the paper surface. The coated substrate was subjected to an additional heating step at 140°C for 2-3 minutes. The laminate film was glossy, flexible, and well adhered to the surface precluding the need for both film and laminating adhesive.
  • compositions and methods are described in terms of “comprising,” “containing,” or “including” various components or steps, the compositions and methods can also “consist essentially of” or “consist of” the various components and steps. All numbers and ranges disclosed above may vary by some amount. Whenever a numerical range with a lower limit and an upper limit is disclosed, any number and any included range falling within the range is specifically disclosed . In particular, every range of values (of the form, “from about a to about b,” or, equivalently, “from approximately a to b,” or, equivalently, “from approximately a-b”) disclosed herein is to be understood to set forth every number and range encompassed within the broader range of values.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne des esters de cellulose fortement plastifiés qui peuvent être utiles en tant qu'adhésifs, y compris pour une utilisation dans la production de stratifiés. Par exemple, la production d'un stratifié peut comprendre la fourniture d'un produit fondu adhésif qui comprend un adhésif contenant un ester de cellulose et un plastifiant, le plastifiant inclus en une quantité d'environ 30 % à environ 75 % en poids de l'adhésif ; l'application du produit fondu adhésif sur un substrat ; et le refroidissement naturel du produit fondu adhésif de façon à donner un stratifié sur le substrat.
EP14779331.9A 2013-03-12 2014-02-27 Adhésifs thermofusibles et sensibles à la pression qui comprennent des esters de cellulose fortement plastifiés et procédés et articles associés Withdrawn EP2970721A4 (fr)

Applications Claiming Priority (5)

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US13/796,005 US20140262017A1 (en) 2013-03-12 2013-03-12 Hot Melt and Pressure Sensitive Adhesives that Include Highly-Plasticized Cellulose Esters and Methods and Articles Relating Thereto
US13/796,234 US20140262018A1 (en) 2013-03-12 2013-03-12 Hot Melt and Pressure Sensitive Adhesives that Include Highly-Plasticized Cellulose Esters and Methods and Articles Relating Thereto
US13/795,779 US20140262016A1 (en) 2013-03-12 2013-03-12 Hot Melt and Pressure-Sensitive Adhesives that Include Highly-Plasticized Cellulose Esters and Methods and Articles Relating Thereto
US13/930,117 US20140272131A1 (en) 2013-03-12 2013-06-28 Hot Melt and Pressure Sensitive Adhesives that Include Highly-Plasticized Cellulose Esters and Methods and Articles Relating Thereto
PCT/US2014/018875 WO2014163916A1 (fr) 2013-03-12 2014-02-27 Adhésifs thermofusibles et sensibles à la pression qui comprennent des esters de cellulose fortement plastifiés et procédés et articles associés

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WO2017100156A2 (fr) * 2015-12-07 2017-06-15 Celanese International Corporation Compositions de mastic à bois d'acétate de cellulose
CN106320620A (zh) * 2016-08-23 2017-01-11 柳州市国正机电物资有限责任公司 壁纸
EP3920984B1 (fr) * 2019-02-05 2026-04-08 Bio-Bond LLC Adhésifs biodégradables
FR3100544A1 (fr) 2019-09-09 2021-03-12 Polybridge Colle thermofusible
WO2022015824A1 (fr) 2020-07-15 2022-01-20 Bio-Bond Llc Adhésif de stabilisation de palette
WO2024229781A1 (fr) * 2023-05-11 2024-11-14 Eastman Chemical (China) Co., Ltd. Électrode de dispositif de stockage d'énergie utilisant un liant d'ester de cellulose

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GB438101A (en) * 1934-02-05 1935-11-11 Du Pont Improved adhesive compositions
US2423823A (en) * 1943-06-26 1947-07-15 Bell Telephone Labor Inc Cellulose ester-polyester compositions and methods of preparing them
US3141778A (en) * 1961-04-17 1964-07-21 Celanese Corp Cellulose ester food coating composition and food articles coated therewith
EP0157021B1 (fr) * 1984-04-04 1987-09-16 Agfa-Gevaert N.V. Adjuvant de pelliculage pour des films d'ester de cellulose
TW256845B (fr) * 1992-11-13 1995-09-11 Taisyal Kagaku Kogyo Kk
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JP5470672B2 (ja) * 2004-12-09 2014-04-16 コニカミノルタ株式会社 セルロースエステルフィルムの製造方法
JP5028251B2 (ja) * 2007-12-26 2012-09-19 富士フイルム株式会社 セルロースエステルフィルム、それを用いた位相差フィルム、偏光板、および液晶表示装置
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